CN114470317A - Titanium alloy material for repairing skull and preparation method thereof - Google Patents

Titanium alloy material for repairing skull and preparation method thereof Download PDF

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CN114470317A
CN114470317A CN202210072565.5A CN202210072565A CN114470317A CN 114470317 A CN114470317 A CN 114470317A CN 202210072565 A CN202210072565 A CN 202210072565A CN 114470317 A CN114470317 A CN 114470317A
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powder
mass percent
titanium alloy
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mass
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欧阳春
庄梓良
何莉盈
王培龙
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Jiangsu University of Science and Technology
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract

The invention provides a titanium alloy material for skull repair and a preparation method thereof, wherein a pore-forming agent is added, a biomedical implant porous TiNbZrCuHA/HA alloy is prepared by a powder metallurgy method, an HA coating is filled on the surface of the porous alloy by a hydrothermal method, the mechanical property of the titanium alloy is changed by adjusting the porosity and adjusting the content of alloy elements or HA, so as to obtain the mechanical property similar to that of a bone tissue, the addition of Nb and Zr is beneficial to forming a beta-type titanium alloy with low elastic modulus, the added Cu element can well play a role in sterilization and disinfection, the HA in the alloy can adjust the mechanical property of the alloy and form an active phase, and the HA filled in surface gaps can improve the bioactivity of an implant and promote osteoinduction force and growth.

Description

Titanium alloy material for repairing skull and preparation method thereof
Technical Field
The invention relates to a biomedical material, in particular to a titanium alloy material for repairing skull and a preparation method thereof.
Background
The skull repairing titanium alloy material belongs to biomedical materials, and the biomedical materials are used for diagnosing, treating, repairing and replacing tissues in vivo of organisms. The injury of the human brain and the skull mainly exists in the problems of craniocerebral trauma, large-area cerebral infarction, cerebral hemorrhage and the like, and the brain tissue is easy to be damaged because patients lose the protection function of the skull after craniotomy, so the development of the skull repairing material for protecting the human brain becomes the research focus of medical materials.
The biomedical implant materials used in clinical practice at present are: metals and their alloys, inorganic non-metallic materials, organic materials and composite materials. The metal material is an implant material for bones, teeth, joints and vascular stents because of its easy processing property, high strength and bending resistance, and good plasticity. Medical implant materials have different activities in vivo and can be classified into degradable and non-degradable materials. Medical implantation instruments account for a large proportion of medical systems, and the problems of corrosion rate, biocompatibility, cytotoxicity and the like of the medical implantation instruments need to be solved due to the contact of the medical implantation instruments with cells and human tissues.
The titanium alloy has excellent mechanical property, good corrosion resistance, good biocompatibility, wear resistance and tissue compatibility, and does not influence the examination of medical radiography equipment such as CT, MRI and the like after the skull is repaired, so the titanium alloy is widely applied to surgical skull injury repair materials. At present, the porous titanium alloy is prepared by a powder metallurgy method and applied to an orthopedic repair material, the material achieves an antibacterial effect by element and component design, and HA is added to induce bone growth so as to wrap the mesh porous titanium. The porous titanium-based alloy is prepared by element selection and powder metallurgy, the influence mechanism of the material preparation process on the mechanical property and the corrosion mechanism of the material is explored, and the corrosion products are analyzed and researched, so that the induction of the HA on the bone growth and the action mechanism of the HA on the growth are prompted. The research result has guiding significance for the theoretical research and medical application of the porous titanium alloy.
The major obstacles that currently limit titanium alloy bioimplantation are production cost, biocompatibility, and stress shielding effect. The porous titanium alloy is the alloy mainly used by the current metal implant;
the invention discloses a titanium alloy matrix composition 201810107293.1, which comprises, by mass, 66.88-85.67% of Ti66.0-6.5% of Zr, 3-10% of Nb, 0.5-1.5% of Gd, 6-13% of Fe, 0.8-2.0% of Mo and 0.03-0.12% of Pt. The titanium alloy of the invention has low elastic modulus, but contains elements Gd, Fe and Pt which are unfavorable for human bodies, and the elements which are unfavorable for the human bodies can be dissolved out in the human bodies for a long time, so that the recovery of patients is not facilitated.
The literature, the preparation and performance research of high-strength low-modulus porous NiTi _ HA biological composite materials, Zhangiei, Ph academic thesis of Kunming university of technology, discloses a NiTi-HA porous material (10 wt.% HA), wherein the adopted Ni element is dissolved to cause excessive concentration in human body to generate toxicity to human body;
the invention discloses a gradient medical material and a preparation method thereof 202010134085.8, and discloses a gradient medical material and a preparation method thereof, wherein an alloy strengthening element Zr and a beta-phase stable element Ta are added on the basis of the proportion of Ti-10Mo-28Nb alloy, and the surface coating of the Ti-Mo-Nb-Zr-Ta multi-element alloy is an HA or HA-Cu-Zn composite coating, but the lowest value of the elastic modulus is not lower than 43 GPa.
In the prior art, a skull repairing titanium alloy material which can realize physical properties close to the implanted part, has no toxicity of alloy elements and good biocompatibility, is beneficial to improving the corrosion resistance of the alloy due to a formed microstructure and has certain antibacterial property, is beneficial to forming osteoblasts after being implanted, promotes the combination of an implant and bone tissues, and completely wraps the implant within a certain time is lacked.
Disclosure of Invention
The embodiment of the application provides a titanium alloy material for repairing the skull, the porous TiNbZrCuHA/HA alloy is prepared by a powder metallurgy method, the proportion of alloy elements can be adjusted at any time, the porosity is adjusted to regulate and control the physical properties of the alloy, the elastic modulus of the alloy material is further reduced on the premise of ensuring good biocompatibility and nontoxicity, and the titanium alloy material is simple in preparation process and low in cost.
The embodiment of the application provides a titanium alloy material for repairing skull, the titanium alloy material is divided into a base material and a surface coating material, the porosity of the base material is 40-60%, the pore diameter is 100-300nm, the surface coating is an HA coating with the thickness of 1-2 μm, and the mass percentages of all elements in the base material are respectively as follows: 55-75% of Ti, 5-30% of Nb, 5-30% of Zr, 1-6% of Cu and 1-10% of HA;
the embodiment of the application also provides a preparation method of the titanium alloy material for repairing the skull, which comprises the following steps:
step S1: five element powders of Ti, Nb, Zr, Cu and HA with the average grain diameter of about 50 mu m are selected from 55 to 75 mass percent of Ti powder, 5 to 30 mass percent of Nb powder, 5 to 30 mass percent of Zr powder, 1 to 6 mass percent of Cu powder and 1 to 10 mass percent of HA powder, and then 10 mass percent of pore-forming agent of the total mass of the mixed powder is added for mixing; preferably, the pore-forming agent is NH4HCO3(ii) a Preferably, the ball-to-feed ratio in the mixing process is 1: 4. the rotating speed is 200r/min, and the mixing time is 4 h;
step S2: mixing the original powder with an organic binder according to a certain proportion, wherein the organic binder comprises paraffin and epoxy resin, uniformly mixing to prepare slurry, then putting the slurry into a blank making machine to be pressed into a blank, then pressing and sintering at 1700 ℃, and carrying out heat treatment for 1h at 550 ℃ after sintering.
Preferably, the organic binder is paraffin wax, and a small amount of binder is added to help the powder to be bonded together;
preferably, the original powder and the paraffin are mixed according to a mass ratio of 10: 1, uniformly mixing to prepare slurry.
It should be noted that, in step S2, higher temperature pressing and sintering is adopted, so as to make the titanium part reach the melting point, react with other metal elements, and sinter and form;
step S3: immersing the substrate after heat treatment into a solution containing Ca (OH) at 150 DEG C2And NaH2PO4Wherein the molar ratio of calcium to phosphorus n (Ca)/n (P) is about 1.67, the pores are filled with HA and the HA coating layer with the diameter of 1-2 μm is formed on the surface of the particles.
The NiTi-HA porous material (10 wt.% HA) disclosed in the prior art adopts Ni element which is not friendly to human body, and the invention adopts Nb, Zr and Cu elements to replace the Ni element, and HA is used to fill the surface holes of the porous titanium alloy, so that the Ni-HA porous material is friendly to human body on the premise of obtaining better biocompatibility, wherein Nb and Zr are used to optimize alpha + beta type titanium alloy in Ti alloy, Cu HAs antibacterial effect, and HA in the surface holes is beneficial to forming a biocompatible coating on the surface.
The porous TiNbZrCuHA/HA alloy is prepared by a powder metallurgy method, the aperture is 100-300nm, HA is generated by a surface hydrothermal method to improve the biocompatibility of the material, Cu is added to promote the antibacterial property of the material, and HA can improve the induction and growth of bones. Through the research and development of the project, the product has biocompatibility and no toxicity of corrosion products, can induce the formation of bones, and the bones generated within a certain time completely wrap the implant, thereby finally reaching the clinical application standard. The prepared titanium alloy is pressed into a net structure, is applied to skull injury repair materials, and has mechanical strength and density similar to those of human skull.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
according to the preparation method of the titanium alloy material for repairing the skull, provided by the invention, the pore-forming agent is added, the biomedical implant porous TiNbZrCuHA/HA alloy is prepared by a powder metallurgy method, the HA coating is filled on the surface of the porous alloy by a hydrothermal method, the mechanical property of the titanium alloy is changed by adjusting the porosity and adjusting the content of alloy elements or HA, so that the mechanical property similar to that of the bone tissue is obtained, the addition of Nb and Zr is favorable for forming the beta-type titanium alloy with low elastic modulus, the added Cu element can well play a role in sterilization and disinfection, the HA in the alloy can adjust the mechanical property of the alloy and form an active phase, the HA filled in surface gaps can improve the bioactivity of the implant and promote the bone induction force and growth, the implant HAs great application potential and remarkable social benefit.
The titanium alloy material for repairing the skull provided by the invention mainly comprises titanium as an alloy element, all the elements are nontoxic and cheap, and the added HA and the HA in the coating increase the alloy resistance and are beneficial to the growth of bone tissues. Can be finally applied to the clinical implantation of human skull.
Drawings
FIG. 1 is an electron micrograph of the porous titanium alloy according to the first embodiment of the present application;
FIG. 2 is a table comparing properties of a porous titanium alloy and skull, according to one embodiment of the present disclosure;
Detailed Description
In order to better understand the technical solution, the technical solution will be described in detail with reference to the drawings and the detailed description.
The raw materials, reagents and equipment referred to in the following examples:
ti, Nb, Zr, Cu, HA element powder: shanghai Aladdin Biotechnology, Inc., all 99.5% pure
Pore-forming agent: 99.5% purity, Shanghai Aladdin Biotechnology Ltd
Paraffin wax: shanghai Aladdin Biochemical science and technology, Inc., pathological grade
Example one
The embodiment also provides a titanium alloy material for repairing skull and a preparation method thereof, wherein the method comprises the following steps: step S1: five element powders of Ti, Nb, Zr, Cu and HA with an average grain diameter of about 50 μm, wherein the five element powders are selected from 75 mass percent of Ti powder, 10 mass percent of Nb powder andzr powder with the mass fraction of 10 percent, Cu powder with the mass fraction of 2 percent and HA powder with the mass fraction of 3 percent are selected, NH is added according to the weight of 10 percent of the mass fraction of the mixed powder after the powders are mixed4HCO3Mixing pore-forming agents, wherein the ratio of the ball materials in the mixing is 1: 4. the rotating speed is 200r/min, and the mixing time is 4 h;
step S2: the mass ratio of the original powder to the paraffin is 10: 1, uniformly mixing to prepare slurry, then putting the slurry into a blank making machine to press into a biscuit, then pressing and sintering at 1700 ℃, and carrying out heat treatment for 1h at 550 ℃ after sintering;
step S3: immersing the substrate after heat treatment into a solution containing Ca (OH) at 150 DEG C2And NaH2PO4Wherein the molar ratio of calcium to phosphorus n (Ca)/n (P) is 1.67, the pores are filled with HA and a 2 μm HA coating is formed on the surface of the pores.
Example two
In the titanium alloy material for repairing skull and the preparation method thereof provided in this embodiment, except that the ratio of the powders of five elements, i.e., Ti, Nb, Zr, Cu, and HA in step S1 is different from that in the first embodiment, the other operations are the same as in the first embodiment, specifically, in this embodiment, the mass ratios of the powders of five elements, i.e., Ti, Nb, Zr, Cu, and HA, are respectively: 55 mass percent of Ti powder, 15 mass percent of Nb powder, 15 mass percent of Zr powder, 6 mass percent of Cu powder and 9 mass percent of HA powder.
EXAMPLE III
In the titanium alloy material for skull repairing and the preparation method thereof provided in this embodiment, except that the ratio of the powders of the five elements, i.e., Ti, Nb, Zr, Cu, and HA in step S1 is different from that in the first embodiment and the processing time in step S3 is different, the other operations are the same as in the first embodiment, specifically, in step S1 of this embodiment, the mass ratios of the powders of the five elements, i.e., Ti, Nb, Zr, Cu, and HA, are respectively: 57% of Ti powder, 20% of Nb powder, 20% of Zr powder, 1% of Cu powder and 2% of HA powder;
in step S3 of this example, the substrate was immersed in a solution containing Ca (OH) at 150 ℃ after heat treatment2And NaH2PO4The time in solution of (1) was 1 h.
Test procedure
Physical Properties of the aluminum alloy materials prepared in examples 1 to 3
According to GB5164-1985, namely determination of the porosity of the permeable sintered metal material, the porosity and the density of a sample are tested by a medium soaking method and a JM2102 type electronic balance; the porous titanium alloy is cut into tensile mechanical samples, the tensile property of the porous titanium alloy is measured by using a universal mechanical testing machine (DNS-200), the tensile rate is 1.0mm/min, then the tensile strength and the elastic modulus are calculated, and the test results of the physical properties of the aluminum alloy materials prepared in examples 1 to 3 are shown in figure 2.

Claims (8)

1. The titanium alloy material for repairing the skull is characterized by being divided into a base material and a surface coating material, wherein the porosity of the base material is 40-60%, the pore diameter is 100-300nm, the surface coating is an HA coating with the thickness of 1-2 mu m, and the mass percentages of all elements in the base material are respectively as follows: 55-75% of Ti, 5-30% of Nb, 5-30% of Zr, 1-6% of Cu and 1-10% of HA.
2. The titanium alloy material for cranioplasty according to claim 1, wherein said base material HAs a pore size of 210nm and a surface coating is HA coating having a thickness of 2 μm.
3. The titanium alloy material for repairing skull according to claim 1, wherein the base material comprises the following elements in percentage by mass: 75 mass percent of Ti, 10 mass percent of Nb, 10 mass percent of Zr, 2 mass percent of Cu, and 3 mass percent of HA.
4. A preparation method of a titanium alloy material for repairing skull is characterized by comprising the following steps:
step S1: five element powders of Ti, Nb, Zr, Cu and HA with the average grain diameter of about 50 mu m are selected from 55 to 75 mass percent of Ti powder, 5 to 30 mass percent of Nb powder, 5 to 30 mass percent of Zr powder, 1 to 6 mass percent of Cu powder and 1 to 10 mass percent of HA powder, and then 10 mass percent of pore-forming agent of the total mass of the mixed powder is added for mixing;
step S2: uniformly mixing the original powder and an organic binder to prepare slurry, then putting the slurry into a blank making machine to be pressed into a biscuit, pressing and sintering at 1700 ℃, and carrying out heat treatment for 1h at 550 ℃ after sintering;
step S3: immersing the substrate after heat treatment into a solution containing Ca (OH) at 150 DEG C2And NaH2PO4Wherein the molar ratio of calcium to phosphorus n (Ca)/n (P) is about 1.67, the pores are filled with HA, and a coating of HA with a certain thickness is formed on the surface of the pores.
5. The method of claim 4, wherein the pore-forming agent is NH 14HCO3。
6. The method of claim 4, wherein the organic binder in step S2 is paraffin or epoxy resin.
7. The method for preparing a titanium alloy material for cranioplasty according to claim 4, wherein the ratio of the raw powder to the organic binder in the step S2 is 10: 1, uniformly mixing to prepare slurry.
8. The method of claim 4, wherein in the step S1, the mixture is mixed with the pore-forming agent in an amount of 10% by mass based on the total mass of the mixed powder, and the ratio of the mixed powder to the mixed powder is 1: 4. the rotating speed is 200r/min, and the mixing time is 4 h.
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Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4073999A (en) * 1975-05-09 1978-02-14 Minnesota Mining And Manufacturing Company Porous ceramic or metallic coatings and articles
EP0499392A2 (en) * 1991-02-14 1992-08-19 Nissan Motor Company, Ltd. Method for producing a wear-resistant iron-based sintered alloy
US20060065072A1 (en) * 2004-09-27 2006-03-30 Jfe Steel Corporation Iron-based mixed powder for powder metallurgy and sintered body
CN1854341A (en) * 2005-04-26 2006-11-01 中国科学院金属研究所 Fast preparation of titanium or titanium alloy surface biological active coating
JP2009067669A (en) * 2007-08-20 2009-04-02 Council Of Scientific & Industrial Research Process for preparation of protein mediated calcium hydroxyapatite (hap) coating on metal substrate
CN101696480A (en) * 2009-11-04 2010-04-21 天津科技大学 Nickel-free biomedical titanium alloy Ti-Nb-Zr material and preparation method thereof
US20110020168A1 (en) * 2009-07-22 2011-01-27 The Hong Kong Poltechnic University Rapid fabrication of porous metal-based biomaterial by microwave sintering
WO2011026938A1 (en) * 2009-09-04 2011-03-10 Innotere Gmbh Bioactively coated metal implants and methods for the production thereof
CN102312128A (en) * 2011-09-30 2012-01-11 昆明理工大学 Method for preparing titanium niobium tantalum zirconium biomedical titanium alloys by discharge plasma sintering
CN104841018A (en) * 2015-04-21 2015-08-19 昆明理工大学 Multilayered biological composite material and preparation method thereof
CN104841009A (en) * 2015-04-21 2015-08-19 昆明理工大学 Hydroxyapatite activated titanium alloy surface-layer biological composite material and preparation method thereof
CN104857566A (en) * 2015-04-21 2015-08-26 昆明理工大学 Preparation method of titanium-niobium-zirconium-based hydroxyapatite biological composite material
CN105397090A (en) * 2015-10-30 2016-03-16 昆明理工大学 Preparation method for porous nickel titanium/hydroxyapatite composite material
CN105671364A (en) * 2016-03-29 2016-06-15 昆明理工大学 Preparation method of porous titanium copper calcium material
CN107855528A (en) * 2017-10-31 2018-03-30 太原理工大学 A kind of preparation method of porous zinc magnesium alloy/hydroxyapatite composite material
CN108998684A (en) * 2018-07-18 2018-12-14 昆明理工大学 A kind of preparation method of copper titanium-based biomaterial
CN109602957A (en) * 2018-12-19 2019-04-12 云南大学 A kind of bio-medical porous titanium niobium copper orthopedic implanting material and its preparation method and application
CN111020342A (en) * 2019-12-27 2020-04-17 昆明理工大学 Method for preparing antibacterial titanium alloy through deformation strengthening
WO2020161239A1 (en) * 2019-02-07 2020-08-13 Universiteit Maastricht Porous bioactive metal-calcium phosphate medical implant

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4073999A (en) * 1975-05-09 1978-02-14 Minnesota Mining And Manufacturing Company Porous ceramic or metallic coatings and articles
EP0499392A2 (en) * 1991-02-14 1992-08-19 Nissan Motor Company, Ltd. Method for producing a wear-resistant iron-based sintered alloy
US20060065072A1 (en) * 2004-09-27 2006-03-30 Jfe Steel Corporation Iron-based mixed powder for powder metallurgy and sintered body
CN1854341A (en) * 2005-04-26 2006-11-01 中国科学院金属研究所 Fast preparation of titanium or titanium alloy surface biological active coating
JP2009067669A (en) * 2007-08-20 2009-04-02 Council Of Scientific & Industrial Research Process for preparation of protein mediated calcium hydroxyapatite (hap) coating on metal substrate
US20110020168A1 (en) * 2009-07-22 2011-01-27 The Hong Kong Poltechnic University Rapid fabrication of porous metal-based biomaterial by microwave sintering
WO2011026938A1 (en) * 2009-09-04 2011-03-10 Innotere Gmbh Bioactively coated metal implants and methods for the production thereof
CN101696480A (en) * 2009-11-04 2010-04-21 天津科技大学 Nickel-free biomedical titanium alloy Ti-Nb-Zr material and preparation method thereof
CN102312128A (en) * 2011-09-30 2012-01-11 昆明理工大学 Method for preparing titanium niobium tantalum zirconium biomedical titanium alloys by discharge plasma sintering
CN104841018A (en) * 2015-04-21 2015-08-19 昆明理工大学 Multilayered biological composite material and preparation method thereof
CN104841009A (en) * 2015-04-21 2015-08-19 昆明理工大学 Hydroxyapatite activated titanium alloy surface-layer biological composite material and preparation method thereof
CN104857566A (en) * 2015-04-21 2015-08-26 昆明理工大学 Preparation method of titanium-niobium-zirconium-based hydroxyapatite biological composite material
CN105397090A (en) * 2015-10-30 2016-03-16 昆明理工大学 Preparation method for porous nickel titanium/hydroxyapatite composite material
CN105671364A (en) * 2016-03-29 2016-06-15 昆明理工大学 Preparation method of porous titanium copper calcium material
CN107855528A (en) * 2017-10-31 2018-03-30 太原理工大学 A kind of preparation method of porous zinc magnesium alloy/hydroxyapatite composite material
CN108998684A (en) * 2018-07-18 2018-12-14 昆明理工大学 A kind of preparation method of copper titanium-based biomaterial
CN109602957A (en) * 2018-12-19 2019-04-12 云南大学 A kind of bio-medical porous titanium niobium copper orthopedic implanting material and its preparation method and application
WO2020161239A1 (en) * 2019-02-07 2020-08-13 Universiteit Maastricht Porous bioactive metal-calcium phosphate medical implant
CN111020342A (en) * 2019-12-27 2020-04-17 昆明理工大学 Method for preparing antibacterial titanium alloy through deformation strengthening

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ANQI SHI ET AL: "Development of a low elastic modulus and antibacterial Ti-13Nb-13Zr-5Cu titanium alloy by microstructure controlling", 《MATERIALS SCIENCE & ENGINEERING C》 *
CHANGBO YI ET AL: "Antibacterial Ti-35Nb-7Zr-xCu alloy with excellent mechanical properties generated with a spark plasma sintering method for biological applications", 《JOURNAL OF ALLOYS AND COMPOUNDS》 *
韩振华 等: "Cu-Zr-Ti 基非晶合金中微量 Nb 添加诱发的微观结构演化以及剪切带增殖", 《HOT WORKING TECHNOLOGY》 *

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