CN101967613B - Titanium-based metal glass/hydroxyapatite composite material and preparation method thereof - Google Patents

Titanium-based metal glass/hydroxyapatite composite material and preparation method thereof Download PDF

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CN101967613B
CN101967613B CN2010105221873A CN201010522187A CN101967613B CN 101967613 B CN101967613 B CN 101967613B CN 2010105221873 A CN2010105221873 A CN 2010105221873A CN 201010522187 A CN201010522187 A CN 201010522187A CN 101967613 B CN101967613 B CN 101967613B
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titanium
metal glass
powder
metal
sintering
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CN101967613A (en
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朱胜利
杨贤金
崔振铎
陈翠杰
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Tianjin University
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Tianjin University
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Abstract

The invention relates to a titanium-based metal glass/hydroxyapatite composite material and a preparation method thereof. The composite material consists of titanium-based metal glass and hydroxyapatite in a mass ratio. The preparation method comprises the following processes of: weighing pure metals Ti, Zr, Cu and Pd according to the atomic ratio of elements in the titanium-based metal glass components, and smelting the pure metals into a titanium-based metal glass master alloy; melting the titanium-based metal glass master alloy in an atomic gas atomization device, then performing high-speed ejection and granulation, mixing the titanium-based metal glass powder and the hydroxyapatite powder in a mass ratio after grading, pressing the mixture into a blank, and sintering the blank in an electric spark sintering device to obtain the titanium-based metal glass/hydroxyapatite composite material. The method has the advantages of low temperature and quickness because the electric spark device is adopted in the sintering process; and the prepared composite material has low elastic modulus and good biological and mechanical properties of recoverable strain and biocompatibility.

Description

Titanium-based metal glass/hydroxyapatite composite material and preparation method thereof
Technical field
The present invention relates to a kind of titanium-based metal glass/hydroxyapatite composite material and preparation method thereof, belong to metallic glass based composites technology.
Background technology
The metal medical material is used as hard tissue alternate material usually.Osseous tissue with human body is compared, but the common metal material has high Young's modulus and little recovery strain, and this can cause not matching between embedded material and osseous tissue, produces stress shielding, causes to implant to lose efficacy.Metal glass material is to obtain a kind of type material that many scholars pay close attention to over the past two decades, but its HS, high-wearing feature, low elastic modulus and big recovery strain make metal glass material have good application prospects in technical field of biological material.The requirement that biomaterial must satisfy is an excellent biological compatibility.Win 40350 has composition and the structure close with the body bone tissue inanimate matter, does not have cytotoxicity, therefore has excellent biocompatibility.But the low strength of Win 40350 makes and can not it be directly applied to the body bone tissue replacement that need bear complex stress.Many in recent years researchists have carried out preparing at metal material surface the research of hydroxyapatite coating layer; But combining of hydroxyapatite coating layer and metallic matrix is a problem of making us perplexing always; Coming off of coating can directly cause implanting inefficacy, thereby causes the treatment failure.
Matrix material have single-material incomparable over-all properties, its structure and properties more approaches tissue, the compound bio biomimetic material will be one of most active fields of biomaterial research from now on.There has been the scholar to carry out the research of titanium/hydroxyapatite biological material in recent years, and obtained certain achievement.Yet owing to receive the restriction of high temperature crystallization, traditional powder sintered method can not be applicable to the preparation of the matrix material of metallic glass matrix.Electric spark sintering has low temperature characteristics fast, is an important directions of metal glass material molding research in the last few years.Present research focuses on the densification of sintering metal glass material more or forms nanocrystalline composite material, also rarely has report about the composite study of metallic glass/inorganic particulate.Electric spark sintering is the mixed powder stack discharge power supply at hot pressed metallic glass and Win 40350, because the good electrical conductivity of metal-powder can sudden discharge bond between powder, thereby reaches the agglomerating purpose.And because discharge occurs in very little zone, particle contact position, instantaneous heat can be released very soon, and is unlikely to influence metallic glass particulate amorphous structure.
Summary of the invention
The object of the invention provides a kind of titanium-based metal glass/hydroxyapatite composite material and preparation method thereof.But described matrix material has the biomechanical property and the biocompatibility of low elastic modulus and good recovery strain, and its preparation method has the quick characteristics of low temperature.
The present invention realizes that through following technical proposals a kind of titanium-based metal glass/hydroxyapatite composite material is characterized in that, this matrix material is made up of following component and quality percentage composition thereof:
Titanium-based metal glass (Ti 40Zr 10Cu 36Pd 14): 90-99.999%;
Win 40350: 0.001-10%.
Above-mentioned titanium-based metal glass/hydroxyapatite composite material preparation method is characterized in that comprising following process:
1) atomic ratio by Ti, Zr, Cu and Pd in the titanium-based metal glass ingredient is 40: 10: 36: 14; Take by weighing pure metal Ti, Zr, Cu and Pd; Add in the high vacuum arc-melting furnace and carry out melting; When alloy molten becomes liquid state, kept 5-10 minute, be cooled to room temperature then and form titanium-based metal glass mother alloy;
2) at the titanium-based metal glass mother alloy that under the argon shield atmosphere step 1) is made in atom aerosolization equipment after the fusion; With pressure 0.5MPa-5MPa argon gas titanium-based metal glass mother alloy liquid at high speed is sprayed; And under argon shield, be cooled to room temperature; Make the titanium-based metal glass powder, the sizing screen with micron carries out sieve classification to the titanium-based metal glass powder again, obtains the titanium-based metal glass powder of different-grain diameter scope;
3) be (90-99.999) by the titanium-based metal glass powder of different-grain diameter scope and the mass ratio of hydroxylapatite powder: (0.001-10) both are carried out pre-mixing; In the V-type mixer, mixed 10-12 hour with rotating speed 60-90 rev/min then, it is that 50MPa-100MPa is cold-pressed into blank with pressure that the powder of titanium-based metal glass that mixes and Win 40350 is put into the wolfram varbide formwork for cylindrical columns;
4) the step 3) blank is put into the electric spark sintering device together with mould, under argon shield, being 360 ℃-390 ℃ with temperature is that 200MPa-600MPa carried out sintering 5-20 minute with pressure, obtains titanium-based metal glass/hydroxyapatite composite material.
The invention has the advantages that; In metallic glass/hydroxyapatite composite material; Homodisperse Win 40350 has improved the biocompatibility of metallic biomaterial mutually, but the low elastic modulus of metallic glass matrix and good recovery strain have guaranteed biomechanical property, so metallic glass/hydroxyapatite composite material has the incomparable advantage of traditional metal biomaterial; Occur in very little zone, particle contact position owing to discharge when adopting electric spark sintering; Instantaneous heat can be released very soon, and is unlikely to influence the amorphous structure of metallic glass, thereby its mechanical property is guaranteed; The compressive strength of titanium-based metal glass/hydroxyapatite composite material is 150MPa-1500MPa; Modulus of compression is 30GPa-80GPa, is lower than traditional implantation and uses titanium alloy, and this matrix material has excellent biological compatibility in anthropomorphic dummy's liquid solution.
Description of drawings
Fig. 1 is the prepared titanium-based metal glass powder electron scanning micrograph of the embodiment of the invention 1.
Fig. 2 is the prepared titanium-based metal glass/hydroxyapatite composite material optical microscope photograph of the embodiment of the invention 1.
Fig. 3 is the prepared titanium-based metal glass/hydroxyapatite composite material optical microscope photograph of the embodiment of the invention 2.
Fig. 4 is for being soaked in the embodiment of the invention 1 prepared titanium-based metal glass/hydroxyapatite composite material the electron scanning micrograph that reaches among the SBF after 7 days.
Embodiment
Embodiment 1
Mix greater than 99.9% pure Ti (43.5g), Zr (20.7g), Cu (51.9), Pd (33.8g) with purity, become mother alloy 5 times in the abundant melting of high vacuum arc-melting furnace.With Ti 40Zr 10Cu 36Pd 14Mother alloy places the lower end that the silica tube of Φ 2 apertures is arranged; Under the environment of argon shield, use the radio-frequency induction coil heat fused; Molten alloy is sprayed from the silica tube upper end with 5MPa high pressure argon gas then, 8 high-pressure jet mouths that are provided with below the silica tube simultaneously are the inject high pressure argon gas simultaneously, with the alloy aerosolization; Produce the effect of chilling simultaneously, make Ti 40Zr 10Cu 36Pd 14The metallic glass powder.
The Ti that said process is prepared 40Zr 10Cu 36Pd 14The metallic glass powder carries out size fractionation screening according to particle, and the titanium-based metal glass powder 49g that chooses particle diameter and be 45 μ m-63 μ m mixes less than 120 μ m hydroxyapatite powder 1g with granularity, mixing 12 hours in the V-type mixer then.In tungsten carbide die, is 50MPa with the pressing pressure with mixed part powder, is pressed into the cylinder blank of Φ 15mm, and charge length is 20mm.Mould and blank be placed in the SPS-3.20MK-IV type discharge plasma sintering system carry out sintering, sintering temperature is 380 ℃, and sintering pressure is 600MPa, and sintering time is 10min.Titanium-based metal glass/the hydroxyapatite composite material that makes.Fig. 2 is made sample optical microscope photograph.
Embodiment 2
Taking by weighing particle diameter prepared among the embodiment 1 is the Ti of 45 μ m-63 μ m 40Zr 10Cu 36Pd 14Metallic glass powder 47.5g takes by weighing granularity less than 120 μ m hydroxyapatite powder 2.5g, after it is mixed, in the V-type mixer, mixes 12 hours then.In tungsten carbide die, is 60MPa with the pressing pressure with mixed part powder, is pressed into the cylinder blank of Φ 15mm, and charge length is 20mm.Mould and blank be placed in the SPS-3.20 MK-IV type discharge plasma sintering system carry out sintering, sintering temperature is 390 ℃, and sintering pressure is 550MPa, and sintering time is 20min, the titanium-based metal glass/hydroxyapatite composite material that makes.Fig. 3 is made sample optical microscope photograph.
Embodiment 3
Titanium-based metal glass/the hydroxyapatite composite material of preparation among the embodiment 1 is placed anthropomorphic dummy's liquid solution (SBF), kept 7 days down at 37 ℃, its surface obtains the spherical calcium-phosphate layer of thorn of uniform deposition.Fig. 4 is the titanium-based metal glass/hydroxyapatite composite material surface topography optical microscope photograph that in SBF, soaks after 7 days.

Claims (1)

1. titanium-based metal glass/hydroxyapatite composite material preparation method, this matrix material is made up of following component and quality percentage composition thereof: Ti 40Zr 10Cu 36Pd 14: 90-99.999%; Win 40350: 0.001-10%; It is characterized in that comprising following process:
1) atomic ratio by Ti, Zr, Cu and Pd in the titanium-based metal glass ingredient is 40: 10: 36: 14; Take by weighing pure metal Ti, Zr, Cu and Pd; Add in the high vacuum arc-melting furnace and carry out melting; When alloy molten becomes liquid state, kept 5-10 minute, be cooled to room temperature then and form titanium-based metal glass mother alloy;
2) at the titanium-based metal glass mother alloy that under the argon shield atmosphere step 1) is made in atom aerosolization equipment after the fusion; With pressure 0.5MPa-5MPa argon gas titanium-based metal glass mother alloy liquid at high speed is sprayed; And under argon shield, be cooled to room temperature; Make the titanium-based metal glass powder, the sizing screen with micron carries out sieve classification to the titanium-based metal glass powder again, obtains the titanium-based metal glass powder of different-grain diameter scope;
3) be (90-99.999) by the titanium-based metal glass powder of different-grain diameter scope and the mass ratio of hydroxylapatite powder: (0.001-10) both are carried out pre-mixing; In the V-type mixer, mixed 10-12 hour with rotating speed 60-90 rev/min then, it is that 50MPa-100MPa is cold-pressed into blank with pressure that the powder of titanium-based metal glass that mixes and Win 40350 is put into the wolfram varbide formwork for cylindrical columns;
4) the step 3) blank is put into the electric spark sintering device together with mould, under argon shield, being 360 ℃-390 ℃ with temperature is that 200MPa-600MPa carried out sintering 5-20 minute with pressure, obtains titanium-based metal glass/hydroxyapatite composite material.
CN2010105221873A 2010-10-28 2010-10-28 Titanium-based metal glass/hydroxyapatite composite material and preparation method thereof Active CN101967613B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3542925A1 (en) 2018-03-20 2019-09-25 Heraeus Additive Manufacturing GmbH Production of a metallic solid glass composite material using powder-based, additive manufacturing

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CN104357697B (en) * 2014-12-08 2016-09-14 湖北工业大学 The method utilizing the fine and close biological titanium alloy of discharge plasma sintering method preparation
CN110952042A (en) * 2018-09-27 2020-04-03 天津大学 Zirconium-based pseudo-high-entropy amorphous alloy material without aluminum element and preparation method thereof
CN111363988B (en) * 2020-04-09 2021-04-16 山东大学 TiCuZrPdNi amorphous composite material and preparation method thereof

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3542925A1 (en) 2018-03-20 2019-09-25 Heraeus Additive Manufacturing GmbH Production of a metallic solid glass composite material using powder-based, additive manufacturing

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