CN109865837B - Interface bonding reinforced zinc-aluminum-titanium aluminum nitride biomedical material and preparation method thereof - Google Patents

Interface bonding reinforced zinc-aluminum-titanium aluminum nitride biomedical material and preparation method thereof Download PDF

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CN109865837B
CN109865837B CN201910288622.1A CN201910288622A CN109865837B CN 109865837 B CN109865837 B CN 109865837B CN 201910288622 A CN201910288622 A CN 201910288622A CN 109865837 B CN109865837 B CN 109865837B
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zinc
aluminum
powder
aluminum nitride
titanium
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CN109865837A (en
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帅扬
高成德
帅词俊
彭淑平
杨友文
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Jiangxi Huahu High Tech Co ltd
Jiangxi University of Science and Technology
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Jiangxi Huahu High Tech Co ltd
Jiangxi University of Science and Technology
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Abstract

The invention discloses a zinc-aluminum-titanium aluminum nitride biomedical material with strengthened interface bonding, which is prepared from the following raw materials: 78-88 wt% Zn, 7 wt% Al and 5-15 wt% Ti2AlN, taking zinc powder, aluminum powder and titanium aluminum nitride powder according to the raw materials, ball-milling for 2-4h at ball-material mass ratio of 10-30:1 and ball-milling rotation speed of 250-400r/min in a protective atmosphere to obtain zinc-aluminum-titanium aluminum nitride mixed powder, and preparing Zn-Al-Ti mixed powder with strengthened interface bonding by adopting SLM technology2AlN biomedical material; controlling the laser power to be 50-70W, the scanning speed to be 10-14mm/s, the spot diameter to be 50 mu m, the laser scanning interval to be 20-30 mu m, and the powder spreading thickness to be 0.1-0.2 mm. The invention improves the mechanical property of the zinc matrix based on the strong interface combination characteristic, and can be used for repairing human tissues.

Description

Interface bonding reinforced zinc-aluminum-titanium aluminum nitride biomedical material and preparation method thereof
Technical Field
The invention belongs to the technical field of biomedical materials, and particularly relates to interface bonding reinforced zinc-aluminum-titanium aluminum nitride (Zn-Al-Ti)2AlN) biomedical material and a preparation method thereof.
Background
An ideal bone implant material should have good biocompatibility, suitable biodegradability and excellent mechanical properties. Zinc, a new bone implant material, has attracted the attention of researchers in recent years. On the one hand, zinc is an important trace element in the human body and is involved in regulating various basic biological functions, including nucleic acid metabolism, signal transduction, apoptosis and gene expression. On the other hand, zinc has good degradation performance, and degradation products in a human body can be discharged out of the body through metabolism without causing damage to normal tissues. However, insufficient mechanical properties hinder the application of zinc in the field of bone repair.
It is a common method to improve the mechanical properties of zinc by adding alloying elements to it. The addition of aluminum to zinc can increase the tensile strength and hardness of pure zinc, but zinc-aluminum alloys have not been satisfactory considering that the mechanical support of the biodegradable implant should last for 12-24 weeks during bone repair. The addition of ceramic particles to zinc-based alloys can be another effective way to increase their strength. At present, researchers at home and abroad make a series of researches on ceramic reinforced zinc-based alloy, wherein ceramics serving as a reinforcing phase comprise zirconium oxide, silicon carbide, aluminum oxide and the like. They found that the addition of these ceramics improved the strength of the zinc alloy to varying degrees, but resulted in a significant reduction in the toughness of the zinc alloy due to poor interfacial bonding of the ceramic to the metal. Therefore, how to improve the interface bonding between the zinc alloy and the ceramic becomes a great challenge.
Disclosure of Invention
Aiming at the problems of poor mechanical property and poor interface bonding between the existing zinc-based material and ceramics, the invention provides zinc-aluminum-titanium aluminum nitride (Zn-Al-Ti) with strengthened interface bonding2AlN) biomedical material, based on strong interface combination characteristic, improves the mechanical property of a zinc matrix, has excellent biocompatibility and degradation rate, and can be used for human tissue repair.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
an interface bonding reinforced zinc-aluminum-titanium aluminum nitride biomedical material is prepared from the following raw materials:
Zn 78～88wt％；
Al 7wt％；
Ti2AlN 5～15wt％；
the method specifically comprises the following steps:
step one
Taking zinc powder, aluminum powder and titanium aluminum nitride powder according to the raw material components, and carrying out ball milling for 2-4h under the protective atmosphere at ball-material mass ratio of 10-30:1 and ball milling rotation speed of 250-400r/min to obtain zinc-aluminum-titanium aluminum nitride mixed powder;
step two
Preparing Zn-Al-Ti with interface bonding reinforcement by using the mixed powder of zinc-aluminum-titanium nitride obtained in the step one as a raw material and adopting an SLM (selective laser melting) technology in a protective atmosphere2AlN biomedical material; controlling the laser power to be 50-70W, the scanning speed to be 10-14mm/s, the spot diameter to be 50 mu m, the laser scanning interval to be 20-30 mu m, and the powder spreading thickness to be 0.1-0.2 mm.
Preferably, the interface bonding-strengthened Zn-Al-Ti2The AlN biomedical material is prepared from the following raw materials:
Zn 78～83wt％；
Al 7wt％；
Ti2AlN 10～15wt％。
as a further preferable aspect: the interface bonding strengthened Zn-Al-Ti2The AlN biomedical material is prepared from the following raw materials:
Zn 83wt％；
Al 7wt％；
Ti2AlN 10wt％。
preferably, in the step one, the ball milling conditions are as follows: the ball-material mass ratio is 20:1, the ball milling speed is 350r/min, and the ball milling lasts for 3 hours.
Preferably, in step two, the SLM technique conditions are: the laser power is controlled to be 65W, the scanning speed is 14mm/s, the diameter of a light spot is 50 mu m, the laser scanning interval is 20 mu m, and the powder spreading thickness is 0.1 mm.
Preferably, in the first and second steps, the protective atmosphere is high-purity argon with the purity of 99.999% or more.
Principle and advantages:
the interface bonding strengthened Zn-Al-Ti designed and prepared by the invention2The use of AlN biomedical materials as degradable implants has significant advantages.
The invention firstly tries to prepare Zn-Al-Ti with strengthened interface bonding by adding aluminum and aluminum titanium nitride into the biological zinc alloy by using the SLM process2AlN biomedical materials. The high energy of the laser is utilized to decompose the aluminum titanium nitride part, so that the interface combination of the aluminum titanium nitride part and the zinc alloy matrix is promoted to improve the mechanical property of the zinc alloy.
According to the invention, zinc is used as a base material, aluminum and titanium aluminum nitride are used as auxiliary materials, aluminum element enrichment is generated between the interface of the titanium aluminum nitride and a zinc matrix through the synergistic effect of a ball milling process and an SLM (selective laser melting) process, and meanwhile, the titanium aluminum nitride is uniformly dispersed and partially decomposed in the zinc matrix to promote the interface combination of the titanium aluminum nitride and the zinc alloy matrix to prepare Zn-Al-Ti with strengthened interface combination2AlN biomedical materials.
The invention realizes the uniform mixing of zinc powder, aluminum powder and titanium aluminum nitride powder by optimizing the ball milling process, which provides necessary conditions for enhancing the interface combination of titanium aluminum nitride and zinc alloy. After the ball milling is finished, preparing Zn-Al-Ti by an SLM process within a specific parameter range2AlN biomedical materials. The aluminum atoms in the titanium aluminum nitride are weakly bonded with the titanium atoms and the nitrogen atoms, and the titanium atoms and the nitrogen atoms are strongly bonded by covalent bonds, so that the titanium aluminum nitride can be decomposed into the aluminum atoms at high temperature, and the weak bonding bonds of the aluminum atoms in the titanium aluminum nitride with the titanium atoms and the nitrogen atoms are broken under the higher energy density of the SLM process, so that the aluminum atoms in the titanium aluminum nitride can be easily diffused out. Meanwhile, the molten pool provides a path for the diffusion of aluminum atoms, and the aluminum atoms in the molten pool further promote the diffusion of the aluminum atoms in the aluminum titanium nitride, and in addition, the aluminum atoms are diffusedA small part of titanium atoms are disjointed from the aluminum titanium nitride and combined with aluminum elements in a molten pool to form Al0.64Ti0.36And the interface combination of the aluminum titanium nitride and the zinc matrix is enhanced, and the mechanical property of the zinc matrix is improved.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, through the synergistic effect of the ball milling process and the SLM process, the characteristic that aluminum element is decomposed from the aluminum titanium nitride at high temperature is utilized, the enrichment of the aluminum element between the aluminum titanium nitride and the zinc matrix interface is realized, and the interface combination of the aluminum titanium nitride and the zinc matrix is enhanced, so that the mechanical property of the zinc alloy is enhanced.
(2) The invention promotes the decomposition of the titanium aluminum nitride by the synergistic effect of the ball milling process and the SLM process and the characteristic of large laser energy density of the SLM technology, and combines with the aluminum element enriched on the interface to form Al0.64Ti0.36Thereby further enhancing the interfacial bonding of the titanium aluminum nitride to the zinc matrix.
(3) Zn-Al-Ti developed by the invention2The AlN biomedical material improves the mechanical property of a zinc matrix based on strong interface combination characteristic, has excellent biocompatibility and degradation rate, and can be used for repairing human tissues.
Drawings
FIG. 1 is an EDS line scan at the interface of TiN and substrate;
FIG. 2 shows Zn-Al-Ti after sintering and forming by SLM process2XRD pattern of AlN material.
Detailed Description
The following examples illustrate specific embodiments of the present invention:
example 1
Respectively weighing 8.3 g of zinc powder, 0.7 g of aluminum powder and 1.0 g of titanium aluminum nitride powder according to the mass ratio of 83:7:10, adding the zinc powder, the 0.7 g of aluminum powder and the 1.0 g of titanium aluminum nitride powder into a ball milling tank, and ball milling for 3 hours at the rotating speed of 350r/min under the protection atmosphere of high-purity argon gas of 99.999% according to the mass ratio of 20:1 to obtain the mixed powder of zinc aluminum titanium aluminum nitride. The mixed powder was used as a raw material, and the laser power was 65W, the scanning speed was 14mm/s, the spot diameter was 50 μm,Preparing Zn-Al-Ti by SLM process under the process conditions of scanning interval of 0.1mm, powder spreading thickness of 0.1mm and 99.999% high-purity argon protective atmosphere2AlN biomedical materials.
Microstructure tests show that aluminum element enrichment (figure 1) occurs between the interface of the aluminum titanium nitride and the zinc alloy matrix, and the aluminum titanium nitride is uniformly dispersed in the zinc matrix without agglomeration. And Al is detected0.64Ti0.36Phase and TiN phase (FIG. 2), ultimate compressive strength 193 MPa.
Example 2
Respectively weighing 8.8 g of zinc powder, 0.7 g of aluminum powder and 0.5 g of titanium aluminum nitride powder according to the mass ratio of 88:7:5, adding the zinc powder, the 0.7 g of aluminum powder and the 0.5 g of titanium aluminum nitride powder into a ball milling tank, and ball milling for 3 hours at the rotating speed of 350r/min under the protection atmosphere of high-purity argon gas of 99.999% according to the mass ratio of 20:1, thereby obtaining the mixed powder of zinc aluminum titanium aluminum nitride. The mixed powder is used as a raw material, and under the process conditions of 65W of laser power, 14mm/s of scanning speed, 50 mu m of spot diameter, 0.1mm of scanning interval, 0.1mm of powder spreading thickness and 99.999 percent of high-purity argon protective atmosphere, the SLM process is utilized to prepare Zn-Al-Ti2AlN biomedical materials.
Microstructure tests show that aluminum element enrichment occurs between the aluminum titanium nitride and the zinc alloy matrix interface, and titanium aluminum nitride is uniformly dispersed without agglomeration. And Al is detected0.64Ti0.36Phase and TiN phase, ultimate compressive strength 168 MPa.
Example 3
Weighing 7.8 g of zinc powder, 0.7 g of aluminum powder and 1.5 g of titanium aluminum nitride powder according to the mass ratio of 78:7:15, respectively, adding the zinc powder, the 0.7 g of aluminum powder and the 1.5 g of titanium aluminum nitride powder into a ball milling tank, and ball milling for 3 hours at the rotating speed of 350r/min under the protection atmosphere of high-purity argon gas of 99.999% according to the mass ratio of 20:1, thereby obtaining the mixed powder of zinc aluminum titanium aluminum nitride. The mixed powder is used as a raw material, and under the process conditions of 65W of laser power, 14mm/s of scanning speed, 50 mu m of spot diameter, 0.1mm of scanning interval, 0.1mm of powder spreading thickness and 99.999 percent of high-purity argon protective atmosphere, the SLM process is utilized to prepare Zn-Al-Ti2AlN biomedical materials.
Microstructure test findingThe enrichment of aluminum element appears between the interface of the aluminum titanium nitride and the zinc alloy matrix, and the titanium aluminum nitride is dispersed uniformly without agglomeration. And Al is detected0.64Ti0.36Phase and TiN phase, ultimate compressive strength 178 MPa.
Comparative example 1
The other conditions were the same as in example 1 except that: 9.2 g of zinc powder, 0.7 g of aluminum powder and 0.1 g of titanium aluminum nitride powder were weighed in a mass ratio of 92:7: 1. Testing of undetected Al0.64Ti0.36Phase and TiN phase, the ultimate compressive strength is 130 MPa.
Comparative example 2
The other conditions were the same as in example 1 except that: in a mass ratio of 73:7:20, 7.3 g of zinc powder, 0.7 g of aluminum powder, and 2 g of titanium aluminum nitride powder were weighed. Tests show that the obtained product forms a large amount of titanium aluminum nitride agglomerates and has the ultimate compressive strength of 110 MPa.
Comparative example 3
The other conditions were the same as in example 1 except that: during ball milling, the ball milling is carried out for 2 hours at the rotating speed of 200 r/min. Tests show that the titanium aluminum nitride in the obtained product is extremely non-uniform in distribution and has the ultimate compression strength of 115 MPa.
Comparative example 4
The other conditions were the same as in example 1 except that: the product was obtained at a laser power of 30W and a scanning speed of 14 mm/s. The obtained product was found to be free from Al0.64Ti0.36Phase and TiN phase, ultimate compressive strength 103 MPa.

Claims (6)

1. An interface bonding reinforced zinc-aluminum-titanium aluminum nitride biomedical material is characterized in that: the compound is prepared from the following raw materials:
Zn 78～88wt％；
Al 7wt％；
Ti2AlN 5～15wt％；
the method specifically comprises the following steps:
step one
Taking zinc powder, aluminum powder and titanium aluminum nitride powder according to the raw material components, and carrying out ball milling for 2-4h at ball-material mass ratio of 10:1-30:1 and ball milling rotation speed of 250-400r/min under protective atmosphere to obtain zinc-aluminum-titanium aluminum nitride mixed powder;
step two
Preparing Zn-Al-Ti with interface bonding reinforcement by using the Zn-Al-Ti nitride mixed powder obtained in the step one as a raw material and adopting an SLM (selective laser melting) technology in a protective atmosphere2AlN biomedical material; controlling the laser power to be 50-70W, the scanning speed to be 10-14mm/s, the spot diameter to be 50 mu m, the laser scanning interval to be 20-30 mu m, and the powder spreading thickness to be 0.1-0.2 mm.
2. The interface bond-strengthened zinc-aluminum-titanium aluminum nitride biomedical material as claimed in claim 1, wherein: the interface bonding strengthened Zn-Al-Ti2The AlN biomedical material is prepared from the following raw materials:
Zn 78～83wt％；
Al 7wt％；
Ti2AlN 10～15wt％。
3. the interface bond-strengthened zinc-aluminum-titanium aluminum nitride biomedical material as claimed in claim 2, wherein: the interface bonding strengthened Zn-Al-Ti2The AlN biomedical material is prepared from the following raw materials:
Zn 83wt％；
Al 7wt％；
Ti2AlN 10wt％。
4. the interface bond-strengthened zinc-aluminum-titanium aluminum nitride biomedical material as claimed in claim 1, wherein: in the first step, the ball milling conditions are as follows: the ball-material mass ratio is 20:1, the ball milling speed is 350r/min, and the ball milling lasts for 3 hours.
5. The interface bond-strengthened zinc-aluminum-titanium aluminum nitride biomedical material as claimed in claim 1, wherein: in the second step, the conditions of the SLM technology are as follows: the laser power is controlled to be 65W, the scanning speed is 14mm/s, the diameter of a light spot is 50 mu m, the laser scanning interval is 20 mu m, and the powder spreading thickness is 0.1 mm.
6. The interface bond-strengthened zinc-aluminum-titanium aluminum nitride biomedical material as claimed in claim 1, wherein: in the first step and the second step, the protective atmosphere is high-purity argon with the purity of more than or equal to 99.999 percent.
CN201910288622.1A 2019-04-11 2019-04-11 Interface bonding reinforced zinc-aluminum-titanium aluminum nitride biomedical material and preparation method thereof Expired - Fee Related CN109865837B (en)

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CN110724854B (en) * 2019-08-30 2021-08-27 中南大学 Needle-shaped eutectic-enhanced biological Zn-Al-Sn alloy and preparation method thereof
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CN101172167A (en) * 2006-11-03 2008-05-07 德普伊产品公司 Aluminum oxide coating implant article and components
CN108504922A (en) * 2018-05-09 2018-09-07 江西理工大学 A kind of biodegradable iron-zinc alloy and preparation method thereof
CN109112361A (en) * 2018-09-04 2019-01-01 江西理工大学 A kind of biological kirsite and preparation method thereof of tiny lamellar eutectic structure

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EP2990013B1 (en) * 2014-09-01 2017-06-21 Jossi Holding AG Artificial articulated shell

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101172167A (en) * 2006-11-03 2008-05-07 德普伊产品公司 Aluminum oxide coating implant article and components
CN108504922A (en) * 2018-05-09 2018-09-07 江西理工大学 A kind of biodegradable iron-zinc alloy and preparation method thereof
CN109112361A (en) * 2018-09-04 2019-01-01 江西理工大学 A kind of biological kirsite and preparation method thereof of tiny lamellar eutectic structure

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