CN109464286B - Layered dental titanium alloy material and preparation method thereof - Google Patents
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/84—Preparations for artificial teeth, for filling teeth or for capping teeth comprising metals or alloys
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
-
- B22F1/0003—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
- C22C1/0458—Alloys based on titanium, zirconium or hafnium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/248—Thermal after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2207/00—Aspects of the compositions, gradients
- B22F2207/01—Composition gradients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Abstract
The invention belongs to the field of false tooth manufacturing, and particularly relates to a layered dental titanium alloy material and a preparation method thereof. The layered dental titanium alloy material comprises, by total mass, 100 parts of a raw material 1 positioned on an upper layer, a raw material 2 positioned on a bottom layer and a transition layer positioned on a middle layer, wherein the raw material comprises 35-45 parts of pure titanium and 55-65 parts of titanium alloy; the raw material 1 is 20-24 parts of pure titanium material, the raw material 2 is 33-34.2 parts of titanium alloy material, and the transition layer is composed of the remaining parts of pure titanium and titanium alloy; the grain size of the pure titanium and the titanium alloy is 100-120 nm. The top end of the alloy material is made of pure titanium material, has low mechanical strength, is used for manufacturing the cutting end and the occlusal surface of the false tooth, is in contact with the jaw, and has small abrasion to natural teeth. The middle part and the bottom part have higher strength, and the artificial tooth has good mechanical property and can bear larger occlusal force as a main body structure of the artificial tooth; the biocompatibility is good.
Description
Technical Field
The invention belongs to the field of false tooth manufacturing, and particularly relates to a layered dental titanium alloy material and a preparation method thereof.
Background
At present, the metal materials for repairing the oral dentures are mainly cobalt-chromium alloy, pure titanium and titanium alloy. The cobalt-chromium alloy has low price, and the conventional process, namely casting process, adopted when the material is used for producing the false tooth is simpler and has low failure rate, and meanwhile, the cobalt-chromium alloy can form good combination with the existing porcelain powder, so the cobalt-chromium alloy is widely applied to the oral industry. However, the cobalt-chromium alloy contains harmful elements such as nickel, has high density, is rough in casting process, and the like, so that the situations of poor biocompatibility, strong foreign body sensation in the mouth, non-adhesion at the edge and the like occur.
Pure titanium and titanium alloy materials have good biocompatibility, low density and good processability, and thus the application range of dentistry is continuously expanded. When the pure titanium and titanium alloy materials are initially used for manufacturing false teeth, a casting process is adopted to manufacture a metal full anatomical crown or a metal inner crown (the outer layer is subjected to porcelain baking process treatment). However, the melting point of the titanium alloy is very high, and meanwhile, the molten titanium liquid is very active in chemical property, and is easy to react with other substances to lose the original physicochemical property, more impurities are brought by the chemical reaction, and the biocompatibility is reduced. In addition, due to the inaccuracy of the casting process, the bonding strength between titanium and titanium alloy and the existing porcelain powder is low, the porcelain feeding operation is complex, and the porcelain breaking condition in the mouth in the later period is serious. Titanium alloys have high strength and much higher hardness than natural teeth, causing greater wear on natural teeth of the jaw. The above reasons result in that the application of titanium and its alloy materials in dentistry is greatly inhibited.
The dental titanium alloy has the advantages that due to the characteristics of good biocompatibility, corrosion resistance, small density and the like, the dental titanium alloy can not be substituted by other materials in the medical industry, and the market and the industry are not selected to give up. However, the current situation is changed by urgently needing a titanium material which can be applied to a high-precision machining process and is more in line with the requirements of human bodies. The introduction of CAD/CAM technology into dentistry has laid a good foundation for this change. With the aid of the mechanical industry, the principle of numerically controlled cutting machines. Dental pure titanium disks and dental titanium alloy disks appear on the market. The method comprises the steps of manufacturing titanium and titanium alloy materials into a circular disc-shaped structure which can be clamped by a numerical control cutting machine, importing tooth three-dimensional data which are designed through CAD into cutting software, performing typesetting and calculation, and then cutting. Due to the mature and accurate numerical control process, virtual three-dimensional data can be truly converted into a real object. The method solves the problems of poor precision and unmatched original teeth in the mouth caused by casting technology. However, each specification and model of the dental titanium material is made of the same titanium material. The market is mainly dominated by pure titanium with the designation TA2 and titanium alloy with the designation TC 4. Different materials are selected according to different requirements. Pure titanium has very high purity, very low impurity content, good biocompatibility, low hardness and strength and good toughness, and is mainly suitable for movable stents and full-anatomical metal crowns. The titanium alloy is added with elements such as aluminum, vanadium and the like, so that the mechanical strength of the material is improved, the titanium alloy is suitable for repairing types such as metal crown bridges, rod clamps and bridge frames which are stressed more, but the abrasion to natural teeth is increased simultaneously due to the increase of the hardness of the titanium alloy.
In conclusion, there is a need in the industry for a titanium material that has good biocompatibility, low density, and a weak foreign body sensation, can withstand a large biting force, and has low abrasion to natural teeth.
Disclosure of Invention
The invention aims to provide a layered dental titanium alloy material and a preparation method thereof.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a layered dental titanium alloy material comprises, by total mass, 100 parts of 35-45 parts of pure titanium and 55-65 parts of titanium alloy; the particle size of the pure titanium and the titanium alloy is 100-120 nm;
the pure titanium comprises the following elements in percentage by mass: fe is less than or equal to 0.3 percent, C is less than or equal to 0.1 percent, N is less than or equal to 0.05 percent, H is less than or equal to 0.015 percent, O is less than or equal to 0.25 percent, other impurities are less than or equal to 0.4 percent, and the balance is Ti;
the titanium alloy comprises the following elements in percentage by mass: al is more than or equal to 5.5 percent and less than or equal to 6.75 percent, V is more than or equal to 3.5 and less than or equal to 4.5 percent, Fe is less than or equal to 0.3 percent, C is less than or equal to 0.08 percent, N is less than or equal to 0.05 percent, H is less than or equal to 0.015 percent, O is less than or equal to 0.2 percent, the rest impurities are less than or equal to 0..
Preferably, in the pure titanium, except Ti, other elements account for less than or equal to 0.01 percent of the total weight.
Preferably, in the titanium alloy, 5.5 percent to 6.5 percent of Al, 3.5 percent to 4 percent of V and the balance of Ti are contained.
Correspondingly, the method for preparing the layered dental titanium alloy material comprises the following steps:
(1) respectively weighing 20-24 parts of pure titanium and 33-34.2 parts of titanium alloy by total mass of 100 parts as raw materials 1 and 2; weighing the residual pure titanium and titanium alloy, uniformly mixing the pure titanium and the titanium alloy to be used as a transition layer raw material;
(2) sequentially putting the raw materials into a die according to the sequence of the raw material 2, the transition layer raw material and the raw material 1, keeping the pressure of 50-60 tons for more than 0.5h, and preliminarily pressing the raw materials into an alloy material with a required shape;
(3) sealing the alloy material, putting the alloy material into liquid, applying 200-230 tons of pressure to the liquid, and keeping the pressure for more than 1 hour;
(4) and then putting the alloy material into a vacuum annealing furnace, heating to 960-1200 ℃ at the speed of 10 ℃/m, preserving the heat for 4-6 hours, naturally cooling, and then machining according to the requirement.
Preferably, the specific preparation method of the transition layer raw material in the step (1) comprises the following steps:
weighing 5-7 parts of pure titanium and 5-7 parts of titanium alloy, wherein the pure titanium and the titanium alloy are equal in quantity, and uniformly mixing the pure titanium and the titanium alloy to serve as a raw material 3; weighing 5-7 parts of pure titanium and 7.5-10.5 parts of titanium alloy, wherein the mass ratio of pure titanium: titanium alloy 1:1.5, and uniformly mixing the titanium alloy and the titanium alloy to obtain a raw material 4; weighing 5-7 parts of pure titanium and 9.5-13.3 parts of pure titanium according to the mass ratio: titanium alloy 1:1.9, and uniformly mixing the titanium alloy and the titanium alloy to obtain a raw material 5;
the sequence of putting into the mould is as follows in sequence: raw material 2, raw material 5, raw material 4, raw material 3 and raw material 1.
Preferably, the raw material 3 is divided into two parts of 1:3 by weight, namely a raw material 31 and a raw material 32; dividing the raw material 4 into three parts of 1:1:2, namely a raw material 41, a raw material 42 and a raw material 43; dividing the raw material 5 into two parts of 1:3, namely a raw material 51 and a raw material 52; pouring 31, 41, 42 and 51 raw materials into a mold respectively, keeping the pressure of 10-20 tons for 5-10 min, and pressing into a first connection layer, a second connection layer, a third connection layer and a fourth connection layer respectively, wherein at least one connection structure is arranged on each of the upper surface and the lower surface of each connection layer;
the sequence of putting into the mould is as follows in sequence: raw material 2, fourth tie layer, raw material 52, third tie layer, raw material 43, second tie layer, raw material 32, first tie layer, raw material 1.
Preferably, each connecting layer is in a fishbone shape.
Preferably, the specific method for uniformly mixing comprises the following steps: pouring the powder into a liquid medium with the volume at least twice of the total amount of the powder, drying the powder in an environment with the temperature less than or equal to 65 ℃ while carrying out ultrasonic vibration for more than or equal to 10min, and removing all the liquid medium to obtain the required uniformly mixed raw material; the liquid medium neither reacts with nor dissolves pure titanium and titanium alloys.
Preferably, the liquid medium is deionized water.
The invention has the following beneficial effects:
1. although titanium and titanium alloy have better biocompatibility, and also have the advantages of corrosion resistance, small density and the like, pure titanium has the problems of lower hardness and strength and the like, and the application place is limited. The titanium alloy with the elements of aluminum, vanadium and the like added in the pure titanium has good mechanical property, overcomes partial defects of the pure titanium, and has the problems of increasing abrasion to natural teeth and the like because of higher strength.
The invention has simple formula, only uses common pure titanium and titanium alloy, provides the dental titanium alloy with hardness and softness under the condition of not adding other special materials, and simultaneously meets the requirements of complex and contradictory false teeth; and the preparation process of the invention is very simple and easy to realize. The top end of the finally obtained alloy material is made of pure titanium material, has low mechanical strength, is used for manufacturing the incised end and the occlusal surface of the false tooth, is in contact with the jaw, and has small abrasion to the natural tooth. The middle part and the bottom part have higher strength, and the artificial tooth has good mechanical property and can bear larger occlusal force as a main body structure of the artificial tooth; the biocompatibility is good.
2. In the prior art, the improvement of titanium alloy for dental use or the improvement of metal alloy provides an alloy with uniformly distributed elements, and the more uniformly distributed elements are desired to be better, but the alloy has single characteristics and cannot simultaneously have multiple performances. The invention overcomes the technical bias in the field, and creatively provides a layered dental titanium alloy material with non-uniform distribution of elements, so that the layered dental titanium alloy material has different characteristics at different positions.
3. If the pure titanium and the titanium alloy are simply combined, the fault condition of the joint can occur, the joint is not tightly combined, and the performance breakpoint can easily occur in the using process. The invention also provides a method for carrying out good transition combination on the pure titanium and the titanium alloy, which enlarges the junction of the pure titanium and the titanium alloy from two dimensions to three dimensions and from single side to three dimensions, thereby effectively avoiding the fault problem of the junction. Meanwhile, the pure titanium and the titanium alloy at the combination part form a new transition material, so that the titanium alloy has the characteristics of the pure titanium and the titanium alloy and also has a certain buffering effect.
Drawings
FIG. 1 is a schematic view of a tie layer structure according to the present invention;
FIG. 2 is a schematic diagram of a preferred tie layer structure of the present invention;
FIG. 3 is a schematic view of the structure between the alloy layers according to the present invention.
Detailed Description
1. The invention relates to a formula: the formula comprises 35-45 parts of pure titanium and 55-65 parts of titanium alloy according to 100 parts of the total weight. The pure titanium and the titanium alloy are both powder, and the particle size is 100-120 nm. If the particle size is too large, the particles cannot be uniformly distributed, and the initial strength is low and the mechanical property is poor after molding; if the particle size is too small, the flowability is too poor, and molding under pressure is difficult.
The particle size of the raw material powder sold on the market is about 40nm generally, the raw material powder is very uneven, the raw material powder is difficult to form by direct pressing, the uniformity is very low, and the requirement of the invention cannot be met. Therefore, if commercially available pure titanium and titanium alloy are used, the powder and the liquid colloid are mixed uniformly according to the mass ratio of 1:1, then the coarse powder is obtained by a spray drying method, and then the coarse powder is sieved to obtain the raw material with the required particle size. The liquid colloid comprises the following components in percentage by mass: 5% of polyvinyl alcohol, 1% of sodium carbonate (dispersant) and the balance of water. The present invention is not limited to the use of this method, but is not limited to providing a method for obtaining the desired particle size.
(1) Pure titanium containing no impurity element is preferable, but pure titanium containing a certain amount of impurities may be used in consideration of its high price and low availability in daily use. For convenience of operation, for example, the mainstream titanium on the market is TA 2. Through detection, the pure titanium comprises the following elements in percentage by mass: fe is less than or equal to 0.3 percent, C is less than or equal to 0.1 percent, N is less than or equal to 0.05 percent, H is less than or equal to 0.015 percent, O is less than or equal to 0.25 percent, the sum of other impurity elements is less than or equal to 0.4 percent, the single content is less than or equal to 0.1 percent, and the balance is Ti. In principle, the object of the invention can be achieved as long as the mass of pure titanium is not less than the mass of TA2 mentioned above.
(2) The titanium alloy preferably only contains three elements of Al, Ti and V, and according to the mass fraction, 5.5 percent to 6.5 percent of Al, 3.5 percent to 4 percent of V, and the balance of Ti. Considering that the cost may be high if only such an alloy is used, a titanium alloy containing a certain impurity may be used. Such as the mainstream titanium alloy on the market today, under the designation TC 4. Through detection, the titanium alloy comprises the following elements in percentage by mass: al is more than or equal to 5.5 percent and less than or equal to 6.75 percent, V is more than or equal to 3.5 percent and less than or equal to 4.5 percent, Fe is less than or equal to 0.3 percent, C is less than or equal to 0.08 percent, N is less than or equal to 0.05 percent, H is less than or equal to 0.015 percent, O is less than or equal to 0.2 percent, the sum of the other impurity elements is less than or equal to 0.4 percent, the single impurity element is. The titanium alloy with quality superior to or equal to TC4 can achieve the aim of the invention.
2. The preparation method comprises the following steps:
(1) respectively weighing 20-24 parts of pure titanium and 33-34.2 parts of titanium alloy as raw materials 1 and 2; weighing 5-7 parts of pure titanium and 5-7 parts of titanium alloy (the pure titanium and the titanium alloy are equivalent), and uniformly mixing to obtain a raw material 3; weighing 5-7 parts of pure titanium and 7.5-10.5 parts of titanium alloy (the mass ratio of the pure titanium to the titanium alloy is 1:1.5), and uniformly mixing to obtain a raw material 4; weighing 5-7 parts of pure titanium and 9.5-13.3 parts of titanium alloy (the mass ratio of the pure titanium to the titanium alloy is 1:1.9), and uniformly mixing to obtain a raw material 5.
The concrete method for uniformly mixing comprises the following steps: pouring the raw material powder of pure titanium and titanium alloy to be uniformly mixed into deionized water with the volume at least twice of the total amount of the powder, or pouring other liquid media which does not react with the pure titanium and the titanium alloy, does not dissolve the pure titanium and the titanium alloy and is easy to evaporate/sublimate, drying at low temperature (less than or equal to 65 ℃) while carrying out ultrasonic vibration after 10min of ultrasonic vibration, and removing all the liquid media to obtain the required uniformly mixed raw material. Of course, when water is used as the liquid medium, it may be removed by direct lyophilization, for example, using a commercially available metal powder lyophilizer or the like. Of course, a general kneading method such as direct stirring and kneading may be used, but the effect is not as good as the above method.
(2) Dividing the raw material 3 into two parts of 1:3, namely a raw material 31 and a raw material 32; dividing the raw material 4 into three parts of 1:1:2, namely a raw material 41, a raw material 42 and a raw material 43; the raw material 5 is divided into two parts of 1:3, namely a raw material 51 and a raw material 52. The raw materials 31, 41, 42 and 51 are poured into a mold respectively, and are kept for 5-10 min by using 10-20 tons of pressure, and are pressed into a first connecting layer, a second connecting layer, a third connecting layer and a fourth connecting layer respectively as shown in figure 1. At least one connecting structure is arranged on the upper surface and the lower surface of each connecting layer. As shown in FIG. 2, each tie layer is preferably arranged in a fishbone-like configuration to provide a tight bond with the remaining layers during subsequent operations.
(3) As shown in fig. 3, the raw materials are sequentially placed into a die according to the sequence of the raw material 2, the fourth connecting layer, the raw material 52, the third connecting layer, the raw material 43, the second connecting layer, the raw material 32, the first connecting layer and the raw material 1, and the raw materials are preliminarily pressed into the layered dental titanium alloy material with the required shape by using a pressure of 50-60 tons and keeping the pressure for more than 0.5 h.
Of course, in the steps (2) and (3), the pure titanium and the titanium alloy left after the raw materials 1 and 2 are weighed can also be directly and uniformly mixed to be used as the raw material of the intermediate transition layer, and then the raw material 2, the raw material of the transition layer and the raw material 3 are directly poured into a mould for pressing. However, the layered dental titanium alloy material prepared by the method is easy to generate fault, and the effect is not as stable as that of the layered dental titanium alloy material prepared by the method.
(4) Sealing the layered dental titanium alloy material, putting the sealed layered dental titanium alloy material into liquid, applying 200-230 tons of pressure to the liquid, and keeping the pressure for more than 1 hour to ensure that the bonding is more uniform and compact; according to the required compactness of the false tooth, the raw material with the total amount of 100g can be prepared into 24-25 cm3The layered dental titanium alloy material.
The sealing can be realized by directly placing the layered dental titanium alloy material into a plastic bag for vacuum sealing, and the liquid is biodegradable hydraulic oil, such as plant hydraulic oil or synthetic hydraulic oil.
(5) And (3) putting the layered dental titanium alloy material into a vacuum annealing furnace, heating to 960 ℃ at a speed of 10 ℃/min under the protection of argon, heating to 1200 ℃ at a speed of 5 ℃/min, and preserving heat for 4-6 hours.
(6) And after the alloy material is annealed, reducing the temperature to be below 200 ℃ at the speed of 10 ℃/min, and then naturally cooling to obtain the required alloy material. The layered dental titanium alloy material prepared by the method has a compact internal structure, the transition region is not a simple combined single-layer structure, but a three-dimensional transition region formed by new alloys with different lattices, and the whole layered dental titanium alloy material has natural internal transition, tight combination and certain buffering capacity. Meanwhile, the minimum density in the whole layered dental titanium alloy material is increased to 4.5g/cm3。
(7) And then machining the layered dental titanium alloy material to reach the required size. Generally, denture materials need to be machined to the precise size and shape that the engraving and milling equipment can hold, for example, 98mm phi, with a 2mm step.
The invention is further illustrated by the following specific examples.
The first embodiment is as follows: effect of impurities on the Properties of layered dental titanium alloy materials
1. The 20 combined gold material is prepared by the formula and the method, wherein in the uniformly mixing method, the liquid medium is water, the drying method is low-temperature drying, and the structure of each connecting layer is a fishbone-shaped structure. And (3) in the vacuum annealing furnace, the heat preservation temperature is 1100 ℃, and the heat preservation time is 4.5 h.
Specific pure titanium and titanium alloys used in each group are shown in table 1, wherein the values are in mass percent and elements below 0.01% are considered as ignored. Pure titanium: the ratio of the titanium alloy is, for example, 9:13 by mass, i.e., 45 parts of pure titanium and 65 parts of titanium alloy per 100 parts of the total amount.
TABLE 1 detailed parameter tables for each group
2. The 20 groups of titanium alloys are prepared to be 5 multiplied by 5cm3The test results are shown in Table 2. Wherein, the wear resistance is represented by hardness and is detected by GB/T231.1-2009. The applicant finds in practice that the hardness of the alloy material on the upper surface is controlled to be 200-290 HB, the mechanical property requirement can be met, and the abrasion to natural teeth is minimum. Because of individual differences, the hardness suitable for each person is different, and generally speaking, the upper surface of the layered dental titanium alloy material can achieve better effect when controlled within the hardness range. The embodiment also provides a plurality of schemes, can provide different hardness, and can produce titanium alloys with different hardness in specific work so as to adapt to different conditions.
The hardness of the lower surface of the layered dental titanium alloy material is controlled to be 293-360 HB, and the effect is better when the hardness approaches 360HB (namely the maximum hardness approaches the maximum hardness of a common TC4 titanium alloy); the higher the hardness is, the higher the strength is, the larger the force can be borne by the smaller thickness during processing, meanwhile, the higher the hardness is, the toughness is correspondingly reduced, the cutter is not easy to adhere during processing, the processing difficulty is reduced, and the processing precision is improved.
Table 2 demonstration of the properties of each group
Example two: effect of index Process on titanium alloy Properties
1. 17 sets of layered dental titanium alloy materials were prepared using the above formulation and method, with the formulation selected from group 1 of example one. The specific preparation processes and parameters of each group are shown in table 3; wherein, the prepressing refers to that all the connecting layers are manufactured firstly and then are pressed and formed, and the non-prepressing refers to that all the raw materials are added in sequence and then are directly pressed and formed.
TABLE 3 Process parameters for the respective groups
2. The above 17 groups of titanium alloys were prepared to 5X 5cm3The test results are shown in Table 4.
Table 4 demonstration of the properties of each group
Claims (10)
1. A layered dental titanium alloy material, characterized in that: the layered dental titanium alloy material comprises, by total mass, 100 parts of a raw material 1 positioned on an upper layer, a raw material 2 positioned on a bottom layer and a transition layer positioned on a middle layer, and comprises 35-45 parts of pure titanium and 55-65 parts of titanium alloy; the raw material 1 is 20-24 parts of pure titanium material, the raw material 2 is 33-34.2 parts of titanium alloy material, and the transition layer is composed of the remaining parts of pure titanium and titanium alloy;
the particle size of the pure titanium and the titanium alloy is 100-120 nm;
the pure titanium comprises the following elements in percentage by mass: fe is less than or equal to 0.3 percent, C is less than or equal to 0.1 percent, N is less than or equal to 0.05 percent, H is less than or equal to 0.015 percent, O is less than or equal to 0.25 percent, other impurities are less than or equal to 0.4 percent, and the balance is Ti;
the titanium alloy comprises the following elements in percentage by mass: al is more than or equal to 5.5 percent and less than or equal to 6.75 percent, V is more than or equal to 3.5 and less than or equal to 4.5 percent, Fe is less than or equal to 0.3 percent, C is less than or equal to 0.08 percent, N is less than or equal to 0.05 percent, H is less than or equal to 0.015 percent, O is less than or equal to 0.2 percent, the rest impurities are less than or equal to 0.;
the preparation method of the layered dental titanium alloy material comprises the following steps:
(1) the total mass of the raw materials is calculated by 100 parts, and comprises 35-45 parts of pure titanium and 55-65 parts of titanium alloy; respectively weighing 20-24 parts of pure titanium and 33-34.2 parts of titanium alloy as raw materials 1 and 2; weighing the residual parts by mass of pure titanium and titanium alloy as the raw materials of the transition layer;
(2) sequentially putting the raw materials into a die according to the sequence of the raw material 2, the transition layer raw material and the raw material 1, keeping the pressure of 50-60 tons for more than 0.5h, and preliminarily pressing the raw materials into an alloy material with a required shape;
(3) sealing the alloy material, putting the alloy material into liquid, applying 200-230 tons of pressure to the liquid, and keeping the pressure for more than 1 hour;
(4) and then putting the alloy material into a vacuum annealing furnace, heating to 960-1200 ℃ at the speed of 10 ℃/m, preserving the heat for 4-6 hours, naturally cooling, and then machining according to the requirement.
2. The layered dental titanium alloy material according to claim 1, wherein: in the pure titanium, except Ti, other elements account for less than or equal to 0.01 percent of the total weight.
3. The layered dental titanium alloy material according to claim 1 or 2, wherein: in the titanium alloy, 5.5 percent to 6.5 percent of Al, 3.5 percent to 4 percent of V and the balance of Ti.
4. A method for preparing the layered dental titanium alloy material according to any one of claims 1 to 3, wherein: the method comprises the following steps:
(1) respectively weighing 20-24 parts of pure titanium and 33-34.2 parts of titanium alloy by total mass of 100 parts as raw materials 1 and 2; weighing the residual parts by mass of pure titanium and titanium alloy as the raw materials of the transition layer;
(2) sequentially putting the raw materials into a die according to the sequence of the raw material 2, the transition layer raw material and the raw material 1, keeping the pressure of 50-60 tons for more than 0.5h, and preliminarily pressing the raw materials into an alloy material with a required shape;
(3) sealing the alloy material, putting the alloy material into liquid, applying 200-230 tons of pressure to the liquid, and keeping the pressure for more than 1 hour;
(4) and then putting the alloy material into a vacuum annealing furnace, heating to 960-1200 ℃ at the speed of 10 ℃/m, preserving the heat for 4-6 hours, naturally cooling, and then machining according to the requirement.
5. The method of making the layered dental titanium alloy material of claim 4, wherein: and (4) the liquid in the step (3) is biodegradable hydraulic oil.
6. The method of making the layered dental titanium alloy material of claim 4, wherein: the specific preparation method of the transition layer raw material in the step (1) comprises the following steps:
weighing 5-7 parts of pure titanium and 5-7 parts of titanium alloy, wherein the pure titanium and the titanium alloy are equal in quantity, and uniformly mixing the pure titanium and the titanium alloy to serve as a raw material 3; weighing 5-7 parts of pure titanium and 7.5-10.5 parts of titanium alloy, wherein the mass ratio of pure titanium: titanium alloy 1:1.5, and uniformly mixing the titanium alloy and the titanium alloy to obtain a raw material 4; weighing 5-7 parts of pure titanium and 9.5-13.3 parts of titanium alloy, wherein the mass ratio of pure titanium: titanium alloy 1:1.9, and uniformly mixing the titanium alloy and the titanium alloy to obtain a raw material 5;
in the step (2), the sequence of putting the mold is as follows: raw material 2, raw material 5, raw material 4, raw material 3 and raw material 1.
7. The method of making the layered dental titanium alloy material of claim 6, wherein: dividing the raw material 3 into two parts of 1:3 by weight, namely a raw material 31 and a raw material 32; dividing the raw material 4 into three parts of 1:1:2, namely a raw material 41, a raw material 42 and a raw material 43; dividing the raw material 5 into two parts of 1:3, namely a raw material 51 and a raw material 52; pouring 31, 41, 42 and 51 raw materials into a mold respectively, keeping the pressure of 10-20 tons for 5-10 min, and pressing into a first connection layer, a second connection layer, a third connection layer and a fourth connection layer respectively, wherein at least one connection structure is arranged on each of the upper surface and the lower surface of each connection layer;
the sequence of putting into the mould is as follows in sequence: raw material 2, fourth tie layer, raw material 52, third tie layer, raw material 43, second tie layer, raw material 32, first tie layer, raw material 1.
8. The method of making the layered dental titanium alloy material of claim 7, wherein: each connecting layer is in a fishbone shape.
9. The method of producing the layered dental titanium alloy material according to any one of claims 4 to 8, wherein: the concrete method for uniformly mixing comprises the following steps: pouring the required uniformly mixed substances into a liquid medium with the volume at least twice of the total volume of the substances to be uniformly mixed, drying the substances in an environment with the temperature of less than or equal to 65 ℃ while performing ultrasonic vibration for more than or equal to 10min, and removing all the liquid medium to obtain the required uniformly mixed raw materials; the liquid medium neither reacts with nor dissolves pure titanium and titanium alloys.
10. The method of making the layered dental titanium alloy material of claim 9, wherein: the liquid medium is deionized water.
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Denomination of invention: A layered dental titanium alloy material and its preparation method Effective date of registration: 20210604 Granted publication date: 20200424 Pledgee: Chengdu SME financing Company Limited by Guarantee Pledgor: CHENGDU BESMILE BIOTECHNOLOGY Co.,Ltd. Registration number: Y2021510000085 |