WO2023143489A1

WO2023143489A1 - Surface-enhanced ceramic artificial joint convex spherical friction component, and preparation method therefor

Info

Publication number: WO2023143489A1
Application number: PCT/CN2023/073512
Authority: WO
Inventors: 李亚东; 李亚军; 朱阳光
Original assignee: 苏州鼎安科技有限公司
Priority date: 2022-01-26
Filing date: 2023-01-28
Publication date: 2023-08-03
Also published as: CN114409383A

Abstract

A surface-enhanced ceramic artificial joint convex spherical friction component, and a preparation method therefor. The surface-enhanced ceramic artificial joint convex spherical friction component comprises a gradient permeation layer having a depth of 0-2500 μm and containing a component, which is the same as or different from the matrix. By means of surface prestress self-enhancement and/or surface component gradient composite enhancement, there is a surface compressive prestress of -50 MPa or above, and the compressive prestress and/or the component content is gradually decreased in a gradient manner from the surface to the inside in the radial direction. The preparation method for the surface-enhanced ceramic artificial joint convex spherical friction component comprises: S1, preparation of surface gradient seeping slurry and modified granulation powder; S2, green body forming; S3, green body pre-sintering; S4, ceramic spherical processing of the pre-sintered green body; S5, surface seeping of the pre-sintered ceramic spherical green body; S6, densification sintering of the ceramic spherical blank; S7, coarse grinding, fine grinding and polishing the surface of the ceramic spherical blank; S8, machining of the surface-enhanced ceramic artificial joint convex spherical friction component; S9, final polishing of the surface of the surface-enhanced ceramic artificial joint convex spherical friction component; and S10, inspection, marking and packaging.

Description

A surface-enhanced ceramic artificial joint convex-spherical friction component and its preparation method

technical field

The invention relates to the technical field of artificial joints, in particular to a surface-enhanced ceramic artificial joint convex spherical friction component and a preparation method thereof.

Background technique

Artificial joint replacement is a surgical method to replace the articular surface damaged by disease or injury with an artificial joint, to achieve resection of lesions, pain relief, and restoration of joint activity and original functions, including artificial hip joints, artificial knee joints and Artificial shoulder joint and many other artificial joint replacement operations. As we all know, the artificial joint friction pair, as the core component of the above-mentioned various artificial joints, is usually composed of convex spherical and concave spherical or aspheric convex spherical friction parts, and the artificial joint is realized through the relative sliding between the two friction surfaces. Movement function of joints.

Clinical application shows that various ceramic artificial joint convex spherical friction parts such as ceramic ball head, ceramic femoral unicondylar prosthesis and ceramic humeral ball head have good biocompatibility, high wear resistance and corrosion resistance, It has been widely welcomed by doctors and patients, and will become the basis for the promotion and application of ceramic artificial joint replacement in the future. However, in the prior art, the convex-spherical friction parts of traditional ceramic artificial joints are prepared from single or multi-component uniform composite powders as raw materials. Therefore, although they have the characteristics of high surface hardness, wear resistance and corrosion resistance, However, they all have low flexural strength and fracture toughness, are prone to brittle cracking, or have defects such as low-temperature aging or hydration degradation to varying degrees, so there are still problems such as sudden cracking or long-term service life reduction in clinical applications. In addition, a large number of research results show that the spherical surface processing method and low processing accuracy of traditional ceramic artificial joint convex spherical friction parts still lead to high initial wear rate, long-term clinical failure and high repair rate another main reason.

At present, the convex spherical friction parts of traditional ceramic artificial joints are formed by cold isostatic pressing process, and various convex spherical friction parts are prepared by CNC machine tools, and then the convex spherical friction parts green bodies are preformed. After sintering and hot isostatic pressing, the surface of the convex spherical friction parts needs to be roughly ground, finely ground or polished one by one with a variety of special equipment. Therefore, the convex-spherical friction parts of ceramic artificial joints obtained by traditional processing technology often have low bending strength and fracture toughness, are prone to brittle cracking, or have defects such as low-temperature aging or hydration degradation to varying degrees, so they are widely used in clinical applications. There are still risks such as sudden cracking or reduced service life in the long run. In addition, the processing technology of traditional ceramic artificial joint convex spherical friction parts is not only very cumbersome and the utilization rate of raw material powder is low, but also needs to be processed one by one, the production efficiency is very low, and the formed green body obtained by cold isostatic pressing The strength is very low. When the convex spherical friction part is molded and clamped or turned, a slight collision or vibration can easily cause micro-cracks or surface defects to form inside, and such internal micro-cracks or surface defects will be eliminated in the subsequent production process. It is difficult to completely eliminate it, which will greatly increase the risk of brittle cracking and rapid surface wear of ceramic artificial joint convex spherical friction components during clinical application. At the same time, all kinds of convex spherical friction parts of ceramic artificial joints are non-integral spheres. Therefore, the ultra-precision machining of the spherical surface not only requires expensive special equipment, but also is very difficult to precisely process, especially the convex spherical friction parts of ceramic artificial joints. The consistency of ball diameter deviation, spherical roundness, spherical surface roughness and ball diameter batch diameter is difficult to guarantee. Therefore, the yield of various ceramic artificial joint convex ball friction parts is greatly affected, and the manufacturing cost is significantly increased. It can be seen that how to further improve the quality of the friction pairs of various ceramic artificial joints, reduce the wear between friction pairs; Difficulties to be solved urgently in material and process innovation.

In order to solve the above problems, in the prior art, in addition to selecting ceramic raw materials with high hardness, good wear resistance and corrosion resistance, and no low-temperature aging phenomenon, the second phase is often dispersed in the ceramic raw materials or a multi-layer composite structure is used. To realize the strengthening and toughening of convex spherical friction parts of ceramic artificial joints, however, while the second phase is toughened, other performances of ceramic components are often affected. For example, the use of ZrO2 second phase dispersion strengthened alumina ceramics will reduce the surface hardness, wear resistance and low temperature aging resistance.

CN109336592A discloses a zirconia ceramic bone implant prosthesis and its preparation method, which makes an orthopedic implant prosthesis in which a small amount of mullite crystal grains are dispersedly distributed in the zirconia matrix, and improves the performance of the zirconia ceramic bone implant prosthesis. Grain size, density, mechanical properties and low temperature aging resistance.

F.Sommer et al. studied the mechanical properties of 1mol% yttria partially stabilized zirconia toughened alumina homogeneous ceramics (Mechanical properties of zirconia toughened alumina with 10-24 vol.%1Y-TZP reinforcement, Journal of the European Ceramic Society 32 (2012) 4177-4184), when the content of 1mol% yttria partially stabilized zirconia is 17vol.%, a zirconia toughened zirconia with a flexural strength of 1198MPa and a fracture toughness of 8.5MPa m ^1/2 can be obtained Alumina homogeneous ceramics, but the hardness HV10 drops to 1926. Claudia Ortmann et al. studied Y, Zr ion solution infiltration of alumina ceramic femoral head calcined body to obtain homogeneous zirconia toughened alumina ceramics and zirconia gradient infiltration layer on the surface of the cone hole (Preparation and characterization of ZTA bioceramics with and Without gradient in composition, Journal of the European Ceramic Society 32 (2012) 777–785) improves the microstructure of alumina ceramics and increases the crushing strength of alumina ceramic femoral heads. However, the use of Y and Zr ion solutions for infiltration can easily lead to the rapid disappearance of the gradient permeation layer due to the saturation of the ion concentration in the matrix, and the final loss of the surface compressive stress enhancement effect.

CN101947149A discloses an artificial hip joint composed of multilayer shell-core composite structural parts, including an artificial acetabulum and an artificial femoral head that cooperate with each other. The transition layer is composed of porous metal, porous alloy or porous toughened ceramic acetabular shell; the artificial femoral head has a multi-layer shell-core composite structure, which is composed of a ceramic spherical shell layer, a transition layer and a toughened ceramic inner core. The artificial acetabular lining and the artificial femoral head shell layer prepared by the invention have high hardness, corrosion resistance and wear resistance; the artificial acetabular shell layer and the femoral head inner core layer have high toughness and impact resistance; the transition layer adopts the composition The gradient composite material between the shell layer and the inner core layer has the functions of increasing the bonding strength between the shell layer and the inner core layer and reducing the interface stress between the shell layer and the inner core layer. The artificial hip joint has a long life and high reliability. and high performance features. However, the production process is complicated, and special equipment is required for surface grinding and polishing. Not only is the investment huge, but also the production efficiency is very low. The indicators such as ball diameter deviation, spherical roundness, spherical roughness, and ball diameter batch diameter still need to be further improved.

CN102009175A discloses a method for preparing a multi-layer shell-core composite structure part. In this method, the green body of the shell-core composite structure part is produced layer by layer by using the powder injection molding method, and then the shell core is prepared by degreasing, sintering and machining. The ceramic femoral head and ceramic femoral condyle and other products with composite structure have achieved the purpose of high friction surface hardness, wear resistance and uniform and controllable shell thickness. However, this technology needs to prepare different injection molds according to the size requirements of the shell layer, transition layer and core layer, and requires multiple injections on multiple or one multi-color injection molding machine to complete, and the investment in molds and equipment is relatively large. The production process is cumbersome and requires high quality control. At the same time, the processing of the aspheric surface of the convex spherical friction part of the final ceramic artificial joint is not only difficult and requires expensive special equipment, but also can only be processed one by one, the production efficiency is extremely low, and batch processing cannot be realized.

In order to reduce the cost of processing the aspherical surface of the convex spherical friction part, CN102058618A discloses an outer spherical surface machining device, which includes a machine base, a machine track, a machine tailstock, a fixture, a machining shaft, a slide plate, a horizontal continuously variable speed changer and grinding head. It can be used for spherical processing of non-complete spheres such as ceramic femoral heads, which is convenient and fast. After gradually grinding and polishing with different abrasives, it will not cause damage to the sphere, and there is no potential processing defect. However, this kind of equipment cannot meet the precise control of ball diameter deviation, spherical roundness, spherical surface roughness and ball diameter batch diameter. At the same time, it can only be processed one by one. The production efficiency and yield are low, and the manufacturing cost is high.

In order to overcome the problems of zirconia-based low-temperature aging and high brittleness of alumina-based ceramics, CN109464225A discloses a silicon nitride ceramic artificial hip joint. The ceramic artificial femoral head and other components involved are all formed by isostatic pressing of silicon nitride powder. Then it is machined according to the drawings to obtain a shaped green body, and then it is sintered and ground and polished.

CN105984019A discloses a press-forming method for a ceramic friction pair, in which a cold-isostatic pressed green body is subjected to mechanical processing of key dimensions to obtain a ceramic green body. However, the prior art usually requires processing the green body of the ceramic friction pair first. Since the strength of the formed green body after cold isostatic pressing is very low, a slight collision or vibration can easily cause the Microcracks or surface defects are formed inside the green body of the ceramic friction pair, and such internal microcracks or surface defects are difficult to completely eliminate in the subsequent production process, which will greatly increase the risk of brittle cracking during the clinical application of the ceramic friction pair.

CN106625191A discloses a method for processing silicon nitride ceramic balls, which includes steps such as rough round finding, aging treatment, fine grinding, final grinding, appearance sorting, and fine grinding. Although this method has high machining efficiency, low cost, and high precision for the whole ball, it cannot be directly used to process ceramic convex spherical non-full circle parts, and the rounding of the blank will not only lead to a significant decrease in machining efficiency, but also give the sphere Bring defects such as surface micro-cracks.

Contents of the invention

Aiming at the deficiencies in the prior art, the invention provides a surface-reinforced ceramic artificial joint convex spherical friction component and a preparation method thereof. The surface-reinforced ceramic artificial joint convex spherical friction part provided by the invention can be divided into two types: surface prestressed self-reinforced type and surface component gradient composite reinforced type. The surface prestressed self-reinforced ceramic artificial joint convex spherical friction part uses nano powder slurry with the same composition as the matrix to infiltrate the surface of the ceramic ball pre-fired biscuit, so that the surface density of the ceramic ball pre-fired biscuit forms a gradient change, After subsequent densification and sintering, the surface precompression stress gradually decreases from the surface to the inside along the radial direction, realizing the self-reinforcement effect of the surface precompression stress; The powder slurry infiltrates the surface of the ceramic ball pre-fired biscuit, so that the surface density of the ceramic ball pre-fired biscuit forms a gradient change, and at the same time, the surface component content changes from the surface to the inside along the radial gradient, and is obtained by subsequent densification and sintering. While the surface compressive stress gradually decreases along the radial direction from the surface to the inside, it realizes the composite strengthening and toughening effect of the surface component content gradient.

The surface-reinforced ceramic artificial joint convex spherical friction part provided by the present invention adopts a vacuum-assisted surface grouting process to obtain a gradient permeable layer of the same or different components within the depth of 0-2500mm on the spherical surface, and the surface of the permeable layer has the same or different components. The powder content is increased by more than 5 vol.%; after densification and sintering, the grain size is less than 1 μm, and there is at least a surface precompression stress of -50 MPa or more in the direction of the spherical tangent plane, and it is precompressed from the surface to the inside along the radial direction The stress or/and component content changes gradually; then the surface of the ceramic ball is roughly ground, finely ground, and polished to obtain a spherical roughness Ra of less than 0.005 μm, a spherical error of 0.04-0.06 μm, and a spherical roundness of 0. -0.005mm, ball batch diameter deviation less than 0.1μm, surface Vickers hardness HV ₁₀₀₀ greater than 1650, matrix flexural strength greater than 500 MPa, fracture toughness greater than 5 MPa·m ^1/2 Ceramic spheres with tensile strength greater than 45 MPa and shear strength greater than 50 MPa. Finally, through cutting and/or crowning and/or drilling and/or grinding and/or chamfering machining and final surface polishing to obtain surface-enhanced ceramic artificial joint convex spherical friction parts, the spherical surface roughness Ra is better than 0.002 mm, The abrasion resistance is better than 1×10 ^-6 cm ³ /year.

The raw material components of the surface-enhanced ceramic artificial joint convex spherical friction part include the following raw material components in parts by weight: 100 parts of powder, 0.2-4 parts of surfactant, and 0.1-5 parts of binder; The powder includes main components and sintering aids; the weight ratio of the main components and sintering aids is 94.5-99.999:0.001-5.5; the main components are nano-alumina powder, nano-zirconia powder body, nano silicon nitride powder, nano silicon carbide powder, nano zirconia toughened alumina powder, nano zirconia toughened silicon nitride powder, nano zirconia toughened silicon carbide powder, nano oxide One or more of aluminum-reinforced zirconia powder, nano-alumina-reinforced silicon nitride powder, and nano-alumina-reinforced silicon carbide powder; the sintering aids are nano-magnesia powder and nano-yttrium oxide powder body, nano-calcium oxide powder, nano-cerium oxide powder, nano-alumina powder, nano-lutetium oxide powder, nano-boron carbide powder; the surfactant is Tween 80, polyethylene glycol octylbenzene one or more of base ether, ammonium citrate, ammonia polyacrylate; the binder is polyvinyl alcohol, polyethylene glycol, polyvinyl pyrrolidone, carboxymethyl cellulose, polyethyleneimine, poly One or more of vinyl butyral and water-based phenolic resin; the surface-enhanced ceramic artificial joint convex spherical friction part includes a matrix and a gradient containing the same or different components as the matrix with a depth of 0-2500mm Penetration layer.

Preferably, the grain size of the surface-reinforced ceramic artificial joint convex spherical friction part is less than 1 μm, the Vickers hardness HV ₁₀₀₀ of the surface is greater than 1650, the bending strength of the matrix is greater than 500 MPa, and the fracture toughness is greater than 5 MPa·m ^1/2 , The tensile strength between the gradient permeable layer and the matrix is greater than 45 MPa, and the shear strength is greater than 50 MPa.

Preferably, the surface-reinforced ceramic artificial joint convex-spherical friction component is self-reinforced by surface prestress and/or surface component gradient composite reinforcement, and the spherical tangent plane direction of the surface-enhanced ceramic artificial joint convex-spherical friction component is There is a surface precompression stress above -50 MPa, and the internal precompression stress or/and component content gradually decreases in the radial direction from the surface to the inside; the spherical surface of the surface-enhanced ceramic artificial joint convex spherical friction component The degree Ra is less than 0.002 mm, the spherical error is 0.04-0.06 μm, the roundness of the spherical surface is 0-0.005 mm, and the diameter deviation of the ball batch is less than 0.1 μm; the wear resistance of the surface-enhanced ceramic artificial joint convex spherical friction component< 1×10 ^-6 cm ³ /year.

The above-mentioned method for preparing the surface-reinforced ceramic artificial joint convex-spherical friction component is characterized in that the steps of the preparation method are as follows:
S1. Preparation of surface gradient infiltration slurry and modified granulation powder: add sintering aid, surfactant, binding agent to the main component and mix to obtain a mixed slurry with a solid content of 5-45 vol%. As a surface gradient infiltration slurry; add sintering aids, surfactants, and binders to the main components for mixing, and spray dry to obtain modified granulated powder;
S2. Green body molding: put the modified granulated powder prepared in step S1 into a metal mold, and perform bidirectional pre-pressing to obtain a green body, vacuum-pack the green body in a plastic bag, and put it into cold isostatic pressing Cold isostatic pressing in the machine to make a green body;
S3. Pre-firing the green body: putting the formed green body prepared in step S2 into an atmosphere electric furnace for pre-firing to obtain a pre-fired green body with a relative density of 50-70%;
S4. Ceramic ball pre-fired biscuit processing: using a CNC numerical control machine tool to machine the pre-fired biscuit obtained in step S3 to obtain a ceramic ball pre-fired biscuit;
S5. Surface infiltration of ceramic ball pre-fired biscuit: put the ceramic ball pre-fired biscuit prepared in step S4 into a vacuum tank, pour the surface gradient infiltration slurry prepared in step S1 into it, and cover it Vacuumize, hold the pressure for infiltration, take out and dry, repeat the infiltration and drying for many times, and make the surface pre-infiltration blank;
S6. Densification and sintering of ceramic ball billets: the surface pre-infiltrated billet prepared in step S5 is put into an atmosphere electric furnace for pre-firing again to obtain a pre-fired billet with a relative density of 90-97%, which is put into hot isostatic pressing Hot isostatic pressing and co-sintering in a sintering furnace to produce a densified ceramic ball with a relative density greater than 99.9% and a continuous gradient change in the surface component content from the surface to the inside;
S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball: the densified ceramic ball prepared in step S6 is subjected to rough grinding, semi-finishing, fine grinding, super-finishing, and polishing to obtain a diameter of 14-56 mm of surface-enhanced ceramic spheres;
S8. Machining of surface-reinforced ceramic artificial joint convex-spherical friction part: machining the surface-reinforced ceramic sphere prepared in step S7 to obtain a semi-finished surface-enhanced ceramic artificial joint convex-spherical friction part; the machining is One or more of cutting, crowning, drilling, grinding, chamfering;
S9. Surface-reinforced ceramic artificial joint convex-spherical friction part surface final polishing: the friction surface of the surface-enhanced ceramic artificial joint convex-spherical friction part semi-finished product is finally polished to prepare the surface-enhanced ceramic artificial joint convex-spherical friction part ;
S10. Inspection, marking, and packaging: Carry out all quality assurance inspections on the convex spherical friction parts of the surface-enhanced ceramic artificial joint, and mark and pack the qualified products on the surface.

Preferably, in step S2, the inner diameter of the metal mold is 40-90 mm, the pressure of the two-way pre-compression is ≥ 50 MPa, the height of the blank is 100-150 mm, and the cold isostatic The hydrostatic pressure of pressure is 100-450 MPa.

Preferably, in step S3, the atmosphere used for pre-burning is one or more of air, nitrogen, argon, and hydrogen, and the pre-burning temperature for pre-burning is 1000-1700°C. The burning time is 1-10 hours, and the heating and cooling rate is 0.1-20°C/min.

Preferably, in step S4, the diameter of the ceramic ball pre-fired biscuit is 30-75mm; in step S5, the nano-powder content increase on the surface of the surface pre-infiltrated biscuit is ≥ 5 vol.%, forming Gradient permeable layer of the same or different composition as the matrix.

Preferably, in step S6, the atmosphere used for the re-calcination is one or more of air, nitrogen, argon, and hydrogen, and the re-calcination temperature is 1150-1900 ℃, the pre-sintering time is 1-10 hours, and the heating and cooling rate is 0.1-20 ℃/min; the sintering pressure for the hot isostatic pressing densification co-sintering is 5-200 MPa, and the sintering temperature is 1250-1950 ℃ , Sintering time 1-5 hours, heating and cooling rate <1 ℃ / min.

Preferably, in step S7, the grinding method is one or more of the V-groove grinding method, the self-rotation angle active control grinding method, the magnetic fluid grinding method, and the four-abrasive grinding method.

Preferably, in step S8, the semi-finished surface-enhanced ceramic artificial joint convex spherical friction component is a surface-enhanced ceramic ball head with a nominal spherical diameter of 14-52 mm, a surface-enhanced ceramic femur with a nominal spherical diameter of 40.6-55 mm Unicompartmental prosthesis, one of the surface-reinforced ceramic humeral ball heads with a nominal spherical diameter of 32-56mm.

The beneficial effects of the present invention are reflected in:
(1) The ceramic convex spherical friction part produced by the method provided by the present invention is composed of a matrix and a gradient penetration layer with a depth of 0-2500mm containing the same or different components as the matrix. It not only has surface prestress self-reinforcement and surface The component gradient composite enhances the two effects, and the spherical surface roughness Ra of the obtained ceramic convex ball friction part is 5 times lower than the surface roughness of the traditional ceramic convex ball friction part, the spherical error is 0.04-0.06μm, and the spherical surface is round The precision is 0-0.005mm, and the diameter deviation of the ball batch is less than 0.1μm; therefore, when used in conjunction with ultra-high molecular weight or high cross-linked polyethylene or ceramic friction surfaces, it can further reduce its wear rate and improve the service life of ceramic artificial joints.

(2) The method provided by the present invention performs machining on the pre-fired biscuit of the ceramic convex ball friction part, avoiding the internal microstructures that are prone to occur during the processing process due to the low strength of the green body of the convex ball friction part in the traditional technology. Cracks and surface defects, improve the pass rate and surface quality of ceramic convex spherical friction parts, reduce the risk of brittle cracking in the clinical application of ceramic artificial joint convex spherical friction parts; The pre-fired billet of the spherical friction part has good roundness, and the net size ceramic ball billet can be obtained after densification and sintering, which eliminates the rounding process during the precision machining of the whole ball, and greatly improves the machining accuracy and production efficiency.

(3) The method provided by the present invention uses vacuum-assisted infiltration of the nano-ceramic powder slurry on the surface of the pre-fired biscuit of the ceramic convex spherical friction part, and after densification and sintering, it forms a surface precompressed stress and a gradient change in composition. The shell-layer composite structure of the transition layer obtains two surface strengthening effects: surface prestressed self-reinforcement type and surface component gradient composite reinforcement type, so as to further improve the spherical hardness, wear resistance and fatigue failure resistance of ceramic artificial joint convex spherical friction parts ability.

(4) The method provided by the present invention adopts the traditional ceramic integral ball processing technology, completely avoids the difficulty of ultra-precision machining of non-integral spheres, and realizes the spherical diameter deviation, spherical roundness, spherical surface roughness and spherical diameter of ceramic convex spherical friction components. The precise control of the batch diameter further reduces the initial wear rate, clinical failure and repair rate of the friction interface of the ceramic artificial joint convex spherical friction part, and improves the service life of the surface-enhanced ceramic artificial joint convex spherical friction part.

(5) The method provided by the present invention adopts the traditional ceramic whole ball processing technology to prepare the surface-reinforced ceramic whole ball, and then cuts, crowns, grinds, and chamfers the surface-enhanced ceramic ball to ensure the deviation of the ball diameter and the roundness of the spherical surface Degree, spherical roughness, and ball diameter batch diameter consistency, to achieve high-efficiency, high-quality, and mass production of surface-enhanced ceramic artificial joint convex ball friction components.

Description of drawings

In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings that need to be used in the description of the specific embodiments or the prior art. Throughout the drawings, similar elements or parts are generally identified by similar reference numerals. In the drawings, elements or parts are not necessarily drawn in actual scale.

Fig. 1 is the flow chart of preparation method provided by the present invention;
Figure 2 is a typical schematic diagram and section view AA of a surface-enhanced ceramic ball head;
Figure 3 is one of the typical schematic diagrams of the surface-enhanced ceramic spherical femoral unicondyle and the cross-sectional view BB;
Fig. 4 is a typical schematic diagram of surface-enhanced ceramic spherical femoral unicondyle II and section view CC;
Fig. 5 is a typical schematic diagram and cross-sectional view DD of a surface-enhanced ceramic humeral ball head.

1-Surface-enhanced ceramic ball head, 1-1 Surface-enhanced ceramic ball head gradient penetration layer, 1-2 Surface-enhanced ceramic ball head matrix, 1-3 Surface-enhanced ceramic ball head taper hole; 2-Surface-enhanced ceramic femoral spherical unicondyle One, 2-1 surface-reinforced ceramic femoral unicondyle one gradient permeable layer, 2-2 surface-reinforced ceramic femoral unicondyle one base; 3- surface-reinforced ceramic femoral unicondyle 2, 3-1 surface enhancement Ceramic femoral spherical unicondyle two gradient infiltration layer, 3-2 surface reinforced ceramic femoral spherical unicondyle two matrix; 4-surface reinforced ceramic humeral ball head, 4-1 surface enhanced ceramic humeral ball head gradient infiltration layer, 4-2 Surface-reinforced ceramic humerus ball head matrix, 4-3 surface-reinforced ceramic humerus ball head taper hole.

Implementation

Embodiments of the technical solutions of the present invention will be described in detail below in conjunction with the accompanying drawings. The following examples are only used to illustrate the technical solutions of the present invention more clearly, and therefore are only examples, rather than limiting the protection scope of the present invention.

It should be noted that, unless otherwise specified, the technical terms or scientific terms used in this application shall have the usual meanings understood by those skilled in the art to which the present invention belongs.

The preparation method provided by the embodiments of the present invention and the obtained surface-enhanced ceramic artificial joint convex spherical friction parts; wherein, the structures of Examples 1-13 are shown in Figure 2, and the structures of Examples 14-20 are shown in Figure 3 , The structure of Embodiment 21-25 is shown in Figure 4, and the structure of Embodiment 26-36 is shown in Figure 5.

Example 1: Surface self-reinforced nano-alumina ceramic ball head
S1. Formulation/milling and preparation of surface gradient slurry and modified granulated powder: Weigh an appropriate amount of nano-alumina powder with a purity of 99.9 wt.% or more, add 0.1 wt% of its mass to nano-magnesia for sintering Auxiliary agent, 0.3 wt.% Tween 80 surfactant and 3wt.% polyvinyl alcohol are made into water-based slurry with a solid content of 25vol%, part of which is used as surface gradient slurry; the other part is made by spray drying granulation process The modified nano-alumina granulated powder is obtained.

S2. Green body molding: put the modified nano-alumina granulated powder obtained in step S1 into a metal mold with an inner diameter of 70 mm, and bidirectionally pre-press at 50 MPa to form a preform with a height of 100 mm, and then put the modified nano-alumina The aluminum powder dry-pressed blank is vacuum-packed in a plastic bag, put into a cold isostatic press, and subjected to cold isostatic pressing under a hydrostatic pressure of 250 MPa to obtain a modified nano-alumina powder molded green body.

S3. Blank pre-sintering: Put the modified nano-alumina powder formed green body obtained in step S2 into an electric furnace for pre-sintering. The air atmosphere, pre-sintering temperature is 1180 ° C, pre-sintering holding time is 2 hours, and the temperature is raised and lowered. The speed was 5°C/min, and a modified nano-alumina ceramic calcined green body with a relative density of 52% was obtained.

S4. Ceramic ball pre-fired biscuit processing: According to the size requirements of the drawing, the modified nano-alumina ceramic pre-fired bisque obtained in step S3 is machined with a CNC machine tool to obtain a modified nano-alumina ceramic with a diameter of 44 mm. Ball pre-fired biscuit.

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the modified nano-alumina ceramic ball pre-fired biscuit obtained in step S4 into a vacuum tank, and then pour the nano-alumina surface gradient infiltration slurry obtained in step S1 , the cover is evacuated to -0.08MPa, and after holding the pressure for 5 minutes, the surface gradient infiltration slurry is gradually infiltrated into the surface layer of the modified nano-alumina ceramic ball pre-fired biscuit, and the content of nano-alumina powder on the surface of the infiltration layer increases by 7.3vol .%, to obtain a modified nano-alumina ceramic ball pre-infiltration green body with a surface pre-infiltration gradient nano-alumina ceramic slurry, and the depth of the gradient infiltration layer is 1500 microns.

S6. Densification and sintering of ceramic ball billets: firstly, put the pre-infiltrated body of nano-alumina ceramic balls obtained in S5 into an air electric furnace for further pre-sintering. min, the modified nano-alumina ceramic ball pre-sintered body with a relative density of 97% was obtained; finally, the modified nano-alumina ceramic ball pre-sintered body was put into a hot isostatic pressing sintering furnace for densification sintering, and the sintering temperature was 1500°C, sintering holding time of 2 hours, heating and cooling rate of 1°C/min, sintering gas pressure of 200MPa, the final diameter is 32.6mm, the relative density is 99.92%, the grain size is 528nm, gradient infiltration coating and substrate The tensile strength between them is 45.8 MPa, the shear strength is 65.5 MPa, the matrix flexural strength is 510 MPa, and the fracture toughness is 4.5 MPa·m ^1/2 surface prestressed self-reinforced nano-alumina ceramic sphere.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the surface prestressed self-reinforced nano-alumina dense ceramic ball blank obtained in S6 into a V-shaped groove grinding device for at least rough grinding, semi-finishing, Finishing, ultra-finishing and polishing are processed into a nominal diameter of 32 mm, a ball surface roughness Ra of 0.005 mm, a spherical error of 0.04 μm, a spherical roundness of 0.003 mm, and a ball batch diameter deviation of 0.06 μm , the surface hardness HV ₁₀₀₀ is 2100, there is a prestress of -280 MPa in the direction of the spherical tangent plane, and the surface prestressed self-reinforced nano-alumina ceramic balls change gradually from the surface to the inside in the radial direction.

S8. Machining of surface prestressed reinforced nano-alumina ceramic ball head: According to the size requirements of the surface prestressed reinforced nano-alumina ceramic ball head drawing, the surface prestressed self-reinforced ceramic ball obtained in S7 is cut and/or crowned and/or or drilling and/or chamfering to prepare a surface prestressed self-stressed surface with a nominal diameter of 32 mm, a gradient permeable layer depth of 800 mm, a spherical cap height of 28 mm, a taper hole diameter of 14 mm, and a hole taper of 1:10. Reinforced nano-alumina ceramic ball head.

S9. Final polishing of the surface prestressed nano-alumina ceramic ball head: the final polishing of the spherical surface of the surface prestressed self-reinforced nano-alumina ceramic ball head, so that the spherical surface roughness Ra is 0.002mm, and the wear resistance is 0.8×10 ^-6 cm ³ /year.

S10. Inspection/marking/packaging: Carry out all quality assurance inspections on the surface prestressed self-reinforced nano-alumina ceramic ball heads, and mark and pack qualified products on the surface.

Example 2: Surface self-reinforced nano-zirconia ceramic ball head
S1. Formulation/milling and preparation of surface gradient infiltration slurry and modified granulated powder: Weigh an appropriate amount of nanometer 3 mol% yttrium oxide partially stabilized zirconia powder with a purity of 99.9 wt.% or more, and add its mass of 0.2 Wt.% Tween 80 and 2wt.% polyvinyl alcohol are made into aqueous slurry with a solid content of 35vol%, part of which is used as a surface gradient slurry; the other part is made of nanometer 3 mol% yttrium oxide by spray drying and granulation process Stabilized zirconia spherical powder.

S2. Green body molding: put the nanometer 3 mol% yttrium oxide partially stabilized zirconia spherical powder obtained in the step S1 into a metal mold with an inner diameter of 70 mm, and bidirectionally prepress at 100 MPa to form a preform with a height of 100 mm, and then The dry-pressed preform of nanometer 3 mol% yttrium oxide partially stabilized zirconia spherical powder was vacuum-packed in a plastic bag, put into a cold isostatic press, and cold isostatic pressed under a hydrostatic pressure of 150MPa to obtain nanometer 3 mol% yttrium oxide partially stabilized zirconia powder to form a green body.

S3. Pre-sintering of the biscuit: put the green body formed by the nanometer 3 mol% yttrium oxide partially stabilized zirconia powder obtained in the step S2 into an electric furnace for pre-sintering, the air atmosphere, the pre-sintering temperature is 1050°C, and the pre-sintering time is 2 hours , the heating and cooling rate was 5°C/min, and the relative density was 51% to obtain a partially stabilized zirconia ceramic calcined body with nanometer 3 mol% yttria.

S4. Ceramic ball pre-fired biscuit processing: according to the size requirements of the drawings, CNC numerical control machine tools are used to machine the nanometer 3 mol% yttrium oxide partially stabilized zirconia ceramic pre-fired bisque obtained in step S3 to obtain nanometer balls with a diameter of 49 mm. 3 mol% yttria partially stabilized zirconia ceramic balls pre-fired biscuits.

S5. Surface infiltration of ceramic ball pre-fired biscuits: put the nanometer 3 mol% yttrium oxide partially stabilized zirconia ceramic ball pre-fired biscuits obtained in step S4 into a vacuum tank, and then pour the surface gradient infiltration obtained in step S1 Slurry, the cover is vacuumed to -0.08 MPa, so that the surface gradient infiltration slurry gradually infiltrates into the surface layer of the pre-fired biscuit of nanometer 3 mol% yttrium oxide partially stabilized zirconia ceramic balls. After holding the pressure for 20 minutes, a surface pre-infiltration Gradient nanometer 3 mol% yttria partially stabilized zirconia ceramic slurry pre-infiltrated green body with nanometer 3 mol% yttria partially stabilized zirconia ceramic balls, the content of nano zirconia powder on the surface of the infiltration layer increased by 13.8 vol.%, and the gradient infiltration layer The depth is 2500 microns.

S6. Densification and sintering of ceramic ball billets: firstly, put the pre-infiltrated green body of nanometer 3 mol% yttrium oxide partially stabilized zirconia ceramic balls obtained in S5 into an air electric furnace for further pre-sintering, the sintering temperature is 1450°C, and the sintering holding time is 2 hours, the heating and cooling rate was 5°C/min, and the calcined green body of nanometer 3 mol% yttrium oxide partially stabilized zirconia ceramic balls with a relative density of 97% was obtained; then, the nanometer 3 mol% yttrium oxide partially stabilized zirconia ceramic balls were The sintered body was put into a hot isostatic sintering furnace for densification sintering. The sintering temperature was 1420 °C, the sintering gas pressure was 110 MPa, the sintering time was 1 hour, and the heating and cooling rate was 1 °C/min. The density is 99.9%, the grain size is 332 nanometers, the tensile strength between the gradient infiltration coating and the substrate is 68 MPa, the shear strength is 76.5 MPa, the flexural strength of the substrate is 1500 MPa, and the fracture toughness is 10 MPa m ^{1 /2} nanometer 3 mol% yttria partially stabilized zirconia ceramic spheres.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nanometer 3 mol% yttrium oxide partially stabilized zirconia ceramic ball blank obtained in S6 into the grinding equipment with active control of the rotation angle for at least rough grinding and semi-finishing step by step , lapping, ultra-finishing, and polishing are processed into a nominal diameter of 36 mm, a ball surface roughness Ra of 0.005 mm, a spherical error of 0.04 μm, a spherical roundness of 0.002 mm, and a ball batch diameter deviation of 0.09 μm, surface hardness HV ₁₀₀₀ is 1650, surface prestressed self-reinforced nanometer 3 mol% yttrium oxide partially stabilized zirconia dense ceramic balls with -135 MPa precompression stress on the surface.

S8. Machining of surface prestressed self-reinforced nano-zirconia ceramic ball head: According to the size requirements of the surface pre-stressed self-reinforced nano-zirconia ceramic ball head drawing, the surface pre-stressed self-reinforced 3 mol% yttrium oxide obtained in step S7 is partially stabilized Zirconia ceramic balls are prepared by cutting and/or crowning and/or drilling and/or chamfering to a nominal diameter of 36 mm, a depth of gradient permeation layer of 1600 mm, a spherical crown height of 31.4 mm, and a cone diameter of 14 mm. mm, surface prestressed self-reinforced 3 mol% yttria partially stabilized nano-zirconia ceramic ball heads with a hole taper of 1:10.

S9, surface prestressed self-reinforced nano-zirconia ceramic ball head surface final polishing: the spherical surface of the surface pre-stressed enhanced 3 mol% yttrium oxide partially stabilized nano-zirconia ceramic ball head is finally polished, so that the surface roughness Ra is 0.002mm, The abrasion resistance is 0.6×10 ^-6 cm ³ /year.

S10. Inspection/marking/packaging: The surface prestressed self-reinforced 3 mol% yttrium oxide partially stabilized nano-zirconia ceramic ball head is subjected to all quality assurance inspections, and the bottom surface of qualified products is laser marked and packaged.

Embodiment 3: surface self-reinforced nano-silicon nitride ceramic ball head
S1. Formulation/milling and preparation of surface gradient slurry and modified granulated powder: Weigh an appropriate amount of silicon nitride powder with a purity of 99.9 wt.% or more, and add 0.5 wt% of its mass to nano-alumina powder body and 0.1wt% nano-yttrium oxide powder, 0.5 wt.% Tween 80 and 2 wt.% polyvinylpyrrolidone to make an aqueous slurry with a solid content of 30vol%, part of which is used as a surface gradient slurry; the other part is passed through Nano-modified silicon nitride granulated powder was prepared by spray drying granulation process.

S2. Green body molding: put the nano-modified silicon nitride granulated powder obtained in step S1 into a metal mold with an inner diameter of 75 mm, and bidirectionally pre-press at 120 MPa to form a pre-form with a height of 150 mm. The dry-pressed preform of non-toxic silicon nitride granulated powder is vacuum-packed in a plastic bag, put into a cold isostatic press, and cold isostatic pressed under a hydrostatic pressure of 250MPa to obtain nano-modified silicon nitride granules. Powder molding green body.

S3. Blank pre-sintering: put the nano-modified silicon nitride granulated powder formed green body obtained in step S2 into a pressure sintering electric furnace for pre-sintering, nitrogen atmosphere, pre-sintering temperature of 1650°C, and pre-sintering time of 2 hours , the heating and cooling rate was 2°C/min, and a nano-modified silicon nitride ceramic calcined green body with a relative density of 55% was obtained.

S4. Ceramic ball pre-fired biscuit processing: according to the size requirements of the drawing, use CNC numerical control machine tools to machine the nano-modified silicon nitride ceramic pre-fired bisque obtained in step S3 to obtain nano-modified silicon nitride ceramic pre-fired biscuits with a diameter of 54 mm. Silicon ceramic ball pre-fired biscuit.

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the nano-modified silicon nitride ceramic ball pre-fired biscuit obtained in step S4 into a vacuum tank, then pour the surface gradient infiltration slurry obtained in step S1, cover The cover is vacuumed to -0.10 MPa, so that the surface gradient infiltration slurry gradually infiltrates into the surface layer of the pre-fired biscuit of nano-modified silicon nitride ceramic balls through the capillary. The nano-modified silicon nitride ceramic ball pre-infiltrated green body of silicon slurry, the content of nano-silicon nitride powder on the surface of the permeation layer increased by 10.2 vol.%, and the depth of the gradient permeation layer was 1500 microns.

S6. Densification and sintering of ceramic ball billets: firstly, put the pre-infiltrated body of nano-modified silicon nitride ceramic balls obtained in S5 into an atmosphere-protected electric furnace for further pre-sintering. The sintering temperature is 1820°C, and the sintering time is 5 hours. The speed is 1°C/min, and the nano-modified silicon nitride ceramic ball pre-sintered body with a relative density of 97% is obtained; then, the nano-modified silicon nitride ceramic ball pre-sintered body is placed in a hot isostatic pressing sintering furnace for densification Chemical sintering, the sintering temperature is 1720°C, the sintering gas pressure is 180 MPa, the sintering time is 4 hours, the heating and cooling rate is 1°C/min, and finally the diameter is 40.5 mm, the relative density is 99.85%, the grain size is 508 nm, The tensile strength between the gradient infiltration coating and the substrate is 128 MPa, the shear strength is 176.5 MPa, the flexural strength of the substrate is 1200 MPa, and the fracture toughness is 8 MPa·m ^1/2 . Modified silicon nitride ceramic ball blank.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nano-modified silicon nitride ceramic ball blank obtained in S6 into the magnetic fluid grinding equipment for at least rough grinding and semi-finishing in steps. , lapping, ultra-finishing, and polishing are processed into a nominal diameter of 40 mm, a ball surface roughness Ra of 0.004 mm, a spherical error of 0.04 μm, a spherical roundness of 0.001 mm, and a ball batch diameter deviation of 0.06 μm, surface hardness HV ₁₀₀₀ is 1980, surface prestressed self-reinforced nano-modified silicon nitride ceramic balls with -320 MPa prestress on the surface.

S8. Machining of surface prestressed self-reinforced nano-silicon nitride ceramic ball head: according to the size requirements of the surface pre-stressed self-reinforced nano-silicon nitride ceramic ball head drawing, the surface prestressed self-reinforced nano-modified nitride obtained in step S7 Silicon ceramic balls are prepared by cutting and/or crowning and/or drilling and/or chamfering to a nominal diameter of 40 mm, a gradient penetration layer depth of 900 mm, a spherical crown height of 34.9 mm, and a cone diameter of 14 mm , The surface prestressed self-reinforced nano-modified silicon nitride ceramic ball head with a hole taper of 1:10.

S9. Final polishing of the surface prestressed self-reinforced nano-silicon nitride ceramic ball head: the final polishing of the spherical surface of the surface prestressed self-reinforced nano-modified silicon nitride ceramic ball head, so that the surface roughness Ra is 0.002mm, and the surface roughness Ra is 0.002mm. The abrasiveness is 0.3×10 ^-6 cm ³ /year.

S10. Inspection/marking/packaging: The surface prestressed self-reinforced nano-modified silicon nitride ceramic ball head is subjected to all quality assurance inspections, and the bottom surface of qualified products is laser marked and packaged.

Embodiment 4: surface self-reinforced nano-silicon carbide ceramic ball head
S1. Formulation/milling and preparation of surface gradient slurry and modified granulated powder: Weigh an appropriate amount of silicon carbide powder with a purity of 99.9 wt.% or more, and add 2.1 wt% of nano-boron carbide powder As a sintering aid, 0.8 wt.% Tween 80 as a surfactant and 2.5 wt.% polyvinylpyrrolidone as a binder to make an aqueous slurry with a solid content of 30vol%, one part is used as a surface gradient slurry; the other part The nano-modified silicon carbide granulated powder is prepared through a spray-drying granulation process.

S2. Green body molding: put the nano-modified silicon carbide granulated powder obtained in step S1 into a metal mold with an inner diameter of 75 mm, and bidirectionally pre-press 120 MPa into a preform with a height of 120 mm, and then put the nano-modified silicon carbide The dry-pressed blank of the granulated powder is vacuum-packed in a plastic bag, placed in a cold isostatic press, and subjected to cold isostatic pressing under a hydrostatic pressure of 350 MPa to obtain a nano-modified silicon carbide granulated powder. Blank.

S3. Blank pre-sintering: put the nano-modified silicon carbide granulated powder formed green body obtained in step S2 into a gas pressure sintering electric furnace for pre-sintering, in an argon atmosphere, at a pre-sintering temperature of 1650°C, and at a pre-sintering time of 2 hours , the heating and cooling rate was 2°C/min, and a nano-modified silicon carbide ceramic calcined green body with a relative density of 55% was obtained.

S4. Ceramic ball pre-fired bisque processing: according to the size requirements of the drawings, use CNC numerical control machine tools to machine the nano-modified silicon carbide ceramic pre-fired bisque obtained in step S3 to obtain nano-modified silicon carbide ceramics with a diameter of 59 mm Ball pre-fired biscuit.

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the nano-modified silicon carbide ceramic ball pre-fired biscuit obtained in step S4 into a vacuum tank, then pour the surface gradient infiltration slurry obtained in step S1, and cover Vacuum down to -0.10 MPa to make the surface gradient infiltration slurry gradually infiltrate into the surface layer of the nano-modified silicon carbide ceramic ball pre-fired biscuit. After holding the pressure for 30 minutes, a nano Modified silicon carbide ceramic ball pre-infiltrated body, the content of nano-silicon carbide powder on the surface of the infiltration layer increased by 10.3 vol.%, and the depth of the gradient infiltration layer was 2000 microns.

S6. Densification and sintering of ceramic ball billets: firstly, put the pre-infiltrated body of nano-modified silicon carbide ceramic balls obtained in S5 into an atmosphere-protected electric furnace for further pre-sintering. The sintering temperature is 1890°C, and the sintering time is 5 hours. 1°C/min to obtain a nano-modified silicon carbide ceramic ball pre-sintered body with a relative density of 98%; then, put the nano-modified silicon carbide ceramic ball pre-sintered body into a hot isostatic pressing sintering furnace for densification and sintering. The sintering temperature was 1820°C, the sintering gas pressure was 180 MPa, the sintering time was 3 hours, and the heating and cooling rate was 1°C/min. Finally, a gradient infiltration coating with a diameter of 44.2 mm, a relative density of 99.9%, and a grain size of 612 nm was obtained. The tensile strength between the layer and the matrix is 78 MPa, the shear strength is 87.2 MPa, the flexural strength of the matrix is 720 MPa, and the fracture toughness is 5.6 MPa m ^1/2 . Silicon ceramic ball blank.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nano-modified silicon carbide ceramic ball blank obtained in S6 into the V-shaped groove grinding equipment for at least rough grinding and semi-finishing in steps. , lapping, ultra-finishing, and polishing are processed into a nominal diameter of 44 mm, a ball surface roughness Ra of 0.004 mm, a spherical error of 0.05 μm, a spherical roundness of 0.002 mm, and a ball batch diameter deviation of 0.08 μm, the surface hardness HV ₁₀₀₀ is 2380, and there is a surface prestressed self-reinforced nano-modified silicon carbide ceramic ball with -490 MPa prestress on the surface.

S8. Machining of surface prestressed self-reinforced nano-silicon carbide ceramic ball head: according to the size requirements of the surface pre-stressed self-reinforced nano-silicon carbide ceramic ball head drawing, the surface prestressed self-reinforced nano-modified silicon carbide ceramic ball obtained in step S7 Crown cutting, drilling and chamfering were performed to prepare a surface prestressed surface with a nominal diameter of 44 mm, a gradient permeable layer depth of 1400 mm, a spherical crown height of 38.3 mm, a taper hole diameter of 14 mm, and a hole taper of 1:10. Self-reinforced nano-modified silicon carbide ceramic ball heads.

S9. Final polishing of the surface prestressed self-reinforced nano-silicon carbide ceramic ball head: the final polishing of the spherical surface of the surface pre-stressed self-reinforced nano-modified silicon carbide ceramic ball head, so that the surface roughness Ra is 0.002 mm, and the wear resistance is improved. 0.8×10 ^-6 cm ³ /year.

S10. Inspection/marking/packaging: The surface prestressed self-reinforced nano-modified silicon carbide ceramic ball head is subjected to all quality assurance inspections, and the bottom surface of qualified products is laser marked and packaged.

Example 5: Surface self-reinforced nano-zirconia toughened alumina composite ceramic ball head
S1. Formulation/milling and preparation of surface gradient slurry and modified granulated powder: Weigh an appropriate amount of 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite powder with a purity of 99.9 wt.% or more , add its quality 0.4 wt.% Tween 80 and 4wt.% polyvinyl alcohol to make an aqueous slurry with a solid content of 25vol%, part of which is used as a surface gradient slurry; % Yttrium oxide partially stabilized nano-zirconia toughened alumina composite granulated powder.

S2. Green body molding: put the 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite granulation powder obtained in the step S1 into a metal mold with an inner diameter of 82 mm, and bidirectionally pre-press at 150 MPa to a height of 120 mm. mm of dry-pressed preform, and then dry-pressed preform of 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite granulation powder in a plastic bag, put it into a cold isostatic press, and Cold isostatic pressing was carried out under a hydrostatic pressure of 250 MPa to obtain a 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite granulated powder to form a green body.

S3, green body pre-sintering: put the 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite granulated powder obtained in step S2 into the green body for pre-sintering in an electric furnace, and the air atmosphere and pre-sintering temperature are 1200 ℃, the pre-firing time is 2 hours, and the heating and cooling rate is 5 ℃/min, and the relative density is 52%, and the 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic calcined green body is obtained.

S4. Ceramic ball pre-fired biscuit processing: According to the size requirements of the drawing, CNC numerical control machine tools are used to machine the 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic pre-fired bisque bisque obtained in step S3, A calcined green body of 3 mol% yttria partially stabilized nano-zirconia toughened alumina composite ceramic balls with a diameter of 65 mm was obtained.

S5. Surface infiltration of ceramic ball pre-fired biscuits: put the 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic ball pre-fired biscuits obtained in step S4 into a vacuum tank, and then pour them into step S1 to obtain The surface gradient infiltration slurry, the cover is evacuated to -0.09 MPa, so that the surface gradient infiltration slurry gradually penetrates into the surface layer of the pre-fired biscuit of 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic balls through the capillary , after holding the pressure for 20 min, a 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic pre-infiltrated body with a pre-infiltrated surface gradient slurry was obtained, and the surface of the infiltrated layer was nano-zirconia-toughened alumina composite The powder content increased by 9.3 vol.%, and the depth of gradient permeation layer was 1600 microns.

S6. Densification and sintering of ceramic ball billets: firstly, the 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic pre-infiltrated green body obtained in S5 was put into an air electric furnace for further pre-sintering, and the sintering temperature was 1450°C. The sintering time was 2 hours, the heating and cooling rate was 5°C/min, and a 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic ball pre-sintered body with a diameter of 48.6 mm and a relative density of 96% was obtained; then, the The 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic ball pre-sintered body was placed in a hot isostatic pressing sintering furnace for densification sintering. The sintering temperature was 1420 °C, the sintering gas pressure was 150 MPa, and the sintering time was 1 hour, the heating and cooling rate is 1°C/min, and finally the relative density is 99.9%, the grain size is 493 nm, the tensile strength between the gradient infiltration coating and the substrate is 128 MPa, and the shear strength is 137 MPa. The flexural strength is 950 MPa, the fracture toughness is 7 MPa·m ^1/2 , and the 3 mol% yttria partially stabilized nano-zirconia toughened alumina composite ceramic sphere has surface prestressed self-reinforcement.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: the surface prestressed self-reinforced 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic ball blank obtained in S6 is put into the grinding equipment with four grinding tools At least 5 processes of rough grinding, semi-finishing, fine grinding, super-finishing and polishing are carried out step by step to produce a nominal diameter of 48 mm, a depth of gradient permeation layer of 950 mm, a spherical surface roughness Ra of 0.005 mm, and a spherical error of 0.05 μm, spherical roundness of 0.005 mm, ball batch diameter deviation of 0.04 μm, surface hardness HV ₁₀₀₀ of 2000, surface prestressed self-reinforced 3 mol% yttrium oxide partly stabilized nano oxide with -240 MPa precompression stress on the surface Zirconium toughened alumina composite ceramic balls.

S8. Machining of surface self-reinforced nano-zirconia toughened alumina composite ceramic ball head: According to the size requirements of the surface self-reinforced nano-zirconia toughened alumina composite ceramic ball head drawing, the surface prestressed self-reinforced 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic balls were cut and/or crowned and/or drilled and/or chamfered to prepare a nominal diameter of 48 mm, a spherical crown height of 41.8 mm, The diameter of the cone hole is 14 mm, and the hole taper is 1:10. The surface prestressed reinforced nanometer 3 mol% yttria partially stabilized zirconia toughened alumina composite ceramic ball head.

S9. Surface self-reinforced nano-zirconia toughened alumina composite ceramic ball head surface final polishing: the surface prestressed self-reinforced 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic ball head friction convex surface is finally polished. Polishing so that the surface roughness Ra is 0.002mm, and the wear resistance is 0.9×10 ^-6 cm ³ /year.

S10. Inspection/marking/packaging: The surface prestressed self-reinforced nano zirconia toughened alumina composite ceramic ball head is subjected to all quality assurance inspections, and the bottom surface of qualified products is laser marked and packaged.

Example 6: Surface self-reinforced nano-alumina reinforced zirconia composite ceramic ball head
S1. Formulation/milling and preparation of surface gradient infiltration slurry and modified granulated powder: Weigh an appropriate amount of nano-alumina reinforced 3 mol% yttria partially stabilized zirconia composite powder with a purity of more than 99.8 wt.%, Add 0.2 wt.% Tween 80 and 3 wt.% polyvinylpyrrolidone to make an aqueous slurry with a solid content of 35 vol%, part of which is used as a surface gradient slurry; the other part is prepared by spray drying granulation process Alumina reinforced 3 mol% yttria partially stabilized zirconia composite granulated powder.

S2. Green body molding: put the nano-alumina reinforced 3 mol% yttria partially stabilized zirconia composite granulation powder obtained in step S1 into a metal mold with an inner diameter of 90 mm, and pre-press bidirectionally at 80 MPa to a height of 150 mm. dry-pressed preform, and then dry-press the preform of nano-alumina reinforced 3 mol% yttrium oxide partially stabilized zirconia composite granulation powder in a plastic bag, put it into a cold isostatic press, and Cold isostatic pressing was carried out under hydrostatic pressure to obtain nano-alumina reinforced 3 mol% yttrium oxide partially stabilized zirconia composite granulated powder to form a green body.

S3. Green body pre-sintering: the nano-alumina reinforced 3 mol% yttrium oxide partially stabilized zirconia composite granulated powder obtained in step S2 is put into an electric furnace for pre-sintering, and the air atmosphere and pre-sintering temperature are 1100°C , The pre-firing time was 2 hours, and the heating and cooling rate was 3°C/min to obtain a calcined green body of nano-alumina reinforced 3 mol% yttria partially stabilized zirconia composite ceramics with a relative density of 55%.

S4. Ceramic ball pre-fired biscuit processing: According to the size requirements of the drawings, CNC numerical control machine tools are used to machine the nano-alumina reinforced 3 mol% yttrium oxide partially stabilized zirconia composite ceramic pre-fired bisque obtained in the step S3, and the obtained diameter is 70 mm nano-alumina reinforced 3 mol% yttria partially stabilized zirconia composite ceramic ball pre-fired green body.

S5. Surface infiltration of ceramic ball pre-fired biscuits: put the nano-alumina reinforced 3 mol% yttrium oxide partially stabilized zirconia composite ceramic ball pre-fired biscuits obtained in step S4 into a vacuum tank, and then pour the obtained in step S1 The surface gradient infiltration slurry, the cover is vacuumed to -0.08MPa, so that the surface gradient infiltration slurry gradually infiltrates the surface layer of the pre-fired biscuit of nano-alumina reinforced 3 mol% yttrium oxide partially stabilized zirconia composite ceramic balls, and the pressure is maintained for 8 After 1 min, the pre-infiltrated green body of nano-alumina reinforced 3 mol% yttria partially stabilized zirconia composite ceramic balls with pre-infiltrated surface gradient slurry was obtained, and the content of nano-alumina-reinforced zirconia composite powder on the surface of the infiltrated layer increased by 12 vol.%, the gradient permeation layer depth is 1800 microns.

S6. Densification and sintering of ceramic ball billets: first, put the pre-infiltrated body of nano-alumina reinforced 3 mol% yttria partially stabilized zirconia composite ceramic balls obtained in S5 into an air electric furnace for further pre-sintering, and the sintering temperature is 1400 °C, The sintering time was 2 hours, the heating and cooling rate was 2°C/min, and the nano-alumina reinforced 3 mol% yttria partially stabilized zirconia composite ceramic balls with a diameter of 52.6 mm and a relative density of 97% were calcined. Then, the nano-alumina reinforced 3 mol% yttria partially stabilized zirconia composite ceramic ball pre-sintered body was put into a hot isostatic pressing sintering furnace for densification and sintering. The sintering temperature was 1420 ° C and the sintering gas pressure was 100 MPa, sintering time of 1 hour, heating and cooling rate of 1°C/min, finally obtained a relative density of 99.9%, a grain size of 378 nm, a tensile strength of 58 MPa between the gradient infiltration coating and the substrate, and a shear strength of Nano-alumina reinforced 3 mol% yttria partially stabilized zirconia composite ceramic spheres with a matrix flexural strength of 1650 MPa and a fracture toughness of 12 MPa m ^1/2 .

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nano-alumina reinforced 3 mol% yttrium oxide partially stabilized zirconia composite ceramic ball blank obtained in S6 into a V-shaped groove grinding device for at least rough grinding, Semi-finishing, lapping, super-finishing and polishing are processed into a nominal diameter of 52 mm, a ball surface roughness Ra of 0.003 mm, a spherical error of 0.06 μm, a roundness of the spherical surface of 0.002 mm, and a ball batch diameter of The deviation is 0.05 μm, the surface hardness HV ₁₀₀₀ is 1800, and the surface prestressed self-reinforced nano-alumina reinforced 3 mol% yttria partially stabilized zirconia composite ceramic balls with -178 MPa precompression stress on the surface.

S8. Machining of surface self-reinforced nano-alumina reinforced zirconia composite ceramic ball head: According to the size requirements of the surface self-reinforced nano-alumina reinforced zirconia composite ceramic ball head, the surface prestressed self-reinforced nano-alumina obtained in step S7 is reinforced. 3 mol% yttrium oxide partially stabilized zirconia composite ceramic balls were prepared by cutting and/or crowning and/or drilling and/or chamfering so that the nominal diameter was 52 mm, the depth of the gradient permeability layer was 1100 mm, and the height of the spherical cap was The surface self-reinforced nano-alumina reinforced zirconia composite ceramic ball head is 45.3 mm, the diameter of the tapered hole is 14 mm, and the hole taper is 1:10.

S9. Final polishing of surface self-reinforced nano-alumina reinforced zirconia composite ceramic ball head surface: final polishing of the spherical surface of surface prestressed self-reinforced nano-alumina reinforced 3 mol% yttrium oxide partially stabilized zirconia composite ceramic ball head, so that the surface The roughness Ra is 0.002mm, and the wear resistance is 0.9×10 ^-6 cm ³ /year.

S10. Inspection/marking/packaging: conduct all quality assurance inspections on the surface self-reinforced nano-alumina reinforced zirconia composite ceramic ball heads, and laser mark and package the bottom surface of qualified products.

Example 7: Nano-alumina surface component gradient composite reinforced zirconia ceramic ball head
S1. Formulation/milling and preparation of surface gradient infiltration slurry and modified granulated powder: First, weigh an appropriate amount of yttrium oxide partially stabilized nano-zirconia powder with a purity of more than 99.9 wt.%, and add 0.6 wt. % Tween 80 and 3.5 wt.% polyvinyl alcohol were made into an aqueous slurry with a solid content of 30vol%, and then the yttrium oxide partly stabilized nano-zirconia granulated powder was obtained by a spray-drying granulation process; then, an appropriate amount of purity was weighed Nano-alumina powder of 99.9 wt.% or more, adding its mass of 0.1wt% nano-magnesia, 0.2 wt.% Tween 80 and 5 wt.% polyvinyl alcohol to make an aqueous slurry with a solid content of 25vol% as Gradient infiltration slurry on the surface.

S2. Green body molding: put the yttrium oxide partially stabilized nano-zirconia granulated powder obtained in step S1 into a metal mold with an inner diameter of 75 mm, and bidirectionally pre-press at 80 MPa to form a green body with a height of 130 mm, and then put the yttrium oxide Partially stabilized nano-zirconia granulated powder dry-pressed preform is vacuum-packed in a plastic bag, placed in a cold isostatic press, and subjected to cold isostatic pressing under a hydrostatic pressure of 350MPa to obtain yttrium oxide partially stabilized nano-zirconia The granulated powder is formed into a green body.

S3. Pre-sintering of the biscuit: put the yttrium oxide partially stabilized nano-zirconia granulated powder formed green body obtained in the step S2 into an electric furnace for pre-sintering, the air atmosphere, the pre-sintering temperature is 1050 ° C, and the pre-sintering time is 2 hours. The heating and cooling rate was 1°C/min, and a yttria partially stabilized nano-zirconia ceramic pre-fired green body with a relative density of 51% was obtained.

S4. Ceramic ball pre-fired biscuit processing: According to the size requirements of the drawing, CNC numerical control machine tools are used to machine the yttrium oxide partially stabilized nano-zirconia ceramic pre-fired bisque obtained in step S3 to obtain a partially stabilized yttrium oxide with a diameter of 58 mm. Nano zirconia ceramic ball calcined biscuit.

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the yttrium oxide partially stabilized nano-zirconia ceramic ball pre-fired biscuit obtained in step S4 into a vacuum tank, and then pour the surface gradient infiltration slurry obtained in step S1, The cover is vacuumed to -0.12 MPa, so that the surface gradient infiltration slurry gradually infiltrates the surface layer of the pre-fired biscuit of yttrium oxide partially stabilized nano-zirconia ceramic balls. After holding the pressure for 5 minutes, a nano-alumina ceramic slurry with surface pre-infiltration gradient is obtained. The yttrium oxide part of the material stabilizes the nano-zirconia ceramic ball pre-infiltrated body, the content of nano-alumina powder on the surface of the permeation layer increases by 10 vol.%, and the depth of the gradient permeation layer is 1800 microns.

S6. Densification and sintering of ceramic ball billets: first, put the yttrium oxide partially stabilized nano-zirconia ceramic ball pre-infiltrated green body obtained in S5 into an air electric furnace for further pre-sintering. The sintering temperature is 1350°C, and the sintering time is 2 hours. At a speed of 1°C/min, yttria partially stabilized nano-zirconia ceramic calcined spheres with a relative density of 97% having a nano-alumina gradient diffusion layer and surface gradient precompression stress were obtained; then, the yttria partially stabilized nano-zirconia ceramics The pre-sintered spheres were placed in a hot isostatic sintering furnace for densification and sintering. The sintering temperature was 1420°C, the sintering gas pressure was 105 MPa, the sintering time was 4 hours, and the heating and cooling rate was 1°C/min. The final diameter was 42.5 mm. , the relative density is 99.9%, the grain size is 308 nanometers, the tensile strength between the gradient infiltration coating and the substrate is 138 MPa, the shear strength is 147 MPa, the flexural strength of the substrate is 1480 MPa, and the fracture toughness is 12 MPa. An m ^1/2 yttria partially stabilized nano-zirconia densified shell-core composite ceramic ball blank with a nano-alumina surface gradient diffusion layer and a surface gradient precompression stress.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the yttrium oxide partially stabilized nano-zirconia densified shell-core composite ceramic ball blank obtained in S6 into a V-shaped groove grinding device for at least rough grinding and semi-finishing step by step. Grinding, lapping, superfinishing and polishing are processed into a nominal diameter of 42 mm, a ball surface roughness Ra of 0.003 mm, a spherical error of 0.02 μm, a spherical roundness of 0.005 mm, and a ball batch diameter deviation of 0.04 μm, the surface hardness HV ₁₀₀₀ is 2100, and the surface has a -452 MPa pre-compression stress on the surface of nano-alumina surface component gradient composite reinforced zirconia ceramic balls.

S8. Machining of nano-alumina surface composition gradient composite reinforced zirconia ceramic ball head: According to the size requirements of the nano-alumina surface composition gradient composite reinforced zirconia ceramic ball head drawing, the yttrium oxide obtained in step S7 is partially stabilized nano-zirconia The densified shell-core composite ceramic ball is prepared by cutting and/or crowning and/or drilling and/or chamfering to a nominal diameter of 42 mm, a gradient permeable layer depth of 1100 mm, a spherical crown height of 36.6 mm, and a tapered hole. The nano-alumina surface composition gradient reinforced zirconia ceramic ball head with a diameter of 14 mm and a hole taper of 1:10.

S9. The final polishing of the surface of the nano-alumina surface composition gradient composite reinforced zirconia ceramic ball head: the final polishing of the spherical surface of the nano-alumina surface composition gradient composite reinforced zirconia ceramic ball head, so that the surface roughness Ra is 0.002mm, The abrasion resistance is 0.8×10 ^-6 cm ³ /year.

S10. Inspection/marking/packaging: Conduct all quality assurance inspections on the nano-alumina surface component gradient composite reinforced zirconia ceramic ball head, and laser mark and package the bottom surface of qualified products.

Example 8: Nano-alumina surface component gradient composite reinforced zirconia-based composite ceramic ball head
S1. Formulation/milling and preparation of surface gradient infiltration slurry and modified granulated powder: First, weigh an appropriate amount of nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite powder with a purity of 99.5 wt.% or more , add its mass 0.2 wt.% Tween 80 and 2.5wt.% polyvinyl alcohol to make an aqueous slurry with a solid content of 20-30vol%, and then make yttrium oxide partially stabilized nano-zirconia composite powder by spray drying and granulation process Then, take an appropriate amount of nano-alumina powder with a purity of more than 99.9 wt.%, add its mass of 0.1wt% nano-magnesia, 0.2 wt.% Tween 80 and 3wt.% polyvinyl alcohol to make a solid content The 25vol% water-based slurry is used as the surface gradient slurry for subsequent use.

S2. Green body molding: put the nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite powder obtained in step S1 into a metal mold with an inner diameter of 50 mm, and bidirectionally pre-press at 80 MPa to form a preform with a height of 120 mm. , and then the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite powder dry-pressed preform is vacuum-packed in a plastic bag, put into a cold isostatic press, and subjected to cold isostatic pressure under a hydrostatic pressure of 350MPa Press to obtain nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite powder molding green body.

S3. Biscuit pre-sintering: the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite powder obtained in step S2 is put into an electric furnace for pre-sintering. The air atmosphere and pre-sintering temperature are 1080°C. The firing time was 2 hours, and the heating and cooling rate was 1°C/min to obtain a composite calcined ceramic green body with nano-alumina reinforced 3mol% yttria and partially stabilized nano-zirconia with a relative density of about 57%.

S4. Ceramic ball pre-fired biscuit processing: According to the size requirements of the drawings, CNC numerical control machine tools are used to machine the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite pre-fired ceramic bisque obtained in the step S3, and the diameter is obtained. 38 mm nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite ceramic ball pre-fired green body.

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite ceramic ball pre-fired biscuit obtained in step S4 into a vacuum tank, and then pour it into the obtained in step S1 Surface gradient infiltration slurry, the cover is vacuumed to -0.12 MPa, so that the surface gradient infiltration slurry gradually infiltrates into the surface layer of the pre-fired biscuit of nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite ceramic balls, and the pressure is maintained at 60 Min later, the nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite ceramic ball pre-infiltrated green body with surface pre-infiltration gradient nano-alumina ceramic slurry was obtained, and the content of nano-alumina powder on the surface of the infiltration layer increased by 9 vol. %, the depth of gradient permeation layer is 3600 microns.

S6. Densification and sintering of ceramic ball billets: firstly, the nano-alumina reinforced 3mol% yttrium oxide partly stabilized nano-zirconia composite ceramic ball pre-infiltrated green body obtained in S5 is put into an air electric furnace for further pre-sintering, and the sintering temperature is 1450°C. The sintering time is 2 hours, the heating and cooling rate is 1°C/min, and the diameter is 28.4 mm, the relative density is 96%, and the nano-alumina reinforced 3mol% yttrium oxide with nano-alumina gradient diffusion layer and surface gradient precompression stress is obtained. Zirconia composite ceramic ball pre-sintered body; then, the nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite ceramic ball pre-sintered body was placed in a hot isostatic pressing sintering furnace for densification and sintering, and the sintering temperature was 1480°C , the sintering gas pressure is 85 MPa, the sintering time is 2 hours, and the heating and cooling rate is 1°C/min. Finally, the relative density is 99.86%, the grain size is 218 nm, and the tensile strength between the gradient infiltration coating and the substrate is 78 MPa, shear strength of 127 MPa, matrix flexural strength of 1650 MPa, fracture toughness of 8 MPa m ^1/2 with nano-alumina surface-enhanced gradient diffusion layer and surface gradient pre-stressed nano-alumina reinforced 3mol% Yttrium oxide partially stabilized nano-zirconia composite ceramic ball blank.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nano-alumina reinforced 3mol% yttrium oxide partly stabilized nano-zirconia composite ceramic ball blank obtained in S6 into a four-grinding tool grinding device for at least rough grinding, step by step, Semi-finishing, finishing, super-finishing and polishing are processed into a nominal diameter of 28 mm, a ball surface roughness Ra of 0.003 mm, a spherical error of 0.02 μm, a spherical roundness of 0.003 mm, and a ball batch diameter of The deviation is 0.06 μm, the surface hardness HV ₁₀₀₀ is 2050, and the surface has a high-precision prestressed nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite ceramic ball with a pre-compressed stress of -412 MPa on the surface.

S8. Machining of nano-alumina surface composition gradient composite reinforced zirconia-based composite ceramic ball head: According to the size requirements of the drawings of nano-alumina surface composition gradient composite-reinforced zirconia-based composite ceramic ball head, the high-precision prefabricated ball head obtained in step S7 is processed. Stressed nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite ceramic balls are prepared by cutting and/or crowning and/or drilling and/or chamfering to a nominal diameter of 28 mm and a gradient penetration layer depth of 2500 mm High-precision prestressed nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite ceramic ball head with a spherical crown height of 24.4 mm, a cone hole diameter of 14 mm, and a hole taper of 1:10.

S9. The final polishing of the surface of the nano-alumina surface composition gradient composite reinforced zirconia-based composite ceramic ball head: the final polishing of the spherical surface of the nano-alumina surface composition gradient composite reinforced zirconia-based composite ceramic ball head, so that the surface roughness Ra is 0.002mm, and the abrasion resistance is 0.7×10 ^-6 cm ³ /year.

S10. Inspection/marking/packaging: Conduct all quality assurance inspections on the nano-alumina surface component gradient composite reinforced zirconia-based composite ceramic ball head, and laser mark and package the bottom surface of qualified products.

Example 9: Composite reinforced alumina-based composite ceramic ball head with nano-alumina surface composition gradient
S1. Formulation/milling and preparation of surface gradient infiltration slurry and modified granulated powder: First, weigh an appropriate amount of nano-3mol% yttria partially stabilized nano-zirconia reinforced nano-alumina composite powder with a purity of more than 99.8 wt.%. body, add its mass 0.2 wt.% Tween 80 and 3wt.% polyethylene glycol to make an aqueous slurry with a solid content of 30vol%, and then make nanometer 3mol% yttrium oxide partially stabilized nanometer zirconia by spray drying granulation process Toughening nano-alumina composite powder; then, weigh an appropriate amount of nano-alumina powder with a purity of 99.9 wt.% or more, add 0.1 wt% nano-magnesia, 0.2 wt.% Tween 80 and 2 wt. % polyethylene glycol to make an aqueous slurry with a solid content of 25vol% as a surface gradient slurry for future use.

S2. Green body molding: put the nanometer 3mol% yttrium oxide partially stabilized nanozirconia reinforced nano-alumina composite powder obtained in the step S1 into a metal mold with an inner diameter of 43 mm, and bidirectionally pre-press at 120 MPa to form a dry mold with a height of 100 mm. Press the preform, then dry-press the preform with nano-3mol% yttrium oxide partly stabilized nano-zirconia reinforced nano-alumina composite powder in a plastic bag, put it in a cold isostatic press, and press it under a hydrostatic pressure of 350MPa Cold isostatic pressing is carried out to obtain a green body formed by nano-sized 3mol% yttrium oxide partially stabilized nano-zirconia reinforced nano-alumina composite powder.

S3. Pre-sintering of the biscuit: put the nano-3mol% yttrium oxide partially stabilized nano-zirconia reinforced nano-alumina composite powder formed green body obtained in the step S2 into an electric furnace for pre-sintering. The air atmosphere and pre-sintering temperature are 1220 ° C. The calcining time was 2 hours, and the heating and cooling rate was 5°C/min to obtain a calcined ceramic green body with a relative density of 53% nanometer 3mol% yttrium oxide partially stabilized nanozirconia reinforced nano-alumina composite powder.

S4. Ceramic ball pre-fired biscuit processing: according to the size requirements of the drawing, CNC numerical control machine tools are used to machine the nano-3mol% yttrium oxide partially stabilized nano-zirconia reinforced nano-alumina composite powder pre-fired ceramic bisque obtained in step S3. A calcined green body of nano-sized 3mol% yttrium oxide partially stabilized nano-zirconia reinforced nano-alumina composite ceramic balls with a diameter of 33 mm was obtained.

S5. Surface infiltration of ceramic ball pre-fired biscuits: put the nanometer 3mol% yttrium oxide partially stabilized nano-zirconia reinforced nano-alumina composite ceramic ball pre-fired biscuits obtained in step S4 into a vacuum tank, and then pour it into the step S1 to obtain The surface gradient infiltration slurry, the cover is evacuated to -0.08MPa, so that the surface gradient infiltration slurry gradually infiltrates into the surface layer of the nano-3mol% yttrium oxide partly stabilized nano-zirconia reinforced nano-alumina composite ceramic pre-fired biscuit, and the pressure is maintained. After 80 min, the pre-infiltrated body of nano-3mol% yttrium oxide partially stabilized nano-zirconia reinforced nano-alumina matrix composite ceramic balls with surface pre-infiltration gradient nano-alumina ceramic slurry was obtained, and the content of nano-alumina powder on the surface of the infiltration layer increased 9 vol.%, the gradient permeation layer depth is 2200 microns.

S6. Densification and sintering of ceramic ball billets: first, put the nano-alumina reinforced nano-3mol% yttrium oxide partly stabilized nano-zirconia-reinforced nano-alumina composite ceramic ball pre-infiltrated body obtained in S5 into an air electric furnace for further pre-sintering and sintering The temperature is 1450°C, the sintering time is 2 hours, and the heating and cooling rate is 1°C/min, and the diameter is 24.4 mm, the relative density is 96%, and the nano-alumina reinforced nano-3mol % yttrium oxide partially stabilized nano zirconia reinforced nano alumina composite ceramic ball calcined billet; then, the nano alumina reinforced nano 3mol% yttrium oxide partially stabilized nano zirconia reinforced nano alumina composite ceramic ball calcined billet is put into the heat etc. Densification sintering was carried out in a static pressure sintering furnace. The sintering temperature was 1500°C, the sintering gas pressure was 80 MPa, the sintering time was 4 hours, and the heating and cooling rate was 5°C/min. Finally, a relative density of 99.9% and a grain size of 338 The tensile strength between the nano-gradient infiltration coating and the substrate is 78 MPa, the shear strength is 127 MPa, the flexural strength of the substrate is 821 MPa, and the fracture toughness is 6.2 MPa·m ^1/2 with nano-alumina surface reinforcement Nano-alumina reinforced nano-3mol% yttria partially stabilized nano-zirconia reinforced nano-alumina composite ceramic ball blank with gradient diffusion layer and surface gradient precompression stress.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nano-alumina reinforced nano-3mol% yttrium oxide partly stabilized nano-zirconia toughened nano-alumina composite ceramic ball blank obtained in S6 into a V-shaped groove grinding device for separation. At least five steps of rough grinding, semi-finishing, fine grinding, super-finishing and polishing are carried out to process the nominal diameter of 24 mm, the depth of gradient permeable layer is 1430 mm, the spherical surface roughness Ra is 0.004 mm, and the spherical error is 0.02 μm, spherical roundness of 0.004 mm, ball diameter deviation of 0.06 μm, surface hardness HV ₁₀₀₀ of 2150, nano-alumina reinforced nano-3mol% yttrium oxide partly stabilized nano-zirconia reinforced with -310 MPa precompression stress on the surface Tough nano-alumina matrix composite ceramic balls.

S8. Machining of nano-alumina surface composition gradient composite reinforced alumina-based composite ceramic ball head: according to the size requirements of the drawings of nano-alumina surface composition gradient composite reinforced alumina-based composite ceramic ball head, the nano-alumina obtained in step S7 Reinforced nano 3mol% yttria partially stabilized nano zirconia toughened nano alumina matrix composite ceramic balls were cut and/or crowned and/or drilled and/or chamfered to prepare a nominal diameter of 24 mm and a height of the spherical crown A nano-alumina surface composition gradient reinforced alumina matrix composite ceramic ball head with a diameter of 20.9 mm, a taper hole diameter of 14 mm, and a hole taper of 1:10.

S9. The final polishing of the surface of the nano-alumina surface composition gradient composite reinforced alumina-based composite ceramic ball head: the final polishing of the spherical surface of the nano-alumina surface composition gradient-reinforced alumina-based composite ceramic ball head, so that the surface roughness Ra is 0.002 mm, wear resistance is 0.9×10 ^-6 cm ³ /year.

S10. Inspection/marking/packaging: Conduct all quality assurance inspections on the nano-alumina surface composition gradient enhanced alumina-based composite ceramic ball head, and laser mark and package the bottom surface of qualified products.

Example 10: Composite reinforced silicon nitride ceramic ball head with nano-alumina surface composition gradient
S1. Formulation/milling and preparation of surface gradient slurry and modified granulated powder: (1) Weigh an appropriate amount of silicon nitride powder with a purity of 99.9 wt.% or more, and add 0.1 wt% of its mass to the nano Alumina, 0.2 wt.% Tween 80 and 3 wt.% polyethylene glycol are made into an aqueous slurry with a solid content of 25vol%, and then the nano-modified silicon nitride granulated powder is produced by a spray drying granulation process; (2) Weigh an appropriate amount of nano-alumina powder with a purity of more than 99.9 wt.%, add 0.1wt% nano-magnesia, 0.2 wt.% Tween 80 and 3wt.% polyethylene glycol to make a solid content The 25vol% water-based slurry is used as the surface gradient slurry for subsequent use.

S2. Green body molding: put the nano-modified silicon nitride granulated powder obtained in step S1 into a metal mold with an inner diameter of 50 mm, and bidirectionally pre-press at 80 MPa to form a pre-form with a height of 130 mm. The silicon nitride powder dry-pressed blank is vacuum-packed in a plastic bag, put into a cold isostatic press, and cold isostatic pressed under a hydrostatic pressure of 450 MPa to obtain a nano-modified silicon nitride granulated powder Formed green body.

S3. Blank pre-sintering: put the nano-modified silicon nitride granulated powder molding green body obtained in step S2 into an electric furnace for pre-sintering, nitrogen atmosphere, pre-sintering temperature is 1650 ° C, and pre-sintering time is 2 hours. The cooling rate was 1°C/min, and the nano-modified silicon nitride powder calcined ceramic green body with a relative density of 58% was obtained.

S4. Ceramic ball pre-fired biscuit processing: According to the size requirements of the drawings, CNC numerical control machine tools are used to machine the nano-modified silicon nitride powder pre-fired ceramic bisque obtained in step S3 to obtain nano-modified silicon nitride powder with a diameter of 38.5 mm. Silicon nitride ceramic ball pre-fired biscuit.

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the nano-modified silicon nitride ceramic ball pre-fired biscuit obtained in step S4 into a vacuum tank, and then pour the nano-alumina for surface gradient infiltration obtained in step S1 For powder slurry, the cover is vacuumed to -0.08MPa, so that the nano-alumina powder slurry gradually penetrates into the surface layer of the pre-fired biscuit of nano-modified silicon nitride ceramic balls. After holding the pressure for 40 minutes, a surface pre-infiltration gradient is obtained. The nano-modified silicon nitride ceramic ball pre-infiltration body of nano-alumina ceramic slurry, the content of nano-alumina powder on the surface of the infiltration layer increased by 7.8 vol.%, and the depth of the gradient pre-infiltration layer was 1680 microns.

S6. Densification and sintering of ceramic ball billets: firstly, put the nano-modified silicon nitride ceramic ball pre-infiltrated body obtained in S5 into an air electric furnace for further pre-sintering. 1°C/min to obtain a nano-silicon nitride shell-core composite ceramic ball pre-sintered body with a diameter of 28.5 mm and a relative density of 97% with a nano-alumina gradient diffusion layer and a surface gradient precompression stress; then, the nano-nitrided The silicon shell core composite ceramic ball pre-sintered body is placed in a hot isostatic pressing sintering furnace, and is densified and sintered under the condition of nitrogen gas distribution. at 1°C/min, the final relative density is 99.9%, the grain size is 428 nm, the tensile strength between the gradient infiltration coating and the substrate is 88 MPa, the shear strength is 132 MPa, and the flexural strength is 1100 MPa. The fracture toughness is 8.2 MPa·m ^1/2 nano-alumina surface composition gradient compound reinforced alumina matrix composite ceramic ball blank.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: the nano-alumina surface component gradient composite reinforced alumina-based composite ceramic ball blank obtained in S6 is placed in a V-shaped groove grinding device for at least rough grinding and semi-finished. The 5 processes of lapping, lapping, ultra-finishing and polishing are processed into a nominal diameter of 28 mm, a gradient penetration layer depth of 1000 mm, a spherical surface roughness Ra of 0.005 mm, a spherical error of 0.02 μm, and a spherical roundness of 0.005 mm, the ball batch diameter deviation is 0.08 μm, the surface hardness HV ₁₀₀₀ is 2200, and there is a -210 MPa pre-compression stress on the surface of the nano-alumina surface component gradient composite reinforced alumina matrix composite ceramic ball.

S8. Machining of nano-alumina surface composition gradient composite reinforced silicon nitride ceramic ball head: according to the size requirements of the nano-alumina surface composition gradient composite reinforced silicon nitride ceramic ball head drawing, the nano-alumina surface composition obtained in step S7 Gradient composite reinforced silicon nitride ceramic balls are prepared by cutting and/or crowning and/or drilling and/or chamfering to a nominal diameter of 28 mm, a spherical crown height of 24.4 mm, and a tapered hole diameter of 14 mm. Nano-alumina surface component gradient composite reinforced silicon nitride ceramic ball head with hole taper of 1:10.

S9. The final polishing of the surface of the nano-alumina surface component gradient composite reinforced silicon nitride ceramic ball head: the final polishing of the spherical surface of the nano-alumina surface component gradient composite reinforced silicon nitride ceramic ball head, so that the surface roughness Ra is 0.002 mm, the abrasion resistance is 0.7×10 ^-6 cm ³ /year.

S10. Inspection/marking/packaging: Conduct all quality assurance inspections on the nano-alumina surface component gradient composite reinforced silicon nitride ceramic ball head, and laser mark and package the bottom surface of qualified products.

Example 11: Composite reinforced silicon carbide ceramic ball head with nano-silicon nitride surface composition gradient
S1. Formulation/milling and preparation of surface gradient slurry and modified granulated powder: (1) Weigh an appropriate amount of nano-silicon carbide powder with a purity of 99.9 wt.% or more, and add 2 wt% of its mass Boron carbide powder was used as a sintering aid, 0.2 wt.% Tween 80 as a surfactant, and 2.5 wt.% carboxymethyl cellulose were used to make an aqueous slurry with a solid content of 32 vol%, which was then spray-dried and granulated. To obtain nano-modified silicon carbide granulated powder; (2) Weigh an appropriate amount of nano-silicon nitride powder with a purity of more than 99.9 wt.%, add its mass of 2 wt% nano-alumina, 2 wt% nano-yttrium oxide and 1 wt% nano-lutetium oxide composite powder as a sintering aid, 0.2 wt.% Tween 80 and 3.5wt.% carboxymethyl cellulose to make an aqueous slurry with a solid content of 25 vol% as a surface gradient slurry material;
S2. Green body molding: put the nano-modified silicon carbide granulated powder obtained in step S1 into a metal mold with an inner diameter of 60 mm, and bidirectionally pre-press at 80 MPa to form a pre-form with a height of 140 mm, and then The silicon carbide granulated powder dry-pressed blank is vacuum-packed in a plastic bag, put into a cold isostatic press, and subjected to cold isostatic pressing under a hydrostatic pressure of 450MPa to obtain nano-modified silicon carbide granulated powder. green body.

S3. Blank pre-sintering: put the nano-modified silicon carbide granulated powder formed green body obtained in step S2 into an electric furnace for pre-sintering, in an argon atmosphere, at a pre-sintering temperature of 1650° C., and at a pre-sintering time of 2 hours. The cooling rate was 1°C/min, and a nano-modified silicon carbide ceramic pre-fired biscuit with a relative density of 58% was obtained.

S4. Ceramic ball pre-fired bisque processing: According to the size requirements of the drawings, use CNC numerical control machine tools to machine the nano-modified silicon carbide ceramic pre-fired bisque obtained in step S3 to obtain nano-modified silicon carbide ceramics with a diameter of 43 mm Ball pre-fired biscuit.

S5. Surface infiltration of ceramic ball pre-fired billet: put the nano-modified silicon carbide ceramic ball pre-fired billet obtained in step S4 into a vacuum tank, then pour the surface gradient infiltration slurry obtained in step S1, cover and pump Vacuum to -0.12 MPa to make the surface gradient infiltration slurry gradually infiltrate into the surface layer of the nano-modified silicon carbide ceramic ball pre-fired biscuit, and hold the pressure for 15 minutes to obtain the nano-silicon nitride surface component with the surface pre-infiltration gradient slurry Gradient composite reinforced silicon carbide ceramic ball pre-infiltration body, the content of nano-silicon nitride powder on the surface of the infiltration layer increased by 7.9 vol.%, and the depth of the pre-infiltration layer was 1560 microns.

S6. Densification and sintering of ceramic ball blanks: firstly, put the nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic ball pre-infiltrated green body obtained in S5 into an air electric furnace for further pre-sintering. 2 hours, heating and cooling rate 1°C/min, to obtain a nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic ball calcined body with a relative density of 97% and a nano-silicon nitride gradient diffusion layer and surface gradient precompression stress ; Then, put the nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic ball pre-sintered body into the hot isostatic pressing sintering furnace, and carry out densification and sintering under the condition of argon gas distribution, the sintering temperature is 1800 ℃, the sintering gas The pressure is 180 MPa, the sintering time is 1 hour, and the heating and cooling rate is 1°C/min. Finally, the tensile strength between the gradient infiltration coating and the substrate is obtained with a diameter of 32.5 mm, a relative density of 99.9%, a grain size of 518 nm, and a gradient penetration coating. The strength is 98 MPa, the shear strength is 112 MPa, the matrix flexural strength is 850 MPa, and the fracture toughness is 6.2 MPa m ^1/2 . Nano-silicon nitride with surface gradient diffusion layer and surface gradient precompression stress Composite reinforced silicon carbide ceramic ball blank with surface composition gradient.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic ball blank obtained in S6 into the four-grinding tool grinding equipment for at least rough grinding and semi-finishing step by step. Grinding, lapping, ultra-finishing and polishing are processed into a nominal diameter of 32 mm, a gradient penetration layer depth of 950 mm, a spherical surface roughness Ra of 0.005 mm, a spherical error of 0.02 μm, and a spherical roundness of 0.002 mm, the ball batch diameter deviation is 0.08 μm, the surface hardness HV ₁₀₀₀ is 2140, and the surface has a -340 MPa pre-compression stress on the surface of nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic balls.

S8. Machining of nano-silicon nitride surface composition gradient composite reinforced silicon carbide ceramic ball head: according to the size requirements of the nano-silicon nitride surface composition gradient composite reinforced silicon carbide ceramic ball head drawing, the nano-silicon nitride surface obtained in step S7 Component-gradient composite reinforced silicon carbide ceramic balls were prepared by crown cutting, drilling and chamfering into a nanometer with a nominal diameter of 32 mm, a spherical crown height of 28 mm, a tapered hole diameter of 14 mm, and a hole taper of 1:10. Silicon nitride surface component gradient compound reinforced silicon carbide ceramic ball head.

S9. The final polishing of the surface of the nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic ball head: the final polishing of the spherical surface of the nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic ball head, so that the surface roughness Ra is 0.002 mm, the abrasion resistance is 0.8×10 ^-6 cm ³ /year.

S10. Inspection/marking/packaging: Carry out all quality assurance inspections of nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic ball heads, laser marking and packaging on the bottom surface of qualified products.

Example 12: Nano-silicon nitride surface component gradient composite reinforced zirconia-based ceramic ball head
S1. Formulation/milling and preparation of surface gradient infiltration slurry and modified granulated powder: (1) First, weigh an appropriate amount of nano-alumina reinforced 3mol% yttrium oxide and partially stabilized nano-zirconia with a purity of more than 99.9wt.%. Composite powder, add its quality 0.2 wt.% Tween 80 as a surfactant and 3.8wt.% polyvinyl alcohol as a binder to make an aqueous slurry with a solid content of 35 vol%, and then make it through a spray-drying granulation process Obtain nano-alumina reinforced 3mol% yttrium oxide and partially stabilized nano-zirconia composite granulation powder; (2) Weigh an appropriate amount of nano-silicon nitride powder with a purity of 99.9 wt.% or more, add its mass of 2 wt% nano-zirconia Aluminum, 2 wt% nano-yttrium oxide and 1 wt% nano-lutetium oxide composite powder as sintering aid, 0.5 wt.% Tween 80 as surfactant and 3.5 wt.% polyvinyl alcohol as binder The water-based slurry with a solid content of 25 vol% is used as the surface gradient slurry;
S2. Green body molding: put the nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite granulation powder obtained in step S1 into a metal mold with an inner diameter of 60 mm, and bidirectionally pre-press at 120 MPa to a height of 125 mm. Then the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite granulation powder dry-pressed preform was vacuum-packed in a plastic bag, put into a cold isostatic press, and heated under a hydrostatic pressure of 450MPa Under cold isostatic pressing, the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite granulated powder was obtained to form a green body.

S3, biscuit pre-sintering: the nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite granulated powder obtained in step S2 is put into an electric furnace for pre-sintering, and the pre-sintering temperature is 1100 in an argon atmosphere. ℃, the pre-firing time is 2 hours, and the heating and cooling rate is 1 ℃/min, the relative density of nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite ceramic calcined green body is obtained.

S4. Ceramic ball pre-fired bisque processing: According to the size requirements of the drawings, the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite ceramic pre-fired bisque obtained in the step S3 is machined with CNC machine tools, and the diameter is obtained. 44 mm nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite ceramic ball pre-fired green body.

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite ceramic ball pre-fired biscuit obtained in step S4 into a vacuum tank, and then pour it into the obtained in step S1 Surface gradient infiltration slurry, the cover is vacuumed to -0.12 MPa, so that the surface gradient infiltration slurry gradually infiltrates into the surface layer of the pre-fired biscuit of nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite ceramic balls, and the pressure is maintained for 15 After 10 min, the nano-silicon nitride surface component gradient composite reinforced zirconia-based ceramic ball pre-infiltration green body with surface pre-infiltration gradient slurry was obtained, and the content of nano-silicon nitride powder on the surface of the infiltration layer increased by 8.1 vol.%. The penetration depth is 1900 microns.

S6. Densification and sintering of ceramic ball blanks: firstly, put the nano-silicon nitride surface component gradient composite reinforced zirconia-based ceramic ball pre-infiltrated green body obtained in S5 into an atmosphere electric furnace for further pre-sintering, under argon protection, and the sintering temperature is 1700°C, sintering time of 2 hours, heating and cooling rate of 1°C/min, to obtain a nano-silicon nitride surface component gradient composite reinforced zirconia with a relative density of 98.5% and a nano-silicon nitride gradient infiltration layer and surface gradient precompression stress Then, put the nano-silicon nitride surface component gradient compound reinforced zirconia-based ceramic ball pre-sintering body into the hot isostatic pressing sintering furnace, and carry out densification and sintering under the condition of argon gas separation, and sintering The temperature is 1750°C, the sintering gas pressure is 150 MPa, the sintering time is 1 hour, and the heating and cooling rate is 1°C/min. The final diameter is 32.4 mm, the relative density is 99.9%, the grain size is 758 nm, and the gradient infiltration coating and The tensile strength between the substrates is 118 MPa, the shear strength is 132 MPa, the flexural strength of the substrate is 1050 MPa, and the fracture toughness is 8.2 MPa m ^1/2 with nano-silicon nitride surface gradient permeation layer and surface gradient preloading Zirconia-based ceramic spheres reinforced by stress-graded composites on the surface of nano-silicon nitride.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nano-silicon nitride surface component gradient composite reinforced zirconia-based ceramic ball blank obtained in S6 into a V-shaped groove grinding device for at least rough grinding and semi-finished grinding. The five processes of lapping, lapping, ultra-finishing and polishing process into a nominal spherical surface with a nominal diameter of 32 mm, a spherical surface roughness Ra of 0.004 mm, a spherical error of 0.05 μm, and a spherical roundness of 0.002 mm. The batch diameter deviation is 0.08 μm, the surface hardness HV ₁₀₀₀ is 1650, and the surface component gradient composite reinforced zirconia-based ceramic balls of nano-silicon nitride surface with -479 MPa pre-compression stress on the surface.

S8. Machining of nano-silicon nitride surface composition gradient composite reinforced zirconia-based ceramic ball head: according to the size requirements of the nano-silicon nitride surface composition gradient composite reinforced zirconia-based ceramic ball head drawing, the nano-nitrided nano-silicon nitride obtained in step S7 Zirconia-based ceramic balls reinforced with graded components on the silicon surface were crowned, drilled and chamfered to produce a nominal diameter of 32 mm, a depth of gradient permeation layer of 1400 mm, a spherical crown height of 28 mm, and a cone diameter of 14 mm. mm, with a hole taper of 1:10, nano-silicon nitride surface component gradient composite reinforced zirconia-based ceramic ball head.

S9. The final polishing of the surface of the nano-silicon nitride surface component gradient composite reinforced zirconia-based ceramic ball head: the final polishing of the spherical surface of the nano-silicon nitride surface component gradient composite reinforced zirconia-based ceramic ball head, so that the surface roughness Ra is 0.002mm, and the abrasion resistance is 0.6×10 ^-6 cm ³ /year.

S10. Inspection/marking/packaging: conduct all quality assurance inspections on the nano-silicon nitride surface component gradient composite reinforced zirconia-based ceramic ball head, and laser mark and package the bottom surface of qualified products.

Example 13: Composite reinforced silicon nitride ceramic ball head with nano-silicon carbide surface composition gradient
S1. Formulation/milling and preparation of surface gradient slurry and modified granulated powder: (1) Weigh an appropriate amount of silicon nitride powder with a purity of 99.9 wt.% or more, and add 0.1 wt% of its mass to the nano Alumina, 0.2 wt.% polyethylene glycol octylphenyl ether and 2.5wt.% carboxymethyl cellulose were made into an aqueous slurry with a solid content of 35vol%, and then nano-modified nitrogen was prepared by spray drying and granulation process (2) Weigh an appropriate amount of silicon carbide powder with a purity of more than 99.9 wt.%, add 2.1 wt% nano-boron carbide powder as a sintering aid, 0.8 wt.% polyethylene glycol Alcohol octyl phenyl ether was used as a surfactant and 2.5 wt.% carboxymethyl cellulose as a binder to prepare an aqueous slurry with a solid content of 30vol% as a surface gradient slurry for future use.

S2. Green body molding: put the nano-modified silicon nitride granulated powder obtained in step S1 into a metal mold with an inner diameter of 60 mm, and bidirectionally pre-press at 80 MPa to form a pre-form with a height of 120 mm, and then the nano-modified The silicon nitride powder dry-pressed blank is vacuum-packed in a plastic bag, put into a cold isostatic press, and subjected to cold isostatic pressing under a hydrostatic pressure of 450MPa to obtain nano-modified silicon nitride granulated powder. green body.

S3. Blank pre-sintering: put the nano-modified silicon nitride granulated powder molding green body obtained in step S2 into an electric furnace for pre-sintering, nitrogen atmosphere, pre-sintering temperature is 1650 ° C, and pre-sintering time is 2 hours. The cooling rate was 1°C/min, and a nano-modified silicon nitride powder calcined ceramic green body with a relative density of 53% was obtained.

S4. Ceramic ball pre-fired biscuit processing: according to the size requirements of the drawings, use CNC numerical control machine tools to machine the nano-modified silicon nitride powder pre-fired ceramic bisque obtained in step S3 to obtain nano-modified silicon nitride powder with a diameter of 38 mm. Silicon nitride ceramic ball pre-fired biscuit.

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the nano-modified silicon nitride ceramic ball pre-fired biscuit obtained in step S4 into a vacuum tank, and then pour the nano-alumina for surface gradient infiltration obtained in step S1 For the powder slurry, the cover is evacuated to -0.08 MPa, so that the nano-silicon carbide powder slurry gradually penetrates into the surface layer of the pre-fired biscuit of nano-modified silicon nitride ceramic balls. After holding the pressure for 60 minutes, a nano The nano-modified silicon nitride ceramic ball pre-infiltration body of silicon carbide ceramic slurry, the content of nano-silicon carbide powder on the surface of the infiltration layer increased by 7.8 vol.%, and the depth of the gradient pre-infiltration layer was 1780 microns.

S6. Densification and sintering of ceramic ball billets: firstly, put the nano-modified silicon nitride ceramic ball pre-infiltrated body obtained in S5 into an air electric furnace for further pre-sintering. 1°C/min to obtain the nano-modified silicon nitride ceramic ball pre-sintered body with a relative density of 97%; then, put the nano-modified silicon nitride ceramic ball pre-sintered body into the hot isostatic pressing sintering furnace, under nitrogen Densification sintering was carried out under different conditions, the sintering temperature was 1780 °C, the sintering gas pressure was 180 MPa, the sintering time was 1 hour, and the heating and cooling rate was 1 °C/min. Finally, the diameter was 28.5 mm, and the relative density was 99.9%. A nano-silicon carbide surface with a size of 338 nm, a tensile strength between the gradient infiltration coating and the substrate of 78 MPa, a shear strength of 102 MPa, a flexural strength of the substrate of 1100 MPa, and a fracture toughness of 6.5 MPa m ^1/2 Component gradient composite reinforced silicon nitride ceramic ball blank.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nano-silicon carbide surface component gradient composite reinforced silicon nitride ceramic ball blank obtained in S6 into the V-shaped groove grinding equipment for at least rough grinding and semi-finishing step by step. Grinding, lapping, superfinishing and polishing are processed into a nominal diameter of 28 mm, a ball surface roughness Ra of 0.005 mm, a spherical error of 0.02 μm, a spherical roundness of 0.004 mm, and a ball batch diameter deviation of 0.08 μm, the surface hardness HV ₁₀₀₀ is 2200, the nano-silicon carbide surface composition gradient compound reinforced silicon nitride ceramic balls with -230 MPa pre-compression stress on the surface.

S8. Machining of nano-silicon carbide surface composition gradient composite reinforced silicon nitride ceramic ball head: According to the size requirements of the nano-silicon carbide surface composition gradient composite reinforced silicon nitride ceramic ball head drawing size requirements, the nano-silicon carbide surface composition obtained in step S7 Gradient composite reinforced silicon nitride ceramic balls are prepared by cutting and/or crowning and/or drilling and/or chamfering to have a nominal diameter of 28 mm, a gradient penetration layer depth of 1085 mm, and a spherical crown height of 24.4 mm. The diameter of the taper hole is 14 mm, and the taper of the hole is 1:10. The nano-silicon carbide surface component gradient composite reinforced silicon nitride ceramic ball head.

S9. The final polishing of the surface of the nano-silicon carbide surface component gradient composite reinforced silicon nitride ceramic ball head: the final polishing of the spherical surface of the nano-silicon carbide surface component gradient composite reinforced silicon nitride ceramic ball head, so that the surface roughness Ra is 0.002 mm, the abrasion resistance is 0.5×10 ^-6 cm ³ /year.

S10. Inspection/marking/packaging: conduct all quality assurance inspections on the nano-silicon carbide surface component gradient composite reinforced silicon nitride ceramic ball head, laser marking and packaging on the bottom surface of qualified products.

Example 14: Surface self-reinforced nano-alumina ceramic femoral spherical unicondyle
S1. Formulation/milling and preparation of surface gradient slurry and modified granulated powder: Weigh an appropriate amount of nano-alumina powder with a purity of 99.9 wt.% or more, add 0.1 wt% of its mass to nano-magnesia, 0.5 Wt.% Tween 80 and 3 wt.% polyvinyl alcohol are used to make aqueous slurry with a solid content of 25 vol%, part of which is used as a surface gradient slurry; the other part is made of nano-alumina granules by spray drying granulation process pink.

S2. Green body molding: put the nano-alumina granulated powder obtained in step S1 into a metal mold with an inner diameter of 70 mm, and pre-press bidirectionally at 50 MPa to form a preform with a height of 150 mm, and then dry the nano-alumina granulated powder The compact was vacuum-packed in a plastic bag, placed in a cold isostatic press, and subjected to cold isostatic pressing under a hydrostatic pressure of 250 MPa to obtain a green compact formed from nano-alumina granulated powder.

S3. Biscuit pre-firing: put the green body formed by the nano-alumina granulated powder obtained in step S2 into an electric furnace for pre-sintering, the air atmosphere, the pre-sintering temperature is 1150°C, the pre-sintering time is 2 hours, and the heating and cooling rate is 5 ℃/min to obtain a nano-alumina pre-fired ceramic green body with a relative density of 52%.

S4. Ceramic ball pre-fired biscuit processing: according to the size requirements of the drawing, use CNC numerical control machine tools to machine the nano-alumina pre-fired ceramic biscuit obtained in step S3 to obtain a nano-alumina ceramic ball pre-fired bisque with a diameter of 55 mm Blank.

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the nano-alumina ceramic ball pre-fired biscuit obtained in step S4 into a vacuum tank, then pour the surface gradient infiltration slurry obtained in step S1, and vacuumize the cover to -0.10 MPa, so that the surface gradient infiltration slurry gradually infiltrates into the surface layer of the nano-alumina ceramic ball pre-fired green body through the pores on the surface of the nano-alumina ceramic ball calcined green body. The nano-alumina ceramic ball pre-infiltrated body of aluminum ceramic slurry, the content of nano-alumina powder on the surface of the infiltration layer increased by 9.2 vol.%, and the depth of the gradient infiltration layer was 1650 microns.

S6. Densification and sintering of ceramic ball billets: firstly, put the pre-infiltrated body of nano-alumina ceramic balls obtained in S5 into an air electric furnace for further pre-sintering. min, to obtain a self-reinforced nano-alumina ceramic ball pre-sintered body with a relative density of 96 %; then, put the nano-alumina ceramic ball pre-sintered body into a hot isostatic pressing sintering furnace for densification Sintering, the sintering temperature is 1520°C, the sintering gas pressure is 120 MPa, the sintering time is 1 hour, the heating and cooling rate is 1°C/min, the final spherical diameter is 40.6 mm, the relative density is 99.9%, the grain size is 448 nm, the gradient The tensile strength between the infiltrated coating and the substrate is 128 MPa, the shear strength is 132 MPa, the substrate flexural strength is 500 MPa, and the fracture toughness is 4.5 MPa·m ^1/2 nano-alumina ceramic spheres.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nano-alumina ceramic ball blank obtained in S6 into a V-shaped groove grinding device for at least rough grinding, semi-finishing, finishing, super-finishing and After five polishing processes, the nominal diameter is 40 mm, the surface roughness Ra of the ball is 0.003 mm, the spherical error is 0.04 μm, the roundness of the spherical surface is 0.002 mm, the ball batch diameter deviation is 0.09 μm, and the surface hardness HV ₁₀₀₀ is 2200 , surface self-reinforced nano-alumina ceramic balls with -350MPa precompression stress on the surface.

S8. Machining of surface self-reinforced nano-alumina ceramic femoral spherical unicondyle: according to the design drawing requirements of ceramic femoral spherical unicondyle, the surface self-reinforced nano-alumina ceramic ball obtained in step S7 was cut, ground and chamfered A self-reinforced nano-alumina ceramic femoral spherical unicondyle with two friction surfaces with a nominal spherical diameter of 40 mm, a gradient permeable layer depth of 970 mm, and a single positioning post was prepared.

S9. Final polishing of the surface self-reinforced nano-alumina ceramic femoral spherical unicondyle surface: the final polishing is performed on the spherical surface of the surface self-reinforced nano-alumina ceramic femoral unicondyle with a single positioning post, so that the surface roughness Ra is 0.002mm.

S10. Inspection/marking/packaging: Perform all quality inspections on the surface self-reinforced nano-alumina ceramic femoral unicondyle with a single positioning post, and mark and pack qualified products.

Example 15: Surface self-reinforced nano-zirconia ceramic femoral spherical unicondyle
S1. Formulation/milling and preparation of surface gradient infiltration slurry and modified granulated powder: Weigh an appropriate amount of 3 mol% yttrium oxide partially stabilized nano-zirconia powder with a purity of 99.95 wt.% or more, and add 0.3 wt. .% Tween 80 and 2.5wt.% polyvinyl alcohol to make an aqueous slurry with a solid content of 30 vol%, part of which is used as a surface gradient slurry; the other part is made of 3 mol% yttrium oxide by spray drying and granulation process Stabilized nano zirconia granulated powder.

S2. Green body molding: put the 3 mol% yttrium oxide partially stabilized nano-zirconia granulated powder obtained in step S1 into a metal mold with an inner diameter of 75 mm, and bidirectionally pre-press at 100 MPa to form a preform with a height of 150 mm, and then Partially stabilized nano-zirconia granulated powder with 3 mol% yttrium oxide was dry-pressed and vacuum-packed in a plastic bag, put into a cold isostatic press, and subjected to cold isostatic pressing under a hydrostatic pressure of 350 MPa to obtain 3 mol% yttrium oxide partially stabilized nano-zirconia granulated powder to form a green body.

S3. Blank pre-sintering: put the 3 mol% yttrium oxide partially stabilized nano-zirconia granulated powder formed green body obtained in the step S2 into an electric furnace for pre-sintering. hours, the heating and cooling rate was 5°C/min, and a 3 mol% yttrium oxide partially stabilized nano-zirconia calcined ceramic green body with a relative density of 50% was obtained.

S4. Ceramic ball pre-fired biscuit processing: According to the size requirements of the drawing, CNC numerical control machine tools are used to machine the 3 mol% yttrium oxide partially stabilized nano-zirconia ceramic pre-fired bisque obtained in the step S3 to obtain a 3 mol% yttrium oxide ceramic pre-fired bisque with a diameter of 58 mm. mol% yttria partially stabilized nano-zirconia ceramic ball pre-fired biscuit.

S5. Surface infiltration of the ceramic ball pre-fired billet: put the 3 mol% yttrium oxide partially stabilized nano-zirconia ceramic ball pre-fired billet obtained in the step S4 into a vacuum tank, and then pour the surface gradient infiltration slurry obtained in the step S1 material, and the cover is vacuumed to -0.08 MPa, so that the surface gradient infiltration slurry gradually penetrates into the surface layer of the pre-fired biscuit of 3 mol% yttrium oxide partially stabilized nano-zirconia ceramic balls. After holding the pressure for 30 minutes, a surface pre-infiltration 3 3 mol% yttrium oxide partially stabilized nano zirconia ceramic ball pre-infiltrated green body with mol% yttria partially stabilized nano zirconia slurry, the content of nano zirconia powder on the surface of the infiltrated layer increased by 11.8 vol.%, and the depth of the gradient infiltrated layer was 2500 Microns.

S6. Densification and sintering of ceramic ball billets: firstly, the 3 mol% yttrium oxide partially stabilized nano-zirconia ceramic ball pre-infiltrated green body obtained in S5 is put into an air electric furnace for further pre-sintering, the sintering temperature is 1350°C, and the sintering time is 2 hours , the heating and cooling rate is 5°C/min, to obtain a 3 mol% yttrium oxide partly stabilized nano-zirconia ceramic ball calcined body with a surface pre-infiltrated layer with a relative density of 97%; then, the 3 mol% The yttrium oxide partially stabilized nano-zirconia ceramic ball pre-sintered body was placed in a hot isostatic pressing sintering furnace for densification sintering. The sintering temperature was 1480°C, the sintering gas pressure was 20 MPa, the sintering time was 3 hours, and the heating and cooling rate was 1°C/ min, the final diameter is 44.4 mm, the relative density is 99.9%, the grain size is 328 nm, the tensile strength between the gradient infiltration coating and the substrate is 88.4 MPa, the shear strength is 132 MPa, and the flexural strength of the substrate is 1500MPa, fracture toughness of 12 MPa·m ^1/2 surface self-reinforced 3 mol% yttria partially stabilized nano-zirconia ceramic spheres.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: the surface self-reinforced 3 mol% yttrium oxide partially stabilized nano-zirconia ceramic ball blank obtained in S6 is placed in a V-shaped groove grinding device for at least rough grinding, semi-finished Finishing, finishing, superfinishing and polishing are processed into a nominal diameter of 44 mm, a ball surface roughness Ra of 0.002 mm, a spherical error of 0.04 μm, a spherical roundness of 0.002 mm, and a ball batch diameter deviation of 0.002 mm. 0.08 μm, surface hardness HV ₁₀₀₀ is 1630, and there are 3 mol% yttria partially stabilized nano-zirconia ceramic balls with -250 MPa precompression stress on the surface.

S8. Machining of surface self-reinforced nano-zirconia ceramic femoral spherical unicondyle: According to the design drawing requirements of ceramic femoral spherical unicondyle, the 3 mol% yttrium oxide partially stabilized nano-zirconia ceramic ball obtained in step S7 was cut and ground And chamfering processing to prepare two friction surfaces with a nominal spherical diameter of 44 mm, a gradient permeable layer depth of 1710 mm, and a self-reinforced nano-zirconia ceramic femoral spherical single condyle with a single positioning post.

S9. Final polishing of the surface self-reinforced nano-zirconia ceramic femoral spherical unicondyle surface: the final polishing is performed on the spherical surface of the surface self-reinforced nano-zirconia ceramic femoral unicondyle with a single positioning post, so that the surface roughness Ra is 0.002mm.

S10. Inspection/marking/packaging: conduct all quality inspections on the surface self-reinforced nano-zirconia ceramic femoral unicondyle with a single positioning post, and mark and pack qualified products.

Example 16: Surface self-reinforced nano-silicon nitride ceramic femoral spherical unicondyle
S1. Formulation/milling and preparation of surface gradient slurry and modified granulated powder: Weigh an appropriate amount of silicon nitride powder with a purity of 99.9 wt.% or more, add 1 wt% magnesium oxide, 2 wt% % lanthanum oxide, 3 wt% yttrium oxide as a sintering aid, 0.5 wt.% Tween 80 as a surfactant and 3 wt.% polyethyleneimine as a binder to make an aqueous slurry with a solid content of 30vol%, part of It is used as the surface gradient infiltration slurry; the other part is made of modified nano-silicon nitride granulated powder through a spray-drying granulation process.

S2. Green body molding: put the modified nano-silicon nitride granulated powder obtained in step S1 into a metal mold with an inner diameter of 82 mm, and bidirectionally pre-press at 120 MPa to form a preform with a height of 150 mm, and then nano-modified The silicon nitride granulated powder dry-pressed blank is vacuum-packed in a plastic bag, put into a cold isostatic press, and subjected to cold isostatic pressing under a hydrostatic pressure of 250 MPa to obtain a modified nano-silicon nitride molded green body.

S3. Blank pre-sintering: put the modified nano-silicon nitride molded green body obtained in step S2 into a pressure sintering electric furnace for pre-sintering, nitrogen atmosphere, pre-sintering temperature of 1750°C, pre-sintering time of 2 hours, heating and cooling speed at 2°C/min, a modified nano-silicon nitride ceramic calciner with a relative density of 56% was obtained.

S4. Ceramic ball pre-fired bisque processing: according to the frictional spherical surface size requirements of the surface self-reinforced nano-silicon nitride ceramic femoral spherical unicondyle, the modified nano-silicon nitride ceramic pre-sintered bisque obtained in step S3 is processed by CNC numerical control machine tools. Machining to obtain a calcined biscuit of modified nano-silicon nitride ceramic balls with a diameter of 64 mm.

S5. Surface grouting of ceramic ball pre-fired billet: put the modified nano-silicon nitride ceramic ball pre-fired billet obtained in step S4 into a vacuum tank, then pour the surface gradient grouting slurry obtained in step S1, and cover Vacuum down to -0.08 MPa to make the surface gradient infiltration slurry gradually infiltrate into the surface layer of the pre-fired biscuit of nano-silicon nitride ceramic balls. After holding the pressure for 25 minutes, the surface self-reinforcement with surface pre-infiltration gradient nano-silicon nitride slurry is obtained. Nano-silicon nitride ceramic balls pre-infiltrate the green body, the content of nano-silicon nitride powder on the surface of the infiltration layer increases by 10 vol.%, and the depth of the gradient infiltration layer is 1500 microns.

S6. Densification and sintering of ceramic ball blanks: firstly, put the surface self-reinforced nano-silicon nitride ceramic ball pre-infiltrated green body obtained in S5 into an atmosphere-protected electric furnace for further pre-sintering. The sintering temperature is 1800°C and the sintering time is 5 hours. The cooling rate is 1°C/min, and the surface self-reinforced nano-silicon nitride ceramic ball pre-sintered body with a relative density of 97% is obtained; then, the surface self-reinforced nano-silicon nitride ceramic ball pre-sintered body is placed in a hot isostatic pressing sintering furnace Densification sintering was carried out in the medium, the sintering temperature was 1720 °C, the sintering gas pressure was 200 MPa, the sintering time was 2 hours, and the heating and cooling rate was 1 °C/min. Finally, the diameter was 48.3 mm, the relative density was 99.9 %, and the grain size was 468 mm. The tensile strength between the nanometer and gradient infiltration coating and the substrate is 98 MPa, the shear strength is 122 MPa, the substrate flexural strength is 1150 MPa, and the fracture toughness is 8 MPa·m ^1/2 surface self-reinforced nano-silicon nitride Ceramic balls.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the surface self-reinforced nano-silicon nitride ceramic ceramic ball blank obtained in S6 into a V-shaped groove grinding device for at least rough grinding, semi-finishing, and finishing in steps. , superfinishing and polishing 5 processes, the nominal spherical diameter is 47.9 mm, the spherical surface roughness Ra is 0.003 mm, the spherical error is 0.04 μm, the spherical roundness is 0.005 mm, and the ball batch diameter deviation is 0.1 μm. The surface hardness HV ₁₀₀₀ is 1910, and there is a surface self-reinforced nano-silicon nitride ceramic ball with -52 MPa precompression stress on the surface.

S8. Machining of surface self-reinforced nano-silicon nitride ceramic femoral spherical unicondyle: according to the design drawings of surface self-reinforced nano-silicon nitride ceramic femoral unicondyle, the surface self-reinforced nano-silicon nitride ceramic ball obtained in step S7 was processed. The surface self-reinforced nano-silicon nitride ceramic femur spherical single condyle with a single positioning post was prepared by cutting, grinding and chamfering.

S9. Final polishing of the surface self-reinforced nano-silicon nitride ceramic femoral spherical unicondyle surface: the final polishing of the spherical surface of the surface self-reinforced nano-silicon nitride ceramic femoral unicondyle with a single positioning post, so that the surface roughness Ra is 0.002mm .

S10. Inspection/marking/packaging: conduct a full quality inspection of the surface self-reinforced nano-silicon nitride ceramic spherical femoral unicondyle with a single positioning post, and mark and pack qualified products.

Example 17: Surface self-reinforced nano-silicon carbide ceramic femoral spherical unicondyle
S1. Formulation/milling and preparation of surface gradient slurry and modified granulated powder: Weigh an appropriate amount of silicon carbide powder with a purity of 99.9 wt.% or more, and add 2.4 wt% of nano-boron carbide powder As a sintering aid, 1.0 wt.% Tween 80 as a surfactant and 3.0 wt.% polyethylene glycol as a binder to make an aqueous slurry with a solid content of 35 vol%, part of which is used as a surface gradient slurry; The other part is made of nano-modified silicon carbide granulated powder by spray drying granulation process.

S2. Green body molding: put the nano-modified silicon carbide granulated powder obtained in step S1 into a metal mold with an inner diameter of 82 mm, and bidirectionally pre-press at 120 MPa to form a pre-form with a height of 150 mm, and then place the nano-modified The silicon carbide granulated powder dry-pressed blank is vacuum-packed in a plastic bag, put into a cold isostatic press, and subjected to cold isostatic pressing under a hydrostatic pressure of 320 MPa to obtain a nano-modified silicon carbide granulated powder Formed green body.

S3. Blank pre-sintering: put the nano-modified silicon carbide granulated powder formed green body obtained in step S2 into a gas pressure sintering electric furnace for pre-sintering, argon atmosphere, pre-sintering temperature of 1750°C, and pre-sintering time of 2 hours , the heating and cooling rate was 2°C/min, and a nano-modified silicon carbide ceramic pre-fired biscuit with a relative density of 57% was obtained.

S4. Pre-fired green billet processing: According to the size requirements of the drawings, CNC numerical control machine tools are used to machine the nano-modified silicon carbide ceramic pre-fired green billet obtained in step S3 to obtain a nano-modified silicon carbide ceramic ball pre-burner with a diameter of 65 mm. Burnt biscuit.

S5. Surface grouting of the pre-fired billet: put the nano-modified silicon carbide ceramic ball pre-fired green body obtained in the step S4 into a vacuum tank, then pour the surface gradient grouting slurry obtained in the step S1, and vacuumize the cover to -0.10 MPa, so that the surface gradient infiltration slurry gradually penetrates into the surface layer of the nano-modified silicon carbide ceramic ball pre-fired biscuit, and after holding the pressure for 42 minutes, the nano-modified silicon carbide slurry with surface pre-infiltration gradient nano-modification is obtained. Silicon carbide ceramic ball pre-infiltrated body, the content of nano-silicon carbide powder on the surface of the infiltration layer increased by 11.2 vol.%, and the depth of the gradient infiltration layer was 2100 microns.

S6. Densification and co-sintering of ceramic ball blanks: firstly, put the pre-infiltrated body of nano-modified silicon carbide ceramic balls obtained in S5 into an atmosphere-protected electric furnace for further pre-sintering. The sintering temperature is 1910°C and the sintering time is 3 hours. The cooling rate is 1°C/min, and the nano-modified silicon carbide ceramic ball pre-sintered body with a relative density of 95% is obtained; then, the nano-modified silicon carbide ceramic ball pre-sintered body is placed in a hot isostatic pressing sintering furnace for densification Sintering, the sintering temperature is 1820°C, the sintering gas pressure is 200 MPa, the sintering time is 6 hours, the heating and cooling rate is 1°C/min, the final diameter is 48.5 mm, the relative density is 99.9%, the grain size is 768 nm, and the gradient infiltration The tensile strength between the coating and the substrate is 218 MPa, the shear strength is 192 MPa, the flexural strength of the substrate is 880 MPa, and the fracture toughness is 6.5 MPa·m ^1/2 , with surface prestressed self-reinforced nano-modification Silicon carbide ceramic ball blank.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nano-modified silicon carbide ceramic ball blank obtained in S6 into the V-shaped groove grinding equipment for at least rough grinding and semi-finishing in steps. , lapping, ultra-finishing, and polishing are processed into a nominal diameter of 47.9 mm, a ball surface roughness Ra of 0.003 mm, a spherical error of 0.04 μm, a spherical roundness of 0.003 mm, and a ball batch diameter deviation of 0.06 μm, surface hardness HV ₁₀₀₀ is 2120, surface prestressed self-reinforced nano-modified silicon carbide ceramic balls with -450 MPa prestress on the surface.

S8. Machining of surface prestressed self-reinforced nano-modified silicon carbide ceramic femoral spherical unicondyle: according to the size requirements of the surface prestressed self-reinforced nano-modified silicon carbide ceramic femoral spherical unicondyle drawing, the surface prestressed self-reinforced obtained in step S7 The nano-modified silicon carbide ceramic ball is processed by cutting, grinding and chamfering to prepare two friction surfaces with a nominal spherical diameter of 47.9 mm, a gradient permeable layer depth of 1320 mm, and a surface prestressed self-reinforcement with a single positioning column. Nano-modified silicon carbide ceramic femoral spherical unicondyle.

S9. Final polishing of surface prestressed self-reinforced nano-modified silicon carbide ceramic femur spherical unicondyle surface: the final polishing of the spherical surface of the surface prestressed self-reinforced nano-modified silicon carbide ceramic femoral unicondyle with a single positioning post, so that the surface The roughness Ra is 0.002mm.

S10. Inspection/marking/packaging: conduct all quality assurance inspections on the surface prestressed self-reinforced nano-modified silicon carbide ceramic femoral unicondyle with a single positioning post, and conduct laser marking and packaging on the bottom surface of qualified products.

Example 18: Surface self-reinforced nano-zirconia toughened alumina composite ceramic femoral spherical unicondyle
S1. Formulation/milling and preparation of surface gradient slurry and modified granulated powder: Weigh an appropriate amount of 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite powder with a purity of 99.9 wt.% or more , add its quality 0.08wt.% magnesium oxide, 0.2 wt.% Tween 80 and 4 wt.% carboxymethyl cellulose to make an aqueous slurry with a solid content of 25vol%, one part is used as a surface gradient slurry; the other part The 3 mol% yttria partially stabilized nano zirconia toughened alumina composite granulated powder was prepared by spray drying granulation process.

S2. Green body molding: put the 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite granulation powder obtained in step S1 into a metal mold with an inner diameter of 80 mm, and bidirectionally pre-press at 150 MPa to a height of 150 mm. mm of dry-pressed preform, and then dry-pressed preform of 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite granulation powder in a plastic bag, put it into a cold isostatic press, and Cold isostatic pressing was carried out under a hydrostatic pressure of 250 MPa to obtain a green body formed by 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite powder.

S3, green body pre-sintering: put the 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite powder formed green body obtained in step S2 into an electric furnace for pre-sintering, the air atmosphere and pre-sintering temperature are 1230 °C, The pre-fired time was 2 hours, and the heating and cooling rate was 5°C/min to obtain a 3 mol% yttria partially stabilized nano-zirconia toughened alumina composite ceramic calcined green body with a relative density of 54%.

S4. Ceramic ball pre-fired biscuit processing: According to the size requirements of the drawings, CNC numerical control machine tools are used to machine the 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic pre-fired bisque obtained in step S3 to obtain diameter The 65 mm 3 mol% yttria partially stabilized nano-zirconia toughened alumina composite ceramic balls were pre-fired.

S5. Surface infiltration of ceramic ball calcined billet: put the 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic ball calcined billet obtained in step S4 into a vacuum tank, and then pour it into the calcined billet obtained in step S1 Surface gradient infiltration slurry, the cover is evacuated to -0.08MPa, so that the surface gradient infiltration slurry gradually infiltrates the surface layer of 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic ball pre-fired biscuit, and the pressure is maintained After 15 minutes, a 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic pre-infiltrated body with a pre-infiltrated surface gradient slurry was obtained, and the content of nano-zirconia toughened alumina powder on the surface of the infiltrated layer increased 8.9 vol.%, the penetration depth is 1600 microns.

S6. Densification and sintering of ceramic ball billets: firstly, the 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic pre-infiltrated green body obtained in S5 was put into an air electric furnace for further pre-sintering, and the sintering temperature was 1450°C. The sintering time was 2 hours, the heating and cooling rate was 5°C/min, and a 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic ball pre-sintered body with a relative density of 98% was obtained; then, 3 mol% yttria The pre-sintered body of partially stabilized nano-zirconia toughened alumina composite ceramic balls was put into a hot isostatic pressing sintering furnace for densification sintering. 1°C/min, the final diameter is 48.6 mm, the relative density is 99.9%, the grain size is 630 nm, the tensile strength between the gradient infiltration coating and the substrate is 68 MPa, and the shear strength is 97 MPa. 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic spheres with a bending strength of 560 MPa and a fracture toughness of 6 MPa m ^1/2 .

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic ball blank obtained in S6 into a V-shaped groove grinding device for at least rough grinding step by step , semi-finishing, lapping, ultra-finishing and polishing 5 processes to produce a nominal diameter of 47.9 mm, a spherical surface roughness Ra of 0.004mm, a spherical error of 0.04 μm, and a roundness of the spherical surface of 0.001 mm. The diameter deviation is 0.1 μm, the surface hardness HV ₁₀₀₀ is 1900, and there is a high-precision prestressed nanometer 3 mol% yttria partially stabilized zirconia toughened alumina composite ceramic ball with a -250 MPa precompression stress on the surface.

S8. Machining of surface self-reinforced nano-zirconia toughened alumina composite ceramic femoral spherical unicondyle: according to the design drawings of ceramic femoral spherical unicondyle, the high-precision prestressed nanometer 3 mol% yttria partly stabilized zirconia obtained in step S7 Toughened alumina composite ceramic balls were processed by cutting, grinding and chamfering to prepare the femoral spherical unicondylar friction surface with a nominal spherical diameter of 47.9 mm, a depth of gradient permeation layer of 910 mm, and a self-reinforced nano-zirconia surface with a single positioning column Toughened alumina composite ceramic femoral spherical unicondyle.

S9. Final polishing of the surface self-reinforced nano-zirconia toughened alumina composite ceramic femoral spherical unicondyle surface: the final polishing of the spherical surface of the surface self-reinforced nano-zirconia toughened alumina composite ceramic femoral unicondyle with a single positioning column, The surface roughness Ra was set to 0.002 mm.

S10. Inspection/marking/packaging: conduct a full quality inspection of the surface self-reinforced nano-zirconia toughened alumina composite ceramic femoral single condyle with a single positioning post, and mark and pack qualified products.

Example 19: Surface self-reinforced nano-alumina reinforced zirconia composite ceramic femoral spherical unicondyle
S1. Formulation/milling and preparation of surface gradient slurry and modified granulated powder: Weigh an appropriate amount of nano-alumina reinforced 3 mol% yttria partially stabilized zirconia composite powder with a purity of 99.9 wt.% or more, Add 0.2 wt.% polyethylene glycol octyl phenyl ether surfactant and 3.5 wt.% polyvinyl butyral binder to make an aqueous slurry with a solid content of 25vol%, part of which is used as a surface gradient slurry Slurry; the other part is made of nano-alumina reinforced 3 mol% yttrium oxide and partially stabilized zirconia composite granulated powder by spray drying granulation process.

S2. Green body molding: put the nano-alumina reinforced 3 mol% yttria partially stabilized zirconia composite granulation powder obtained in step S1 into a metal mold with an inner diameter of 78 mm, and pre-press bidirectionally at 80 MPa to a height of 150 mm dry-pressed preform, and then dry-press the preform of nano-alumina reinforced 3 mol% yttrium oxide partially stabilized zirconia composite granulation powder in a plastic bag, put it into a cold isostatic press, and Cold isostatic pressing was carried out under hydrostatic pressure to obtain nano-alumina reinforced 3 mol% yttrium oxide partially stabilized zirconia composite powder to form a green body.

S3, green body pre-sintering: the nano-alumina reinforced 3 mol% yttria partially stabilized zirconia composite powder obtained in step S2 is put into an electric furnace for pre-sintering. The firing time was 2 hours, and the heating and cooling rate was 3°C/min to obtain a pre-fired bisque of nano-alumina reinforced 3 mol% yttria partially stabilized zirconia composite ceramics with a relative density of 50%.

S4. Ceramic ball pre-fired biscuit processing: According to the size requirements of the drawings, CNC numerical control machine tools are used to machine the nano-alumina reinforced 3 mol% yttrium oxide partially stabilized zirconia composite ceramic pre-fired bisque obtained in the step S3, and the obtained diameter is 60 mm nano-alumina reinforced 3 mol% yttria partially stabilized zirconia composite ceramic ball pre-fired green body.

S5. Surface infiltration of ceramic ball pre-fired biscuits: put the nano-alumina reinforced 3 mol% yttrium oxide partially stabilized zirconia composite ceramic ball pre-fired biscuits obtained in step S4 into a vacuum tank, and then pour the obtained in step S1 Surface gradient infiltration slurry, the cover is vacuumed to -0.08MPa, so that the surface gradient infiltration slurry gradually infiltrates into the surface layer of pre-fired biscuit of nano-alumina reinforced 3 mol% yttrium oxide partially stabilized zirconia composite ceramic balls, and the pressure is kept for 40 After 1 min, the pre-infiltrated body of nano-alumina reinforced 3 mol% yttria partially stabilized zirconia composite ceramic balls with pre-infiltrated surface gradient slurry was obtained, and the content of nano-alumina-enhanced zirconia powder on the surface of the infiltrated layer increased by 9.9 vol .%, the depth of gradient permeable layer is 1500 microns.

S6. Densification and sintering of ceramic ball billets: first, put the pre-infiltrated body of nano-alumina reinforced 3 mol% yttria partially stabilized zirconia composite ceramic balls obtained in S5 into an air electric furnace for further pre-sintering, and the sintering temperature is 1400 °C, The sintering time was 2 hours, and the heating and cooling rate was 2°C/min, so as to obtain a pre-sintered body of nano-alumina reinforced 3 mol% yttria partially stabilized zirconia composite ceramic balls with a relative density of 97% and a surface gradient precompression stress; then, The nano-alumina reinforced 3 mol% yttrium oxide partially stabilized zirconia composite ceramic ball pre-sintered body was placed in a hot isostatic pressing sintering furnace for densification sintering. The sintering temperature was 1450 °C, the sintering gas pressure was 35 MPa, and the sintering time was 2 Hours, heating and cooling rate 1 ℃ / min, the final diameter of 44.4 mm, the relative density of 99.9%, the grain size of 530 nm, the tensile strength between the gradient infiltration coating and the substrate is 128 MPa, the shear strength is 192 MPa, a matrix with a flexural strength of 1480 MPa and a fracture toughness of 10 MPa·m ^1/2 nano-alumina reinforced 3 mol% yttria partially stabilized zirconia composite ceramic ball blank.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nano-alumina reinforced 3 mol% yttrium oxide partially stabilized zirconia composite ceramic ball blank obtained in S6 into a V-shaped groove grinding device for at least rough grinding, Semi-finishing, lapping, super-finishing and polishing are processed into a nominal diameter of 44 mm, a ball surface roughness Ra of 0.004 mm, a spherical error of 0.05 μm, a spherical roundness of 0.002 mm, and a ball batch diameter of The deviation is 0.09 μm, the surface hardness HV ₁₀₀₀ is 1980, and there is a pre-compression stress of -258 MPa on the surface of nano-alumina surface reinforced 3 mol% yttria partially stabilized zirconia composite ceramic balls.

S8. Machining of surface self-reinforced nano-alumina reinforced zirconia composite ceramic femoral spherical unicondyle: According to the design drawings of ceramic femoral unicondyle, the nano-alumina obtained in step S7 was reinforced with 3 mol% yttria and partially stabilized zirconia composite ceramics The ball is divided into two ceramic femoral spherical unicondylar blanks, and then processed by grinding and chamfering to prepare a self-reinforced nano-alumina reinforced surface with a nominal spherical diameter of 44 mm, a gradient penetration layer depth of 910 mm, and a single positioning column. Zirconia composite ceramic femoral spherical unicondyle.

S9. Final polishing of surface self-reinforced nano-alumina-reinforced zirconia composite ceramic femoral spherical unicondyle surface: the final polishing of the spherical surface of the surface self-reinforced nano-alumina reinforced zirconia composite ceramic femoral unicondyle with a single positioning column, so that the surface The roughness Ra is 0.002mm.

S10. Inspection/marking/packaging: conduct a full quality inspection of the surface self-reinforced nano-alumina reinforced zirconia composite ceramic femoral unicondyle with a single positioning post, and mark and pack qualified products.

Example 20: Nano-alumina surface component gradient composite reinforced zirconia ceramic femur spherical unicondyle
S1. Formulation/milling and preparation of surface gradient infiltration slurry and modified granulated powder: First, weigh an appropriate amount of 3mol% yttrium oxide partially stabilized nano-zirconia powder with a purity of 99.8 wt.% or more, and add its mass of 0.3 Wt.% Tween 80 surfactant and 3 wt.% water-based phenolic resin binder are made into an aqueous slurry with a solid content of 30vol%, and then the yttrium oxide partially stabilized nano-zirconia granulated powder is obtained by a spray drying process; Then, weigh an appropriate amount of nano-alumina powder with a purity of 99.8 wt.%, add 0.1 wt% of its mass of nano-magnesia, 0.4 wt.% Tween 80 surfactant and 2.5 wt.% water-based phenolic resin to bond The water-based slurry with a solid content of 25vol% was prepared as a surface gradient slurry.

S2. Green body molding: put the yttrium oxide partially stabilized nano-zirconia powder obtained in step S1 into a metal mold with an inner diameter of 95 mm, and bidirectionally pre-press 120 MPa to form a green body with a height of 150 mm, and then add 3 mol% yttrium oxide Partially stabilized nano-zirconia powder dry-pressed preform is vacuum-packed in a plastic bag, placed in a cold isostatic press, and subjected to cold isostatic pressing under a hydrostatic pressure of 350MPa to obtain 3mol% yttrium oxide partially stabilized nano-zirconia The granulated powder is formed into a green body.

S3. Blank pre-sintering: put the 3mol% yttrium oxide partially stabilized nano-zirconia granulated powder formed green body obtained in step S2 into an electric furnace for pre-sintering. The air atmosphere and pre-sintering temperature are 1080°C and the pre-sintering time is 2 hours, the heating and cooling rate was 1°C/min, and a 3mol% yttrium oxide partially stabilized nano-zirconia ceramic pre-fired green body with a relative density of 53% was obtained.

S4. Processing of ceramic ball pre-fired biscuits: According to the size requirements of the drawings, CNC numerical control machine tools are used to machine the 3 mol% yttrium oxide partially stabilized nano-zirconia ceramic pre-fired biscuits obtained in step S3 to obtain 3 mol% yttrium oxide ceramic pre-fired biscuits with a diameter of 74 mm. mol% yttria partially stabilized nano-zirconia ceramic ball pre-fired biscuit.

S5. Surface infiltration of the ceramic ball pre-fired billet: put the 3 mol% yttrium oxide partially stabilized nano-zirconia ceramic ball pre-fired billet obtained in the step S4 into a vacuum tank, and then pour the surface gradient infiltration slurry obtained in the step S1 material, and the cover is evacuated to -0.08MPa, so that the surface gradient infiltration slurry gradually infiltrates the surface layer of the pre-fired biscuit of 3 mol% yttria partially stabilized nano-zirconia ceramic balls. After holding the pressure for 60 minutes, a surface pre-infiltration gradient is obtained. 3 mol% yttrium oxide in the nano-alumina ceramic slurry partially stabilizes the nano-zirconia ceramic ball pre-infiltrated body, the content of nano-alumina powder on the surface of the infiltration layer increases by 9.1 vol.%, and the depth of the gradient infiltration layer is 1550 microns.

S6. Densification and sintering of ceramic ball billets: firstly, the 3 mol% yttrium oxide partially stabilized nano-zirconia ceramic ball pre-infiltrated green body obtained in S5 is put into an air electric furnace for further pre-sintering, the sintering temperature is 1350°C, and the sintering time is 2 hours , the heating and cooling rate was 1°C/min, and a 3 mol% yttria partially stabilized nano-zirconia ceramic ball calcined body with a relative density of 97% with a nano-alumina gradient diffusion layer and a surface gradient precompression stress was obtained; then, the 3 The mol% yttrium oxide partially stabilized nano-zirconia ceramic ball pre-sintered body is placed in a hot isostatic pressing sintering furnace for densification sintering. The sintering temperature is 1450°C, the sintering gas pressure is 40MPa, the sintering time is 6 hours, and the heating and cooling rate is 1°C /min, the final diameter is 55.5 mm, the relative density is 99.92%, the grain size is 430 nm, the tensile strength between the gradient infiltration coating and the substrate is 138 MPa, the shear strength is 152 MPa, and the flexural strength of the substrate is 3 mol% yttria partially stabilized nano-zirconia ceramic spheres with a surface gradient diffusion layer of nano-alumina and a surface gradient precompression stress of 1200 MPa and a fracture toughness of 14 MPa·m ^1/2 .

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nano-alumina surface gradient compound reinforced 3 mol% yttrium oxide partly stabilized nano-zirconia ceramic ball blank obtained in S6 into the V-shaped groove grinding equipment for at least step by step Rough grinding, semi-finishing, finishing, super-finishing and polishing are processed into a nominal diameter of 55 mm, a spherical surface roughness Ra of 0.005 mm, a spherical error of 0.04 μm, and a spherical roundness of 0.004 mm. The diameter deviation of the ball batch is 0.08 μm, the surface hardness HV ₁₀₀₀ is 2100, and the nano-alumina surface component gradient composite reinforced zirconia ceramic balls with -350 MPa pre-compression stress on the surface.

S8. Machining of nano-alumina surface component gradient composite reinforced zirconia ceramic femoral unicondyle: according to the design drawings of ceramic femoral unicondyle, divide the nano-alumina surface component gradient composite reinforced zirconia ceramic ball obtained in step S7 Two ceramic femoral spherical unicondylar blanks were prepared, and then ground and chamfered to prepare two friction surfaces with a nominal spherical diameter of 55 mm, a gradient permeable layer depth of 950 mm, and a nano-alumina surface assembly with a single positioning column. Gradient composite reinforced zirconia ceramic spherical femoral unicondyle.

S9. Final polishing of nano-alumina surface component gradient compound reinforced zirconia ceramic femoral unicondyle: final polishing of the spherical surface of nano-alumina surface component gradient compound reinforced zirconia ceramic femoral unicondyle with a single positioning column, The surface roughness Ra was set to 0.002 mm.

S10. Inspection/marking/packaging: conduct all quality inspections on the nano-alumina surface component gradient composite reinforced zirconia ceramic femoral single condyle with single positioning column, and mark and pack qualified products.

Example 21: Nano-alumina surface component gradient composite reinforcement zirconia-based composite ceramic femoral spherical unicondyle
S1. Formulation/milling and preparation of surface gradient infiltration slurry and modified granulated powder: First, weigh an appropriate amount of nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite powder with a purity of 99.9 wt.% or more , add its quality 0.5 wt.% Tween 80 surfactant and 3.5wt.% carboxymethyl cellulose to make an aqueous slurry with a solid content of 35 vol%, and then make a nano-alumina reinforced 3mol by spray drying granulation process % yttrium oxide partially stabilized nano-zirconia composite granulation powder; then, weigh an appropriate amount of nano-alumina powder with a purity of 99.9 wt.% or more, add its mass of 0.15 wt% nano-magnesia, 0.3 wt.% Tween 80 and 3.5wt.% carboxymethyl cellulose were made into aqueous slurry with a solid content of 25vol% as surface gradient slurry.

S2. Green body molding: put the nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite powder obtained in step S1 into a metal mold with an inner diameter of 70 mm, and bidirectionally pre-press at 80 MPa to form a pre-form with a height of 130 mm. , and then the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite granulation powder dry-pressed blank was vacuum-packed in a plastic bag, put into a cold isostatic press, and carried out under a hydrostatic pressure of 350 MPa Cold isostatic pressing to obtain nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite granulated powder to form a green body.

S3. Biscuit pre-sintering: put the nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite granulated powder obtained in step S2 into the green body for pre-sintering in an electric furnace, and the air atmosphere and pre-sintering temperature are 1050°C , The pre-firing time was 2 hours, and the heating and cooling rate was 1°C/min to obtain a nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite ceramic calcined green body with a relative density of 52%.

S4. Ceramic ball pre-fired bisque processing: According to the size requirements of the drawings, the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite ceramic pre-fired bisque obtained in the step S3 is machined with CNC machine tools, and the diameter is obtained. 55 mm nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite ceramic ball pre-fired green body.

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite ceramic ball pre-fired biscuit obtained in step S4 into a vacuum tank, and then pour it into the obtained in step S1 Surface gradient infiltration slurry, the cover is vacuumed to -0.09 MPa, so that the surface gradient infiltration slurry gradually infiltrates the surface layer of the pre-fired biscuit of nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite ceramic balls, and the pressure is kept for 40 Min later, the nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite ceramic ball pre-infiltrated green body with surface pre-infiltration gradient nano-alumina ceramic slurry was obtained, and the content of nano-alumina powder on the surface of the infiltration layer increased by 9.3vol. %, the depth of the gradient permeable layer is 2500 microns.

S6. Densification and sintering of ceramic ball billets: first, put the pre-infiltrated body of nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite ceramic balls obtained in S5 into an air electric furnace for further pre-sintering, and the sintering temperature is 1480°C. The sintering time is 2 hours, the heating and cooling rate is 1°C/min, and the nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite ceramic ball with a relative density of 96% has a nano-alumina gradient diffusion layer and a surface gradient precompression stress. The pre-sintered body; then, the nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite ceramic ball pre-sintered body was placed in a hot isostatic sintering furnace for densification sintering, the sintering temperature was 1540 ° C, and the sintering gas pressure was 30MPa, sintering time of 2 hours, heating and cooling rate of 1°C/min, the final diameter is 41.2 mm, the relative density is 99.95%, the grain size is 383 nm, and the tensile strength between the gradient infiltration coating and the substrate is 108 MPa , with a shear strength of 122 MPa, a matrix with a flexural strength of 1320 MPa and a fracture toughness of 12 MPa·m ^1/2, which has a nano-alumina surface-enhanced gradient diffusion layer and a surface gradient pre-stressed nano-alumina reinforced 3mol% oxide Yttrium partially stabilized nano-zirconia composite ceramic ball blank.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite ceramic ball blank obtained in S6 into a V-shaped groove grinding device for at least rough grinding, step by step, Semi-finishing, lapping, super-finishing, and polishing are processed into a nominal diameter of 40.6 mm, a spherical surface roughness Ra of 0.004 mm, a spherical error of 0.05 μm, and a roundness of the spherical surface of 0.002 mm. The diameter deviation is 0.07 μm, the surface hardness HV ₁₀₀₀ is 2120, and there is a nano-alumina composite reinforced 3mol% yttria partially stabilized nano-zirconia composite ceramic ball with a -230MPa pre-compression stress on the surface.

S8. Machining of nano-alumina surface component gradient composite reinforcement zirconia-based composite ceramic femoral spherical unicondyle: according to the design drawings of ceramic femoral unicondyle, the nano-alumina composite reinforced 3mol% yttrium oxide obtained in step S7 was partially stabilized The zirconia composite ceramic ball was divided into two ceramic femoral spherical unicondylar blanks, and then processed by grinding and chamfering to prepare the femoral spherical unicondylar friction surface with a nominal spherical diameter of 40.6 mm, a gradient permeable layer depth of 1770 mm, and a double The nano-alumina surface composition gradient composite reinforcement of the positioning post for the spherical unicondyle of the zirconia ceramic femur.

S9. The final polishing of nano-alumina surface component gradient composite reinforced zirconia-based composite ceramic spherical femoral single condyle surface: the spherical surface of nano-alumina surface component gradient composite reinforced zirconia-based composite ceramic spherical femoral single condyle with double positioning columns Final polishing was performed so that the surface roughness Ra was 0.002 mm.

S10. Inspection/marking/packaging: conduct all quality inspections on the nano-alumina surface component gradient composite reinforced zirconia-based composite ceramic femoral spherical unicondyle with double positioning columns, and mark and pack qualified products.

Example 22: Nano-alumina surface composition gradient reinforced alumina-based composite ceramic femur spherical unicondyle
S1. Formulation/milling and preparation of surface gradient infiltration slurry and modified granulated powder: First, weigh an appropriate amount of 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina composite powder with a purity of 99.9 wt.% or more body, add its mass 0.5 wt.% Tween 80 surfactant and 4.2wt.% polyvinyl butyral to make an aqueous slurry with a solid content of 30vol%, and then make 3mol% yttrium oxide by spray drying and granulation process Partially stabilized nano-zirconia toughened nano-alumina composite granulation powder; then, weigh an appropriate amount of nano-alumina powder with a purity of 99.9 wt.% or more, add its mass of 0.12wt% nano-magnesia sintering aid, 0.5 Wt.% Tween 80 surfactant and 3.5wt.% polyvinyl butyral binder were used to make an aqueous slurry with a solid content of 25vol% as a surface gradient slurry.

S2. Green body molding: put the 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina composite granulated powder obtained in step S1 into a metal mold with an inner diameter of 78 mm, and bidirectionally pre-press at 120 MPa to a height of 150 mm. dry-pressed blank, and then dry-pressed the blank with 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina composite granulation powder in a plastic bag, put it into a cold isostatic press, and Cold isostatic pressing is carried out under a certain hydrostatic pressure to obtain a 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina composite granulated powder to form a green body.

S3, biscuit pre-sintering: put the 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina composite granulated powder obtained in step S2 into the green body for pre-sintering in an electric furnace, and the air atmosphere and pre-sintering temperature are 1210 ℃, pre-firing time 2 hours, heating and cooling rate of 5 ℃ / min, to obtain 3mol% yttria partially stabilized nano-zirconia toughened nano-alumina composite ceramic calcined green body with a relative density of 50%.

S4. Processing of ceramic ball pre-fired biscuits: According to the size requirements of the drawings, CNC numerical control machine tools are used to machine the 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina composite ceramic pre-fired biscuits obtained in step S3 to obtain diameters. 60 mm 3mol% yttria partially stabilized nano-zirconia toughened nano-alumina composite ceramic ball pre-fired biscuit.

S5. Surface infiltration of ceramic ball pre-fired biscuits: put the 3mol% yttria partially stabilized nano-zirconia toughened nano-alumina composite ceramic ball pre-fired biscuits obtained in step S4 into a vacuum tank, and then pour them into step S1 to obtain The surface gradient infiltration slurry, the cover is evacuated to -0.10 MPa, so that the surface gradient infiltration slurry gradually infiltrates the surface layer of the pre-fired biscuit of 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina composite ceramic balls to ensure After pressing for 45 min, a 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina composite ceramic ball pre-infiltrated body with surface pre-infiltration gradient nano-alumina ceramic slurry was obtained, and the content of nano-alumina powder on the surface of the infiltration layer increased 9.8 vol.%, the gradient permeation layer depth is 2200 microns.

S6. Densification and sintering of ceramic ball billets: first, put the 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina composite ceramic ball billets obtained in S5 into an air electric furnace for further pre-sintering. The sintering temperature is 1530°C. The time is 2 hours, the heating and cooling rate is 1°C/min, and the relative density is 96%, and the 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina composite ceramic ball with a nano-alumina gradient diffusion layer and a surface gradient precompression stress is obtained. Pre-sintered billet; then, put 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina composite ceramic ball pre-sintered billet into a hot isostatic sintering furnace for densification and sintering, the sintering temperature is 1570 ° C, the sintering gas pressure The sintering time is 20MPa, the sintering time is 4 hours, and the heating and cooling rate is 5°C/min. The final diameter is 44.5 mm, the relative density is 99.9%, the grain size is 780 nm, and the tensile strength between the gradient infiltration coating and the substrate is 68. MPa, shear strength of 82 MPa, matrix flexural strength of 820 MPa and fracture toughness of 6 MPa m ^1/2 , nano-alumina surface gradient composite reinforcement with nano-alumina surface gradient reinforcement layer and surface gradient precompression stress 3mol %Yttrium oxide partially stabilized nano-zirconia toughened nano-alumina composite ceramic ball blank.

S7. Rough grinding, fine grinding, and polishing of the surface of ceramic ball blanks: put the nano-alumina surface-enhanced 3mol% yttrium oxide partly stabilized nano-zirconia toughened nano-alumina composite ceramic ball blanks obtained in S6 into a V-shaped groove grinding device for separation. At least 5 steps of rough grinding, semi-finishing, finishing, super-finishing and polishing are carried out to process the nominal diameter of 44 mm, the surface roughness of the ball is 0.004 mm, the roundness of the spherical surface is 0.002 mm, and the spherical error is 0.06 μm, ball batch diameter deviation is 0.06 μm, surface hardness HV ₁₀₀₀ is 2150, nano-alumina surface reinforced 3mol% yttria partly stabilized nano-zirconia toughened nano-alumina composite ceramic balls with -380 MPa pre-compression stress on the surface.

S8. Machining of nano-alumina surface component gradient composite reinforcement alumina-based composite ceramic femoral spherical unicondyle: According to the design drawings of ceramic femoral unicondyle, the surface of nano-alumina obtained in step S7 is compositely reinforced with 3mol% yttrium oxide to partially stabilize Nano-zirconia toughened nano-alumina composite ceramic balls were divided into two nano-alumina surface component gradient composite reinforced alumina-based composite ceramic femoral spherical unicondyle blanks, and then processed by grinding and chamfering to prepare two friction The nominal spherical diameter of the surface is 44 mm, the depth of the gradient permeable layer is 1380 mm, and the nano-alumina surface component gradient composite reinforced alumina-based composite ceramic femoral unicondyle with double positioning columns.

S9. Final polishing of nano-alumina surface component gradient compound reinforced alumina-based composite ceramic spherical femoral unicondyle surface: the spherical surface of nano-alumina surface component gradient composite reinforced alumina-based composite ceramic femoral unicondyle with double positioning columns Final polishing was performed so that the surface roughness Ra was 0.002 mm.

S10. Inspection/marking/packaging: conduct all quality inspections on the nano-alumina surface component gradient composite reinforced alumina-based composite ceramic femoral unicondyle with double positioning columns, and mark and pack qualified products.

Example 23: Nano-alumina surface component gradient composite reinforcement of silicon nitride ceramic spherical femoral unicondyle
S1. Formulation/milling and preparation of surface gradient slurry and modified granulated powder: (1) Weigh an appropriate amount of silicon nitride powder with a purity of 99.9 wt.% or more, and add 2.1 wt% of its mass to the nano Alumina was used as a sintering aid, 0.2 wt.% Tween 80 was used as a surfactant and 3.5 wt.% polyvinyl alcohol was used as a binder to make an aqueous slurry with a solid content of 32 vol%, which was then prepared by a spray-drying granulation process To obtain nano-modified silicon nitride granulated powder; (2) Weigh an appropriate amount of nano-alumina powder with a purity of 99.8 wt.% or more, add its mass of 0.25 wt% nano-magnesia sintering aid, 0.4 wt.% Tween 80 surfactant and 3.5 wt.% polyvinyl alcohol were used to make an aqueous slurry with a solid content of 25vol% as a surface gradient slurry.

S2. Green body molding: put the nano-modified silicon nitride granulated powder obtained in step S1 into a metal mold with an inner diameter of 82 mm, and bidirectionally pre-press at 80 MPa to form a preform with a height of 150 mm. The preform of dry-pressed silicon nitride granulated powder is vacuum-packed in a plastic bag, put into a cold isostatic press, and subjected to cold isostatic pressing under a hydrostatic pressure of 450 MPa to obtain nano-modified silicon nitride. Granular powder forming green body.

S3. Blank pre-sintering: put the nano-modified silicon nitride granulated powder molding green body obtained in step S2 into an electric furnace for pre-sintering, nitrogen atmosphere, pre-sintering temperature is 1650 ° C, and pre-sintering time is 2 hours. The cooling rate was 1°C/min, and a nano-modified silicon nitride ceramic calcined green body with a relative density of 55% was obtained.

S4. Ceramic ball pre-fired biscuit processing: According to the size requirements of the drawing, the nano-modified silicon nitride ceramic pre-fired biscuit obtained in step S3 is machined with a CNC machine tool to obtain a nano-modified silicon nitride ceramic pre-fired bisque with a diameter of 66 mm. Silicon ceramic ball pre-fired biscuit.

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the nano-modified silicon nitride ceramic ball pre-fired biscuit obtained in step S4 into a vacuum tank, and then pour the nano-alumina for surface gradient infiltration obtained in step S1 For powder slurry, the cover is evacuated to -0.12 MPa, so that the surface gradient infiltration slurry gradually penetrates into the surface layer of the nano-modified silicon nitride ceramic ball pre-fired biscuit. After holding the pressure for 60 minutes, a surface pre-infiltration gradient nano-oxide The nano-modified silicon nitride ceramic ball pre-infiltration body of aluminum ceramic slurry, the content of nano-alumina powder on the surface of the infiltration layer is increased by 8.5 vol.%, and the depth of the gradient pre-infiltration layer is 2400 microns.

S6. Densification and sintering of ceramic ball blanks: firstly, put the pre-infiltrated body of nano-modified silicon nitride ceramic balls obtained in S5 into an air electric furnace for further pre-sintering, and the sintering temperature is 1810°C. The time is 2 hours, the heating and cooling rate is 1°C/min, and the nano-modified silicon nitride ceramic ball pre-sintered body with a relative density of 97% and a nano-alumina gradient permeation layer and a surface gradient precompression stress is obtained; then, the nano-modified The pre-sintered silicon nitride ceramic balls are placed in a hot isostatic pressing sintering furnace, and are densified and sintered under the condition of nitrogen gas. ℃/min, the final diameter is 48.5 mm, the relative density is 99.95%, the grain size is 680 nm, the tensile strength between the gradient infiltration coating and the substrate is 118 MPa, and the shear strength is 122 MPa. The strength is 1000MPa, and the fracture toughness is 8.3 MPa·m ^1/2 , which has a nano-alumina surface gradient permeation layer and a surface gradient precompression stress. Nano-alumina surface gradient composite reinforced nano-modified silicon nitride ceramic ball blank.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: the nano-alumina surface gradient composite reinforced nano-modified silicon nitride ceramic ball blank obtained in S6 is placed in a V-shaped groove grinding device for at least rough grinding and semi-finished step by step. The 5 processes of lapping, lapping, super-finishing and polishing are processed into a nominal diameter of 47.9 mm, a ball surface roughness Ra of 0.006 mm, a spherical error of 0.04 μm, a spherical roundness of 0.002 mm, and a ball batch diameter deviation of 0.08 μm, the surface hardness HV ₁₀₀₀ is 2210, and there is a -280 MPa pre-compressed stress on the surface of nano-alumina surface component gradient compound reinforced nano-modified silicon nitride ceramic balls.

S8. Machining of nano-alumina surface component gradient composite reinforced silicon nitride ceramic femoral unicondyle: according to the design drawing requirements of nano-alumina surface component gradient composite reinforced silicon nitride ceramic femoral unicondyle, the nano The alumina surface component gradient composite reinforced silicon nitride ceramic ball was divided into two nano-alumina surface component gradient composite reinforced silicon nitride ceramic femoral unicondyle blanks, and then processed by grinding and chamfering to prepare two standard blanks. The diameter of the spherical surface is 47.9 mm, the depth of the gradient permeable layer is 1513 mm, and the nano-alumina surface component gradient composite reinforced silicon nitride ceramic femoral single condyle with double positioning columns.

S9. Final polishing of nano-alumina surface component gradient composite reinforced silicon nitride ceramic spherical femoral unicondyle surface: final polishing of the spherical surface of nano-alumina surface component gradient composite reinforced silicon nitride ceramic femoral unicondyle with double positioning pillars Polish to make the surface roughness Ra 0.002mm.

S10. Inspection/marking/packaging: conduct a full quality inspection of the nano-alumina surface component gradient composite reinforced silicon nitride ceramic femoral unicondyle with double positioning columns, and mark and pack qualified products.

Example 24: Nano-silicon nitride surface composition gradient composite reinforcement silicon carbide ceramic spherical femoral unicondyle
S1. Formulation/milling and preparation of surface gradient slurry and modified granulated powder: (1) Weigh an appropriate amount of nano-silicon carbide powder with a purity of 99.9 wt.% or more, and add 2 wt% of its mass Boron carbide powder was used as a sintering aid, 0.2 wt.% Tween 80 as a surfactant and 2.5wt.% polyvinyl butyral as a binder to make an aqueous slurry with a solid content of 32 vol%, and then spray Dry granulation process to prepare nano-modified silicon carbide granulated powder; (2) Weigh an appropriate amount of nano-silicon nitride powder with a purity of more than 99.9 wt.%, add 2 wt% of its mass of nano-alumina, 2 wt % nanometer yttrium oxide and 1 wt% nanometer lutetium oxide composite powder as sintering aid, 0.2 wt.% Tween 80 as surfactant and 3.5wt.% polyvinyl butyral as binder to make solid The water-based slurry with a content of 25 vol% is used as the surface gradient slurry;
S2, green body molding: put the nano-modified silicon carbide granulated powder obtained in step S1 into a metal mold with an inner diameter of 90 mm, and bidirectionally pre-press 80 MPa into a preform with a height of 150 mm, and then nano-modified The silicon carbide granulated powder dry-pressed blank is vacuum-packed in a plastic bag, put into a cold isostatic press, and subjected to cold isostatic pressing under a hydrostatic pressure of 450MPa to obtain nano-modified silicon carbide granulated powder. green body.

S3. Blank pre-sintering: put the nano-modified silicon carbide granulated powder formed green body obtained in step S2 into an electric furnace for pre-sintering, in an argon atmosphere, at a pre-sintering temperature of 1650° C., and at a pre-sintering time of 2 hours. The cooling rate was 1°C/min, and a nano-modified silicon carbide ceramic calcined biscuit with a relative density of 50.5% was obtained.

S4. Ceramic ball pre-fired bisque processing: According to the size requirements of the drawings, use CNC numerical control machine tools to machine the nano-modified silicon carbide ceramic pre-fired bisque obtained in step S3 to obtain nano-modified silicon carbide ceramics with a diameter of 72 mm Ball pre-fired biscuit.

S5. Surface infiltration of ceramic ball pre-fired billet: put the nano-modified silicon carbide ceramic ball pre-fired billet obtained in step S4 into a vacuum tank, then pour the surface gradient infiltration slurry obtained in step S1, cover and pump Vacuum to -0.12 MPa to make the surface gradient infiltration slurry gradually infiltrate into the surface layer of the nano-modified silicon carbide ceramic ball pre-fired biscuit, and hold the pressure for 15 minutes to obtain the nano-silicon nitride surface component with the surface pre-infiltration gradient slurry Gradient composite reinforced silicon carbide ceramic ball pre-infiltration green body, the content of nano-silicon nitride powder on the surface of the infiltration layer increased by 9.8 vol.%, and the depth of the pre-infiltration layer was 1580 microns.

S6. Densification and sintering of ceramic ball billets: firstly, put the nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic ball pre-infiltrated green body obtained in S5 into an atmosphere electric furnace for further pre-firing, argon as a protective atmosphere, and the sintering temperature The temperature is 1890℃, the sintering time is 2 hours, and the heating and cooling rate is 1℃/min, and the relative density is 97% with nano-silicon nitride gradient infiltration layer and surface gradient precompression stress. Nano-silicon nitride surface component gradient composite enhanced carbonization Silicon ceramic ball pre-sintered body; then, put the nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic ball pre-sintered body into the hot isostatic pressing sintering furnace, and carry out densification and sintering under the condition of argon gas separation, and the sintering temperature The temperature is 1850℃, the sintering gas pressure is 150MPa, the sintering time is 2 hours, and the heating and cooling rate is 1℃/min. The final diameter is 55.5mm, the relative density is 99.9%, the grain size is 720nm, and the gradient penetration coating and the substrate The tensile strength between them is 78.4 MPa, the shear strength is 93 MPa, the flexural strength of the matrix is 850 MPa, and the fracture toughness is 6.2 MPa m ^1/2 . Composite reinforced silicon carbide ceramic spheres with nano-silicon nitride surface composition gradient.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic ball blank obtained in S6 into the V-shaped groove grinding equipment for at least rough grinding and semi-finishing step by step. Grinding, lapping, ultra-finishing and polishing are processed into a nominal diameter of 55 mm, a ball surface roughness Ra of better than 0.005 mm, a spherical error of 0.03 μm, a spherical roundness of 0.005 mm, and a ball batch diameter deviation It is 0.08 μm, the surface hardness HV ₁₀₀₀ is 2140, and the surface has a -340 MPa pre-compression stress on the surface of nano-silicon nitride surface composition gradient composite reinforced silicon carbide ceramic balls.

S8. Machining of nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic femoral unicondyle: according to the design drawing requirements of nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic femoral unicondyle, the nano The silicon carbide ceramic balls reinforced with gradient silicon nitride surface components were divided into two nano-silicon nitride surface composition gradient compound reinforced silicon carbide ceramic femoral unicondyle blanks, and then processed by grinding and chamfering to prepare two standard blanks. The diameter of the spherical surface is 55 mm, the depth of the gradient permeation layer is 970 mm, and the nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic femoral single condyle with double positioning columns.

S9. Final polishing of nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic femoral unicondyle surface: final polishing of the spherical surface of nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic femoral unicondyle with double positioning pillars Polish to make the surface roughness Ra 0.002mm.

S10. Inspection/marking/packaging: conduct all quality assurance inspections on the nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic femoral unicondyle with double positioning columns, and conduct laser marking and packaging on the bottom surface of qualified products.

Example 25: Nano-silicon carbide surface composition gradient composite reinforcement of zirconia-based ceramic spherical femoral unicondyle
S1. Formulation/milling and preparation of surface gradient infiltration slurry and modified granulated powder: (1) First, weigh an appropriate amount of nano-alumina reinforced 3mol% yttrium oxide and partially stabilized nano-zirconia with a purity of more than 99.9wt.%. Composite powder, add its quality 0.2 wt.% Tween 80 as a surfactant and 3.8wt.% polyvinyl alcohol as a binder to make an aqueous slurry with a solid content of 35 vol%, and then make it through a spray-drying granulation process Obtain nano-alumina reinforced 3mol% yttrium oxide and partially stabilized nano-zirconia composite granulation powder; (2) Weigh an appropriate amount of silicon carbide powder with a purity of 99.9 wt.% or more, and add its mass of 2.1 wt% nano-boron carbide powder body as a sintering aid, 0.8 wt.% Tween 80 as a surfactant and 2.5 wt.% polyvinyl alcohol as a binder to make an aqueous slurry with a solid content of 30vol%, part of which is used as a surface gradient slurry;
S2. Green body molding: put the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite granulation powder obtained in step S1 into a metal mold with an inner diameter of 72 mm, and bidirectionally pre-press at 120 MPa to a height of 150 mm. Then the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite granulation powder dry-pressed preform was vacuum-packed in a plastic bag, put into a cold isostatic press, and heated under a hydrostatic pressure of 450MPa Under cold isostatic pressing, the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite granulated powder was obtained to form a green body.

S3. Biscuit pre-sintering: the nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite granulated powder obtained in step S2 is put into an electric furnace for pre-sintering, and the air atmosphere and pre-sintering temperature are 1080°C , The pre-firing time was 2 hours, and the heating and cooling rate was 1°C/min to obtain a nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite ceramic calcined green body with a relative density of 52%.

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite ceramic ball pre-fired biscuit obtained in step S4 into a vacuum tank, and then pour it into the obtained in step S1 Surface gradient infiltration slurry, the cover is vacuumed to -0.12 MPa, so that the surface gradient infiltration slurry gradually infiltrates into the surface layer of the pre-fired biscuit of nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite ceramic balls, and the pressure is maintained for 15 After 10 min, the nano-silicon carbide surface component gradient composite reinforced zirconia-based ceramic ceramic ball pre-infiltration green body with surface pre-infiltration gradient slurry was obtained, and the content of nano-silicon carbide powder on the surface of the infiltration layer increased by 8.1 vol.%, and the pre-infiltration layer The depth is 1500 microns.

S6. Densification and sintering of ceramic ball billets: firstly, put the nano-silicon carbide surface component gradient composite reinforced zirconia-based ceramic ball pre-infiltrated green body obtained in S5 into an atmosphere electric furnace for further pre-sintering, under argon protection, and the sintering temperature is 1500 ℃, sintering time of 2 hours, heating and cooling rate of 1°C/min, to obtain nano-silicon carbide surface component gradient composite reinforced zirconia-based ceramic balls with a relative density of 97% and a nano-silicon carbide gradient infiltration layer and surface gradient precompression stress The pre-sintered body; then, put the nano-silicon carbide surface component gradient composite reinforced zirconia-based ceramic ball pre-sintered body into the hot isostatic pressing sintering furnace, and carry out densification and sintering under the condition of argon gas distribution, and the sintering temperature is 1650°C , the sintering gas pressure is 200MPa, the sintering time is 1 hour, and the heating and cooling rate is less than 1°C/min. The final diameter is 41.2 mm, the relative density is 99.92%, the grain size is 1185 nm, and the gradient between the coating and the substrate is obtained. The tensile strength is 158 MPa, the shear strength is 194.2 MPa, the matrix flexural strength is 1350 MPa, and the fracture toughness is 8.2 MPa m ^1/2 , which has a nano-silicon carbide surface gradient permeation layer and a surface gradient precompression stress. Surface composition gradient composite reinforced zirconia-based ceramic ball blank.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nano-silicon carbide surface component gradient composite reinforced zirconia-based ceramic ball blank obtained in S6 into a V-shaped groove grinding device for at least rough grinding and semi-finishing step by step. Grinding, lapping, ultra-finishing and polishing are processed into a nominal spherical diameter of 40.6 mm, a spherical surface roughness Ra of 0.005 mm, a spherical error of 0.04 μm, a spherical roundness of 0.001 mm, and a ball batch diameter deviation of 0.08 μm, the surface hardness HV ₁₀₀₀ is 1950, and the surface has a -580 MPa pre-compression stress on the surface of nano-silicon carbide surface component gradient composite reinforced zirconia-based ceramic balls.

S8. Nano-silicon carbide surface component gradient composite reinforced zirconia-based ceramic femoral spherical single condyle machining: according to the nano-silicon carbide surface component gradient composite enhanced zirconia-based ceramic ball head drawing size requirements, the nano-silicon carbide obtained in step S7 Surface component gradient composite reinforced zirconia-based ceramic balls were prepared by crown cutting, drilling and chamfering to prepare a nano-silicon carbide surface component gradient composite with a nominal diameter of 40.6 mm, a gradient penetration layer depth of 1020 mm, and double positioning columns. Reinforced zirconia-based ceramic femoral spherical unicondyle.

S9. Final polishing of nano-silicon carbide surface component gradient composite reinforced zirconia-based ceramic femoral spherical unicondyle surface: final polishing of the spherical surface of nano-silicon carbide surface component gradient composite reinforced zirconia-based ceramic femoral unicondyle with double positioning columns Polish to make the surface roughness Ra 0.002mm.

S10. Inspection/marking/packaging: The nano-silicon carbide surface component gradient composite reinforced zirconia-based ceramic femoral spherical unicondyle with double positioning columns is subjected to all quality assurance inspections, and the bottom surface of qualified products is laser marked and packaged.

Example 26: Surface self-reinforced nano-alumina ceramic humerus ball head
S1. Formulation/milling and preparation of surface gradient infiltration slurry and modified granulated powder: Weigh an appropriate amount of nano-alumina powder with a purity of 99.9 wt.% or more, add 0.1 wt% of its mass of nano-magnesia as sintering Auxiliary agent, 0.8wt.% Tween 80 as surfactant and 4.5wt.% polyvinyl alcohol as binder to make water-based slurry with solid content of 25vol%, one part is used as surface gradient slurry; the other part is sprayed Nano-modified alumina granulated powder is prepared by dry granulation process.

S2. Green body molding: put the nano-modified alumina granulation powder obtained in step S1 into a metal mold with an inner diameter of 90 mm, and bidirectionally pre-press at 50 MPa to form a preform with a height of 150 mm, and then put the nano-modified alumina The dry-pressed blank of the granulated powder is vacuum-packed in a plastic bag, put into a cold isostatic press, and subjected to cold isostatic pressing under a hydrostatic pressure of 250 MPa to obtain a shaped green body of nano-modified alumina granulated powder.

S3. Biscuit pre-firing: Put the nano-modified alumina granulated powder shaped green body obtained in step S2 into an electric furnace for pre-sintering, the air atmosphere, pre-sintering temperature is 1150°C, pre-sintering time is 2 hours, and the heating and cooling speed at 5°C/min to obtain a calcined biscuit of nano-modified alumina ceramics with a relative density of 52%.

S4. Ceramic ball pre-fired bisque processing: According to the size requirements of the drawing, use CNC numerical control machine tools to machine the nano-modified alumina ceramic pre-fired bisque obtained in step S3 to obtain nano-modified alumina ceramics with a diameter of 74 mm Ball pre-fired biscuit.

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the nano-modified alumina ceramic ball pre-fired biscuit obtained in step S4 into a vacuum tank, then pour the surface gradient infiltration slurry obtained in step S1, and cover Vacuum down to -0.08MPa to make the surface gradient infiltration slurry gradually infiltrate into the surface layer of the calcined biscuit of nano-modified alumina ceramic balls. The green body is pre-infiltrated with permanent alumina ceramic balls, the content of nano-alumina powder on the surface of the infiltration layer increases by 9.8 vol.%, and the depth of the gradient infiltration layer is 2050 microns.

S6. Densification and sintering of ceramic ball billets: firstly, put the nano-modified alumina ceramic ball pre-infiltrated body obtained in S5 into an air electric furnace for further pre-sintering. °C/min, to obtain a pre-sintered body of nano-modified alumina ceramic balls with a relative density of 97% and a surface gradient pre-compression stress; then, put the pre-sintered body of nano-modified alumina ceramic balls into a hot isostatic pressing sintering furnace Densification sintering was carried out in the medium, the sintering temperature was 1500°C, the sintering gas pressure was 50MPa, the sintering time was 2 hours, and the heating and cooling rate was 1°C/min. Finally, the diameter was 55.6 mm, the relative density was 99.9%, and the grain size was 663 nm. , The tensile strength between the gradient infiltration coating and the substrate is 58 MPa, the shear strength is 72 MPa, the substrate flexural strength is 522 MPa and the fracture toughness is 4.8 MPa·m ^1/2 surface self-reinforced nano-modified alumina Ceramic balls.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the surface self-reinforced nano-modified alumina ceramic ball blank obtained in S6 into a V-shaped groove grinding device for at least rough grinding, semi-finishing, and finishing in steps. , ultra-finishing and polishing 5 processes, the nominal spherical diameter is 55 mm, the spherical surface roughness Ra is 0.004 mm, the spherical error is 0.04 μm, the spherical roundness is 0.002 mm, and the ball batch diameter deviation is 0.06 μm. The surface hardness HV ₁₀₀₀ is 2140, and there is a surface self-reinforced nano-alumina ceramic ball with -285 MPa precompression stress on the surface.

S8. Machining of surface self-reinforced nano-alumina ceramic humerus ball head: According to the design drawings of surface self-reinforced nano-alumina ceramic humerus ball head, the surface self-reinforced nano-alumina ceramic ball obtained in step S7 is divided into two surface self-reinforced The nano-alumina ceramic humerus ball head blank is then processed by cutting, grinding and chamfering to prepare at least two surface self-reinforced nano-alumina ceramic humerus ball heads with a nominal spherical diameter of 55 mm and a gradient penetration layer depth of 1240 mm .

S9. Final polishing of the surface of the self-reinforced nano-alumina ceramic humeral ball head: the final polishing is performed on the spherical surface of the self-reinforced nano-alumina ceramic humeral ball, so that the surface roughness Ra is 0.002mm.

S10. Inspection/marking/packaging: conduct all quality inspections of the surface self-reinforced nano-alumina ceramic humerus ball head, and laser mark and package the bottom of qualified products.

Example 27: Surface self-reinforced nano-zirconia ceramic humerus ball head
S1. Formulation/milling and preparation of surface gradient slurry and modified granulated powder: Weigh an appropriate amount of 3mol% yttrium oxide partially stabilized nano-zirconia powder with a purity of more than 99.9 wt.%, and add 0.8 wt. % Tween 80 as a surfactant and 3.5wt.% polyvinyl alcohol as a binder to make an aqueous slurry with a solid content of 28 vol%, part of which is used as a surface gradient slurry; the other part is made by spray drying granulation process 3 mol% yttrium oxide partially stabilized nano-zirconia granulated powder was obtained.

S2. Green body molding: put the 3 mol% yttrium oxide partially stabilized nano-zirconia granulation powder obtained in step S1 into a metal mold with an inner diameter of 75 mm, and bidirectionally pre-press at 100 MPa to form a preform with a height of 130 mm, and then The 3 mol% yttrium oxide partially stabilized nano-zirconia granulated powder dry-pressed preform was vacuum-packed in a plastic bag, put into a cold isostatic press, and cold isostatic pressed under a hydrostatic pressure of 350 MPa to obtain 3 mol% yttrium oxide partially stabilized nano-zirconia granulated powder to form a green body.

S3. Blank pre-sintering: put the 3 mol% yttrium oxide partially stabilized nano-zirconia granulated powder formed green body obtained in the step S2 into an electric furnace for pre-sintering. hours, the heating and cooling rate was 5°C/min, and a 3 mol% yttrium oxide partially stabilized nano-zirconia ceramic pre-fired green body with a relative density of 52% was obtained.

S4. Ceramic ball pre-fired biscuit processing: according to the size requirements of the drawings, CNC numerical control machine tools are used to machine the 3 mol% yttrium oxide partially stabilized nano-zirconia ceramic pre-fired bisque obtained in step S3 to obtain a 3 mol% yttrium oxide ceramic pre-fired bisque with a diameter of 60 mm mol% yttria partially stabilized nano-zirconia ceramic ball pre-fired biscuit.

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the 3 mol% yttrium oxide partially stabilized nano-zirconia ceramic ball pre-fired biscuit obtained in step S4 into a vacuum tank, and then pour the surface gradient infiltration obtained in step S1 Slurry, the cover is vacuumed to -0.08MPa, so that the surface gradient infiltration slurry gradually infiltrates the surface layer of the pre-fired biscuit of 3 mol% yttrium oxide partially stabilized nano-zirconia ceramic balls. After holding the pressure for 60 minutes, a surface pre-infiltration Gradient 3 mol% yttria partially stabilized nano zirconia ceramic slurry with 3 mol% yttria partially stabilized nano zirconia ceramic ball pre-infiltrated green body, the content of nano zirconia powder on the surface of the infiltrated layer increased by 10.5 vol.%, and the gradient infiltrated layer The depth is 2430 microns.

S6. Densification and sintering of ceramic ball billets: firstly, the 3 mol% yttrium oxide partially stabilized nano-zirconia ceramic ball pre-infiltrated green body obtained in S5 is put into an air electric furnace for further pre-sintering, the sintering temperature is 1450°C, and the sintering time is 2 hours , the heating and cooling rate was 5°C/min, and the 3 mol% yttrium oxide partially stabilized nano-zirconia ceramic ball calcined body with a relative density of 97% and a surface gradient precompression stress was obtained; then, the 3 mol% yttrium oxide partially stabilized nano The zirconia ceramic ball pre-sintered body was put into a hot isostatic pressing sintering furnace for densification and sintering. The sintering temperature was 1460°C, the sintering gas pressure was 60MPa, the sintering time was 3 hours, and the heating and cooling rate was 1°C/min. Finally, the obtained diameter was 45.4 mm, the relative density is 99.9%, the grain size is 362 nm, the tensile strength between the gradient infiltration coating and the substrate is 128 MPa, the shear strength is 142 MPa, the flexural strength of the substrate is 1510 MPa and the fracture toughness is 12.2 MPa·m ^1/2 surface self-reinforced 3 mol% yttria partially stabilized nano-zirconia ceramic spheres.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: the surface self-reinforced 3 mol% yttrium oxide partially stabilized nano-zirconia ceramic ball blank obtained in S6 is placed in a V-shaped groove grinding device for at least rough grinding, semi-finished The 5 processes of lapping, lapping, ultra-finishing and polishing are processed into a nominal spherical diameter of 45 mm, a spherical surface roughness Ra of 0.003 mm, a spherical error of 0.06 μm, a spherical roundness of 0.004 mm, and a ball batch diameter of The deviation is 0.1 μm, the surface hardness HV ₁₀₀₀ is 1650, and the surface is self-reinforced with 3 mol% yttria and partially stabilized nano-zirconia ceramic balls with -450MPa precompression stress on the surface.

S8. Machining of surface self-reinforced nano-zirconia ceramic humerus ball head: according to the design drawings of surface self-reinforced nano-zirconia ceramic humerus ball head, the surface self-reinforced 3 mol% yttrium oxide partly stabilized nano-zirconia ceramic ball obtained in step S7 Divide into at least 2 surface self-reinforced nano zirconia ceramic humeral ball head blanks, and then perform grinding and chamfering to prepare at least 2 surface self-reinforced nanostructures with a nominal spherical diameter of 45 mm and a gradient penetration layer depth of 1640mm. Alumina ceramic humerus ball head.

S9. Final polishing of the surface of the surface self-reinforced nano-zirconia ceramic humeral ball head: the final polishing is performed on the spherical surface of the surface self-reinforced nano-zirconia ceramic humeral ball head, so that the surface roughness Ra is 0.002mm.

S10. Inspection/marking/packaging: The surface self-reinforced nano-zirconia ceramic humerus ball head is subjected to all quality inspections, and the bottom of qualified products is laser marked and packaged.

Example 28: Surface self-reinforced nano-silicon nitride ceramic humerus ball head
S1. Formulation/milling and preparation of surface gradient infiltration slurry and modified granulated powder: Weigh an appropriate amount of silicon nitride powder with a purity of 99.8 wt.% or more, and add 0.1 wt% of its mass of nano-alumina as sintered Additives, 0.8 wt.% Tween 80 as a surfactant and 3.5wt.% polyvinyl alcohol to make an aqueous slurry with a solid content of 30vol%, part of which is used as a surface gradient slurry; the other part is spray-dried and granulated The nano-modified silicon nitride granulated powder is prepared.

S2. Green body molding: put the nano-silicon nitride granulated powder obtained in step S1 into a metal mold with an inner diameter of 60 mm, and bidirectionally pre-press at 120 MPa to form a green body with a height of 120 mm, and then nano-modified and nitrided The silicon granulation powder dry-pressed blank is vacuum-packed in a plastic bag, placed in a cold isostatic press, and subjected to cold isostatic pressing under a hydrostatic pressure of 250MPa to obtain a nano-modified silicon nitride granulated powder molding green body .

S3. Blank pre-sintering: put the nano-modified silicon nitride granulated powder shaped green body obtained in step S2 into a pressure sintering electric furnace for pre-sintering, nitrogen atmosphere, pre-sintering temperature of 1750°C, and pre-sintering time of 2 hours. The heating and cooling rate was 2°C/min, and a nano-modified silicon nitride ceramic pre-fired biscuit with a relative density of 54% was obtained.

S4. Ceramic ball pre-fired biscuit processing: According to the size requirements of the ceramic femoral full condyle friction spherical surface, CNC numerical control machine tools are used to machine the nano-modified silicon nitride ceramic pre-fired bisque obtained in step S3 to obtain a diameter of 45 mm. Nano-modified silicon nitride ceramic ball calcined biscuit.

S5. Surface grouting of the ceramic ball pre-fired billet: put the nano-modified silicon nitride ceramic ball pre-fired billet obtained in the step S4 into a vacuum tank, then pour the surface gradient grouting slurry obtained in the step S1, and cover it Vacuum down to -0.08MPa to make the surface gradient infiltration slurry gradually infiltrate into the surface layer of the pre-fired biscuit of nano-modified silicon nitride ceramic balls. After holding the pressure for 40 minutes, a nano The silicon nitride ceramic ball pre-infiltrated green body, the content of nano-silicon nitride powder on the surface of the infiltration layer increased by 10.6 vol.%, and the depth of the gradient infiltration layer was 1510 microns.

S6. Densification and sintering of ceramic balls: firstly, put the pre-infiltrated body of nano-silicon nitride ceramic balls obtained in S5 into an atmosphere-protected electric furnace for further pre-firing. hour, the heating and cooling rate is 1°C/min, and the nano-silicon nitride ceramic ball pre-sintered body with a relative density of 97% is obtained; then, the nano-silicon nitride ceramic ball pre-sintered body is placed in a hot isostatic pressing sintering furnace for compaction Chemical sintering, the sintering temperature is 1720°C, the sintering gas pressure is 180MPa, the sintering time is 6 hours, the heating and cooling rate is 1°C/min, the final diameter is 34.3 mm, the relative density is 99.96%, the grain size is 463 nm, and the gradient infiltration The tensile strength between the coating and the substrate is 112 MPa, the shear strength is 132 MPa, the substrate flexural strength is 1200 MPa and the fracture toughness is 8.3 MPa m ^1/2 surface self-reinforced nano-modified silicon nitride ceramic balls Blank.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the surface self-reinforced nano-modified silicon nitride ceramic ball blank obtained in S6 into a V-shaped groove grinding device for at least rough grinding, semi-finishing, and finishing in steps. Grinding, ultra-finishing and polishing are processed into a nominal spherical diameter of 34 mm, a spherical surface roughness Ra of 0.003 mm, a spherical error of 0.05 μm, a spherical roundness of 0.004 mm, and a ball batch diameter deviation of 0.1 μm. , surface hardness HV ₁₀₀₀ is 1940, surface self-reinforced nano-modified silicon nitride ceramic balls with -455 MPa precompression stress on the surface.

S8. Machining of surface self-reinforced nano-silicon nitride ceramic humerus ball head: according to the design drawing requirements of surface self-reinforced nano-silicon nitride ceramic humerus ball head, the surface self-reinforced nano-modified silicon nitride ceramic ball obtained in step S7 is divided into At least 2 self-reinforced nano-zirconia ceramic humeral ball head blanks, and then grind and chamfer to prepare at least 2 self-reinforced nano-nitrided surfaces with a nominal spherical diameter of 34 mm and a gradient penetration layer depth of 1000 mm Silicon ceramic humerus ball head.

S9. Final polishing of the surface of the self-reinforced nano-silicon nitride ceramic humeral ball head surface: the final polishing is performed on the spherical surface of the self-reinforced nano-silicon nitride ceramic humeral ball head, so that the surface roughness Ra is 0.002 mm.

S10. Inspection/marking: The surface self-reinforced nano-silicon nitride ceramic humerus ball head is subjected to all quality inspections, and the bottom of qualified products is laser marked and packaged.

Example 29: Surface prestressed self-reinforced nano silicon carbide ceramic humerus ball head
S1. Formulation/milling and preparation of surface gradient slurry and modified granulated powder: Weigh an appropriate amount of silicon carbide powder with a purity of 99.9 wt.% or more, and add 2.1 wt% of nano-boron carbide powder As a sintering aid, 1.8 wt.% ammonium citrate as a surfactant and 2.5 wt.% polyvinyl butyral as a binder to make an aqueous slurry with a solid content of 35 vol%, part of which is used as a surface gradient slurry The other part is made of nano-modified silicon carbide granulated powder by spray drying granulation process.

S2. Green body molding: put the nano-modified silicon carbide granulated powder obtained in step S1 into a metal mold with an inner diameter of 55 mm, and bidirectionally pre-press at 120 MPa to form a pre-form with a height of 110 mm, and then place the nano-modified The silicon carbide granulated powder dry-pressed blank is vacuum-packed in a plastic bag, put into a cold isostatic press, and subjected to cold isostatic pressing under a hydrostatic pressure of 350 MPa to obtain a nano-modified silicon carbide granulated powder Formed green body.

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the nano-modified silicon carbide ceramic ball pre-fired biscuit obtained in step S4 into a vacuum tank, then pour the surface gradient infiltration slurry obtained in step S1, and cover Vacuum to -0.10 MPa to make the surface gradient infiltration slurry gradually infiltrate into the surface layer of the pre-fired biscuit of nano-modified silicon carbide ceramic balls. After holding the pressure for 30 minutes, a nano Modified silicon carbide ceramic ball pre-infiltrated body, the content of nano-silicon carbide powder on the surface of the infiltration layer increased by 12 vol.%, and the depth of the gradient infiltration layer was 2050 microns.

S6. Densification and co-sintering of ceramic ball billets: firstly, put the pre-infiltrated body of nano-modified silicon carbide ceramic balls obtained in S5 into an atmosphere-protected electric furnace for further pre-sintering. The sintering temperature is 1880°C and the sintering time is 5 hours. The cooling rate is 1°C/min, and the nano-modified silicon carbide ceramic ball pre-sintered body with a relative density of 94% is obtained; then, the nano-modified silicon carbide ceramic ball pre-sintered body is placed in a hot isostatic pressing sintering furnace for densification Sintering, the sintering temperature is 1820°C, the sintering gas pressure is 200MPa, the sintering time is 1 hour, the heating and cooling rate is 1°C/min, and finally a gradient infiltration coating with a diameter of 32.5 mm, a relative density of 99.9%, a grain size of 530 nm is obtained The tensile strength between the matrix and the matrix is 88.4 MPa, the shear strength is 98.9 MPa, the flexural strength of the matrix is 720 MPa, and the fracture toughness is 5.6 MPa m ^1/2 . Nano-modified silicon carbide with surface prestress self-reinforcement Ceramic balls.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nano-modified silicon carbide ceramic ball blank obtained in S6 into the V-shaped groove grinding equipment for at least rough grinding and semi-finishing in steps. , lapping, ultra-finishing, and polishing are processed into a nominal spherical diameter of 32 mm, a spherical surface roughness Ra of 0.003 mm, a spherical error of 0.04 μm, a spherical roundness of 0.004 mm, and a ball batch diameter deviation of 0.1μm, surface hardness HV ₁₀₀₀ is 2180, surface prestressed self-reinforced nano-modified silicon carbide ceramic balls with -270 MPa prestress on the surface.

S8. Machining of surface prestressed self-reinforced nano-silicon carbide ceramic humerus ball head: according to the size requirements of the surface pre-stressed self-reinforced nano-silicon carbide ceramic humerus ball head drawing, the surface prestressed self-reinforced nano-modified silicon carbide obtained in step S7 The ceramic ball is divided into at least 2 surface prestressed self-reinforced nano-modified silicon carbide ceramic humeral ball head blanks, and then ground and chamfered to prepare at least 2 nominal spherical diameters of 32 mm and gradient penetration layer depth The surface prestressed self-reinforced nano silicon carbide ceramic humeral ball head is 1300mm.

S9. Final polishing of the surface prestressed self-reinforced nano-silicon carbide ceramic humeral ball head: the final polishing is performed on the spherical surface of the surface pre-stressed self-reinforced nano-silicon carbide ceramic humeral ball head, so that the surface roughness Ra is 0.002 mm.

S10. Inspection/marking/packaging: The surface prestressed self-reinforced nano-silicon carbide ceramic humerus ball head is subjected to all quality assurance inspections, and the bottom surface of qualified products is laser marked and packaged.

Example 30: Surface self-reinforced nano-zirconia toughened alumina composite ceramic humerus ball head
S1. Formulation/milling and preparation of surface gradient slurry and modified granulated powder: Weigh an appropriate amount of 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite powder with a purity of 99.9 wt.% or more , adding 0.1wt.% magnesium oxide as a sintering aid, 0.2 wt.% ammonium polyacrylate as a surfactant and 4 wt.% polyvinyl alcohol as a binder to make an aqueous slurry with a solid content of 25vol%. It is used as surface gradient infiltration slurry; the other part is prepared by spray drying granulation process to obtain 3 mol% yttrium oxide partially stabilized nano zirconia toughened alumina composite granulated powder.

S2. Green body molding: put the 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite granulation powder obtained in step S1 into a metal mold with an inner diameter of 60 mm, and bidirectionally pre-press at 150 MPa to a height of 120 mm. mm of dry-pressed preform, and then dry-pressed preform of 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite granulation powder in a plastic bag, put it into a cold isostatic press, and Cold isostatic pressing was carried out under a hydrostatic pressure of 250 MPa to obtain a green body formed by 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite granulated powder.

S3, green body pre-sintering: put the 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite granulated powder obtained in step S2 into the green body for pre-sintering in an electric furnace, and the air atmosphere and pre-sintering temperature are 1200 ℃, the pre-firing time is 2 hours, and the heating and cooling rate is 5 ℃/min, and the relative density of 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic calcined green body is obtained.

S4. Ceramic ball pre-fired biscuit processing: According to the size requirements of the drawings, CNC numerical control machine tools are used to machine the 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic pre-fired bisque obtained in step S3 to obtain diameter 44 mm 3 mol% yttria partially stabilized nano-zirconia toughened alumina composite ceramic ball pre-fired biscuit.

S5. Surface infiltration of ceramic ball pre-fired biscuits: put the 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic ball pre-fired biscuits obtained in step S4 into a vacuum tank, and then pour them into step S1 to obtain The surface gradient infiltration slurry, the cover is vacuumed to -0.10 MPa, so that the surface gradient infiltration slurry gradually infiltrates the surface layer of the pre-fired biscuit of 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic balls, ensuring After pressing for 45 min, a 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic ball pre-infiltrated green body with pre-infiltrated surface gradient grouting slurry was obtained, and nano-zirconia toughened alumina composite powder on the surface of the infiltrated layer The volume content increased by 9.3 vol.%, and the depth of the gradient permeability layer was 1630 microns.

S6. Densification and sintering of ceramic ball billets: firstly, put the 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic ball pre-fired green billet obtained in S5 into an air electric furnace for further pre-sintering, and the sintering temperature is 1450°C , The sintering time is 2 hours, the heating and cooling rate is 5°C/min, and a 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic ball pre-sintered body with a relative density of 98% and a surface gradient precompression stress is obtained; then , and then put 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic ball pre-sintered body into a hot isostatic pressing sintering furnace for densification and sintering. The time is 2 hours, the heating and cooling rate is 1°C/min, and the final diameter is 32.4 mm, the relative density is 99.9%, the grain size is 460 nm, the tensile strength between the gradient infiltration coating and the substrate is 118 MPa, and the shear strength is 118 MPa. The strength is 122 MPa, the matrix flexural strength is 670 MPa and the fracture toughness is 6.1 MPa·m ^1/2 surface self-reinforced 3 mol% yttria partially stabilized nano-zirconia toughened alumina composite ceramic sphere.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the surface self-reinforced 3 mol% yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic ball blank obtained in S6 into the magnetic fluid grinding equipment for at least one step at a time. Rough grinding, semi-finishing, finishing, super-finishing and polishing are processed into 5 processes to produce a nominal spherical diameter of 32 mm, a spherical surface roughness Ra of 0.001 mm, a spherical error of 0.04 μm, and a spherical roundness of 0.002 mm. , The diameter deviation of the ball batch is 0.1 μm, the surface hardness HV ₁₀₀₀ is 2080, and the surface has a surface self-reinforced nano-zirconia toughened alumina composite ceramic ball with a -450 MPa pre-compression stress on the surface.

S8. Machining of surface self-reinforced nano-zirconia toughened alumina composite ceramic humeral ball head: According to the size requirements of the surface self-reinforced nano-zirconia toughened alumina composite ceramic humeral ball head, the surface self-reinforced 3 mol %Yttrium oxide partially stabilized nano-zirconia toughened alumina composite ceramic ball is divided into at least 2 surface self-reinforced nano-zirconia toughened alumina composite ceramic humerus ball head blanks, and then processed by grinding and chamfering to prepare at least 2 A self-reinforced nano-zirconia toughened alumina composite ceramic humeral ball head with a nominal spherical diameter of 32 mm and a gradient permeable layer depth of 1200 mm.

S9. Final polishing of surface self-reinforced nano-zirconia-toughened alumina composite ceramic humerus ball head surface: final polishing of the spherical surface of surface self-reinforced nano-zirconia toughened alumina composite ceramic humerus ball head, so that the surface roughness Ra is 0.002 mm.

S10. Inspection/marking/packaging: The surface self-reinforced nano zirconia toughened alumina composite ceramic humerus ball head is subjected to all quality assurance inspections, and the bottom of qualified products is laser marked and packaged.

Example 31: Surface self-reinforced nano-alumina reinforced zirconia composite ceramic humerus ball head
S1. Formulation/milling and preparation of surface gradient infiltration slurry and modified granulated powder: Weigh an appropriate amount of nano-alumina reinforced 3 mol% yttria partially stabilized nano-zirconia composite powder with a purity of 99.9 wt.% or more , add its quality 0.6 wt.% Tween 80 as a surfactant and 3.2wt.% polyvinyl alcohol as a binder to make a water-based slurry with a solid content of 30 vol%, part of which is used as a surface gradient slurry; the other part Nano-alumina reinforced 3 mol% yttria partially stabilized nano-zirconia composite granulated powder was prepared by spray-drying granulation process.

S2. Green body molding: put the nano-alumina reinforced 3 mol% yttria partially stabilized nano-zirconia composite granulation powder obtained in the step S1 into a metal mold with an inner diameter of 40 mm, and bidirectionally pre-press at 80 MPa to a height of 100 mm. mm of dry-pressed preform, and then the dry-pressed preform of nano-alumina reinforced 3 mol% yttrium oxide partially stabilized nano-zirconia composite granulation powder is vacuum-packaged in a plastic bag, put into a cold isostatic press, and Cold isostatic pressing was carried out under a hydrostatic pressure of 300 MPa to obtain a green body formed by nano-alumina reinforced 3 mol% yttrium oxide partially stabilized nano-zirconia composite granulated powder.

S3. Green body pre-sintering: the nano-alumina reinforced 3 mol% yttrium oxide partially stabilized nano-zirconia composite granulated powder obtained in step S2 is put into an electric furnace for pre-sintering, and the air atmosphere and pre-sintering temperature are 1100 ℃, pre-fired for 2 hours, and the heating and cooling rate was 3 ℃/min, and the relative density was 53% to obtain nano-alumina reinforced 3 mol% yttria partially stabilized nano-zirconia composite ceramic calcined green body.

S4. Ceramic ball pre-fired biscuit processing: According to the size requirements of the drawing, use CNC numerical control machine tools to machine the nano-alumina reinforced 3 mol% yttrium oxide partially stabilized nano-zirconia composite ceramic pre-fired bisque obtained in step S3 to obtain the diameter 30 mm nano-alumina reinforced 3 mol% yttria partially stabilized nano-zirconia composite ceramic balls were pre-fired.

S5. Surface infiltration of ceramic ball pre-fired biscuits: put the nano-alumina reinforced 3 mol% yttrium oxide partially stabilized nano-zirconia composite ceramic ball pre-fired biscuits obtained in step S4 into a vacuum tank, and then pour them into the step S1 to obtain The surface gradient infiltration slurry, the cover is evacuated to -0.08MPa, so that the surface gradient infiltration slurry gradually infiltrates the surface layer of the pre-fired biscuit of nano-alumina reinforced 3 mol% yttrium oxide partially stabilized nano-zirconia composite ceramic balls, ensuring After pressing for 65 min, the nano-alumina reinforced 3 mol% yttria partially stabilized zirconia composite ceramic ball pre-infiltrated body with pre-infiltrated surface gradient slurry was obtained, and the content of nano-alumina-reinforced zirconia composite powder on the surface of the infiltrated layer With an increase of 8.8 vol.%, the depth of the gradient permeation layer is 2200 microns.

S6. Densification and sintering of ceramic ball blanks: firstly, put the pre-infiltrated body of nano-alumina reinforced 3 mol% yttria partially stabilized nano-zirconia composite ceramic balls obtained in S5 into an air electric furnace for further pre-sintering, and the sintering temperature is 1420°C , The sintering time is 2 hours, the heating and cooling rate is 2°C/min, and the nano-alumina reinforced 3 mol% yttria partially stabilized nano-zirconia composite ceramic ball pre-sintered body with a relative density of 97% and a surface gradient precompression stress is obtained; and then , and then put the nano-alumina reinforced 3 mol% yttria partially stabilized nano-zirconia composite ceramic ball pre-sintered body into the hot isostatic sintering furnace for densification sintering. The time is 2 hours, the heating and cooling rate is 1°C/min, and the final diameter is 22.4 mm, the relative density is 99.9%, the grain size is 345 nm, the tensile strength between the gradient infiltration coating and the substrate is 136.4 MPa, and the shear strength is 136.4 MPa. The strength is 124.2 MPa, the matrix flexural strength is 1280 MPa and the fracture toughness is 10.5 MPa·m ^1/2 surface self-reinforced nano-alumina reinforced 3 mol% yttria partially stabilized nano-zirconia composite ceramic sphere.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the surface self-reinforcing nano-alumina reinforced 3 mol% yttrium oxide partly stabilized nano-zirconia composite ceramic ball blank obtained in S6 into the V-shaped groove grinding equipment step by step at least Carry out 5 processes of rough grinding, semi-finishing, finishing, super-finishing and polishing to produce a nominal spherical diameter of 22 mm, a spherical surface roughness Ra of 0.004mm, a spherical error of 0.05 μm, and a spherical roundness of 0.003 mm, the diameter deviation of the ball batch is 0.1 μm, the surface hardness HV ₁₀₀₀ is 1860, and there is a nano-alumina reinforced 3 mol% yttria partially stabilized nano-zirconia composite ceramic ball with a pre-compression stress of -345 MPa on the surface.

S8. Machining of surface self-reinforced nano-alumina-reinforced zirconia composite ceramic humerus ball head: According to the size requirements of the surface self-reinforced nano-alumina-reinforced zirconia composite ceramic humerus ball head, the nano-alumina obtained in step S7 is reinforced by 3 mol%. The yttrium oxide partially stabilized nano-zirconia composite ceramic ball is divided into at least 2 surface self-reinforced nano-alumina reinforced zirconia composite ceramic humeral ball head blanks, and then processed by grinding and chamfering to prepare at least 2 nominal spherical diameters of The surface self-reinforced nano-alumina reinforced zirconia composite ceramic humeral ball head with a gradient penetration layer depth of 22 mm and a depth of 1442 mm.

S9. Final polishing of the surface self-reinforced nano-alumina-reinforced zirconia composite ceramic humeral ball head: the final polishing of the surface self-reinforced nano-alumina-reinforced zirconia composite ceramic humeral ball head, so that the surface roughness Ra is 0.002mm.

S10. Inspection/marking/packaging: The surface self-reinforced nano-alumina reinforced zirconia composite ceramic humeral ball head is subjected to all quality assurance inspections, and the bottom of qualified products is laser marked and packaged.

Example 32: Nano-alumina surface component gradient composite reinforced zirconia ceramic humerus ball head
S1. Formulation/milling and preparation of surface gradient slurry and modified granulated powder: (1) Weigh an appropriate amount of 3mol% yttrium oxide partially stabilized nano-zirconia powder with a purity of more than 99.9 wt.%, add other 0.6 wt.% ammonium polyacrylate as a surfactant and 5 wt.% polyvinyl alcohol as a binder to make an aqueous slurry with a solid content of 30 vol%, and then a 3mol% yttrium oxide fraction was prepared by a spray-drying granulation process Stable nano-zirconia granulated powder; (2) Weigh an appropriate amount of nano-alumina powder with a purity of more than 99.9 wt.%, add 0.12 wt% nano-magnesia as a sintering aid, 0.8 wt.% polyacrylic acid Ammonia was used as surface active and 4.5wt.% polyvinyl alcohol was used as binder to prepare aqueous slurry with solid content of 25vol% as surface gradient slurry.

S2. Green body molding: put the 3mol% yttrium oxide partially stabilized nano-zirconia granulated powder obtained in step S1 into a metal mold with an inner diameter of 55 mm, and bidirectionally prepress at 120 MPa to form a preform with a height of 100 mm, and then The 3mol% yttrium oxide partially stabilized nano-zirconia granulated powder dry-pressed preform was vacuum-packed in a plastic bag, put into a cold isostatic press, and cold isostatic pressed under a hydrostatic pressure of 350MPa to obtain 3mol% The yttrium oxide partially stabilized nano-zirconia granulated powder is used to form a green body.

S3. Pre-sintering of ceramic green body: Put the 3mol% yttrium oxide partially stabilized nano-zirconia granulated powder obtained in step S2 into the green body for pre-sintering in an electric furnace. For 2 hours, the heating and cooling rate was 1°C/min, and a 3mol% yttrium oxide partially stabilized nano-zirconia ceramic calciner with a relative density of 55.6% was obtained.

S4. Ceramic ball pre-fired biscuit processing: According to the size requirements of the drawing, CNC numerical control machine tools are used to machine the 3mol% yttrium oxide partially stabilized nano-zirconia ceramic pre-fired biscuit obtained in step S3 to obtain a 3mol% yttrium oxide ceramic pre-fired bisque with a diameter of 38.5 mm. Yttrium oxide partially stabilized nano zirconia ceramic ball pre-fired biscuit.

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the 3mol% yttrium oxide partially stabilized nano-zirconia ceramic ball pre-fired biscuit obtained in step S4 into a vacuum tank, and then pour the surface gradient infiltration slurry obtained in step S1 The cover is vacuumed to -0.10 MPa, so that the surface gradient infiltration slurry gradually infiltrates the surface layer of the pre-fired biscuit of 3mol% yttrium oxide partially stabilized nano-zirconia ceramic balls. After holding the pressure for 30 minutes, a surface pre-infiltration gradient is obtained. The 3mol% yttrium oxide part of the nano-alumina ceramic slurry pre-infiltrated the body with nano-zirconia ceramic balls, the content of nano-zirconia powder on the surface of the infiltration layer increased by 11 vol.%, and the depth of the gradient infiltration layer was 1520 microns.

S6. Densification and sintering of ceramic ball billets: firstly, the 3mol% yttrium oxide partially stabilized nano-zirconia ceramic ball pre-infiltrated green body obtained in S5 was put into an air electric furnace for further pre-sintering, the sintering temperature was 1450°C, and the sintering time was 2 hours. The heating and cooling rate is 1°C/min, and a 3mol% yttrium oxide partially stabilized nano-zirconia ceramic ball calcined body with a relative density of 97% having a nano-alumina gradient diffusion layer and a surface gradient precompression stress is obtained; then, the 3mol% oxide The yttrium partially stabilized nano-zirconia ceramic ball pre-sintered body was put into a hot isostatic sintering furnace for densification and sintering. The sintering temperature was 1480°C, the sintering gas pressure was 120MPa, the sintering time was 2 hours, and the heating and cooling rate was 1°C/min. The final obtained diameter is 28.4 mm, the relative density is 99.9%, the grain size is 420 nm, the tensile strength between the gradient infiltration coating and the substrate is 112 MPa, the shear strength is 126 MPa, and the flexural strength of the substrate is 1240 MPa and A 3mol% yttria partially stabilized nano-zirconia ceramic sphere with a fracture toughness of 14 MPa·m ^1/2 having a gradient permeation layer on the surface of nano-alumina and a gradient surface precompression stress.

S7. Rough grinding, fine grinding, and polishing of the surface of ceramic ball blanks: put the nano-alumina surface gradient composite reinforced zirconia ceramic ball blanks obtained in S6 into a V-shaped groove grinding device for at least rough grinding, semi-finishing, and finishing in steps. Grinding, ultra-finishing and polishing are processed into a nominal spherical diameter of 28 mm, a spherical surface roughness Ra of 0.005 mm, a spherical error of 0.04 μm, a spherical roundness of 0.003 mm, and a ball batch diameter deviation of 0.08 μm. , the surface hardness HV ₁₀₀₀ is 2050, and there is a nano-alumina surface gradient composite reinforced with 3mol% yttria to partially stabilize nano-zirconia ceramic balls with a pre-compression stress of -285 MPa on the surface.

S8. Machining of nano-alumina surface composition gradient compound reinforced zirconia ceramic humerus ball head: According to the size requirements of the drawings of nano-alumina surface composition gradient composite enhanced zirconia ceramic humerus ball head, the nano-alumina surface gradient obtained in step S7 Composite reinforced 3mol% yttrium oxide partially stabilized nano-zirconia ceramic balls were divided into at least 2 nano-alumina surface component gradient composite reinforced zirconia ceramic humeral ball head blanks, and then prepared by grinding and chamfering into at least 2 standard The spherical diameter is 28 mm, and the depth of the gradient permeable layer is 920 mm. The nano-alumina surface composition is gradient composite reinforced zirconia ceramic humeral ball head.

S9. The final polishing of the surface of the nano-alumina surface composition gradient composite reinforced zirconia ceramic humerus ball head: the final polishing of the spherical surface of the nano-alumina surface composition gradient composite reinforced zirconia ceramic humerus ball head, so that the surface roughness Ra is 0.002 mm.

S10. Inspection/marking/packaging: The nano-alumina surface component gradient composite reinforced zirconia ceramic humerus ball head is subjected to all quality assurance inspections, and the bottom of qualified products is laser marked and packaged.

Example 33: Nano-alumina surface component gradient composite reinforcement zirconia-based composite ceramic humerus ball head
S1. Formulation/milling and preparation of surface gradient slurry and modified granulated powder: (1) Weigh an appropriate amount of nano-alumina reinforced 3mol% yttrium oxide and partially stabilized nano-zirconia compound with a purity of 99.9 wt.% or more Powder, add its mass 0.2 wt.% Tween 80 as a surfactant and 3.8wt.% polyvinyl alcohol as a binder to make an aqueous slurry with a solid content of 35 vol%, and then make it through a spray-drying granulation process Nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite granulation powder; (2) Weighing an appropriate amount of nano-alumina powder with a purity of more than 99.9 wt.%, adding its mass of 0.15wt% nano-magnesia as A sintering aid, 0.6 wt.% Tween 80 as a surfactant and 4 wt.% polyvinyl alcohol as a binder were used to prepare an aqueous slurry with a solid content of 26 vol% as a surface gradient slurry.

S2. Green body molding: put the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite granulation powder obtained in step S1 into a metal mold with an inner diameter of 60 mm, and bidirectionally pre-press at 100 MPa to a height of 130 mm. Then the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite granulation powder dry-pressed preform was vacuum-packed in a plastic bag, put into a cold isostatic press, and heated in 350 MPa of static water Cold isostatic pressing is carried out under high pressure to obtain a green body formed by nano-alumina reinforced 3mol% yttrium oxide and partially stabilized nano-zirconia composite granulated powder.

S3. Biscuit pre-sintering: the nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite granulated powder obtained in step S2 is put into an electric furnace for pre-sintering, and the air atmosphere and pre-sintering temperature are 1160°C , The pre-firing time was 2 hours, and the heating and cooling rate was 1°C/min to obtain a calcined biscuit of nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite ceramics with a relative density of 58%.

S4. Ceramic ball pre-fired bisque processing: According to the size requirements of the drawings, the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite ceramic pre-fired bisque obtained in the step S3 is machined with CNC machine tools, and the diameter is obtained. 48.5 mm nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite ceramic ball calcined green body.

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite ceramic ball pre-fired biscuit obtained in step S4 into a vacuum tank, and then pour it into the obtained in step S1 Surface gradient infiltration slurry, the cover is vacuumed to -0.10 MPa, so that the surface gradient infiltration slurry gradually infiltrates into the surface layer of the pre-fired biscuit of nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite ceramic balls, and the pressure is maintained at 45 Min later, the nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite ceramic ball pre-infiltrated green body with surface pre-infiltration gradient nano-alumina ceramic slurry was obtained, and the content of nano-alumina powder on the surface of the infiltration layer increased by 8.1 vol. %, the depth of the gradient permeable layer is 1570 microns.

S6. Densification and sintering of ceramic ball billets: firstly, the nano-alumina reinforced 3mol% yttrium oxide partly stabilized nano-zirconia composite ceramic ball pre-infiltrated green body obtained in S5 is put into an air electric furnace for further pre-sintering, and the sintering temperature is 1450°C. The sintering time is 2 hours, the heating and cooling rate is 1°C/min, and the nano-alumina reinforced 3mol% yttria partially stabilized nano-zirconia composite ceramic balls with a relative density of 97.4% and a gradient infiltration layer of nano-alumina and surface gradient precompression stress are obtained. The pre-sintered body; then, put the nano-alumina reinforced 3mol% yttrium oxide partially stabilized nano-zirconia composite ceramic ball pre-sintered body into a hot isostatic sintering furnace for densification sintering, the sintering temperature is 1500 ° C, and the sintering gas pressure is 100MPa, sintering time of 2 hours, heating and cooling rate of 1°C/min, the final diameter is 36.4 mm, the relative density is 99.9%, the grain size is 350 nm, and the tensile strength between the gradient infiltration coating and the substrate is 123 MPa , with a shear strength of 172 MPa, a matrix flexural strength of 1580 MPa, and a fracture toughness of 10.6 MPa m ^1/2 , which has a nano-alumina surface-enhanced gradient permeation layer and a surface gradient precompression stress. The nano-alumina surface gradient composite reinforcement 3mol %Yttrium oxide partially stabilized nano-zirconia matrix composite ceramic ball blank.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nano-alumina surface gradient compound reinforced 3mol% yttrium oxide partly stabilized nano-zirconia matrix composite ceramic ball blank obtained in S6 into the V-shaped groove grinding equipment step by step. Rough grinding, semi-finishing, finishing, super-finishing and polishing are processed into 5 processes to produce a nominal spherical diameter of 36 mm, a spherical surface roughness Ra of 0.006 mm, a spherical error of 0.05 μm, and a spherical roundness of 0.002 mm, the ball batch diameter deviation is 0.08 μm, the surface hardness HV ₁₀₀₀ is 1920, and the nano-alumina surface component gradient composite reinforced 3mol% yttria partially stabilized nano-zirconia matrix composite ceramic balls with -520 MPa precompression stress on the surface.

S8. Machining of nano-alumina surface composition gradient composite reinforced zirconia-based composite ceramic humerus ball head: According to the size requirements of the drawings of nano-alumina surface composition gradient composite reinforced zirconia-based composite ceramic humerus ball head, the nano Alumina surface component gradient composite reinforced 3mol% yttria partially stabilized nano-zirconia matrix composite ceramic balls were divided into at least 2 nano-alumina surface component gradient composite reinforced zirconia-based composite ceramic humerus ball head blanks, and then ground and chamfering to prepare at least two humeral ball heads with a nominal spherical diameter of 36 mm and a depth of a gradient permeable layer of 980 mm, with gradient composite reinforcement on the surface of nano-alumina and zirconia-based composite ceramics.

S9. The final polishing of the surface of nano-alumina surface component gradient composite reinforced zirconia-based composite ceramic humerus ball: the final polishing of the spherical surface of nano-alumina surface component gradient composite reinforced zirconia-based composite ceramic humerus ball to make the surface rough The degree Ra is 0.002mm.

S10. Inspection/marking/packaging: The nano-alumina surface component gradient composite reinforced zirconia-based composite ceramic humeral ball head is subjected to all quality assurance inspections, and the bottom of qualified products is laser marked and packaged.

Example 34: Nano-alumina surface component gradient composite reinforcement alumina-based composite ceramic humerus ball head
S1. Formulation/milling and preparation of surface gradient infiltration slurry and modified granulated powder: First, weigh an appropriate amount of 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina composite powder with a purity of 99.9 wt.% or more body, adding 0.15wt% of its mass of nano-magnesia as a sintering aid, 0.8wt.% ammonium citrate as a surfactant and 3.5wt.% polyvinyl alcohol as a binder to make a water-based slurry with a solid content of 32 vol%. Then, 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina matrix composite granulation powder was obtained by spray drying and granulation process; then, an appropriate amount of nano-alumina powder with a purity of 99.9 wt.% or more was weighed , adding 0.15 wt% of its mass of nano-magnesia as a sintering aid, 0.8 wt.% ammonium citrate as a surfactant and 3.5wt.% polyvinyl alcohol as a binder to make an aqueous slurry with a solid content of 28 vol% As a surface gradient slurry.

S2. Green body forming: put the 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina matrix composite granulation powder obtained in step S1 into a metal mold with an inner diameter of 70 mm, and bidirectionally pre-press at 120 MPa to a height of 130 mm. mm of dry-pressed preform, and then dry-pressed preform of 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina composite granulation powder in a plastic bag, put it into a cold isostatic press, and Cold isostatic pressing was carried out under a hydrostatic pressure of 320 MPa to obtain a molded green body of 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina matrix composite granulated powder.

S3, biscuit pre-sintering: put the 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina matrix composite granulation powder formed green body obtained in the step S2 into an electric furnace for pre-sintering, and the air atmosphere and pre-sintering temperature are 1250°C, pre-fired for 2 hours, and the temperature rise and fall rate was 5°C/min, to obtain a 3mol% yttria partially stabilized nano-zirconia toughened nano-alumina matrix composite ceramic calciner with a relative density of 51%.

S4. Ceramic ball pre-fired bisque processing: according to the size requirements of the drawings, CNC numerical control machine tools are used to machine the 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina matrix composite ceramic pre-fired bisque obtained in step S3 to obtain 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina matrix composite ceramic ball calcined green body with a diameter of 54 mm.

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina matrix composite ceramic ball pre-fired bisque obtained in step S4 into a vacuum tank, and then pour it into step S1 The obtained surface gradient infiltration slurry, the cover is vacuumed to -0.08MPa, so that the surface gradient infiltration slurry gradually infiltrates the surface layer of the pre-fired biscuit of 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina matrix composite ceramic balls , after holding the pressure for 45 min, a 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina matrix composite ceramic ball pre-infiltrated billet with surface pre-infiltration gradient nano-alumina ceramic slurry was obtained, and the surface of the infiltration layer was nano-alumina powder The content increased by 10.7 vol.%, and the depth of the gradient permeability layer was 1820 microns.

S6. Densification and sintering of ceramic ball billets: firstly, the 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina matrix composite ceramic ball pre-infiltrated billet obtained in S5 was put into an air electric furnace for further pre-sintering, and the sintering temperature was 1450°C , The sintering time is 2 hours, the heating and cooling rate is 1°C/min, and the nano-alumina surface reinforcement with 3mol% yttria and partially stabilized nano-zirconia reinforcement with a nano-alumina gradient permeation layer and a surface gradient precompression stress with a relative density of 96% is obtained. Tough nano-alumina-based composite ceramic ball pre-sintered billet; then, the nano-alumina surface reinforced 3mol% yttrium oxide partially stabilized nano-zirconia toughened nano-alumina-based composite ceramic ball pre-sintered billet was placed in a hot isostatic pressing sintering furnace Densification sintering is carried out, the sintering temperature is 1520°C, the sintering gas pressure is 180MPa, the sintering time is 4 hours, and the heating and cooling rate is 5°C/min, the final diameter is 40.3mm, the relative density is 99.9%, the grain size is 580nm, The tensile strength between the gradient infiltration coating and the substrate is 88.8 MPa, the shear strength is 79.8 MPa, the flexural strength of the substrate is 720 MPa, and the fracture toughness is 6.1 MPa·m ^1/2 . Gradient diffusion layer with nano-alumina surface enhancement The nano-alumina matrix composite ceramic ball blank reinforced by nano-3mol% yttrium oxide partially stabilized nano-zirconia reinforced nano-alumina based composite ceramic ball with surface gradient precompression stress.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nano-alumina surface component gradient enhanced 3mol% yttrium oxide partly stabilized nano-zirconia toughened nano-alumina matrix composite ceramic ball blank obtained in S6 into the V-shaped groove In the grinding equipment, at least 5 processes of rough grinding, semi-finishing, finishing, super-finishing and polishing are carried out step by step to produce a nominal spherical diameter of 40 mm, a spherical surface roughness Ra of 0.005 mm, and a spherical error of 0.06 μm. The roundness of the spherical surface is 0.004 mm, the deviation of the ball batch diameter is 0.06 μm, the surface hardness HV ₁₀₀₀ is 2120, and there is a pre-compression stress of -380 MPa on the surface. The surface composition gradient of nano-alumina composite reinforcement 3mol% yttrium oxide partially stabilized nano-zirconia Toughened nano-alumina matrix composite ceramic balls.

S8. Machining of nano-alumina surface component gradient composite reinforced alumina-based composite ceramic humerus ball head: According to the size requirements of the drawings of the nano-alumina surface component gradient composite-reinforced alumina-based composite ceramic humerus ball head, the nano Alumina surface component gradient composite reinforced 3mol% yttria partially stabilized nano-zirconia toughened nano-alumina matrix composite ceramic balls were divided into at least 2 nano-alumina surface component gradient composite reinforced alumina matrix composite ceramic humeral ball head blanks, Then, grinding and chamfering were performed to prepare at least two humeral ball heads with nano-alumina surface components gradient composite reinforced alumina-based composite ceramics with a nominal spherical diameter of 40 mm and a gradient penetration layer depth of 1210 mm.

S9. Final polishing of the surface of the nano-alumina surface component gradient composite reinforced alumina-based composite ceramic humerus ball head: the final polishing of the spherical surface of the nano-alumina surface component gradient composite-reinforced alumina-based composite ceramic humerus ball to make the surface rough The degree Ra is 0.002mm.

S10. Inspection/marking/packaging: conduct all quality assurance inspections on the nano-alumina surface component gradient composite reinforced alumina-based composite ceramic humerus ball head, and laser mark and package the bottom of qualified products.

Example 35: Composite reinforced silicon nitride ceramic humeral ball head with nano-alumina surface component gradient
S1. Formulation/milling and preparation of surface gradient slurry and modified granulated powder: (1) Weigh an appropriate amount of silicon nitride powder with a purity of 99.9 wt.% or more, and add 0.1 wt% of its mass to the nano Alumina, 0.6 wt.% Tween 80 as a surfactant and 3.5 wt.% polyvinyl alcohol as a binder were used to make an aqueous slurry with a solid content of 32 vol%, and then the nano-modified Silicon nitride granulated powder; (2) Weigh an appropriate amount of nano-alumina powder with a purity of more than 99.9 wt.%, add its mass of 0.12 wt% nano-magnesia as a sintering aid, 0.5 wt.% Tween 80 As a surfactant and 4.5wt.% polyvinyl alcohol as a binder, an aqueous slurry with a solid content of 25vol% is used as a surface gradient slurry.

S2. Green body molding: put the nano-modified silicon nitride powder obtained in step S1 into a metal mold with an inner diameter of 70 mm, and bidirectionally pre-press at 120 MPa to form a green body with a height of 130 mm, and then add nano-modified nitrogen The dry-pressed preform of silicon nitride granulated powder is vacuum-packed in a plastic bag, put into a cold isostatic press, and subjected to cold isostatic pressing under a hydrostatic pressure of 450 MPa to obtain nano-modified silicon nitride granulated powder Body molding green body.

S3. Blank pre-sintering: put the nano-modified silicon nitride granulated powder molding green body obtained in step S2 into an electric furnace for pre-sintering, nitrogen atmosphere, pre-sintering temperature is 1650 ° C, and pre-sintering time is 2 hours. The cooling rate was 1°C/min, and a nano-modified silicon nitride ceramic pre-fired biscuit with a relative density of 53% was obtained.

S4. Ceramic ball pre-fired biscuit processing: According to the size requirements of the drawings, the nano-modified silicon nitride ceramic pre-fired biscuit obtained in step S3 is machined with CNC machine tools to obtain nano-modified silicon nitride ceramic pre-fired biscuits with a diameter of 53 mm. Silicon ceramic ball pre-fired biscuit.

S5. Surface grouting of ceramic ball pre-fired biscuit: put the nano-modified silicon nitride ceramic ball pre-fired biscuit obtained in step S4 into a vacuum tank, and then pour the surface gradient grout obtained in step S1 into nano-modified For the alumina powder slurry, the cover is evacuated to -0.08 MPa, so that the surface gradient infiltration slurry gradually infiltrates into the surface layer of the pre-fired biscuit of nano-modified silicon nitride ceramic balls. After holding the pressure for 60 minutes, a surface pre-infiltration The nano-modified silicon nitride ceramic ball pre-infiltration body of gradient nano-alumina ceramic slurry, the content of nano-alumina powder on the surface of the infiltration layer increased by 9.1 vol.%, and the depth of the gradient pre-infiltration layer was 1800 microns.

S6. Densification and sintering of ceramic ball billets: firstly, put the nano-alumina surface gradient enhanced nano-modified silicon nitride ceramic ball pre-infiltrated body obtained in S5 into an atmosphere electric furnace for further pre-sintering, under argon protection, and the sintering temperature is 1810 ℃, the sintering time is 2 hours, and the heating and cooling rate is 1 ℃/min, to obtain a nano-modified silicon nitride ceramic ball pre-sintered body with a relative density of 97% and a nano-alumina gradient infiltration layer and a surface gradient pre-compression stress; then, Put the pre-sintered nano-modified silicon nitride ceramic ball into a hot isostatic pressing sintering furnace, and carry out densification and sintering under the condition of nitrogen gas distribution. The cooling rate is 1°C/min, and the final diameter is 40.4 mm, the relative density is 99.9%, the grain size is 418 nm, the tensile strength between the gradient infiltration coating and the substrate is 108 MPa, and the shear strength is 98 MPa. Nano-alumina surface composition gradient compound reinforced nano-modified silicon nitride ceramics with a matrix flexural strength of 1100 MPa and a fracture toughness of 8.6 MPa m ^1/2 with a nano-alumina surface gradient infiltration layer and a surface gradient precompression stress Blank.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nano-alumina surface component gradient composite reinforced nano-modified silicon nitride ceramic ball blank obtained in S6 into the magnetic fluid grinding equipment for at least rough grinding, step by step, Semi-finishing, lapping, super-finishing, and polishing are processed into a diameter of 40 mm, a ball surface roughness Ra of 0.006 mm, a spherical error of 0.02 μm, a spherical roundness of 0.004 mm, and a ball batch diameter deviation of 0.05 μm, surface hardness HV ₁₀₀₀ is 2010, nano-alumina surface component gradient enhanced nano-modified silicon nitride ceramic balls with -253MPa pre-compression stress on the surface.

S8. Machining of nano-alumina surface component gradient composite reinforced silicon nitride ceramic humerus ball head: according to the size requirements of the drawings of nano-alumina surface component gradient composite reinforced silicon nitride ceramic humerus ball head, the nano-alumina obtained in step S7 The surface gradient composite reinforced nano-modified silicon nitride ceramic ball is divided into at least 2 nano-alumina surface gradient composite reinforced silicon nitride ceramic humerus ball head blanks, and then processed by grinding and chamfering to prepare at least 2 nominal spherical surfaces The diameter is 40 mm, the depth of the gradient permeation layer is 1180 mm, and the nano-alumina surface component is gradient composite reinforced silicon nitride ceramic humeral ball head.

S9. The final polishing of the surface of the nano-alumina surface composition gradient composite reinforced silicon nitride ceramic humeral ball head: the final polishing of the spherical surface of the nano-alumina surface composition gradient composite reinforced silicon nitride ceramic humeral ball head, so that the surface roughness Ra 0.002mm.

S10. Inspection/marking/packaging: The nano-alumina surface component gradient compound reinforced silicon nitride ceramic humerus ball head is subjected to all quality assurance inspections, and the bottom of qualified products is laser marked and packaged.

Example 36: Composite reinforced silicon carbide ceramic humeral ball head with nano-silicon nitride surface composition gradient
S1. Formulation/milling and preparation of surface gradient infiltration slurry and modified granulated powder: (1) Weigh an appropriate amount of nano-silicon carbide powder with a purity of 99.9 wt.% or more, and add 2 wt% of its mass of nano-silicon carbide Boron powder is used as sintering aid, 0.2 wt.% ammonium polyacrylate is used as surfactant and 2.5wt.% polyvinyl alcohol is used as binder to make an aqueous slurry with a solid content of 32 vol%, which is then spray-dried and granulated Prepare nano-modified silicon carbide granulated powder; (2) Weigh an appropriate amount of nano-silicon nitride powder with a purity of more than 99.9 wt.%, add its mass of 2.5 wt% nano-alumina, 2 wt% nano-oxide The composite powder of yttrium and 1 wt% nano-lutetium oxide was used as sintering aid, 0.5 wt.% ammonium polyacrylate was used as surfactant and 3.5 wt.% polyvinyl alcohol was used as binder to make water-based slurry with solid content of 25 vol%. The material is used as the surface gradient slurry;
S2. Green body molding: put the nano-modified silicon carbide granulated powder obtained in step S1 into a metal mold with an inner diameter of 90 mm, and bidirectionally pre-press at 120 MPa to form a pre-form with a height of 150 mm. The silicon carbide granulated powder dry-pressed blank is vacuum-packed in a plastic bag, put into a cold isostatic press, and subjected to cold isostatic pressing under a hydrostatic pressure of 450MPa to obtain nano-modified silicon carbide granulated powder. green body.

S3. Blank pre-sintering: put the nano-modified silicon carbide granulated powder formed green body obtained in step S2 into an electric furnace for pre-sintering, in an argon atmosphere, at a pre-sintering temperature of 1650° C., and at a pre-sintering time of 2 hours. The cooling rate was 1°C/min, and a nano-modified silicon carbide ceramic pre-fired biscuit with a relative density of 53% was obtained.

S4. Ceramic ball pre-fired bisque processing: According to the size requirements of the drawings, use CNC numerical control machine tools to machine the nano-modified silicon carbide ceramic pre-fired bisque obtained in step S3 to obtain nano-modified silicon carbide ceramics with a diameter of 67 mm Ball pre-fired biscuit.

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the nano-modified silicon carbide ceramic ball pre-fired biscuit obtained in step S4 into a vacuum tank, then pour the surface gradient infiltration slurry obtained in step S1, and cover Vacuum down to -0.12 MPa to make the surface gradient infiltration slurry gradually infiltrate into the surface layer of the nano-modified silicon carbide ceramic ball pre-fired biscuit. After holding the pressure for 15 minutes, the nano-silicon nitride surface composition with surface pre-infiltration gradient slurry is obtained. Gradient compound reinforced silicon carbide ceramic ball pre-infiltration body, the content of nano-silicon nitride powder on the surface of the infiltration layer increased by 8.1 vol.%, and the depth of the pre-infiltration layer was 1300 microns.

S6. Densification and sintering of ceramic ball billets: firstly, put the nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic ball pre-infiltrated green body obtained in S5 into an atmosphere electric furnace for further pre-sintering, under argon protection, and the sintering temperature is 1900 ℃, sintering time of 2 hours, temperature rise and fall rate of 1°C/min, to obtain a nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic with a relative density of 97% and a nano-silicon nitride gradient infiltration layer and surface gradient precompression stress The ball pre-sintered body; then, put the nano-silicon nitride surface component gradient compound reinforced silicon carbide ceramic ball pre-sintered body into the hot isostatic pressing sintering furnace, and carry out densification and sintering under the condition of argon gas distribution, and the sintering temperature is 1850 ℃, the sintering gas pressure is 150MPa, the sintering time is 1 hour, and the heating and cooling rate is 1℃/min, the final diameter is 50.5mm, the relative density is 99.9%, the grain size is 658nm, and the gradient between the coating and the substrate is obtained. The tensile strength is 75.9 MPa, the shear strength is 83.2 MPa, the matrix flexural strength is 850 MPa, and the fracture toughness is 6.3 MPa m ^1/2 . Nano-nitrogen with nano-silicon nitride surface gradient permeation layer and surface gradient precompression stress Silicon carbide surface component gradient composite reinforced silicon carbide ceramic ball blank.

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: put the nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic ball blank obtained in S6 into the V-shaped groove grinding equipment for at least rough grinding and semi-finishing step by step. Grinding, lapping, ultra-finishing and polishing are processed into a nominal spherical diameter of 50 mm, a spherical surface roughness Ra of 0.005 mm, a spherical error of 0.04 μm, a spherical roundness of 0.005 mm, and a ball batch diameter deviation of It is 0.08μm, the surface hardness HV ₁₀₀₀ is 2250, and the surface has a -340 MPa pre-compression stress on the surface of nano-silicon nitride surface composition gradient composite reinforced silicon carbide ceramic balls.

S8. Machining of nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic humeral ball head: according to the size requirements of the nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic humeral ball head drawing, the nano-nitrided ceramic obtained in step S7 Silicon surface component gradient compound reinforced silicon carbide ceramic ball is divided into at least 2 nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic humerus ball head blanks, and then processed by grinding and chamfering to prepare at least 2 nominal The diameter of the spherical surface is 50 mm, the depth of the gradient permeation layer is 730 mm, and the nano-silicon nitride surface component gradient is compounded to strengthen the silicon carbide ceramic humeral ball head.

S9. The final polishing of the surface of the nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic humeral ball head: the final polishing of the spherical surface of the nano-silicon nitride surface component gradient compound reinforced silicon carbide ceramic humeral ball head, so that the surface roughness Ra 0.002mm.

S10. Inspection/marking/packaging: conduct all quality assurance inspections on the nano-silicon nitride surface component gradient composite reinforced silicon carbide ceramic humerus ball head, and laser mark and package the bottom surface of qualified products.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than limiting them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: It is still possible to modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the various embodiments of the present invention. All of them should be covered by the scope of the claims and description of the present invention.

Claims

A surface-enhanced ceramic artificial joint convex-spherical friction part, characterized in that: the surface-enhanced ceramic artificial joint convex-spherical friction part comprises the following raw material components in parts by weight: 100 parts of powder, 0.2- 4 parts, 0.1-5 parts of binder; the powder includes the main component and the sintering aid; the weight ratio of the main component and the sintering aid is 94.5-99.999:0.001-5.5; the The main components are nano alumina powder, nano zirconia powder, nano silicon nitride powder, nano silicon carbide powder, nano zirconia toughened alumina powder, nano zirconia toughened silicon nitride powder, nano One or more of zirconia toughened silicon carbide powder, nano-alumina-reinforced zirconia powder, nano-alumina-reinforced silicon nitride powder, and nano-alumina-reinforced silicon carbide powder; the sintering The auxiliary agent is nano-magnesia powder, nano-yttrium oxide powder, nano-calcium oxide powder, nano-cerium oxide powder, nano-alumina powder, nano-lutetium oxide powder, nano-boron carbide powder; the surface active The agent is one or more of Tween 80, polyethylene glycol octylphenyl ether, ammonium citrate, polyacrylic acid ammonia; the binder is polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone , carboxymethyl cellulose, polyethylene imine, polyvinyl butyral, water-based phenolic resin or one or more; the surface-enhanced ceramic artificial joint convex spherical friction part includes a matrix and a depth of 0- 2500μm gradient permeation layer containing the same or different components as the matrix;

Prepared by the following preparation method:

S1. Preparation of surface gradient infiltration slurry and modified granulated powder: Add sintering aid, surfactant, and binder to the main components for mixing to obtain a mixed slurry with a solid content of 5‑45vol%. Surface gradient infiltration slurry; add sintering aids, surfactants, and binders to the main components for mixing, and spray drying to obtain modified granulated powder;

S2. Green body molding: put the modified granulated powder prepared in step S1 into a metal mold, and perform bidirectional pre-pressing to obtain a green body, vacuum-pack the green body in a plastic bag, and put it into cold isostatic pressing Cold isostatic pressing in the machine to make a green body;

S3. Bisque pre-firing: put the formed green body prepared in step S2 into an atmosphere electric furnace for pre-firing to obtain a pre-fired biscuit with a relative density of 50-70%;

S4. Ceramic ball pre-fired biscuit processing: using a CNC numerical control machine tool to machine the pre-fired biscuit obtained in step S3 to obtain a ceramic ball pre-fired bisque;

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the ceramic ball pre-fired biscuit prepared in step S4 into a vacuum tank, pour the surface gradient infiltration slurry prepared in step S1 into it, and cover it Vacuumize, hold the pressure for infiltration, take out and dry, repeat the infiltration and drying for many times, and make the surface pre-infiltration blank;

S6. Densification and sintering of ceramic ball billets: put the surface pre-infiltrated billet prepared in step S5 into an atmosphere electric furnace for pre-firing again to obtain a pre-fired billet with a relative density of 90-97%, and then put it into a hot isostatic Hot isostatic pressing densification co-sintering is carried out in a pressure sintering furnace to produce a densified ceramic ball with a relative density greater than 99.9% whose surface component content gradually decreases from the surface to the inside; hot isostatic pressing densification co-sintering The sintering pressure is 20-200MPa;

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: the densified ceramic ball blank obtained in step S6 is subjected to rough grinding, semi-finish grinding, fine grinding, super-finish grinding, and polishing to obtain a diameter of 14-56mm surface-enhanced ceramic spheres;

S8. Machining of surface-reinforced ceramic artificial joint convex-spherical friction parts: machining the surface-reinforced ceramic spheres prepared in step S7 to obtain a semi-finished product of surface-enhanced ceramic artificial joint convex-spherical friction parts; the machining is One or more of cutting, crowning, drilling, grinding, chamfering;

S9. Surface-enhanced ceramic artificial joint convex-spherical friction part surface final polishing: the friction surface of the surface-enhanced ceramic artificial joint convex-spherical friction part semi-finished product is finally polished to obtain the surface-enhanced ceramic artificial joint convex-spherical friction part ;

S10. Inspection, marking, and packaging: Carry out all quality assurance inspections on the surface-enhanced ceramic artificial joint convex spherical friction parts, and mark and pack the qualified products on the surface.
The surface-reinforced ceramic artificial joint convex-spherical friction part according to claim 1, characterized in that: the grain size of the surface-reinforced ceramic artificial joint convex-spherical friction part is less than 1 μm, and the surface Vickers hardness HV 1000 is greater than 1650 , The flexural strength of the matrix is greater than 500MPa, the fracture toughness is greater than 5 MPa·m 1/2 , the tensile strength between the gradient permeation layer and the matrix is greater than 45MPa, and the shear strength is greater than 50MPa.
The surface-reinforced ceramic artificial joint convex-spherical friction part according to claim 1, characterized in that: the surface-reinforced ceramic artificial joint convex-spherical friction part is self-reinforced by surface prestress and/or compositely reinforced by surface component gradient , the surface-reinforced ceramic artificial joint convex-spherical friction component has a surface precompression stress of more than -50 MPa in the direction of the tangential plane of the spherical surface, and the internal precompression stress or/and component content gradually decreases radially from the surface to the inside Variation; the spherical surface roughness Ra of the surface-enhanced ceramic artificial joint convex spherical friction part is less than 0.002 μm, the spherical error is 0.04-0.06 μm, the spherical roundness is 0-0.005 mm, and the ball batch diameter deviation is less than 0.1 μm; The wear resistance of the surface-enhanced ceramic artificial joint convex spherical friction part is less than 1×10 -6 cm 3 /year.
The preparation method of the surface-reinforced ceramic artificial joint convex spherical friction part according to any one of claims 1-3, characterized in that: the preparation method, the steps are as follows:

S1. Preparation of surface gradient infiltration slurry and modified granulated powder: Add sintering aid, surfactant, and binder to the main components for mixing to obtain a mixed slurry with a solid content of 5‑45vol%. Surface gradient infiltration slurry; add sintering aids, surfactants, and binders to the main components for mixing, and spray drying to obtain modified granulated powder;

S2. Green body molding: put the modified granulated powder prepared in step S1 into a metal mold, and perform bidirectional pre-pressing to obtain a green body, vacuum-pack the green body in a plastic bag, and put it into cold isostatic pressing Cold isostatic pressing in the machine to make a green body;

S3. Bisque pre-firing: put the formed green body prepared in step S2 into an atmosphere electric furnace for pre-firing to obtain a pre-fired biscuit with a relative density of 50-70%;

S4. Ceramic ball pre-fired biscuit processing: using a CNC numerical control machine tool to machine the pre-fired biscuit obtained in step S3 to obtain a ceramic ball pre-fired bisque;

S5. Surface infiltration of ceramic ball pre-fired biscuit: put the ceramic ball pre-fired biscuit prepared in step S4 into a vacuum tank, pour the surface gradient infiltration slurry prepared in step S1 into it, and cover it Vacuumize, hold the pressure for infiltration, take out and dry, repeat the infiltration and drying for many times, and make the surface pre-infiltration blank;

S6. Densification and sintering of ceramic ball billets: put the surface pre-infiltrated billet prepared in step S5 into an atmosphere electric furnace for pre-firing again to obtain a pre-fired billet with a relative density of 90-97%, and then put it into a hot isostatic Hot isostatic pressing densification co-sintering is carried out in a pressure sintering furnace to produce a densified ceramic ball with a relative density greater than 99.9% whose surface component content gradually decreases from the surface to the inside; hot isostatic pressing densification co-sintering The sintering pressure is 20-200MPa;

S7. Rough grinding, fine grinding, and polishing of the surface of the ceramic ball blank: the densified ceramic ball blank obtained in step S6 is subjected to rough grinding, semi-finish grinding, fine grinding, super-finish grinding, and polishing to obtain a diameter of 14-56mm surface-enhanced ceramic spheres;

S8. Machining of surface-reinforced ceramic artificial joint convex-spherical friction parts: machining the surface-reinforced ceramic spheres prepared in step S7 to obtain a semi-finished product of surface-enhanced ceramic artificial joint convex-spherical friction parts; the machining is One or more of cutting, crowning, drilling, grinding, chamfering;

S9. Surface-enhanced ceramic artificial joint convex-spherical friction part surface final polishing: the friction surface of the surface-enhanced ceramic artificial joint convex-spherical friction part semi-finished product is finally polished to obtain the surface-enhanced ceramic artificial joint convex-spherical friction part ;

S10. Inspection, marking, and packaging: Carry out all quality assurance inspections on the surface-enhanced ceramic artificial joint convex spherical friction parts, and mark and pack the qualified products on the surface.
The method for preparing surface-reinforced ceramic artificial joint convex spherical friction parts according to claim 4, characterized in that: in step S2, the inner diameter of the metal mold is 40-90 mm, and the pressure of the bidirectional preloading is ≥ 50MPa, the height of the blank is 100-150mm, and the hydrostatic pressure for cold isostatic pressing is 100-450MPa.
The method for preparing surface-reinforced ceramic artificial joint convex spherical friction parts according to claim 4, characterized in that: in step S3, the atmosphere used for pre-firing is one of air, nitrogen, argon, and hydrogen One or more kinds, the pre-burning temperature is 1000-1700°C, the pre-burning time is 1-10 hours, and the heating and cooling rate is 0.1-20°C/min.
The method for preparing surface-reinforced ceramic artificial joint convex spherical friction parts according to claim 4, characterized in that: in step S4, the diameter of the ceramic ball pre-fired biscuit is 30-75mm; in step S5, the The increase of nano powder content on the surface of the surface pre-infiltrated blank is more than or equal to 5vol.%, forming a gradient permeation layer with the same or different components as the matrix.
The method for preparing surface-reinforced ceramic artificial joint convex-spherical friction parts according to claim 4, characterized in that: in step S6, the atmosphere used for the second pre-firing is air, nitrogen, argon, hydrogen One or more of them, the pre-burning temperature for the second pre-burning is 1150-1900°C, the pre-burning time is 1-10 hours, and the heating and cooling rate is 0.1-20°C/min; the heating, etc. The sintering temperature of static pressure densification co-sintering is 1250-1950°C, the sintering time is 1-5 hours, and the heating and cooling rate is less than 1°C/min.
The method for preparing a surface-reinforced ceramic artificial joint convex-spherical friction part according to claim 4, characterized in that: in step S7, the grinding method is a V-shaped groove grinding method and an active control grinding method of rotation angle , one or more of the magnetic fluid grinding processing method, and the four-abrasive grinding processing method.
The method for preparing a surface-reinforced ceramic artificial joint convex-spherical friction part according to claim 4, characterized in that: in step S8, the semi-finished product of the surface-enhanced ceramic artificial joint convex-spherical friction part has a nominal spherical diameter of 14 ‑52mm surface-reinforced ceramic ball head, surface-reinforced ceramic femoral unicondylar prosthesis with a nominal spherical diameter of 40.6‑55mm, and surface-reinforced ceramic humeral ball head with a nominal spherical diameter of 32‑56mm.