CN111996415B - Cobalt-chromium alloy biological material and preparation method thereof - Google Patents

Cobalt-chromium alloy biological material and preparation method thereof Download PDF

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CN111996415B
CN111996415B CN202010634372.5A CN202010634372A CN111996415B CN 111996415 B CN111996415 B CN 111996415B CN 202010634372 A CN202010634372 A CN 202010634372A CN 111996415 B CN111996415 B CN 111996415B
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俞光锋
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Zhongyi (Shenzhen) Medical Technology Group Co.,Ltd.
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/045—Cobalt or cobalt alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment

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Abstract

The invention discloses a cobalt-chromium alloy biomaterial and a preparation method thereof, wherein the cobalt-chromium alloy biomaterial comprises the following components in percentage by weight:
Figure DDA0002567435300000011
Figure DDA0002567435300000012
the balance being Co. The preparation method of the material comprises the steps of weighing raw materials in proportion, mixing and smelting Co, Mo, Cr, Si, Fe, C and N, homogenizing, and then casting and molding according to biological requirements; ZrO spraying on the surface of a cast and uncooled article2Then naturally cooling to obtain the cobalt-chromium alloy biomaterial; the scheme improves the composition of the alloy material, effectively improves the mechanical property and biocompatibility of the material, and modifies the surface of the alloy material by spraying, so that the surface of the alloy material generates phase change, the strength of the alloy surface is improved, and the internal toughness of the alloy is maintained, so that the surface of the material is more wear-resistant, and the higher service life of the material is further ensured.

Description

Cobalt-chromium alloy biological material and preparation method thereof
Technical Field
The invention relates to the technical field of alloy materials, in particular to a cobalt-chromium alloy biological material and a preparation method thereof.
Background
With the continuous development of modern science and technology, the medical level is more and more developed, the biological material is used as the most important field of life science research, most organs of the human body can be replaced by medical instruments such as artificial organs and the like implanted in the living body, and hard tissues of the human body such as bones of the human body, cardiac pacemakers and the like can be replaced by metal titanium alloy and chromium alloy. Since medical instruments implanted in a living body, alloys, or in direct contact with the surface of a living body, these medical instruments are required to have high corrosion resistance and biocompatibility. In addition, when these medical instruments are used as artificial joint materials, they are required to have high strength and high wear resistance, and also to have a longer life span of the materials, avoiding damage to living tissues due to frequent replacement.
Because of the above excellent properties, ASTM F90 alloy is widely used as a stent material for very small blood vessels, such as an aortic stent, a coronary stent, and a stent for bile ducts. However, since the ASTM F90 alloy contains a large amount of Ni, the presence of which causes biotoxicity, and Ni, which is gradually precipitated when used as a bioimplant, causes severe allergy and makes it difficult to secure the performance of the alloy, an alloy material containing no Ni has been developed, and chinese patent application No. 201310062930.5 discloses a Co-based alloy for a living body, which is a Co-based alloy for a Co-Cr-W-Fe-based living body, and a stent. The alloy consists of Cr:
Figure BDA0002567435290000011
W：
Figure BDA0002567435290000012
Figure BDA0002567435290000013
Fe：
Figure BDA0002567435290000014
the balance being Co and unavoidable impurities. This patent describes a nickel-cobalt-free alloy that is considered ideal for stent materials because of its good elastic modulus, biocompatibility, and processability. However, the alloy prepared by casting has large surface grains, and has low mechanical property and wear resistance, so that the characteristics of high hardness and high wear resistance required by the alloy as an artificial joint and surgical instrument material are difficult to ensure, and the service life of the alloy is difficult to ensure.
Therefore, how to provide a cobalt-chromium alloy material with high performance and longer service life is a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a cobalt-chromium alloy biomaterial and a preparation method thereof, which effectively improve the performance and service life of the alloy material and improve the biocompatibility by improving the composition and preparation process of the alloy material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the cobalt-chromium alloy biomaterial comprises the following components in percentage by weight: mo
Figure BDA0002567435290000021
Cr
Figure BDA0002567435290000022
Si
Figure BDA0002567435290000023
ZrO2
Figure BDA0002567435290000024
Fe
Figure BDA0002567435290000025
C
Figure BDA0002567435290000026
N
Figure BDA0002567435290000027
Figure BDA0002567435290000028
The balance being Co.
Preferably, the composition comprises the following components in percentage by weight: mo
Figure BDA0002567435290000029
Cr
Figure BDA00025674352900000210
Si
Figure BDA00025674352900000211
ZrO2
Figure BDA00025674352900000212
Fe
Figure BDA00025674352900000213
C
Figure BDA00025674352900000214
N
Figure BDA00025674352900000215
The balance being Co.
Preferably, the composition comprises the following components in percentage by weight: 26% of Mo, 14.5% of Cr, 3.5% of Si, and ZrO22.0 percent, Fe 0.9 percent, C0.5 percent, N0.3 percent and the balance of Co.
Preferably, the ZrO2Has an average particle diameter of
Figure BDA00025674352900000216
The beneficial effects of the preferred technical scheme are as follows: an average particle diameter of less than 0.05mm results in a light weight of the shot material and difficulty in sufficient treatment of the alloy surface, while an average particle diameter of more than 1.0mm results in a prolonged surface treatment time and a serious reduction in treatment efficiency.
Preferably, the ZrO2Vickers hardness of
Figure BDA00025674352900000217
The beneficial effects of the preferred technical scheme are as follows: the Vickers hardness is less than 500, which is difficult to cause enough phase change in a certain depth range, while the Vickers hardness is more than 1200, which leads to the increase of surface roughness, easy generation of cracks and difficult satisfaction of use requirements.
The invention also provides a preparation method of the cobalt-chromium alloy biomaterial, which comprises the following steps:
(1) weighing raw materials according to the weight ratio, then mixing and smelting Co, Mo, Cr, Si, Fe, C and N, homogenizing, and then casting and molding according to biological requirements;
(2) spraying ZrO on the surface of the product which is cast and molded in the step (1) and is not cooled2Then naturally cooling to obtain the cobalt-chromium alloy biomaterial.
Preferably, ZrO is sprayed in the step (1)2Has a material density of
Figure BDA0002567435290000031
The beneficial effects of the preferred technical scheme are as follows: the density of the material is less than 1g/cm3The spraying material has low strength caused by low density, is difficult to modify to ensure that the phase of the material is changed to a certain depth, and the density of the material is more than 10g/cm3The surface roughness is increased, and cracks and fractures are easy to occur, so that the use requirement is difficult to meet.
Preferably, the spraying in the step (2) adopts air pressure spraying, and the spraying pressure is
Figure BDA0002567435290000032
The beneficial effects of the preferred technical scheme are as follows: when the injection pressure is less than 0.1MPa, a good injection adhesion effect is difficult to achieve, and when the injection pressure is more than 0.5MPa, the hardness after modification is easily too high, so that the toughness is influenced.
Preferably, the surface roughness of the cobalt-chromium alloy biomaterial obtained in the step (2) is less than or equal to 10 microns.
The beneficial effects of the preferred technical scheme are as follows: when the surface roughness is more than 10 mu m, the polishing solution is used for polishing biological materials, not only the treatment efficiency is low, but also the outer spray layer is abraded in the polishing process, and the quality of the alloy is influenced.
Through the technical scheme, compared with the prior art, the invention provides the cobalt-chromium alloy biomaterial and the preparation method thereof, the composition of the alloy material is improved, wherein the chromium-cobalt mesh is taken as the main alloy, the addition of silicon is controlled, the wear resistance and corrosion resistance of the alloy are ensured, and the toughness of the alloy is not influenced; iron is adopted to replace the traditional nickel element, so that the mechanical property of the alloy is improved; the carbide formed by the carbon element and the nitride formed by the nitrogen element are dispersed in the alloy matrix, so that the alloy has good biocompatibility, and the elastic modulus, the tensile strength and the wear resistance of the alloy are effectively improved; the zirconia is sprayed on the surface of the alloy, and because the thermal conductivity of the zirconia is low, a spraying layer with low thermal conductivity is formed on the surface, thermal stress is concentrated on the outermost layer of the alloy, and the surface layer is subjected to phase change under the covering of the spraying layer, so that the surface of the alloy is selectively converted into an epsilon phase, the strength of the surface of the alloy is improved, the internal toughness of the alloy is maintained, the surface of the material is more wear-resistant, and the material is ensured to have longer service life.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, ZrO2Has an average particle diameter of
Figure BDA0002567435290000041
Vickers hardness
Figure BDA0002567435290000042
A density of
Figure BDA0002567435290000043
Example 1
The cobalt-chromium alloy biomaterial comprises the following components in percentage by weight: 22.0% of Mo, 18.5% of Cr, 2.0% of Si, ZrO23.0％，Fe 0.5％，C 0.6％，N 0.2％，Co 53.2％。
Example 2
The cobalt-chromium alloy biomaterial comprises the following components in percentage by weight: 28.0% of Mo, 7.5% of Cr, 4.0% of Si, ZrO21.0％，Fe 1.2％，C 0.3％，N 0.3％，Co 57.7％。
Example 3
The cobalt-chromium alloy biomaterial comprises the following components in percentage by weight: 24.0% of Mo, 16.5% of Cr, 3.0% of Si, ZrO22.2％，Fe 0.7％，C 0.5％，N 0.2％，Co 62.9％。
Example 4
The cobalt-chromium alloy biomaterial comprises the following components in percentage by weight: 27.0% of Mo, 9.5% of Cr, 3.8% of Si, and ZrO21.8％，Fe 1.0％，C 0.4％，N 0.3％，Co 56.2％。
Example 5
The cobalt-chromium alloy biomaterial comprises the following components in percentage by weight: 26.0% of Mo, 14.5% of Cr, 3.5% of Si, ZrO22.0％，Fe 0.9％，C 0.5％，N 0.3％，Co 52.3％。
The alloy materials of examples 1-5 were all prepared using the following process:
(1) weighing raw materials according to the weight ratio, then mixing and smelting Co, Mo, Cr, Si, Fe, C and N, homogenizing, and then casting and molding according to biological requirements;
(2) spraying ZrO on the surface of the product which is cast and molded in the step (1) and is not cooled2Wherein the spraying pressure is
Figure BDA0002567435290000051
Then naturally cooling to obtain the cobalt-chromium alloy biomaterial with the surface roughness less than 10 mu m.
The materials prepared in examples 1-5 above were tested and the results are as follows:
0.2% yield strength/MPa Surface Hardness (HV) Tensile strength/MPa
Example 1 965 531 1405
Example 2 957 533 1411
Example 3 971 529 1384
Example 4 977 527 1398
Example 5 980 535 1420
The test result shows that the biological alloy material prepared by the technical scheme of the invention has good mechanical property, the surface hardness is greatly improved by the zirconium oxide surface spraying modification, the biological use requirement is met, the service life is effectively prolonged, the replacement frequency is reduced, and the practical application value is higher.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (8)

1. The cobalt-chromium alloy biomaterial is characterized by comprising the following components in percentage by weight: 22.0 to 28.0% of Mo, 7.5 to 18.5% of Cr, 2.0 to 4.0% of Si, ZrO21.0-3.0% of Fe, 0.5-1.2% of C, 0.3-0.6% of N, 0.2-0.3% of N and the balance of Co;
the preparation method of the cobalt-chromium alloy biomaterial comprises the following steps:
(1) weighing raw materials according to the weight ratio, then mixing and smelting Co, Mo, Cr, Si, Fe, C and N, homogenizing, and then casting and molding according to biological requirements;
(2) spraying ZrO on the surface of the product which is cast and molded in the step (1) and is not cooled2Form ZrO on the surface2The thermal stress is concentrated on the outermost layer of the alloy by the spray coating, the surface layer is subjected to phase change under the covering of the spray coating, the surface of the alloy is selectively converted into an epsilon phase, the strength of the surface of the alloy is improved, the internal toughness of the alloy is maintained, and the cobalt-chromium alloy biomaterial is obtained by natural cooling.
2. The cobalt-chromium alloy biomaterial according to claim 1, wherein the biomaterial is characterized byThe paint comprises the following components in percentage by weight: 24-27% of Mo, 9.5-16.5% of Cr, 3.0-3.8% of Si, and ZrO21.8-2.2% of Fe, 0.7-1.0% of C, 0.4-0.5% of N, 0.2-0.3% of N and the balance of Co.
3. The cobalt-chromium alloy biomaterial according to claim 1, comprising the following components in percentage by weight: 26% of Mo, 14.5% of Cr, 3.5% of Si, and ZrO22.0 percent, Fe 0.9 percent, C0.5 percent, N0.3 percent and the balance of Co.
4. The cobalt-chromium alloy biomaterial according to claim 1, wherein the ZrO-Si-O-R-O-R is2The average particle diameter of (B) is 0.05 to 1.0 mm.
5. The cobalt-chromium alloy biomaterial according to claim 1, wherein the ZrO-Si-O-R-O-R is2The Vickers hardness of 500 to 1200.
6. The cobalt-chromium alloy biomaterial as claimed in claim 1, wherein the ZrO coating in step (1)2The density of the material is 1-10 g/cm3。
7. The cobalt-chromium alloy biomaterial as claimed in claim 1, wherein the spraying in step (2) is performed by air pressure spraying, and the spraying pressure is 0.1-0.5 MPa.
8. The cobalt-chromium alloy biomaterial according to claim 1, wherein the surface roughness of the cobalt-chromium alloy biomaterial obtained in step (2) is less than or equal to 10 μm.
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