CN113481408B - Powder metallurgy Ti-Zr alloy for dentistry and preparation method thereof - Google Patents
Powder metallurgy Ti-Zr alloy for dentistry and preparation method thereof Download PDFInfo
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- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910001093 Zr alloy Inorganic materials 0.000 title claims abstract description 55
- 238000004663 powder metallurgy Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 46
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 41
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000010936 titanium Substances 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 229910000734 martensite Inorganic materials 0.000 claims abstract description 13
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 238000004321 preservation Methods 0.000 claims description 20
- 238000001125 extrusion Methods 0.000 claims description 15
- 238000005096 rolling process Methods 0.000 claims description 13
- 239000000001 dental powder Substances 0.000 claims description 12
- 238000005496 tempering Methods 0.000 claims description 12
- 238000002490 spark plasma sintering Methods 0.000 claims description 7
- 238000009694 cold isostatic pressing Methods 0.000 claims description 6
- 238000007731 hot pressing Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 20
- 239000000956 alloy Substances 0.000 abstract description 16
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 229910045601 alloy Inorganic materials 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- 239000012535 impurity Substances 0.000 description 11
- 239000006104 solid solution Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 229910001069 Ti alloy Inorganic materials 0.000 description 8
- 238000005728 strengthening Methods 0.000 description 8
- 238000009864 tensile test Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 238000005098 hot rolling Methods 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 239000012856 weighed raw material Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005204 segregation Methods 0.000 description 4
- 239000004053 dental implant Substances 0.000 description 3
- 239000007943 implant Substances 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001192 hot extrusion Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 230000000399 orthopedic effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical class [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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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
-
- 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]
-
- 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
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- 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
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- 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
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
-
- 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
-
- 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
-
- 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
-
- 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
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
-
- 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
Abstract
The invention discloses a powder metallurgy Ti-Zr alloy for dentistry and a preparation method thereof, wherein the preparation method comprises the following steps: mixing titanium powder and zirconium powder according to a design proportion to obtain titanium-zirconium composite powder, sintering the titanium-zirconium composite powder to obtain a sintered body with an alpha' martensite phase Widmannstatten structure, thermally deforming the sintered body at 600-1000 ℃ to obtain a Ti-Zr alloy plate or a Ti-Zr alloy bar, wherein in the Ti-Zr alloy plate or the Ti-Zr alloy bar, the titanium is calculated according to the mass ratio: 85-95% of zirconium: 5-15; according to the invention, firstly, a sintered body with an alpha 'martensite phase Widmanschner microstructure is prepared by a powder metallurgy preparation method, then the Widmanschner microstructure is elongated and deformed by thermal deformation under a medium temperature condition on the premise of not damaging the alpha' martensite microstructure, and finally a fibrous heterostructure is formed, so that the strength and plasticity of the Ti-Zr alloy material are synchronously improved. The method has simple process, short flow and stable product performance, and is beneficial to industrial production and clinical application of dentistry.
Description
Technical Field
The invention belongs to the technical field of preparation of dental medical Ti-based materials, and particularly relates to a dental powder metallurgy Ti-Zr alloy and a preparation method thereof.
Background
The biomaterial refers to a structural material which can be implanted into a human body, is in the crossing field of material science and biomedicine, and is generally applied to implants in orthopedics and dentistry and clinical application. The dental material is different from industrial material in that it has less consumption, more specifications and strict requirement.
Compared with early gold alloy, cobalt-chromium alloy and nickel-chromium alloy, pure titanium and titanium alloy have excellent biological safety, better corrosion resistance and higher mechanical property, and are widely applied to biomedical materials, especially the field of dental implants. Originally, pure titanium was used only for the production of orthopedic and dental restorative materials and for parts with low bearing forces, for example for the production of crown bridges, but for dental implants, etc., it was slightly insufficient. Pure titanium has good corrosion resistance, but has poor rigidity, strength and abrasion resistance, so that the pure titanium cannot be applied to bearing of larger parts. Therefore, other elements are added into pure titanium to form titanium alloy so as to improve the mechanical property of the titanium alloy. In the later 70's of the 20 th century, TC4(Ti-6A1-4V) applied to aerospace materials is widely applied to surgical repair materials due to higher strength, plasticity and processability. However, in clinical application, Al and V in Ti-6Al-4V are found to be toxic to human body and are not suitable for long-term use as implants.
The element Zr belongs to a life group element without toxic and side effects on human bodies. The Ti-Zr alloy is a novel dental medical Ti alloy, has no toxicity, no allergy, no toxic or side effect on human bodies, higher strength, higher wear resistance and higher biocompatibility, and can be used as a dental biomedical material. Bernhard et al prepared a binary Ti-Zr alloy useful in clinical medicine
Institute Straumann AG, basel, switzerland), wherein the Zr content is 13-17 Zr (wt.%). Medvedev is used for dental implants, in which work the tensile strength of Ti-15Zr (wt.%) isThe values were 968MPa, about 40% higher than the minimum requirements for cp-Ti implants. But the yield strength is less than 800MPa and the uniform elongation is only 6%.
Not only can the Zr solid solution cause solid solution strengthening to strengthen the strength of the Ti alloy, but also the solid solution behavior of the Zr solid solution has an influence on the microstructure of the Ti alloy. It was found that as the solute content of Zr increases, the grains of the α -Ti alloy also become finer. However, by the powder metallurgy method, a Widmannstatten structure is formed during the transformation of alpha' martensite during the temperature reduction, which causes the segregation of Zr element. Therefore, when the strength of the Ti-Zr alloy reaches 900MPa, the elongation is less than 6 percent.
Disclosure of Invention
In view of the defects of the prior art, the first object of the invention is to provide a preparation method of a dental powder metallurgy Ti-Zr alloy, which is simple and controllable.
The second object of the present invention is to provide a dental powder metallurgy Ti-Zr alloy having both high strength and high plasticity.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the invention relates to a preparation method of a dental powder metallurgy Ti-Zr alloy, which comprises the following steps: mixing titanium powder and zirconium powder according to a designed proportion to obtain titanium-zirconium composite powder, sintering the titanium-zirconium composite powder to obtain a sintered body with an alpha' martensite phase Widmannstatten structure, thermally deforming the sintered body at 600-1000 ℃ to obtain a Ti-Zr alloy plate or a Ti-Zr alloy bar, wherein in the Ti-Zr alloy plate or the Ti-Zr alloy bar, the mass ratio of titanium: 85-95% of zirconium: 5 to 15.
The invention provides a preparation method of powder metallurgy Ti-Zr alloy, which comprises the steps of preparing a sintered body with an alpha 'martensite phase Widmanschner microstructure by a powder metallurgy method, then performing thermal deformation at a medium temperature, enabling the Widmanschner microstructure to be elongated and deformed on the premise of not damaging the alpha' martensite microstructure, finally forming a fibrous heterostructure, and hindering grain growth in the thermal deformation process by the fibrous heterostructure and performing solid solution strengthening and fine grain strengthening caused by Zr solid solution, thereby synchronously improving the strength and plasticity of the Ti-Zr alloy material.
The invention ingeniously utilizes the structure which is considered to be harmful in the prior art, and converts the structure into a favorable structure, thereby achieving the effect of improving the mechanical property of the Ti-Zr alloy material and overcoming the prejudice of the prior art.
In the invention, on one hand, the content of Zr needs to be effectively controlled, if the solid solution strengthening effect caused by too small content of Zr is not obvious enough, and too much Zr causes more oxygen to be introduced, and simultaneously, the ideal performance effect cannot be obtained, on the other hand, the thermal deformation needs to be controlled to be at the medium temperature (600 ℃ -1000 ℃), otherwise, the ideal tissue structure cannot be obtained, and finally, the performance improvement is not ideal.
In a preferred scheme, the titanium powder is hydrogenated and dehydrogenated titanium powder, the purity of the titanium powder is more than 99.9%, the particle size is less than or equal to 45 microns, and the titanium powder is preferably 25-45 microns
Preferably, the titanium powder is in an irregular shape. The inventors have found that the formability is optimal with irregular shapes.
Preferably, the zirconium powder is selected from hydrogenated dehydrogenated zirconium powder, the purity of the zirconium powder is more than 99.9%, and the particle size is less than or equal to 5 microns, and preferably 40-75 microns.
Preferably, the form of the zirconium source is irregular.
The titanium powder and the zirconium powder selected by the invention do not contain other element components except titanium and zirconium, and only contain inevitable trace oxygen elements.
Preferably, the mixing is carried out on a V-shaped mixer, and the mixing time is 240min to 480min, preferably 360 min.
In the actual operation process, the ball milling tank containing titanium powder and zirconium powder is placed in a transition bin of a glove box, argon gas is filled in the ball milling tank, mixed powder is packaged, and the whole packaging and mixing process is protected by the argon gas.
Preferably, the sintering is selected from one of spark plasma sintering, hot-press sintering and vacuum sintering.
Further preferably, the conditions of the spark plasma sintering are as follows: the pressure is 10MPa to 40MPa, and the temperature rise speed of 60 to 100 ℃/min is adopted below 950 DEG CThe rate is higher than 950 ℃ and adopts the heating rate of 40-70 ℃/min, the sintering time is 1-10 min, the sintering temperature is 900-1400 ℃, and the vacuum degree is 1 multiplied by 10-3Pa. Further preferred are: the pressure is 30MPa, the sintering time is 5min to 10min, the sintering temperature is 1200 ℃ to 1300 ℃, and the vacuum degree is 1 multiplied by 10- 3Pa。
Further preferably, the conditions of the hot press sintering are as follows: the pressure is 10MPa to 40MPa, the sintering temperature is 900 ℃ to 1400 ℃, the sintering time is 30min to 120min, and the vacuum degree is 1 multiplied by 10-3Pa. Further preferred are: the pressure is 30MPa, the sintering temperature is 1200-1300 ℃, the sintering time is 40-60 min, and the vacuum degree is 1 multiplied by 10-3Pa。
Further preferably, before the vacuum sintering, the titanium zirconium composite powder is pressed into a green body by cold isostatic pressing, wherein the conditions of the cold isostatic pressing are as follows: the pressure intensity is 150 MPa-250 MPa, and the pressure maintaining time is 1 min-10 min. Further preferred are: the pressure is 180 MPa-200 MPa, and the pressure maintaining time is 2 min-5 min; the vacuum sintering conditions are as follows: the sintering temperature is 1200-1500 ℃, the sintering time is 240-720 min, and the vacuum degree is 10-3Pa. Further preferred are: the sintering temperature is 1300-1400 ℃, the sintering time is 480min, and the vacuum degree is 10-3Pa。
In the invention, the three sintering modes are adopted, so that the material can quickly reach the compactness under the conditions, and the Zr can be fully diffused at high temperature. By utilizing Zr segregation in the process of alpha' martensite transformation, stripes with Zr-rich areas are formed in the process of transformation into Widmannstatten structure.
Under the condition of optimal pressure, the density of the sintered body can be improved, the success rate of subsequent hot working deformation is favorably improved, and the compactness of the material is ensured. Under the conditions of the preferred sintering temperature and time, the bonding capacity between the powders can be improved, the occurrence of pores and other defects can be reduced, and the formation of a uniform sintered body can be ensured.
In a preferred embodiment, when the Ti-Zr alloy sheet is prepared, the thermal deformation is medium temperature rolling, and the conditions of the medium temperature rolling are as follows: the temperature is 600-800 ℃, the heat preservation time is 10-50 min, the pass deformation is 5-10%, the inter-pass tempering temperature is 500-800 ℃, the inter-pass tempering time is 1-10 min, and the total rolling deformation is 30-80%.
The more preferable conditions for the medium temperature rolling are: the temperature is 700-750 ℃, the heat preservation time is 20-30 min, the pass deformation is 5%, the inter-pass tempering temperature is 650-750 ℃, the inter-pass tempering time is 3-5 min, and the total rolling deformation is 75%.
Preferably, when the Ti-Zr alloy bar is prepared, the thermal deformation is medium-temperature extrusion and/or medium-temperature swaging, and the medium-temperature extrusion conditions are as follows: the temperature is 800-1000 ℃, the heat preservation time is 60-180 min, and the extrusion ratio is 3-10: 1; the preferable conditions for the medium temperature extrusion are: the temperature is 900-950 ℃, the heat preservation time is 90-120 min, and the extrusion ratio is 6: 1.
The medium-temperature rotary swaging conditions are as follows: the temperature is controlled to be 800-1000 ℃, the heat preservation time is 60-180 min, and the total deformation of the rotary swaging is 50-90%. The preferable conditions of medium-temperature rotary swaging are as follows: the temperature is 900-950 ℃, the heat preservation time is 90-120 min, and the total deformation of the rotary swaging is 80%.
In the invention, by adopting medium-temperature thermal deformation, the structure can be elongated and deformed on the premise of not damaging the structure of the alpha' martensite structure, and finally a fibrous heterostructure is formed. Meanwhile, the Zr solid solution can cause solid solution strengthening and fine grain strengthening, and the fibrous heterostructure can also prevent the crystal grains from growing in the thermal deformation process, thereby improving the strength and the plasticity of the material. Whereas too low a heat distortion temperature may result in cracking of the matrix and the creation of defects, while a desired fibrous heterostructure is not obtained, while too high a heat distortion temperature may also result in recrystallization being too complete and the grains becoming coarse, thereby affecting the ability of heat distortion to control the refined structure.
Of course, other conditions also need to be effectively controlled, such as deformation, if the rolling deformation is too large, internal defects of the material are easily formed, and failure of the material is accelerated; the excessively small rolling deformation can cause incomplete elimination of pores of the material, defects still exist, the stripes with Zr-rich areas can not be fully utilized in the Widmannstatten structure process, an ideal fibrous heterostructure can be obtained, and if the heat preservation time is not well controlled, the plasticity of the material can be influenced. In conclusion, under the coordination of various parameter conditions of the thermal deformation, the Ti-Zr alloy plate or the Ti-Zr alloy bar with the lowest impurity content and the most ideal structure can be obtained, and finally the structure of the material is the most ideal, so that the dental powder metallurgy Ti-Zr alloy with high strength and high plasticity can be obtained.
The invention also provides the powder metallurgy Ti-Zr alloy for dentistry prepared by the preparation method.
Principles and advantages
The key point of the technical scheme of the invention is that a special tissue structure is obtained under the synergistic action of powder metallurgy and a subsequent thermal deformation method. By adopting a powder metallurgy method, particularly spark plasma sintering, hot-pressing sintering or cold isostatic pressing and subsequent vacuum sintering, the material can quickly reach compactness, and Zr can be fully diffused at high temperature. By utilizing Zr segregation in the process of alpha' martensite transformation, stripes with Zr-rich areas are formed in the process of transformation into Widmannstatten structure. Then, the structure is elongated and deformed through medium-temperature thermal deformation on the premise of not damaging the structure of the alpha' martensite structure, and finally a fibrous heterostructure is formed. Meanwhile, the Zr solid solution can cause solid solution strengthening and fine grain strengthening, and the fibrous heterostructure can also prevent the crystal grains from growing in the thermal deformation process, thereby improving the strength and the plasticity of the material.
Therefore, the high-strength and high-plasticity dental medical Ti-Zr alloy prepared by the technical scheme of the invention based on the powder metallurgy method can achieve the room temperature ultimate tensile strength of 733.4-1129.7 MPa, the yield strength of 712.2-1086.9 MPa and the total elongation of 14.9-26.7% in the preferable scheme. Compared with the similar preparation process in the prior art, the preparation method has the following obvious advantages:
(1) the process steps are simple, the energy consumption is low, and the utilization rate of raw materials is high.
(2) Compared with the traditional process method, the sintering temperature and the pressing pressure of the material can be more accurately controlled by adopting the powder metallurgy method for sintering, and the rapid densification and homogenization of the material are achieved.
(3) The widmannstatten structure of the alpha' martensite phase formed by the powder metallurgy method can cause Zr element segregation, and is the reason for forming a heterostructure. The special structure obtained by the powder metallurgy method can form a fibrous heterostructure through thermal deformation, and the strength and the plasticity of the material are improved.
Drawings
FIG. 1 is an XRD pattern of Ti-Zr alloys prepared according to examples 1, 2 and 3 of the present invention.
FIG. 2 is an SEM image of Ti-Zr alloys prepared according to examples 1, 2 and 3 of the present invention.
FIG. 3 is a graph of room temperature tensile curves for the preparation of Ti-Zr alloys according to examples 1, 2 and 3 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the invention provides a powder metallurgy preparation method of a dental medical Ti-Zr alloy with high strength and high plasticity, which comprises the following steps:
(1) high-purity hydrogenated and dehydrogenated titanium powder (less than or equal to 45 mu m) and hydrogenated and dehydrogenated zirconium powder (less than or equal to 75 mu m) are used as raw materials, the alloy element powder does not contain other impurities except a small amount of inevitable impurity oxygen elements, and the raw materials do not contain other element components except titanium and zirconium; weighing titanium powder and zirconium powder according to a mass ratio of 95:5, uniformly mixing the weighed raw material powder by using a V-shaped mixer for 360min, and carrying out protection by using argon in the whole process of packaging and mixing.
(2) Performing spark plasma sintering on the powder fully mixed in the step (1), controlling the pressure during sintering treatment to be 30MPa, adopting a two-stage heating method in the temperature rising process, adopting 100 ℃/min below 950 ℃, adopting 60 ℃/min above 950 ℃, controlling the sintering temperature to be 1200 ℃, controlling the heat preservation time to be 10min, and controlling the vacuum degree to be 1 x 10-3Pa, obtaining a sintered blank.
(3) And (3) carrying out medium-temperature hot rolling processing on the sintered blank prepared in the step (2), wherein the hot rolling temperature is controlled to be 750 ℃, the heat preservation time is 30min, the pass deformation is 5%, the inter-pass tempering temperature is 750 ℃, the inter-pass tempering time is 2min, and the total rolling deformation is 75%, so that the powder metallurgy Ti-5Zr alloy medium-temperature rolled plate is obtained.
(4) When the product of this example is tested by a structure observation method, the XRD pattern and SEM photograph of the powder metallurgy Ti-Zr alloy prepared in this example are respectively shown in fig. 1 and fig. 2(a), the phase is hcp single phase, and the structure is deformed widmannstatten structure.
(5) The material is tested to have the tensile strength of 733.4MPa, the yield strength of 712.2MPa, the elongation of 26.7 percent and the elastic modulus of 110.0GPa by a room-temperature tensile test under the condition of an extensometer, and the tensile curve is shown in figure 3.
Example 2:
the other conditions are the same as those in example 1, except that titanium powder and zirconium powder are weighed and mixed according to the mass ratio of 90:10, and finally the Ti-10Zr alloy is obtained.
When the product of this example is tested by a structure observation method, the XRD chart and SEM photograph of the powder metallurgy Ti-Zr alloy prepared in this example are respectively shown in fig. 1 and fig. 2(b), the phase is hcp single phase, and the structure is deformed widmannstatten structure.
The material is tested to have the tensile strength of 853.1MPa, the yield strength of 810.2MPa, the elongation of 25.2 percent and the elastic modulus of 104.0GPa by a room-temperature tensile test under the condition of an extensometer, and the tensile curve is shown in figure 3.
Example 3:
the other conditions are the same as those in example 1, except that titanium powder and zirconium powder are weighed and mixed according to the mass ratio of 85:15, and finally the Ti-15Zr alloy is obtained.
When the product of this example is tested by a structure observation method, the XRD chart and SEM photograph of the powder metallurgy Ti-Zr alloy prepared in this example are respectively shown in fig. 1 and fig. 2(b), the phase is hcp single phase, and the structure is deformed widmannstatten structure.
The material is tested to have the tensile strength of 947.7MPa, the yield strength of 927.8MPa, the elongation of 23.9 percent and the elastic modulus of 99.9GPa by a room-temperature tensile test under the condition of an extensometer, and the tensile curve is shown in figure 3.
Comparative example 1:
the other conditions are the same as those in example 1, except that titanium powder and zirconium powder are weighed and mixed according to the mass ratio of 70:30, and finally the Ti-30Zr alloy is obtained.
However, in the room-temperature tensile test, the final brittle fracture was found to have a tensile strength of 612MPa and an elongation of 2.9%. The reason is that the oxygen content of Zr powder is high, so that the whole oxygen content is high and exceeds the ductile-brittle transition point of the alpha-Ti alloy, and brittle fracture occurs.
Example 4:
the invention provides a powder metallurgy preparation method of a dental medical Ti-Zr alloy with high strength and high plasticity, which comprises the following steps:
(1) high-purity hydrogenated and dehydrogenated titanium powder (less than or equal to 45 mu m) and hydrogenated and dehydrogenated zirconium powder (less than or equal to 75 mu m) are used as raw materials, the alloy element powder does not contain other impurities except a small amount of inevitable impurity oxygen elements, and the raw materials do not contain other element components except titanium and zirconium; weighing titanium powder and zirconium powder according to a mass ratio of 85:15, uniformly mixing the weighed raw material powder by using a V-shaped mixer for 360min, and protecting by using argon in the whole process of packaging and mixing.
(2) Carrying out hot-pressing sintering on the powder fully mixed in the step (1), controlling the pressure in the sintering treatment to be 30MPa, and controlling the sintering temperatureMaking at 1200 deg.C, holding for 60min, and vacuum degree of 1 × 10-3Pa, obtaining a sintered blank.
(3) And (3) carrying out medium-temperature hot rolling processing on the sintered blank prepared in the step (2), wherein the hot rolling temperature is controlled to be 750 ℃, the heat preservation time is 30min, the pass deformation is 5%, the inter-pass tempering temperature is 750 ℃, the inter-pass tempering time is 2min, and the total rolling deformation is 75%, so that the powder metallurgy Ti-15Zr alloy medium-temperature rolled plate is obtained.
(4) The material is tested to have tensile strength of 925.7MPa, yield strength of 904.3MPa, elongation of 22.5% and elastic modulus of 98.7GPa in room temperature tensile test under the condition of an extensometer.
Example 5:
the invention provides a powder metallurgy preparation method of a dental medical Ti-Zr alloy with high strength and high plasticity, which comprises the following steps:
(1) high-purity hydrogenated and dehydrogenated titanium powder (less than or equal to 45 mu m) and hydrogenated and dehydrogenated zirconium powder (less than or equal to 75 mu m) are used as raw materials, the alloy element powder does not contain other impurities except a small amount of inevitable impurity oxygen elements, and the raw materials do not contain other element components except titanium and zirconium; weighing titanium powder and zirconium powder according to a mass ratio of 85:15, uniformly mixing the weighed raw material powder by using a V-shaped mixer for 360min, and carrying out protection by using argon in the whole process of packaging and mixing.
(2) And (2) carrying out cold isostatic pressing on the fully mixed powder in the step (1), wherein the pressure is 180MPa, and the pressing time is 2 min.
(3) Carrying out vacuum sintering on the pressed compact obtained in the step (2) in a vacuum sintering furnace, wherein the sintering temperature is 1300 ℃, the heat preservation time is 480min, and the vacuum degree is 1 multiplied by 10-3Pa, obtaining a sintered blank.
(4) And (4) carrying out medium-temperature hot rolling processing on the sintered blank prepared in the step (3), wherein the hot rolling temperature is controlled to be 750 ℃, the heat preservation time is 30min, the pass deformation is 5%, the inter-pass tempering temperature is 750 ℃, the inter-pass tempering time is 2min, and the total rolling deformation is 75%, so that the powder metallurgy Ti-15Zr alloy medium-temperature rolled plate is obtained.
(4) The material is tested to have the tensile strength of 951.2MPa, the yield strength of 932.7MPa, the elongation of 20.8 percent and the elastic modulus of 102.8GPa by a room-temperature tensile test under the condition of an extensometer.
Example 6:
the invention provides a powder metallurgy preparation method of a dental medical Ti-Zr alloy with high strength and high plasticity, which comprises the following steps:
(1) high-purity hydrogenated dehydrogenated titanium powder (less than or equal to 45 mu m) and hydrogenated dehydrogenated zirconium powder (less than or equal to 75 mu m) are used as raw materials, the alloy element powder does not contain other impurities except a small amount of inevitable impurity oxygen elements, and the raw materials do not contain other element components except titanium and zirconium; weighing titanium powder and zirconium powder according to a mass ratio of 85:15, uniformly mixing the weighed raw material powder by using a V-shaped mixer for 360min, and carrying out protection by using argon in the whole process of packaging and mixing.
(2) Performing spark plasma sintering on the powder fully mixed in the step (1), controlling the pressure during sintering treatment to be 30MPa, adopting a two-stage heating method in the temperature rising process, adopting 100 ℃/min below 950 ℃, adopting 60 ℃/min above 950 ℃, controlling the sintering temperature to be 1200 ℃, controlling the heat preservation time to be 10min, and controlling the vacuum degree to be 1 x 10-3Pa, obtaining a sintered blank.
(3) And (3) performing medium-temperature hot extrusion processing on the sintered blank prepared in the step (2), wherein the extrusion temperature is 950 ℃, the heat preservation time is 120min, and the extrusion ratio is 6:1, so as to obtain the powder metallurgy Ti-15Zr alloy medium-temperature extrusion bar.
(4) The material is tested to have the tensile strength of 932.6MPa, the yield strength of 914.5MPa, the elongation of 23.6 percent and the elastic modulus of 102.1GPa by a room-temperature tensile test under the condition of an extensometer.
Example 7:
the invention provides a powder metallurgy preparation method of a dental medical Ti-Zr alloy with high strength and high plasticity, which comprises the following steps:
(1) high-purity hydrogenated and dehydrogenated titanium powder (less than or equal to 45 mu m) and hydrogenated and dehydrogenated zirconium powder (less than or equal to 75 mu m) are used as raw materials, the alloy element powder does not contain other impurities except a small amount of inevitable impurity oxygen elements, and the raw materials do not contain other element components except titanium and zirconium; weighing titanium powder and zirconium powder according to a mass ratio of 85:15, uniformly mixing the weighed raw material powder by using a V-shaped mixer for 360min, and carrying out protection by using argon in the whole process of packaging and mixing.
(2) Performing spark plasma sintering on the powder fully mixed in the step (1), controlling the pressure during sintering treatment to be 30MPa, adopting a two-stage heating method in the temperature rising process, adopting 100 ℃/min below 950 ℃, adopting 60 ℃/min above 950 ℃, controlling the sintering temperature to be 1200 ℃, controlling the heat preservation time to be 10min, and controlling the vacuum degree to be 1 x 10-3Pa, obtaining a sintered blank.
(3) And (3) performing medium-temperature hot extrusion processing on the sintered blank prepared in the step (2), wherein the extrusion temperature is 950 ℃, the heat preservation time is 120min, and the extrusion ratio is 6:1, so as to obtain the powder metallurgy Ti-15Zr alloy medium-temperature extrusion bar.
(4) And (4) carrying out medium-temperature hot rotary swaging processing on the medium-temperature extrusion bar obtained in the step (3), wherein the rotary swaging temperature is 950 ℃, the heat preservation time is 90min, and the total rotary swaging deformation is 80%.
(5) The material is tested to have the tensile strength of 1129.7MPa, the yield strength of 1086.9MPa, the elongation of 14.9 percent and the elastic modulus of 104.1GPa by a room-temperature tensile test under the condition of an extensometer.
Claims (9)
1. A preparation method of powder metallurgy Ti-Zr alloy for dentistry is characterized in that: the method comprises the following steps: mixing titanium powder and zirconium powder according to a designed proportion to obtain titanium-zirconium composite powder, sintering the titanium-zirconium composite powder to obtain a sintered body with an alpha' martensite phase Widmannstatten structure, thermally deforming the sintered body at 600-1000 ℃ to obtain a Ti-Zr alloy plate or a Ti-Zr alloy bar, wherein in the Ti-Zr alloy plate or the Ti-Zr alloy bar, the mass ratio of titanium: zirconium = 85-95: 5-15;
the titanium powder is hydrogenated and dehydrogenated titanium powder, the purity of the titanium powder is more than 99.9%, the particle size of the titanium powder is less than or equal to 45 mu m, the zirconium powder is selected from hydrogenated and dehydrogenated zirconium powder, the purity of the zirconium powder is more than 99.9%, and the particle size of the zirconium powder is less than or equal to 75 mu m.
2. The method for preparing a dental powder metallurgy Ti-Zr alloy according to claim 1, wherein: and the mixing is carried out on a V-shaped mixer, and the mixing time is 240-480 min.
3. The method for preparing a dental powder metallurgy Ti-Zr alloy according to claim 1, wherein: the sintering is selected from one of spark plasma sintering, hot-pressing sintering and vacuum sintering.
4. The method for preparing a dental powder metallurgy Ti-Zr alloy according to claim 3, wherein: the discharge plasma sintering conditions are as follows: the pressure is 10 MPa-40 MPa, the sintering time is 1 min-10 min, the sintering temperature is 900-1400 ℃, and the vacuum degree is 1 multiplied by 10-3Pa。
5. The method for preparing a dental powder metallurgy Ti-Zr alloy according to claim 3, wherein: the hot-pressing sintering conditions are as follows: the pressure is 10MPa to 40MPa, the sintering temperature is 900 ℃ to 1400 ℃, the sintering time is 30min to 120min, and the vacuum degree is 1 multiplied by 10-3Pa。
6. The method for preparing a dental powder metallurgy Ti-Zr alloy according to claim 3, wherein: before the vacuum sintering, pressing the titanium-zirconium composite powder into a green body by adopting cold isostatic pressing, wherein the conditions of the cold isostatic pressing are as follows: the pressure is 150 MPa-250 MPa, and the pressure maintaining time is 1 min-10 min; the vacuum sintering conditions are as follows: the sintering temperature is 1200-1500 ℃, the sintering time is 240-720 min, and the vacuum degree is 10-3Pa。
7. The method for preparing a dental powder metallurgy Ti-Zr alloy according to claim 1, wherein: when the Ti-Zr alloy plate is prepared, the thermal deformation is medium temperature rolling, and the medium temperature rolling conditions are as follows: the temperature is 600-800 ℃, the heat preservation time is 10-50 min, the pass deformation is 5-10%, the inter-pass tempering temperature is 500-800 ℃, the inter-pass tempering time is 1-10 min, and the total rolling deformation is 30-80%.
8. The method for preparing a dental powder metallurgy Ti-Zr alloy according to claim 1, wherein: when the Ti-Zr alloy bar is prepared, the thermal deformation is medium-temperature extrusion and/or medium-temperature rotary swaging, and the medium-temperature extrusion conditions are as follows: the temperature is 800-1000 ℃, the heat preservation time is 60-180 min, and the extrusion ratio is 3-10: 1; the medium-temperature rotary swaging conditions are as follows: the temperature is 800-1000 ℃, the heat preservation time is 60-180 min, and the total deformation amount of rotary swaging is 50-90%.
9. The powder metallurgy Ti-Zr alloy for dentistry produced by the production method according to any one of claims 1 to 8.
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