CN109881044B - A kind of high-hardness and high-wear-resistant titanium alloy and its preparation method and application - Google Patents
A kind of high-hardness and high-wear-resistant titanium alloy and its preparation method and application Download PDFInfo
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Abstract
本发明公开了一种高硬高耐磨钛合金及其制备方法和应用，其化学组成为TiaPtbMc，其中，M为Pd、Au、Ag、Rh中的至少一种，且70 at.%≤a≤75 at.%，24 at.%≤b≤30 at.%，1 at.%≤c≤5 at.%，另外，a+b+c=100 at.%，本发明选择以Ti、Pt二元合金为基础，进一步合金化Pd、Au、Ag、Rh等元素，可显著提高合金硬度，由于所选择的合金化元素具有较高的化学稳定性，因此能改善合金的耐腐蚀性和生物相容性；并且，其主晶相为Ti3Pt金属间化合物，其显微硬度值大于700 Hv，远高于纯钛及传统医用钛合金，能有效缓解耐磨性差的问题；另外，Pt、Pd、Au、Ag、Rh等为贵金属元素，具有较高的化学稳定性，在生理环境中具有高的耐腐蚀性，能有效降低离子析出，降低生物毒性。The invention discloses a high-hardness and high-wear-resistant titanium alloy and a preparation method and application thereof. The chemical composition is Ti a Pt b Mc , wherein M is at least one of Pd, Au, Ag and Rh, and 70 at.%≤a≤75 at.%, 24 at.%≤b≤30 at.%, 1 at.%≤c≤5 at.%, in addition, a+b+c=100 at.%, the present invention Based on Ti and Pt binary alloys, further alloying Pd, Au, Ag, Rh and other elements can significantly improve the hardness of the alloy. Due to the high chemical stability of the selected alloying elements, it can improve the alloy's hardness. Corrosion resistance and biocompatibility; in addition, its main crystalline phase is Ti 3 Pt intermetallic compound, and its microhardness value is greater than 700 Hv, much higher than pure titanium and traditional medical titanium alloys, which can effectively alleviate the problem of poor wear resistance. In addition, Pt, Pd, Au, Ag, Rh and other precious metal elements have high chemical stability and high corrosion resistance in physiological environment, which can effectively reduce ion precipitation and reduce biological toxicity.
Description
Technical Field
The invention relates to the field of alloy materials and manufacturing thereof, in particular to a high-hardness high-wear-resistance titanium alloy and a preparation method and application thereof.
Background
In addition to numerous applications in the industrial, automotive and aerospace fields, titanium and titanium alloys are also widely used in biomedical implant materials to replace or repair damaged hard tissues of patients. A plurality of in vitro and in vivo biocompatibility experimental researches on different grades of titanium materials show that the commercial pure titanium can spontaneously form a high-inertia and stable oxide layer and is a biological material with excellent biocompatibility. In addition, titanium and titanium alloys have high specific strength and low ion deposition levels in aqueous solutions, and these properties have also promoted their use in biomedical materials. In addition, titanium is one of the few materials with osteointegration capability. These properties have led to the widespread use of titanium in devices such as artificial knee and hip joints, screws and shunts for fracture fixation, bone plates, pacemakers, and heart valve prostheses. Titanium is also commonly used in the dental field, including implants and their components, such as inlays, crowns, covers, etc.
However, pure titanium is not strong enough to meet the requirements of many medical devices, and therefore, it is necessary to develop a high-quality alloy material. Although the strength and hardness of titanium can be improved by alloying other metal elements, care must be taken to maintain the biocompatibility of titanium. Reported studies have shown that alloying with copper or silver can increase the hardness of titanium by a factor of two. The use of alloying elements with the same valence as copper and silver but with higher mass density results in higher valence electron density, which may result in higher bond strength and thus increased hardness. This finding indicates that gold is a suitable alloying candidate in titanium binary alloys because it has almost twice the density of copper or silver. The gold-based implant materials that are currently in widespread use demonstrate their biocompatibility and corrosion resistance.
In pursuit of higher mechanical properties and biocompatibility, the development of new titanium-based alloy systems is a research focus of researchers. Platinum, gold, palladium and silver belong to noble metals, and have similar chemical properties, the density of platinum is equivalent to that of gold, and the chemical stability, the biological corrosion resistance and the biocompatibility of platinum are superior to those of gold elements, but no research report on high-hardness titanium-platinum series alloy exists at present.
At present, medical pure titanium and titanium alloy have low hardness and poor wear resistance, and the wide application of the medical pure titanium and the titanium alloy in the biomedical field is limited. The hardness and wear resistance of titanium and titanium alloys can be improved by alloying elements, but some metal elements, such as Cu or Ni, can reduce the corrosion resistance and biocompatibility of the titanium alloy.
Disclosure of Invention
Aiming at the condition of the prior art, the invention aims to provide a high-hardness and high-wear-resistance titanium alloy and a preparation method and application thereof, the titanium alloy is a novel titanium-based alloy, elements such as palladium, gold, silver, rhodium and the like are further alloyed on the basis of binary titanium-platinum alloy, and the alloy crystal phase is mainly Ti3The Pt intermetallic compound has ultrahigh hardness, wear resistance and excellent biocompatibility, and shows good application prospect in the field of biomedical implant materials.
In order to achieve the technical purpose, the invention adopts the technical scheme that:
a high-hardness high-wear-resistance titanium alloy is characterized in that: the chemical composition of which is TiaPtbMcWherein M isAt least one of Pd, Au, Ag, Rh, and 70 at ≦ a ≦ 75 at.%, 24 at ≦ b ≦ 30 at.%, 1 at ≦ c ≦ 5 at.%, and, in addition, a + b + c =100 at.%.
Preferably, M is Pd, Au, Ag and Rh composition, wherein a =71 at.%, b =25 at.%, c =1 at.%; the chemical composition of the titanium alloy is Ti71Pt25Pd1Au1Ag1Rh1。
Further, the hardness of the titanium alloy is more than 700 Hv.
A preparation method of a high-hardness and high-wear-resistance titanium alloy comprises the following steps:
(1) weighing: calculating the proportion of the addition parts of the components according to the atomic percentage of the chemical composition, and correspondingly weighing the components;
(2) putting the components weighed in the step (1) into a vacuum smelting furnace, and then adjusting the degree of vacuum pumping to 5 multiplied by 10-3Pa, then filling argon as protective gas, wherein the pressure of the argon is 0.05 Mpa; then setting the equipment current to be 50-200A and the smelting temperature to be 1000-2000K, then carrying out smelting treatment for at least 4 times, and cooling the prepared product along with the furnace after the smelting treatment is finished, thus obtaining the titanium alloy.
The application of the high-hardness and high-wear-resistance titanium alloy is to apply the titanium alloy to biomedical implant materials and medical instruments.
By adopting the technical scheme, compared with the prior art, the invention has the beneficial effects that: the invention further alloys elements such as Pd, Au, Ag, Rh and the like on the basis of Ti and Pt binary alloy, can obviously improve the alloy hardness, and can improve the corrosion resistance and biocompatibility of the alloy because the selected alloying elements have higher chemical stability; and, its main crystal phase is Ti3The microscopic hardness value of the Pt intermetallic compound is more than 700 Hv, which is much higher than that of pure titanium and traditional medical titanium alloy, so that the problem of poor wear resistance can be effectively alleviated; in addition, the selected alloying elements are Pt, Pd, Au, Ag, Rh and the like which are noble metal elements, have higher chemical stability, have high corrosion resistance in physiological environment and canEffectively reduce ion separation and biological toxicity.
It is further noted that the strength and hardness of titanium can be improved by alloying other metal elements, but care must be taken to maintain the biocompatibility of titanium. Reported studies have shown that alloying with copper or silver can increase the hardness of titanium by a factor of two. The use of alloying elements with the same valence as copper and silver but with higher mass density results in higher valence electron density, which may result in higher bond strength and thus increased hardness. This finding indicates that gold is a suitable alloying candidate in titanium binary alloys because it has almost twice the density of copper or silver. Whereas the gold-based implant materials that are currently in widespread use demonstrate their biocompatibility and corrosion resistance.
In pursuit of higher mechanical properties and biocompatibility, the development of new titanium-based alloy systems is a research focus of researchers. Platinum, gold, palladium and silver belong to noble metals, and have similar chemical properties, the density of platinum is equivalent to that of gold, and the chemical stability, the biological corrosion resistance and the biocompatibility of platinum are superior to those of gold elements, but no research report on high-hardness titanium-platinum series alloy exists at present. The invention provides a novel titanium-based alloy, which is based on binary titanium-platinum alloy and further alloyed with elements such as palladium, gold, silver, rhodium and the like, wherein the alloy crystal phase is mainly Ti3Pt intermetallic compound, has ultrahigh hardness, wear resistance and excellent biocompatibility, and shows good application prospect in the field of biomedical implant materials.
Detailed Description
The scheme of the invention is further illustrated by the following specific embodiments:
a high-hardness high-wear-resistance titanium alloy is characterized in that: the chemical composition of which is TiaPtbMcWherein M is at least one of Pd, Au, Ag, Rh, and 70 at.% or more, a or less than 75 at.%, 24 at.% or more, b or more than 30 at.%, 1 at.% or more, c or less than 5 at.%, and, in addition, a + b + c =100 at.%.
Preferably, M is Pd, Au, Ag and Rh composition, wherein a =71 at.%, b =25 at.%, c =1 at.%; the titanium alloy is formedChemical composition of Ti71Pt25Pd1Au1Ag1Rh1。
Further, the hardness of the titanium alloy is more than 700 Hv.
A preparation method of a high-hardness and high-wear-resistance titanium alloy comprises the following steps:
(1) weighing: calculating the proportion of the addition parts of the components according to the atomic percentage of the chemical composition, and correspondingly weighing the components;
(2) putting the components weighed in the step (1) into a vacuum smelting furnace, and then adjusting the degree of vacuum pumping to 5 multiplied by 10-3Pa, then filling argon as protective gas, wherein the pressure of the argon is 0.05 Mpa; then setting the equipment current to be 50-200A and the smelting temperature to be 1000-2000K, then carrying out smelting treatment for at least 4 times, and cooling the prepared product along with the furnace after the smelting treatment is finished, thus obtaining the titanium alloy.
Examples
This example prepares Ti by copper mold casting71Pt25Pd1Au1Ag1Rh1Bulk amorphous alloys are an example.
Which comprises the following steps:
the method comprises the following steps: weighing each element
Calculating the proportion of each component element according to the atomic percentage of the chemical composition, and then weighing the raw materials for each element related to the component element according to the weight;
step two: smelting preparation of Ti71Pt25Pd1Au1Ag1Rh1Master alloy
Putting the required raw materials weighed in the step (1) into a vacuum smelting furnace, and adjusting the degree of vacuum pumping to 5 multiplied by 10-3Pa, filling argon protective gas with the pressure of 0.05 MPa; adjusting the current 120A and the smelting temperature 1800K; repeatedly smelting for 4 times or more than 4 times, cooling with the furnace, and taking out to obtain Ti71Pt25Pd1Au1Ag1Rh1A master alloy;
testing and sample preparation
Preparation of Ti71Pt25Pd1Au1Ag1Rh1Titanium alloy test specimen
Putting the mother alloy prepared in the second step into an induction furnace of a rapid solidification device, and adjusting the degree of vacuum pumping to 5 multiplied by 10-3Pa, filling argon protective gas with the pressure of 0.05 MPa; adjusting the current 6A and the induction temperature 1300K; and after the smelting time is 2 min, pouring the melt into a copper mold, and cooling along with the copper mold to obtain the titanium alloy bar or plate.
Cutting the prepared titanium alloy bar by wire cutting to obtain amorphous alloy plate with the specification of 10 mm multiplied by 15 mm multiplied by 2 mm, grinding and polishing the surface of a sample, carrying out X-ray phase structure test, and analyzing that the main crystal phase is Ti3A Pt intermetallic compound. The microhardness was measured to be 805 HV. A reciprocating friction and wear testing machine is adopted to carry out a friction and wear test on the sample, the normal load is 5N, the friction rate is 2 m/min, and a friction mating part is Si3N4Ceramic balls with a diameter of 6 mm. The wear rate was determined to be 5X 10-8 mm3 mm N-1. Testing the electrokinetic potential polarization curve in the PBS solution to obtain the electroerosion current density of 0.5 mA/m2。
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (3)
1. A preparation method of a high-hardness and high-wear-resistance titanium alloy is characterized by comprising the following steps: the chemical composition of which is TiaPtbMcWherein M is composed of Pd, Au, Ag and Rh, and the preparation method comprises the following steps:
(1) weighing: calculating the proportion of the addition parts of the components according to the atomic percentage of the chemical composition, and correspondingly weighing the components;
(2) weighing in the step (1)Putting the components into a vacuum smelting furnace, and then adjusting the degree of vacuum pumping to 5 multiplied by 10-3Pa, then filling argon as protective gas, wherein the pressure of the argon is 0.05 Mpa; then setting the equipment current to be 50-200A and the smelting temperature to be 1800K, then carrying out smelting treatment for at least 4 times, and cooling the prepared product along with the furnace after the smelting treatment is finished to obtain the titanium alloy, wherein the chemical composition of the prepared titanium alloy is Ti71Pt25Pd1Au1Ag1Rh1。
2. The method for preparing the high-hardness high-wear-resistance titanium alloy according to claim 1, wherein the method comprises the following steps: the hardness of the titanium alloy is 805 Hv.
3. Use of a high-hardness high-wear-resistance titanium alloy according to any one of claims 1 to 2, wherein: it is applied to biomedical implant materials and medical devices.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4139373A (en) * | 1975-11-27 | 1979-02-13 | Johnson, Matthey & Co., Limited | Alloys of titanium |
| CN102277543A (en) * | 2011-08-09 | 2011-12-14 | 北京科技大学 | Titanium-based block amorphous alloy with high palladium content and low copper content and preparation method thereof |
| CN107475596A (en) * | 2017-08-10 | 2017-12-15 | 哈尔滨工业大学 | A kind of high entropy intermetallic compound |
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| JP4128975B2 (en) * | 2004-04-02 | 2008-07-30 | 株式会社古河テクノマテリアル | Superelastic titanium alloy for living body |
| EP3040790A1 (en) * | 2014-12-29 | 2016-07-06 | Montres Breguet S.A. | Timepiece or piece of jewellery made of a light titanium-based precious alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4139373A (en) * | 1975-11-27 | 1979-02-13 | Johnson, Matthey & Co., Limited | Alloys of titanium |
| CN102277543A (en) * | 2011-08-09 | 2011-12-14 | 北京科技大学 | Titanium-based block amorphous alloy with high palladium content and low copper content and preparation method thereof |
| CN107475596A (en) * | 2017-08-10 | 2017-12-15 | 哈尔滨工业大学 | A kind of high entropy intermetallic compound |
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