CN1215191C - Embedded material of austenitic stainless steel in medical use - Google Patents
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- CN1215191C CN1215191C CN 03110896 CN03110896A CN1215191C CN 1215191 C CN1215191 C CN 1215191C CN 03110896 CN03110896 CN 03110896 CN 03110896 A CN03110896 A CN 03110896A CN 1215191 C CN1215191 C CN 1215191C
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- 229910000963 austenitic stainless steel Inorganic materials 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 61
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 29
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 27
- 239000010935 stainless steel Substances 0.000 claims abstract description 26
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 21
- 239000010959 steel Substances 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 239000007943 implant Substances 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000011651 chromium Substances 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000007613 environmental effect Effects 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 239000011733 molybdenum Substances 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 238000007669 thermal treatment Methods 0.000 claims description 6
- 229910001566 austenite Inorganic materials 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 5
- 238000005242 forging Methods 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 239000000956 alloy Substances 0.000 claims 1
- 230000006698 induction Effects 0.000 abstract description 5
- 238000003723 Smelting Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 229910019590 Cr-N Inorganic materials 0.000 abstract 2
- 229910019588 Cr—N Inorganic materials 0.000 abstract 2
- 229910018648 Mn—N Inorganic materials 0.000 abstract 1
- 229910001199 N alloy Inorganic materials 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 9
- 229910018487 Ni—Cr Inorganic materials 0.000 description 4
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 241001417490 Sillaginidae Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 208000007536 Thrombosis Diseases 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002473 artificial blood Substances 0.000 description 1
- HZUJFPFEXQTAEL-UHFFFAOYSA-N azanylidynenickel Chemical compound [N].[Ni] HZUJFPFEXQTAEL-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 210000004351 coronary vessel Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000028709 inflammatory response Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- 201000008482 osteoarthritis Diseases 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 210000002381 plasma Anatomy 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002980 postoperative effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 208000037803 restenosis Diseases 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Abstract
The present invention relates to embedded austenitic stainless steel in medical use, which is characterized in that the embedded austenitic stainless steel has chemical compositions of the weight percentage: 17 to 22 of chromium, 12 to 20 of manganese, 1 to 3 of molybdenum, 0.5 to 1.5 of copper, 0.40 to 0.7 of nitrogen, at most 0.02 of nickel, at most 0.03 of carbon, at most 0.75 of silicon, at most 0.010 of sulfur, at most 0.025 of P and Fe as the rest. A vacuum induction furnace is used for smelting, nitrogen in the steel is added in a granular high nitrogen alloy (such as Fe-Cr-N, Cr-N and Mn-N) method. The nickel free austenitic stainless steel in medical use does not contain a toxic nickel element, and has the obvious advantage for being used as the embedded materials of a human body, which greatly improves the long-term using security of biologic embedded materials. The present invention can be used for implants of a human body, medical appliances, food and restaurant apparatus, jewelry and other stainless steel products that the human body frequently contact, and can also be widely used for the fields, such as chemical engineering, environmental protection, etc.
Description
Technical field:
The present invention relates to a kind of medical embedded nickel-less austenitic stainless steel material and application thereof.
Background technology:
Medical embedded stainless steel be use in the bio-medical material at most, a widest class material, but wherein contain toxic nickel (Ni) element usually.Medical 316L stainless steel for example commonly used clinically at present is nickeliferous to be 10-14%; after its implant into body; owing to reasons such as corrosion or wearing and tearing cause its surperficial passivation layer or protective layer to destroy; cause metallic nickel ions wherein to be easy to be enriched near the tissue of implant, influence the eubolism of organism.Nickel element is a kind of potential sensitizing factor, and organism is had teratogenesis, carcinogenic hazardness, the report of irritated relevant for nickel very early and canceration aspect.Near the nickel ion enrichment of implant in vivo can bring out toxic effect, and cytoclasis and inflammatory response take place.Discover that recently the side effect that contains nickel element in the stainless steel also has influence on the postoperative restenosis of coronary artery bracket.The many countries in west formulate already and issue that at the harm of nickel associated documents and standard limit the nickel content in the bio-medical metal.Therefore at the widespread popularity of medical stainless steel and the hazardness of nickel wherein, the medical free nickel stainless steel of research and development excellent property (being not less than the nickel chromium triangle medical stainless steel of present widespread usage) becomes inexorable trend.
Structure just obtains development and application with the nickelles stainless steel material as far back as the fifties in last century, its excellent comprehensive performances makes it obtain to use preferably.Because nickel to the toxicity of human body, develops the medical free nickel stainless steel and at home and abroad launches gradually nearly decades.
Summary of the invention:
The purpose of this invention is to provide a kind of bio-medical and implant stainless material, it does not contain the toxicity nickel element, have good obdurability combination, and the no nickel nitrogen of relative low price is strengthened austenitic stainless steel.
The invention provides a kind of high-nitrogen austenitic stainless steel, it is characterized in that chemical ingredients composition weight percent is: chromium Cr 17～22, manganese Mn 10～20, aluminium Mo 1～3, copper Cu 0.5～1.5, nitrogen N 0.40～0.7, nickel≤0.02, carbon C≤0.03, silicon Si≤0.75, sulphur S≤0.010, phosphorus P≤0.025, iron Fe surplus.
In the medical embedded austenitic stainless steel provided by the present invention, should control nickel≤0.02 (wt) %.Medical free nickel austenitic stainless steel of the present invention is owing to abandoned valuable nickel element, so cheap nitrogen element just becomes a kind of important alloying element, the austenitizing ability of nitrogen approximately is 20-30 a times of nickel.Be to guarantee the single austenitic structure of steel, nitrogen content should greater than, add too many nitrogen in the steel and form pore in the steel easily, and improve steel-making cost, the suggestion nitrogen content is controlled at 0.70 (wt) below the %.Nitrogen also can improve the pitting resistance of steel simultaneously.
Carbon also is important austenizer, but too much carbon can have a strong impact on the plasticity and the solidity to corrosion of steel, so carbon content should be strict controlled in 0.03 (wt) below the %.
Manganese is a kind of more weak austenizer, can increase the solubleness of nitrogen in steel, therefore should have the above manganese element of 10 (wt) % at least, but too much manganese element influences the performance of steel, so manganese should be controlled at 20 (wt) below the %.
Chromium is ferrite former, and however, because it is an anti-corrosion element main in the stainless steel, and improves the solubleness of nitrogen, chromium content should be controlled at and be not more than 23 (wt) %.
The adding of molybdenum can improve the solubleness of nitrogen, interact with nitrogen and can improve the pitting resistance of steel, but content too much can reduce the toughness of steel, therefore is controlled at 2-3 (wt) %.
Copper also is more weak austenizer, also suitably improves solidity to corrosion, and the content of copper is not more than 1.5 (wt) % if be higher than the forging property that 4 (wt) % will obviously influence steel so must control copper content.Silicon can impel ferritic formation, so silicone content is lower than 0.5 (wt) %.
Impurity element sulphur and phosphorus should be controlled at 0.010 (wt) % and 0.020 (wt) respectively below the %, to improve the over-all properties of steel.
The present invention also provides the preparation method of above-mentioned medical embedded nickel-less austenitic stainless steel, it is characterized in that aftertreatment technology is:
Hot-work: steel ingot was handled 2～6 hours in 1050～1150 ℃ of homogenizing, and cogging divides many fire to forge into bar and breaking down blank, and final forging temperature is not less than 950 ℃.
Thermal treatment: 1100～1150 ℃ of solution treatment 0.5～4 hour, air cooling or water-cooled are to room temperature, and the gained microstructure is single-phase austenite.
Nickel-less austenitic medical stainless steel of the present invention has been abandoned fully sensitization, bring out the toxicity nickel element of thrombosis and carcinogenesis, has great advantage as body implanting material, will improve the life-time service security of biological implantation material greatly.This stainless steel is with respect to traditional nickel chromium triangle medical stainless steel, have better wear and corrosion behavior (particularly spot corrosion) and more good obdurability combination, and cost is lower, can be used for load parts, orthopedic of dentistry and tube chamber implant frames etc. such as the osteoarthrosis main materials used of implant into body device over a long time.Can be used on the stainless steel product aspect that body implant, medicine equipment, food food and drink apparatus, jewellery and other and human body often contact, and might progressively replace existing nickel chromium triangle medical stainless steel, and can be widely used in fields such as chemical industry, environmental protection.
Description of drawings:
Fig. 1 is the metallograph after the thermal treatment of free nickel high nitrogen austenitic stainless steel, demonstrates the austenite one phase tissue, and this provides the structure assurance for stainless steel has good comprehensive performances.
Fig. 2 is medical free nickel stainless steel and the anodic polarization curves of conventional medical 316L stainless steel in 37 ℃ of 0.9%NaCl solution, the corrosion resisting property that shows the new medical nickelles stainless steel is compared more excellent with the 316L stainless steel, pitting resistance particularly, this implants security for a long time for medical metal material basic premise is provided.
Embodiment:
Medical free nickel austenitic stainless steel of the present invention adopts conventional vacuum induction furnace (not adding malleation) to smelt, and smelts following processing of process of gained stainless steel and thermal treatment:
Hot-work: steel ingot is handled more than 2 hours in 1100 ℃ ± 15 ℃ homogenizing, and cogging divides two fire to forge into bar and breaking down blank, and final forging temperature is not less than 950 ℃.The breaking down blank is rolled into the performance test blank 1100 ℃ ± 15 ℃ temperature open rollings through multi-pass.
Thermal treatment: 1100 ℃ ± 5 ℃ solution treatment (1 ± 0.1) hour, air cooling or water-cooled are to room temperature, and gained is organized as single-phase austenite.
The mechanical property of gained bar and rolled plate: σ
b〉=780MPa, σ
0.2〉=400MPa, δ
5〉=50%, Ψ 〉=60%, H
V0.5=190-320, a
k〉=120J/cm
2
Embodiment:
The chemical ingredients scope that sets according to the present invention has been smelted 4 stove steel in 25 kg capacity vacuum induction furnaces, its concrete chemical ingredients is as shown in table 1.This 4 stove steel is poured into each one on φ 120 * 450 steel ingots respectively, and processes by above processing and heat treatment regime.
All along taking a sample perpendicular to rolling direction, through after the above thermal treatment, steel of the present invention is single austenite structure (as shown in Figure 1) under room temperature state to all test samples, and the mechanical property that records is as shown in table 2.Adopt electrochemical method to study the anodic polarization curves of medical free nickel austenitic stainless steel in 37 ℃ of equivalent physiological solutions, the result shows that the novel non-nickel Corrosion Resistance of Stainless Steels compares more excellent with medical 316L stainless steel, pitting resistance particularly, as shown in Figure 2.Measure the anti-pitting potential of new medical nickelles stainless steel in 37 ℃ artificial blood plasma equivalent solution and be about 550mv, and medical 316L stainless steel is about 370mv.From embodiment as can be seen, the interpolation of nitrogen has substituted the effect of nickel effectively, and the obdurability of medical free nickel austenitic stainless steel of the present invention and solidity to corrosion have reached and surpassed the level of traditional nickel chromium triangle medical stainless steel.
The chemical ingredients of the high nitrogen steel of table 1 vacuum induction furnace smelting
| Heat (batch) number | C | Cr | Mn | N | Mo | Cu | Ni | Si | S | |
| 1 | 0.029 | 17.05 | 12.58 | 0.46 | 2.38 | 1.44 | 0.01 | 0.42 | 0.003 | 0.0065 |
| 2 | 0.016 | 17.58 | 12.77 | 0.43 | 2.35 | 0.88 | 0.02 | 0.45 | 0.0056 | 0.007 |
| 3 | 0.017 | 17.64 | 12.96 | 0.40 | 2.34 | 0.86 | 0.02 | 0.45 | 0.0054 | 0.0052 |
| 4 | 0.018 | 17.61 | 12.76 | 0.41 | 2.38 | 0.86 | 0.01 | 0.48 | 0.005 | 0.0074 |
The mechanical property of the high nitrogen steel of table 2 vacuum induction furnace smelting
| Heat (batch) number | Yield strength σ 0.2 (MPa) | Tensile strength sigma b (MPa) | Unit elongation δ 5 (％) | Sectional shrinkage ψ (%) | Summer is than V-type ballistic work a k(J/cm 2) | |
| 1 | 555 | 936 | 51 | 65 | 124 | 286 |
| 2 | 450 | 812 | 60 | 73 | 193 | 270 |
| 3 | 428 | 794 | 55 | 63 | 164 | 252 |
| 4 | 430 | 802 | 59 | 70 | 171 | 246 |
Technological test shows that this medical free nickel austenitic stainless steel has good hot-work and cold-forming property and excellent corrosion resistant performance.
Claims (3)
1, a kind of medical embedded austenitic stainless steel material, it is characterized in that chemical ingredients composition weight percent is: chromium Cr 17～22, manganese Mn 12～20, molybdenum Mo 1～3, copper Cu 0.5～1.5, nitrogen N 0.40～0.70, nickel≤0.02, carbon C≤0.03, silicon Si≤0.75, sulphur S≤0.010, phosphorus P≤0.025, iron Fe: surplus.
2, the preparation method of the described medical embedded austenitic stainless steel material of a claim 1 is characterized in that the aftertreatment technology of alloy is:
Hot-work: steel ingot was handled 2～6 hours in 1050～1150 ℃ of homogenizing, and cogging divides many fire to forge into bar and breaking down blank, and final forging temperature is not less than 950 ℃,
Thermal treatment: 1100～1150 ℃ of solution treatment 0.5～4 hour, air cooling or water-cooled are to room temperature, and the gained microstructure is single-phase austenite.
3, the described medical embedded austenitic stainless steel material of claim 1 is used in body implant, medicine equipment, food food and drink apparatus, jewellery and other and the stainless steel product aspect that human body often contacts, and perhaps is applied to chemical industry, environmental protection field.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03110896 CN1215191C (en) | 2003-01-20 | 2003-01-20 | Embedded material of austenitic stainless steel in medical use |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03110896 CN1215191C (en) | 2003-01-20 | 2003-01-20 | Embedded material of austenitic stainless steel in medical use |
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| CN1215191C true CN1215191C (en) | 2005-08-17 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101385669B (en) * | 2007-09-12 | 2010-12-08 | 中国科学院金属研究所 | Anti-coagulation stainless steel coronary arterial bracket and uses thereof |
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| CN102199738A (en) * | 2010-03-23 | 2011-09-28 | 重庆仪表材料研究所 | Low carbon, nickel-saving, high-strength, high-toughness, corrosion-resistant and nonmagnetic austenite stainless steel |
| CN102551904A (en) * | 2010-12-09 | 2012-07-11 | 中国科学院金属研究所 | Dental magnetic retainer |
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| CN102787277A (en) * | 2011-05-18 | 2012-11-21 | 中国科学院金属研究所 | Medical nickel-free high-nitrogen austenite antimicrobial stainless steel, its preparation and its application |
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| CN111793775B (en) * | 2019-04-08 | 2022-04-05 | 中国科学院金属研究所 | High-nitrogen nickel-free high-specific gravity medical austenitic stainless steel |
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| CN111745104B (en) * | 2020-07-02 | 2022-04-29 | 无锡航亚科技股份有限公司 | Forging method for improving grain size of high-nitrogen stainless steel |
| CN113088652A (en) * | 2021-03-31 | 2021-07-09 | 长春工业大学 | Preparation method of diffusion-strengthened high-stability medical high-nitrogen nickel-free austenitic stainless steel |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101385669B (en) * | 2007-09-12 | 2010-12-08 | 中国科学院金属研究所 | Anti-coagulation stainless steel coronary arterial bracket and uses thereof |
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