CN105256174A - Biotic bone composite material and preparing method thereof - Google Patents
Biotic bone composite material and preparing method thereof Download PDFInfo
- Publication number
- CN105256174A CN105256174A CN201510695976.XA CN201510695976A CN105256174A CN 105256174 A CN105256174 A CN 105256174A CN 201510695976 A CN201510695976 A CN 201510695976A CN 105256174 A CN105256174 A CN 105256174A
- Authority
- CN
- China
- Prior art keywords
- matrix material
- powder
- bone matrix
- biological bone
- powdered alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention discloses a biotic bone composite material and a preparing method thereof and belongs to the technical field of materials. The composite material is formed by combining CoCrMo alloy powder, CeO2 alloy powder and ZrO2 alloy powder and comprises, by mass, 92-98% of CoCrMo alloy powder, 1-3% of CeO2 alloy powder and 1-5% of ZrO2 alloy powder. The particle size range of the CoCrMo powder is 100-200 meshes, the particle size range of the CeO2 powder is 0.5-1 microns, and the particle size range of the ZrO2 powder is 30-80 nm, wherein the three kinds of powder are in spherical shapes. The preparing method includes the steps that firstly, the composite powder is mixed; secondly, a base material which is directly deposited and formed with lasers is pretreated; and thirdly, the technological method for direct depositing and forming with lasers is adopted, a laser 3D printer is adopted, inert gas shielding is conducted, and a laser device conducts continuous scanning for n layers and returns to the position of XY plane origin coordinates. The composite material has good toughness, wear resistance and corrosion resistance, rigidity reaches 619 HV, the tensile strength reaches 686 MPa, the biotic bone composite material is soaked in manual simulation saliva for 7 days, and the concentration of the Cr ion is 0.11 mg/L. The composite material is applied to preparing of artificial bone false teeth.
Description
Technical field
The invention belongs to field of material technology, particularly a kind of biological bone matrix material and preparation method thereof.
Background technology
Along with living standards of the people progressively improve, in addition modern science and technology develop rapidly, the attention rate of people to the health level of the quality of life in the modern life and human body also improves year by year, and the phenomenons such as the loss of tooth caused for the impact due to factors such as pathology, natural disaster, burst accident, weather agings or fracture folding take place frequently.Under the prerequisite meeting the good bio-compatibility of nontoxic guarantee, preparing and drop into the artificial tooth possessing the differing materials of the excellent mechanical properties such as good wear resistance, high solidity to corrosion, enough hardness of clinical application, is one of worldwide study hotspot.Since Co-Cr base ladle refining to biomedical aspect application, Co-Cr base alloy is just widely used research because of its good solidity to corrosion and wear resistance and cheap price.
Cochrome surface can form CoC
xand Cr
2o
3solidity to corrosion and the good compound of wear resistance, passive state can be kept after implant into body, do not produce with tissue and react, and its passive film is more stable compared with stainless steel, corrosion resisting property is good, in addition the chromium metallic substance that inherently solidity to corrosion is good, therefore the corrosion resisting property of cochrome is due to other materials.Wherein the spot corrosion tendency of vitallium is very little, and counter stress corrosion cracking is insensitive, but casting vitallium is very low to the ability to bear of notch shock.The cochrome of casting is because its excellent biological property and mechanical property are applied to tooth and biologic medical field very early.Co-Ni-Cr-Mo and Co-Cr-Mo alloy at present for casting and forging is worldwide very extensive for the research of human body artificial tooth material.But simple metallic substance cannot obtain high strength, high-wearing feature, high anti-corrosion as stupalith all the time, and traditional ceramics material also cannot reach the high ductility of metallic substance, thus the manufacturing technology of Co-Cr based composites and advanced person thereof is the trend of biological bone artificial tooth Materials.
Laser direct deposition forming technique (3D shaping) is the modern technique grown up gradually from phase early 1980s.The combine with technique such as CAD, CAM, high power laser cladding and rapid prototype manufacturing get up by it, utilize the stratified sedimentation thought of rapid prototyping, adopt laser melting coating to carry out the method for metal parts direct forming.Can realize high-performance complex construction metal parts without mould, quick, complete fine and close direct forming, there is the advantages such as high flexibility, short period, environmental friendliness, low cost and market respond be fast.Therefore be frontier nature research topic both domestic and external since it occurs always.
At present, in laser direct deposition shaping, material used mainly contains titanium alloy, stainless steel, nickel-base alloy, copper alloy and cochrome etc.But due to the process that laser direct deposition formation of parts is a complexity, multifactor effect, be mainly concerned with the synergy between composition of raw material composition, laser parameter and impact, in laser direct deposition forming process, due to material be by experienced by uneven rapid heating and process of cooling multiple spot pile up form, therefore the structure and properties of drip molding and the structure and properties of conventional cast part different.So still there is the difficult problem of " distortion and cracking " so far in shaping Co-Cr base biological bone alloy sample, this difficult problem governs industrial applications and the development of this technology.Obtain even, smooth, zero defect, excellent property stamped metal part, often to optimize material composition composition, microstructure and laser energy density and action time etc. factor, make it to reach optimum combination, molding just can be made to have good weave construction and obdurability matching relationship.
Around these problems, originally researched and proposed with the highly malleablized research of laser direct deposition shaping (3D printing) metal composite as core, by technological approaches such as polynary, multi-phase components design, induced with laser In-situ reaction and laser parameter optimizations thereof, deeply systematically have studied the internal relation between the microstructure of laser direct deposition CoCr alloy and based composites thereof and highly malleablized thereof and compacting mechanism thereof, performance and the influence factors thereof such as mechanics, the burn into of research shaping sample are wear-resisting, biocompatibility.Therefore, research and development laser direct deposition (3D printing) high-performance biological bone matrix material and preparation modern technique thereof, not only have important scientific research meaning but also have important using value.
Summary of the invention
Prepare the strain cracking problem of Co-Cr base compound bio bone material existence for existing laser direct deposition shaping (3D printing), the invention provides a kind of biological bone matrix material and preparation method thereof.The present invention, from design of material angle, is prepared as target with the laser of the Co-Cr base compound bio bone material of good obdurability, wear resistance and erosion resistance, selects CoCrMo powdered alloy, by adding appropriate CeO
2with nanometer ZrO
2powder forms new complex alloy powder, under the composite powder component prescription optimized and laser direct deposition forming technique technique, investigated biological bone matrix material and laser direct deposition and to be shaped advanced technology of preparing.
Biological bone matrix material of the present invention, by CoCrMo powdered alloy, CeO
2powdered alloy and ZrO
2powdered alloy is composited; Wherein, by mass percentage, CoCrMo powdered alloy: CeO
2powdered alloy: ZrO
2powdered alloy=(92 ~ 98): (1 ~ 3): (1 ~ 5); CoCrMo powder diameter scope 100 ~ 200 order, CeO
2powder diameter scope 0.5 ~ 1 μm, ZrO
2powder diameter scope 30 ~ 80nm, three kinds of powder are spherical morphology; The chemical composition of CoCrMo powdered alloy is by mass percentage: w (Cr)=25 ~ 27%, w (Mo)=5 ~ 7%, w (W)=4 ~ 6%, w (Si)=0.5 ~ 1.2%, w (Fe)=0.8 ~ 1.2%, w (C)=0.02 ~ 0.05%, surplus is Co.
Above-mentioned biological bone matrix material has the high-strong toughness weave construction of flawless gas hole defect.
The preparation method of biological bone matrix material of the present invention, adopts laser direct deposition method, comprises the steps:
Step 1, the batch mixing of composite powder:
(1) cetyl trimethylammonium bromide is mixed with ethylene glycol solution be placed in open glass container, mechanical stirring, rotating speed 300 ~ 500 turns/min, stir 15 ~ 20min; Wherein, cetyl trimethylammonium bromide is 0.005 ~ 0.01g/mL in the concentration of ethylene glycol solution;
(2) form according to the quality of biological bone matrix material, take CeO
2powdered alloy and ZrO
2powdered alloy, adds open glass container, Keep agitation 40 ~ 80min;
(3) form according to the quality of biological bone matrix material, take CoCrMo powdered alloy and add open glass container, after stirring 7 ~ 10h, leave standstill 20 ~ 30h, go to upper strata to contain alveolate solution, leave lower floor's mixture;
(4) by lower floor's mixture, at temperature 80 ~ 95 DEG C, 60 ~ 80h is dried, after drying completely, at 140 ~ 160 DEG C, insulation 20 ~ 60min;
(5) by the powder mull after oven dry, cross 100 mesh sieves, form biological bone complex alloy powder;
Step 2, the body material pre-treatment that laser direct deposition is shaped:
Baseplate material is Q235, through rust cleaning, surface finish, to deoil and after pickling, for subsequent use with alcohol washes;
Step 3, laser direct deposition is shaped:
Adopt laser 3D printer, processing parameter is: power 840 ~ 1450w, sweep velocity 4 ~ 8mm/s, defocusing amount 6 ~ 10mm, overlapping rate 30 ~ 35%, powder feeding rate are 5 ~ 8g/min, protection of inert gas; Laser apparatus continuous sweep n layer gets back to XY plane origin coordinate place, n be greater than 1 natural number, every layer of Z axis miles of relative movement 0.6 ~ 1mm; Print formation 3 through multilayer and tie up three-dimensional biological bone matrix material.
Wherein, in step 1, (4) adopt drying baker to dry; In step 2, Q235 first eliminates rust to its surface with emery wheel, makes its surface-brightening clean, then carries out surface treatment with 100 ~ No. 1000 sand paper to it, and acetone is dispelled greasy dirt, chlorohydric acid pickling, finally with alcohol rinse totally, dry up for subsequent use; In step 3, rare gas element is argon gas; In step 3, XY plane origin coordinate place is got back in laser apparatus continuous sweep 4 layers.
Principle of the present invention is from design of material angle, for the strain cracking problem that laser direct deposition shaping (3D printing) Co-Cr alloy exists, be shaped with the laser direct deposition of the Co-Cr base compound bio bone material of good obdurability, wear resistance and erosion resistance and be prepared as target, select medical grade CoCrMo alloys powder, by adding appropriate CeO
2, ZrO
2powder forms complex alloy powder, forms the heterogeneous synergy mechanism of metal alloy, rare earth oxide and nano ceramics composition, plays CeO
2crystal grain thinning, nanometer ZrO
2the effect that particle reinforce alloy wear-resisting is anti-corrosion, prepares the Co-Cr-Mo-CeO of the high-strong toughness weave construction with flawless gas hole defect
2-ZrO
2biological bone matrix material.
Preparation method's environmental protection of the present invention, utilizes the preparation of laser direct deposition shaping (3D printing) advanced method to have the biological bone composite material of high rigidity, high abrasion and corrosion resistance nature.By material composition and Laser Technology of Composing regulation and control, the hardness of the matrix material of preparation can reach for 619HV, and tensile strength can reach 686MPa; The corrosion current density of matrix material galvanic corrosion is minimum, to be soaked in the artificial simulate saliva of neutrality of pH=6.8 seven days, the concentration value 0.11mg/L of Cr ion.Biological bone matrix material prepared by the inventive method has good wear-resisting and corrosion resistance nature.The present invention is applied to the preparation of artificial bone artificial tooth, has important using value.
Accompanying drawing explanation
Fig. 1 is the laser scans path schematic diagram of the laser direct deposition of the embodiment of the present invention; Wherein scheming (a) is the 1st layer of path; Figure (b) is the 2nd layer of path; Figure (c) is the 3rd layer of path; Figure (d) is the 4th layer of path;
The sample macro morphology of the thing bone composite material of Fig. 2 embodiment of the present invention;
The Metallograph of the biological bone matrix material of Fig. 3 embodiment of the present invention;
The SEM microstructure of the biological bone matrix material of Fig. 4 embodiment of the present invention;
The XRD analysis figure of the biological bone matrix material of Fig. 5 embodiment of the present invention;
The TEM of the biological bone matrix material of Fig. 6 embodiment of the present invention and diffraction pattern, wherein Fig. 6 (a) is matrix, and Fig. 6 (b) is precipitated phase, and Fig. 6 (c) is A point-like electron diffraction, and Fig. 6 (d) is B point-like electron diffraction;
The microhardness analysis of the biological bone matrix material of Fig. 7 embodiment of the present invention;
The abrasion loss schematic diagram of the biological bone matrix material of Fig. 8 embodiment of the present invention;
The wear morphology of the biological bone matrix material of Fig. 9 embodiment of the present invention;
The tensile stress-strain curve of the biological bone matrix material of Figure 10 embodiment of the present invention;
The biological bone matrix material tension specimen of Figure 11 embodiment of the present invention stretching fracture pattern;
Figure 12 is laser direct deposition CoCrMo alloy, laser direct deposition Co-Cr-Mo-CeO
2matrix material and laser direct deposition biological bone matrix material, the polarization curve in manual simulation's saliva; Wherein (a) pH=3.0; (b) pH=6.8;
After the biological bone matrix material of Figure 13 embodiment of the present invention soaks 7 days, composite material surface SEM pattern;
The Co-Cr-Mo-CeO of Figure 14 embodiment of the present invention
2-ZrO
2the Metallograph of biological bone matrix material;
The Co-Cr-Mo-CeO of Figure 15 embodiment of the present invention
2-2ZrO
2the Metallograph of biological bone matrix material;
The Co-Cr-Mo-CeO of Figure 16 embodiment of the present invention
2-3ZrO
2the Metallograph of biological bone matrix material;
The Co-Cr-Mo-CeO of Figure 17 embodiment of the present invention
2-4ZrO
2the Metallograph of biological bone matrix material;
The Co-Cr-Mo-CeO of Figure 18 embodiment of the present invention
2-5ZrO
2the Metallograph of biological bone matrix material;
Figure 19 embodiment of the present invention different content ZrO
2biological bone matrix material grain-size statistics;
Figure 20 embodiment of the present invention different content ZrO
2the XRD analysis of biological bone matrix material
Figure 21 embodiment of the present invention different content ZrO
2the microhardness analysis of biological bone matrix material; Wherein, Figure 21 (a) is Hardness Distribution, Figure 21 (b) hardness mean value;
Figure 22 embodiment of the present invention different content ZrO
2the abrasion loss of biological bone matrix material;
Figure 23 embodiment of the present invention different content ZrO
2the polarization curve of biological bone matrix material in manual simulation's saliva; Wherein Figure 23 (a) pH=3.0, Figure 23 (b) pH=6.8.
Embodiment
In following examples, baseplate material is Q235 is that market is bought.
Embodiment 1
A kind of biological bone matrix material, by CoCrMo powdered alloy, CeO
2powdered alloy and ZrO
2powdered alloy is composited; Wherein, by mass percentage, CoCrMo powdered alloy: CeO
2powdered alloy: ZrO
2powdered alloy=98: 1: 1, in table 1; CoCrMo powder diameter scope 100 ~ 200 order, CeO
2powder diameter scope 0.5 ~ 1 μm, ZrO
2powder diameter scope 30 ~ 80nm, three kinds of powder are spherical morphology; Adopt medical grade CoCrMo alloys powder, chemical composition is by mass percentage: w (Cr)=26%, w (Mo)=6%, w (W)=5%, w (Si)=1%, w (Fe)=1%, w (C)=0.04%, surplus is Co.
The one-tenth of table 1 biological bone matrix material is grouped into (wt.%)
The preparation method of biological bone matrix material of the present invention, specific as follows:
Step 1, the batch mixing of composite powder:
(1) 2.5g cetyl trimethylammonium bromide is mixed with ethylene glycol solution be placed in the beaker of 500mL, mechanical stirring, rotating speed 500 turns/min, stir 15min, form mixing solutions;
(2) form according to the quality of biological bone matrix material, take 5gCeO
2powdered alloy and 5gZrO
2powdered alloy, adds open glass container, continues 40min, forms dispersion.
(3) form according to the quality of biological bone matrix material, take 490gCoCrMo powdered alloy and add Glass Containers, after stirring 8h, leave standstill 24h, go to upper strata to contain alveolate solution, leave lower floor's mixture;
(4) by lower floor's mixture, after drying 72h at 90 DEG C, after drying completely, at 150 DEG C, insulation 30min.
(5) by the powder mull after oven dry, cross 100 mesh sieves, form biological bone complex alloy powder.
Step 2, the body material pre-treatment that laser direct deposition is shaped:
Baseplate material is Q235, Q235 steel plate is cut into the block of 10cm × 20cm × 1cm, eliminates rust and oxide skin to its surface with emery wheel, makes its surface-brightening clean; Polish to its surface with No. 100 sand paper, use 400, No. 600 sand paper treat surface afterwards respectively, last acetone is dispelled greasy dirt, and chlorohydric acid pickling, totally dries up for subsequent use with alcohol rinse;
Step 3, laser direct deposition is shaped:
Adopt YLS-1000-CUT-YR type optical-fiber laser 3D printer, processing parameter is: power 850w, sweep velocity 5.94mm/s, defocusing amount 6mm, overlapping rate 30%, powder feeding rate 5g/min, and preparation process adopts argon shield; For avoiding the existence of otherness, XY plane origin coordinate place is got back in laser apparatus continuous sweep 4 layers, every layer of Z axis miles of relative movement 0.6mm; Fig. 1 is laser scans path schematic diagram, the first layer is prepared by Fig. 1 (a) the 1st layer of path, the second layer is prepared on the first layer by Fig. 1 (b) the 2nd layer of path, third layer is prepared on the second layer by Fig. 1 (c) the 3rd layer of path, third layer prepares the 4th layer by Fig. 1 (d) the 4th layer of path, so circulates through multilayer and print the biological bone matrix material that solid is tieed up in formation 3.
The results of property of biological bone matrix material prepared by embodiment:
Fig. 2 is the macro morphology of biological bone matrix material prepared by embodiment, a 15mm × 7.5mm × 18mm sample, and its plasticity is good, produces without macrocrack defect.
The Metallograph of biological bone matrix material prepared by Fig. 3 embodiment, prepares flawless gas hole defect in sample microtexture and generates, fine microstructures, CeO
2there is the effect of crystal grain thinning.The microstructure metallograph that Fig. 3 (a) is sample specimens top, can find that top tissue is main mainly with equiax crystal, the fine dendrites tissue of not growing up on a small quantity, Fig. 3 (b) is equiaxed grain structure, and Fig. 3 (c) is dendritic structure.Fig. 3 (d) is 500 times of lower equiaxed grain structures, finds that there is tiny particle and separates out, serve the effect strengthening tissue.
The SEM microstructure picture of biological bone matrix material prepared by Fig. 4 embodiment.Fig. 4 (a) and Fig. 4 (b) is equiax crystal, Fig. 4 (c) and Fig. 4 (d) dentrite, as can be seen from the figure, the microstructure of matrix material under the micro-Electronic Speculum of SEM, three kinds of main tissues are dendrite, equiax crystal and columanar structure, and wherein white crystal boundary and subgrain boundary place are made up of sheet.
Fig. 5 is the XRD analysis figure of biological bone matrix material prepared by embodiment.In sample tissue, the diffraction peak of (200) and (311) of the α-Co phase of fcc structure obviously reduces as can be seen from Figure 5, and the martensite ε-Co of hcp structure (
) diffraction peak of the diffraction peak in face and the α-Co (220) of fcc structure is overlapping, and overlapping peaks showed increased, the α-Co demonstrating fcc structure there occurs transformation to the martensite ε-Co of hcp structure.
Fig. 6 is transmission electron microscope pattern and the electron diffraction spot figure of biological bone matrix material prepared by embodiment.The matrix light field phase photo of Fig. 6 (a) alloy sample, the diffraction spot that Fig. 6 (c) is matrix, be diffracted to face-centered cubic along zone axis [
] standard diffraction spot, the α-Co being fcc structure is herein corresponding with XRD analysis result.((b) figure is the pattern of precipitate to Fig. 6, extracts in B position the diffraction spot that diffraction spot obtains (d) figure.By the diffraction spot of demarcating, calculate diffraction spot be face-centred cubic structure along [
] standard zone axis, prove that precipitate is Cr
23c
6, serve the effect of particle reinforce alloy substrate hardness.
Fig. 7 is the hardness analysis figure of biological bone matrix material prepared by embodiment.Use WILSON-WORPER-450SVD Vickers hardness tester, the microhardness of testing laser 3D printed sample.Load 200g, loading time 10s, adopt and get 3 rows by top ready to bottom, often arranges 20 points, and point is 0.4 millimeter with the spacing of point, the average hardness 619HV of sample.Due to nanometer ZrO
2add, serve ZrO
2the effect that ceramic particle strengthens.The average hardness of 619HV is still higher than the requirement of human teeth hardness 350HV, and the matrix material prepared in hardness has exceeded the hardness of natural tooth.
Fig. 8 is the abrasion loss schematic diagram of biological bone matrix material prepared by embodiment.Find in 2kg load, rotating speed 300r/min, when friction 2min, three average abrasion amounts of sample prepared by the former alloying constituent laser of CoCrMo are 0.0622g, and add 1%CeO
2and 1%CeO
2and 1%ZrO
2the average abrasion amount of rear sample is respectively 0.05g and 0.05373g, proves to add nanometer ZrO
2and CeO
2the wear resistance of Co-Cr matrix material can be improved.
Fig. 9 is the wear morphology schematic diagram of biological bone matrix material prepared by embodiment, finds that there is a small amount of grinding, and polishing scratch is even, and the overall wear resistance of material is good.
Figure 10 is the tensile stress-strain curve of biological bone matrix material prepared by embodiment, and the tensile strength of sample 1 is 894MPa, and the tensile strength of sample 2 is 686MPa.
Figure 11 is the fracture apperance of biological bone matrix material tension specimen prepared by embodiment, and find that fracture is all rupture from defective locations, the fracture of other positions has part to be cleavage fracture form.
Neutral artificial saliva (pH=6.8) and acid artificial saliva (pH=3.0) is simulated according to ISO/TR10271 standard configuration.Figure 12 is laser direct deposition CoCrMo alloy, laser direct deposition Co-Cr-Mo-CeO
2matrix material and laser direct deposition biological bone matrix material, the polarization curve in manual simulation's saliva; Figure 12 (a) is the polarization curves of three kinds of materials in pH=3.0 simulate saliva, and Figure 12 (b) is the polarization curves of three kinds of materials in pH=6.8 simulate saliva.
Table 2 is matrix material polarization curve data in pH=3.0 simulate saliva, and table 3 is matrix material polarization curve analytical resultss in pH=6.8 simulate saliva.By table 2 can be more original CoCrMo alloy, add 1%CeO
2rear alloy and add 1%CeO
2and 1%ZrO
2the corrosion current density of rear composite alloy in the simulation artificial saliva of pH=3.0 and corrosion potential, prove to add 1%CeO
2and 1%ZrO
2the corrosion current density of matrix material minimum, corrosion potential is maximum, and in acid simulate saliva, matrix material is the most anti-corrosion.Can find from table 3 and Figure 12 (b), although the corrosion potential of virgin alloy is maximum, 1%CeO
2and 1%ZrO
2the corrosion current density of matrix material minimum, so in the artificial simulate saliva of the neutrality of pH=6.8 1%CeO
2and 1%ZrO
2matrix material the most anti-corrosion.
Table 2 laser prepares CoCrMo alloy and the polarization curve data of matrix material in pH=3.0 simulate saliva thereof
Table 3 laser prepares CoCrMo alloy and the polarization curve analytical data of matrix material in pH=6.8 simulate saliva thereof
Co-Cr-Mo alloy possesses good solidity to corrosion as good oral medical material, but due to the special environment for use of oral medical material, require the precipitating metal ion that the Co-Cr-Mo alloy in implantation oral cavity is in use as far as possible few, this is because the metal ion of separating out directly contacts with histocyte in the oral cavity, for the ion of bio-compatibility difference, this all will damage cell tissue, gently then damage technical ability, heavy then cause toxic reaction and fatal.Be shaped laser direct deposition Co-Cr-Mo-CeO
2-ZrO
2composite processing becomes the sample of Φ 25mm × 1.5mm, and being soaked in pH value is in the artificial simulate saliva of neutrality of 6.8, and by holding the test tube of simulate saliva and sample as filling in the beaker of water, being placed in air dry oven, temperature being adjusted to 37 DEG C.Take out after 7 days, the erosion profile on observing samples surface under scanning electron microscope.Figure 13 is immersion sample surfaces SEM pattern after 7 days, and indistinct projection is as shown in the figure the subgrain boundary of rich Cr, because Cr is anti-corrosion, so in immersion after seven days, the corrosion of rich Cr position is comparatively light, as can be seen from Fig. point corrosion not obvious.
Table 4 is immersions after 7 days, the elemental release concentration of biological bone matrix material in neutral simulation artificial saliva.In all metal ions discharged after matrix material corrosion, the harm of Cr ion is maximum, and it is mainly with trivalent chromic ion (Cr
3+) release, Cr
3+toxicity is lower, can with protein bound, this experiment Cr ionic concn is 0.11mg/L, prove prepare matrix material there is good resistance to artificial saliva corrosive nature.
Table 4 sample is the middle concentration of metal ions of artificial simulate saliva (pH=6.8) after soaking 7d
Embodiment 2
A kind of biological bone matrix material, by CoCrMo powdered alloy, CeO
2powdered alloy and ZrO
2powdered alloy is composited; Wherein, by mass percentage, CoCrMo powdered alloy: CeO
2powdered alloy: ZrO
2powdered alloy=97: 1: 2, in table 1; CoCrMo powder diameter scope 100 ~ 200 order, CeO
2powder diameter scope 0.5 ~ 1 μm, ZrO
2powder diameter scope 30 ~ 80nm, three kinds of powder are spherical morphology; Adopt medical grade CoCrMo alloys powder, chemical composition is by mass percentage: w (Cr)=25%, w (Mo)=5%, w (W)=4%, w (Si)=0.5%, w (Fe)=0.8%, w (C)=0.02%, surplus is Co.
The preparation method of biological bone matrix material of the present invention, specific as follows:
Step 1, the batch mixing of composite powder:
(1) 2.5g cetyl trimethylammonium bromide is mixed with ethylene glycol solution be placed in the beaker of 500mL, mechanical stirring, rotating speed 300 turns/min, stir 20min, form mixing solutions;
(2) form according to the quality of biological bone matrix material, take 5gCeO
2powdered alloy and 10gZrO
2powdered alloy, adds open glass container, continues 60min, forms dispersion.
(3) according to biological bone matrix material quality composition, take 485gCoCrMo powdered alloy and add Glass Containers, after stirring 7h, leave standstill 20h, go to upper strata to contain alveolate solution, leave lower floor's mixture;
(4) by lower floor's mixture, 80h is dried at 80 DEG C, after drying completely, at 140 DEG C, insulation 60min.
(5) by the powder mull after oven dry, cross 100 mesh sieves, form biological bone complex alloy powder.
Step 2, the body material pre-treatment that laser direct deposition is shaped:
Baseplate material is Q235, Q235 steel plate is cut into the block of 10cm × 20cm × 1cm, eliminates rust and oxide skin to its surface with emery wheel, makes its surface-brightening clean; Polish to its surface with No. 200 sand paper, use 400, No. 800 sand paper treat surface afterwards respectively, last acetone is dispelled greasy dirt, and chlorohydric acid pickling, totally dries up for subsequent use with alcohol rinse;
Step 3, laser direct deposition is shaped:
Adopt YLS-1000-CUT-YR type optical-fiber laser 3D printer; Processing parameter is: power 840w, sweep velocity 6mm/s, defocusing amount 8mm, overlapping rate 35%, powder feeding rate 8g/min, and preparation process adopts argon shield; For avoiding the existence of otherness, XY plane origin coordinate place is got back in laser apparatus continuous sweep 4 layers, every layer of Z axis miles of relative movement 0.6mm; Fig. 1 is laser scans path schematic diagram, the first layer is prepared by Fig. 1 (a) the 1st layer of path, the second layer is prepared on the first layer by Fig. 1 (b) the 2nd layer of path, third layer is prepared on the second layer by Fig. 1 (c) the 3rd layer of path, third layer prepares the 4th layer by Fig. 1 (d) the 4th layer of path, so circulates through multilayer and print the biological bone matrix material that solid is tieed up in formation 3.
Embodiment 3
A kind of biological bone matrix material, by CoCrMo powdered alloy, CeO
2powdered alloy and ZrO
2powdered alloy is composited; Wherein, by mass percentage, CoCrMo powdered alloy: CeO
2powdered alloy: ZrO
2powdered alloy=96: 1: 3, in table 1; CoCrMo powder diameter scope 100 ~ 200 order, CeO
2powder diameter scope 0.5 ~ 1 μm, ZrO
2powder diameter scope 30 ~ 80nm, three kinds of powder are spherical morphology; Adopt medical grade CoCrMo alloys powder, chemical composition is by mass percentage: w (Cr)=27%, w (Mo)=7%, w (W)=6%, w (Si)=1.2%, w (Fe)=1.2%, w (C)=0.05%, surplus are Co.
The preparation method of biological bone matrix material of the present invention, specific as follows:
Step 1, the batch mixing of composite powder:
(1) 5g cetyl trimethylammonium bromide is mixed with ethylene glycol solution be placed in the beaker of 500mL, mechanical stirring, rotating speed 500 turns/min, stir 15min, form mixing solutions;
(2) form according to the quality of biological bone matrix material, take 5gCeO
2powdered alloy and 15gZrO
2powdered alloy, adds open glass container, continues 60min, forms dispersion.
(3) according to biological bone matrix material quality composition, take 480gCoCrMo powdered alloy and add Glass Containers, after stirring 8h, leave standstill 24h, go to upper strata to contain alveolate solution, leave lower floor's mixture;
(4) by lower floor's mixture, 72h is dried at 90 DEG C, after drying completely, at 150 DEG C, insulation 30min.
(5) by the powder mull after oven dry, cross 100 mesh sieves, form biological bone complex alloy powder.
Step 2, the body material pre-treatment that laser direct deposition is shaped:
Baseplate material is Q235, Q235 steel plate is cut into the block of 10cm × 20cm × 1cm, eliminates rust and oxide skin to its surface with emery wheel, makes its surface-brightening clean; Polish to its surface with No. 200 sand paper, afterwards respectively 800, No. 1000 sand paper treat surface, last acetone is dispelled greasy dirt, and chlorohydric acid pickling, totally dries up for subsequent use with alcohol rinse again;
Step 3, laser direct deposition is shaped:
Use the semiconductor laser 3D printer of FL-Dlight02-3000w, processing parameter is: power 1450w, sweep velocity 4mm/s, defocusing amount 10mm, overlapping rate 30%, powder feeding rate 7g/min, and preparation process adopts argon shield; For avoiding the existence of otherness, XY plane origin coordinate place is got back in laser apparatus continuous sweep 4 layers, every layer of Z axis miles of relative movement 1mm; Fig. 1 is laser scans path schematic diagram, the first layer is prepared by Fig. 1 (a) the 1st layer of path, the second layer is prepared on the first layer by Fig. 1 (b) the 2nd layer of path, third layer is prepared on the second layer by Fig. 1 (c) the 3rd layer of path, third layer prepares the 4th layer by Fig. 1 (d) the 4th layer of path, so circulates through multilayer and print the biological bone matrix material that solid is tieed up in formation 3.
Embodiment 4
A kind of biological bone matrix material, by CoCrMo powdered alloy, CeO
2powdered alloy and ZrO
2powdered alloy is composited; Wherein, by mass percentage, CoCrMo powdered alloy: CeO
2powdered alloy: ZrO
2powdered alloy=95: 1: 4, in table 1; CoCrMo powder diameter scope 100 ~ 200 order, CeO
2powder diameter scope 0.5 ~ 1 μm, ZrO
2powder diameter scope 30 ~ 80nm, three kinds of powder are spherical morphology; Adopt medical grade CoCrMo alloys powder, chemical composition is by mass percentage: w (Cr)=26%, w (Mo)=6%, w (W)=5%, w (Si)=0.5%, w (Fe)=0.8%, w (C)=0.02%, surplus are Co.
The preparation method of biological bone matrix material of the present invention, specific as follows:
Step 1, the batch mixing of composite powder:
(1) 4g cetyl trimethylammonium bromide is mixed with ethylene glycol solution be placed in the beaker of 500mL, mechanical stirring, rotating speed 400 turns/min, stir 15min, form mixing solutions;
(2) form according to the quality of biological bone matrix material, take 5gCeO
2powdered alloy and 20gZrO
2powdered alloy, adds open glass container, continues 80min, forms dispersion.
(3) form according to the quality of biological bone matrix material, take 475gCoCrMo powdered alloy and add Glass Containers, after stirring 9h, leave standstill 20h, go to upper strata to contain alveolate solution, leave lower floor's mixture;
(4) by lower floor's mixture, 60h is dried at 95 DEG C, after drying completely, at 140 DEG C, insulation 60min.
(5) by the powder mull after oven dry, cross 100 mesh sieves, form biological bone complex alloy powder.
Step 2, the body material pre-treatment that laser direct deposition is shaped:
Baseplate material is Q235, Q235 steel plate is cut into the block of 10cm × 20cm × 1cm, eliminates rust and oxide skin to its surface with emery wheel, makes its surface-brightening clean; Polish to its surface with No. 100 sand paper, use 400, No. 600 sand paper treat surface afterwards respectively, last acetone is dispelled greasy dirt, and chlorohydric acid pickling, totally dries up for subsequent use with alcohol rinse;
Step 3, laser direct deposition is shaped:
Adopt YLS-1000-CUT-YR type optical-fiber laser 3D printer; Processing parameter is: power 850w, sweep velocity 5.94mm/s, defocusing amount 6mm, overlapping rate 32%, powder feeding rate 6g/min, and preparation process adopts argon shield; For avoiding the existence of otherness, XY plane origin coordinate place is got back in laser apparatus continuous sweep 4 layers, every layer of Z axis miles of relative movement 1mm; Fig. 1 is laser scans path schematic diagram, the first layer is prepared by Fig. 1 (a) the 1st layer of path, the second layer is prepared on the first layer by Fig. 1 (b) the 2nd layer of path, third layer is prepared on the second layer by Fig. 1 (c) the 3rd layer of path, third layer prepares the 4th layer by Fig. 1 (d) the 4th layer of path, so circulates through multilayer and print the biological bone matrix material that solid is tieed up in formation 3.
Embodiment 5
A kind of biological bone matrix material, by CoCrMo powdered alloy, CeO
2powdered alloy and ZrO
2powdered alloy is composited; Wherein, by mass percentage, CoCrMo powdered alloy: CeO
2powdered alloy: ZrO
2powdered alloy=94: 1: 5, in table 1; CoCrMo powder diameter scope 100 ~ 200 order, CeO
2powder diameter scope 0.5 ~ 1 μm, ZrO
2powder diameter scope 30 ~ 80nm, three kinds of powder are spherical morphology; Adopt medical grade CoCrMo alloys powder, chemical composition is by mass percentage: w (Cr)=26%, w (Mo)=6%, w (W)=5%, w (Si)=1%, w (Fe)=0.8%, w (C)=0.02%, surplus are Co.
The preparation method of biological bone matrix material of the present invention, specific as follows:
Step 1, the batch mixing of composite powder:
(1) 5g cetyl trimethylammonium bromide is mixed with ethylene glycol solution be placed in the beaker of 500mL, mechanical stirring, rotating speed 500 turns/min, stir 15min, form mixing solutions;
(2) form according to the quality of biological bone matrix material, take 5gCeO
2powdered alloy and 25gZrO
2powdered alloy, adds open glass container, continues 60min, forms dispersion.
(3) according to biological bone matrix material quality composition, take 470gCoCrMo powdered alloy and add Glass Containers, after stirring 10h, leave standstill 24h, go to upper strata to contain alveolate solution, leave lower floor's mixture;
(4) by lower floor's mixture, 80h is dried at 80 DEG C, after drying completely, at 150 DEG C, insulation 30min.
(5) by the powder mull after oven dry, cross 100 mesh sieves, form biological bone complex alloy powder.
Step 2, the body material pre-treatment that laser direct deposition is shaped:
Baseplate material is Q235, Q235 steel plate is cut into the block of 10cm × 20cm × 1cm, eliminates rust and oxide skin to its surface with emery wheel, makes its surface-brightening clean; Polish to its surface with No. 100 sand paper, use 400, No. 800 sand paper treat surface afterwards respectively, last acetone is dispelled greasy dirt, and chlorohydric acid pickling, totally dries up for subsequent use with alcohol rinse;
Step 3, laser direct deposition is shaped:
Use the semiconductor laser 3D printer of FL-Dlight02-3000w, processing parameter is: power 1350w, sweep velocity 5mm/s, defocusing amount 8mm, overlapping rate 35%, powder feeding rate 5g/min, and preparation process adopts argon shield; For avoiding the existence of otherness, XY plane origin coordinate place is got back in laser apparatus continuous sweep 4 layers, every layer of Z axis miles of relative movement 0.8mm; Fig. 1 is laser scans path schematic diagram, the first layer is prepared by Fig. 1 (a) the 1st layer of path, the second layer is prepared on the first layer by Fig. 1 (b) the 2nd layer of path, third layer is prepared on the second layer by Fig. 1 (c) the 3rd layer of path, third layer prepares the 4th layer by Fig. 1 (d) the 4th layer of path, so circulates through multilayer and print the biological bone matrix material that solid is tieed up in formation 3.
Below in conjunction with embodiment 1 ~ 5, the biological bone composite property prepared is introduced:
Figure 14 ~ 18 are respectively different content ZrO
2the Metallograph of biological bone matrix material, in preparing product microtexture, flawless gas hole defect generates, fine microstructures, CeO
2there is the effect of crystal grain thinning.As can be seen from Figure 14 to Figure 18, along with ZrO
2increasing of content, tissue odds's evenness of alloy increases, and mixed and disorderly state is more and more obvious.Add 1%ZrO
2after, alloy structure is more evenly having a small amount of dendritic structure, and it is thicker that overlapping regions tissue compares other regional organizations, and majority is equiaxed grain structure.Work as ZrO
2when content rises to 2%, there is rectangular column crystal and the dendritic structure of obvious bulk zone in alloy structure.Work as ZrO
2when content increases to 3% and 4%, the mixed and disorderly degree of tissue is more obvious, has minority dendritic growth direction perpendicular to most of dendritic growth direction.Work as ZrO
2when content is increased to 5%, occur a small amount of hole after alloy completes, reason is ZrO
2content is too much, affects powder feeding link in Alloy by Laser forming process, causes powder sending quantity uneven, simultaneously ZrO
2in laser forming process, part is melted decomposition and provides O element, and to make in forming process the more gas of bad student, be not able to do in time discharge before solidifying cooling.
Figure 19 adds different content ZrO
2the grain-size statistical graph of biological bone matrix material, along with ZrO
2increasing of content, the grain-size of laser direct deposition shaping sample increases to some extent, wherein 1%ZrO
2the grain-size of sample is minimum is 1.3 μm.
Figure 20 is different content ZrO
2the XRD analysis of biological bone matrix material.As can be seen from Fig., the position at all peaks does not have anything to change, and only has the passivation that the peak of about 70 ° becomes.In sample, dominant has mutually: α-Co, ε-Co, Cr
23c
6and Mo
2c.
Figure 21 adds different content ZrO
2the microhardness analysis of biological bone matrix material.Found out along with ZrO by figure
2the increase of content, the microhardness of alloy reduces gradually.
Figure 22 adds different content ZrO
2the wear map of biological bone matrix material, add 3%ZrO as can be seen from Fig.
2average abrasion amount minimum 0.0482g, 1%ZrO
2average abrasion amount be 0.0496g, 2%ZrO
2three abrasion losies comparatively evenly but its average abrasion amount more greatly 0.0538g, 5%ZrO
2average abrasion amount be up to 0.0532g.
Figure 23 is different content ZrO
2the polarization curve of biological bone matrix material in manual simulation's saliva, table 5 is different content ZrO
2the polarization curve analysis of biological bone matrix material in pH=3.0 simulate saliva, table 6 is different content ZrO
2the polarization curve analysis of biological bone matrix material in pH=6.8 simulate saliva.Find by scheming and showing contrast, 1%ZrO
2sample corrosion current density is minimum, and corrosion potential is the highest simultaneously, in the artificial simulate saliva of the neutrality of pH=6.8, adds 1%ZrO
2the corrosion resisting property of alloy best.
Therefore, along with nanometer ZrO
2the increase grain-size of content increases, hardness reduces gradually, and corrosion resisting property reduces, and comprehensive wear resisting property, determines ZrO
2optimum component prescription be 1%.Namely containing 1%CeO
2and 1%ZrO
2complex alloy powder laser direct deposition be shaped sample there is good over-all properties.
Table 5 different content ZrO
2the polarization curve analysis of biological bone matrix material in pH=3.0 simulate saliva
Table 6 is different content ZrO
2the polarization curve analysis of biological bone matrix material in pH=6.8 simulate saliva
Claims (8)
1. a biological bone matrix material, is characterized in that, described biological bone matrix material is by CoCrMo powdered alloy, CeO
2powdered alloy and ZrO
2powdered alloy is composited; Wherein, by mass percentage, CoCrMo powdered alloy: CeO
2powdered alloy: ZrO
2powdered alloy=(92 ~ 98): (1 ~ 3): (1 ~ 5); Described CoCrMo powder diameter scope 100 ~ 200 order, CeO
2powder diameter scope 0.5 ~ 1 μm, ZrO
2powder diameter scope 30 ~ 80nm, three kinds of powder are spherical morphology.
2. biological bone matrix material according to claim 1, it is characterized in that, the chemical composition of described CoCrMo powdered alloy is by mass percentage: w (Cr)=25 ~ 27%, w (Mo)=5 ~ 7%, w (W)=4 ~ 6%, w (Si)=0.5 ~ 1.2%, w (Fe)=0.8 ~ 1.2%, w (C)=0.02 ~ 0.05%, surplus is Co.
3. biological bone matrix material according to claim 1, is characterized in that, described biological bone matrix material has the weave construction of flawless gas hole defect.
4. a preparation method for biological bone matrix material, is characterized in that, comprises the steps:
Step 1, the batch mixing of composite powder:
(1) cetyl trimethylammonium bromide is mixed with ethylene glycol solution be placed in open glass container, mechanical stirring, rotating speed 300 ~ 500 turns/min, stir 15 ~ 20min; Wherein, cetyl trimethylammonium bromide is 0.005 ~ 0.01g/mL in the concentration of ethylene glycol solution;
(2) form according to the quality of biological bone matrix material, take CeO
2powdered alloy and ZrO
2powdered alloy, adds open glass container, Keep agitation 40 ~ 80min;
(3) form according to the quality of biological bone matrix material, take CoCrMo powdered alloy and add open glass container, after stirring 7 ~ 10h, leave standstill 20 ~ 30h, go to upper strata to contain alveolate solution, leave lower floor's mixture;
(4) by lower floor's mixture, at temperature 80 ~ 95 DEG C, 60 ~ 80h is dried, after drying completely, at 140 ~ 160 DEG C, insulation 20 ~ 60min;
(5) by the powder mull after oven dry, cross 100 mesh sieves, form biological bone complex alloy powder;
Step 2, the body material pre-treatment that laser direct deposition is shaped:
Baseplate material is Q235, through rust cleaning, surface finish, to deoil and after pickling, for subsequent use with alcohol washes;
Step 3, laser direct deposition is shaped:
Adopt laser 3D printer, processing parameter is: power 840 ~ 1450w, sweep velocity 4 ~ 8mm/s, defocusing amount 6 ~ 10mm, overlapping rate 30 ~ 35%, powder feeding rate are 5 ~ 8g/min, protection of inert gas; Laser apparatus continuous sweep n layer gets back to XY plane origin coordinate place, n be greater than 1 natural number, every layer of Z axis miles of relative movement 0.6 ~ 1mm; Print formation 3 through multilayer and tie up three-dimensional biological bone matrix material.
5. the preparation method of biological bone matrix material according to claim 4, is characterized in that, adopts drying baker to dry in described step 1 in (4).
6. the preparation method of biological bone matrix material according to claim 4, it is characterized in that, in described step 2, Q235 first eliminates rust to its surface with emery wheel, makes its surface-brightening clean, then carries out surface treatment with 100 ~ No. 1000 sand paper to it, acetone is dispelled greasy dirt, chlorohydric acid pickling, finally clean with alcohol rinse, dry up for subsequent use.
7. the preparation method of biological bone matrix material according to claim 4, is characterized in that, in described step 3, rare gas element is argon gas.
8. the preparation method of biological bone matrix material according to claim 4, is characterized in that, in described step 3, XY plane origin coordinate place is got back in laser apparatus continuous sweep 4 layers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510695976.XA CN105256174B (en) | 2015-10-22 | 2015-10-22 | A kind of biological bone composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510695976.XA CN105256174B (en) | 2015-10-22 | 2015-10-22 | A kind of biological bone composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105256174A true CN105256174A (en) | 2016-01-20 |
| CN105256174B CN105256174B (en) | 2017-03-29 |
Family
ID=55096099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510695976.XA Active CN105256174B (en) | 2015-10-22 | 2015-10-22 | A kind of biological bone composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105256174B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106319289A (en) * | 2016-08-29 | 2017-01-11 | 深圳市圆梦精密技术研究院 | Co-Cr-W alloy and processing method and application thereof |
| CN111996415A (en) * | 2020-07-02 | 2020-11-27 | 俞光锋 | Cobalt-chromium alloy biological material and preparation method thereof |
| CN112404454A (en) * | 2020-10-28 | 2021-02-26 | 西北工业大学 | Laser additive manufacturing method of NiTi alloy with large recoverable strain |
| CN114939656A (en) * | 2022-05-31 | 2022-08-26 | 南昌航空大学 | Method for improving performance of laser additive manufacturing alloy steel by adding rare earth oxide |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020018851A1 (en) * | 2000-06-21 | 2002-02-14 | Edward Chang | Manufacturing method for surgical implants having a layer of bioactive ceramic coating |
| JP2009108336A (en) * | 2007-10-26 | 2009-05-21 | Mitsubishi Materials Corp | MANUFACTURING METHOD OF Co-BASE SINTERED ALLOY SPUTTERING TARGET FOR FORMING MAGNETIC RECORDING FILM OF LOW RELATIVE MAGNETIC PERMEABILITY |
| US20100016987A1 (en) * | 2008-07-16 | 2010-01-21 | Zimmer, Inc. | Thermally treated ceramic coating for implants |
| CN102990058A (en) * | 2012-12-18 | 2013-03-27 | 江苏新亚特钢锻造有限公司 | Oxide particle reinforced laser-clad high abrasion resistance cobalt-base alloy powder and preparation method thereof |
| CN103667800A (en) * | 2013-12-06 | 2014-03-26 | 中国航空工业集团公司北京航空材料研究院 | Precise forging method for CoCrMo alloy artificial joint |
-
2015
- 2015-10-22 CN CN201510695976.XA patent/CN105256174B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020018851A1 (en) * | 2000-06-21 | 2002-02-14 | Edward Chang | Manufacturing method for surgical implants having a layer of bioactive ceramic coating |
| JP2009108336A (en) * | 2007-10-26 | 2009-05-21 | Mitsubishi Materials Corp | MANUFACTURING METHOD OF Co-BASE SINTERED ALLOY SPUTTERING TARGET FOR FORMING MAGNETIC RECORDING FILM OF LOW RELATIVE MAGNETIC PERMEABILITY |
| US20100016987A1 (en) * | 2008-07-16 | 2010-01-21 | Zimmer, Inc. | Thermally treated ceramic coating for implants |
| CN102990058A (en) * | 2012-12-18 | 2013-03-27 | 江苏新亚特钢锻造有限公司 | Oxide particle reinforced laser-clad high abrasion resistance cobalt-base alloy powder and preparation method thereof |
| CN103667800A (en) * | 2013-12-06 | 2014-03-26 | 中国航空工业集团公司北京航空材料研究院 | Precise forging method for CoCrMo alloy artificial joint |
Non-Patent Citations (4)
| Title |
|---|
| YUNZHI YANG等: "Deposition of highly adhesive ZrO2 coating on Ti and CoCrMo implant materials using plasma spraying", 《BIOMATERIALS》 * |
| 刘剑敏: "氧化锆制备及氧化锆和Co-Cr-Mo合金烧结行为研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 郑玉峰等: "《生物医用材料学》", 31 August 2005, 哈尔滨工业大学出版社 * |
| 陈玉勇等: "TiAl基金属间化合物熔模密铸造研究进展", 《金属学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106319289A (en) * | 2016-08-29 | 2017-01-11 | 深圳市圆梦精密技术研究院 | Co-Cr-W alloy and processing method and application thereof |
| CN106319289B (en) * | 2016-08-29 | 2018-06-15 | 深圳市圆梦精密技术研究院 | Co-Cr-W alloys and its processing method and application |
| CN111996415A (en) * | 2020-07-02 | 2020-11-27 | 俞光锋 | Cobalt-chromium alloy biological material and preparation method thereof |
| CN111996415B (en) * | 2020-07-02 | 2021-04-27 | 中怡(深圳)医疗科技集团有限公司 | Cobalt-chromium alloy biological material and preparation method thereof |
| CN112404454A (en) * | 2020-10-28 | 2021-02-26 | 西北工业大学 | Laser additive manufacturing method of NiTi alloy with large recoverable strain |
| CN114939656A (en) * | 2022-05-31 | 2022-08-26 | 南昌航空大学 | Method for improving performance of laser additive manufacturing alloy steel by adding rare earth oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105256174B (en) | 2017-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Corrosion behavior and characteristics of passive films of laser powder bed fusion produced Ti–6Al–4V in dynamic Hank’s solution | |
| Kong et al. | Bio-functional and anti-corrosive 3D printing 316L stainless steel fabricated by selective laser melting | |
| Wang et al. | Effects of laser polishing on surface microstructure and corrosion resistance of additive manufactured CoCr alloys | |
| Shuai et al. | Selective laser melted Fe-Mn bone scaffold: microstructure, corrosion behavior and cell response | |
| Stango et al. | Development of hydroxyapatite coatings on laser textured 316 LSS and Ti-6Al-4V and its electrochemical behavior in SBF solution for orthopedic applications | |
| Araghi et al. | Fabrication and characterization of functionally graded hydroxyapatite/TiO2 multilayer coating on Ti–6Al–4V titanium alloy for biomedical applications | |
| CN105256174A (en) | Biotic bone composite material and preparing method thereof | |
| Liens et al. | Effect of alloying elements on the microstructure and corrosion behavior of TiZr-based bulk metallic glasses | |
| Yamanaka et al. | Developing high strength and ductility in biomedical Co–Cr cast alloys by simultaneous doping with nitrogen and carbon | |
| Bernhardt et al. | Surface conditioning of additively manufactured titanium implants and its influence on materials properties and in vitro biocompatibility | |
| Ma et al. | Pulsed laser deposition of magnesium-containing bioactive glass film on porous Ti–6Al–4V substrate pretreated by micro-arc oxidation | |
| Ribeiro et al. | Dense and porous titanium substrates with a biomimetic calcium phosphate coating | |
| Zhou et al. | Microstructural evolution, corrosion behavior and cytotoxicity of Ti-6Al-4V/ZrO2 composite fabricated by directed energy deposition for implant biomaterial | |
| Safdar | A study on electron beam melted ti-6al-4v | |
| Suresh et al. | Processing & Characterization of LENSTM Deposited Co-Cr-W Alloy for Bio-Medical Applications | |
| Naji et al. | Investigations of structure and properties of layered bioceramic HA/TiO2 and ZrO2/Tio2 coatings on Ti-6Al-7Nb alloy by micro-arc oxidation | |
| Drnovšek et al. | Hydrothermal synthesis of a nanocrystalline anatase layer on Ti6A4V implants | |
| Behjat et al. | Enhanced surface properties and bioactivity of additively manufactured 316L stainless steel using different post-treatments | |
| Al-Murshdy et al. | Investigation of the effect of indium addition on the mechanical and electrochemical properties of the Ti–15Mo biomedical alloy | |
| Goldberg et al. | Fine-tuning effect of Direct Laser Interference Patterning on the surface states and the corrosion behavior of a biomedical additively manufactured beta Ti alloy | |
| Wang et al. | Effects of soft sparking on micro/nano structure and bioactive components of microarc oxidation coatings on selective laser melted Ti6Al4V alloy | |
| CN108468001A (en) | Fine copper toughening bio-medical titanium-based metallic glass composite and preparation method thereof | |
| Kowalski et al. | Influence of 45S5 Bioglass addition on microstructure and properties of ultrafine grained (Mg-4Y-5.5 Dy-0.5 Zr) alloy | |
| CN111979541B (en) | Titanium alloy with Ti-Nb alloy coating and preparation method and application thereof | |
| Xu et al. | Additive manufacturing of anti-bacterial and low-cost Ti–Mo (–Ag) alloys using elemental powders through in situ laser alloying |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |