CN110241380A - A kind for the treatment of process of medical free nickel stainless steel - Google Patents
A kind for the treatment of process of medical free nickel stainless steel Download PDFInfo
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- CN110241380A CN110241380A CN201910474086.4A CN201910474086A CN110241380A CN 110241380 A CN110241380 A CN 110241380A CN 201910474086 A CN201910474086 A CN 201910474086A CN 110241380 A CN110241380 A CN 110241380A
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- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/02—Inorganic materials
- A61L31/022—Metals or alloys
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- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
- C23C8/38—Treatment of ferrous surfaces
Abstract
The present invention relates to a kind for the treatment of process of medical free nickel stainless steel, medical stainless steel preparation process in the prior art is improved, the heat treatment step for quenching and being tempered after taking segmentally heating, nitrided surface treatment process is used again, pass through the modified parameter area of strict control heat treating regime and surface, ensure the surface covering performance of stainless steel product, while so that it is had both the requirement of mechanical property and corrosion resistance, excellent biocompatibility is obtained, can satisfy the metal material embedded application demand of medical surgical.
Description
Technical field
The present invention relates to metal heat treatmet fields, in particular to a kind for the treatment of process of medical free nickel stainless steel.
Background technique
Bio-medical material refers to the material for that medically can be implanted into organism or engage with biological tissue, can use
Tissue, organ in diagnoses and treatment, and in replacement living organism promote its function.In numerous biomaterials, medical gold
Belong to material toughness with higher and intensity, is suitable for repairing, displacement human body hard tissue.It has been applied to clinical medical metal material
Material mainly includes several major class such as stainless steel, cobalt-base alloys, titanium alloy, is generation in addition there are the gold, silver of pure metal class, niobium, pick, tantalum
Noble metal and marmem of table etc..
Medical stainless steel has good corrosion resistance and comprehensive mechanical property, is applied in biomedical metal material
At most, most wide a kind of material.Medical stainless steel is after being implanted into human body, causing the blunt of surface due to corroding or wear etc.
When change layer or protective layer destroy, wherein metal ion is easy to be enriched in the tissue near implantation material, influences organism
Eubolism.There is medical free nickel stainless steel excellent obdurability to combine, good resistance to corrosion, it is most important that in steel
Without nickel element, to can avoid sensitization and other tissue reactions caused by nickel element is precipitated in human body.
Medical stainless steel still remains some defects and deficiency in practical clinical.Existing medical stainless steel material
The intensity of material and the mechanical property requirements of Elastoplastic Performances in Simulation and skeleton tissue have a certain gap, long after being implanted into human body
The high stress anaerobic application environment of phase can also reduce the corrosion resistance and service life of stainless steel.Thus it is badly in need of research and development
A kind of new medical stainless steel treatment process, improves its deficiency in clinical application.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind for the treatment of process of medical free nickel stainless steel, this method
The medical stainless steel product with good mechanical performance, corrosion resistance and biocompatibility can be prepared.
A kind of the step for the treatment of process of medical free nickel stainless steel, the technique are as follows:
(1), hot forging is carried out according to the stainless steel billet size of medical material product design and prepares the blank, then to the base
Material is rolled.
(2), the stainless steel after rolling is managed in some tension tripping in furnace treatment, first with the heating speed of 100~150 DEG C/h
500~700 DEG C are warming up to, 1~2h is kept the temperature, austenitizing temperature is then warming up to simultaneously with the heating speed of 400~850 DEG C/min
Keep the temperature 0.5~1h.
(3), be quenched in quenching oil, and after stainless steel is cooled to 160~220 DEG C take out heat preservation 0.5~
1h。
(4), stainless steel is heated to certain temperature tempering 2~3h of heat preservation again, be cooled to room temperature.
(5), the stainless steel material after tempering is cleaned, is put on the nitridation workbench in ionic nitriding equipment, if
It is standby to vacuumize, when being evacuated to 10Pa, ammonia is added to 400~450Pa.
(6), ionic nitriding equipment is warming up to 480~500 DEG C of 5~10h of holding, then is adjusted to 420~440 DEG C, be passed through
25%N2+75% H2Mixed gas simultaneously keeps 5~10h, is finally cooled to room temperature, obtains medical free nickel stainless steel.
The ingredient of the stainless steel blank is C 0.05wt%, Cr 21.0wt%, Mn 8.0wt%, V 0.50wt%, Sn
0.30wt%, Cu 0.25wt%, surplus are iron and inevitable impurity.
In step (1), the rolling is cold rolling.
In step (2), the tension can ensure that the elongation percentage of control stainless steel 1.0%~5.0%.
In step (3), the austenitizing temperature is 850~880 DEG C.
In step (4), the tempering temperature is 350~380 DEG C.
It is 400 DEG C or so that facility environment temperature is kept in step (5), when equipment vacuumizes.
The yield strength of the medical free nickel stainless steel finished product is 550~650MPa, tensile strength be 950~
1050MPa, elongation are 52~56%.
The medical free nickel stainless steel finished product is used for surgical implantation metal material.
The medical free nickel stainless steel finished product is stainless steel bone fixation instrument and anti-coagulation stainless steel angiocarpy bracket
Product steel.
Compared with prior art, the invention has the advantages that changing to medical stainless steel preparation process in the prior art
Into, the heat treatment step for quenching and being tempered after taking segmentally heating, then nitrided surface treatment process is used, pass through strict control heat
The parameter area that resolving system and surface are modified, it is ensured that the surface covering performance of stainless steel product makes it have both mechanical property
While with the requirement of corrosion resistance, excellent biocompatibility is obtained, can satisfy medical surgical implanted metal material
The application demand of material.
Specific embodiment
Many countries including China have lowered the standard content of nickel element in medical stainless steel, and issue
Medical free nickel stainless steel standard.Nickelles stainless steel since it is free of nickel element, and has as a kind of novel bio-medical material
There is excellent comprehensive performance, impressive progress is had been achieved in multiple fields.Material, nickelles stainless steel are implanted into as coronary artery bracket
There is certain inhibiting effect with good blood compatibility, while to the proliferation of vascular smooth muscle cells, to reduction bracket
Caused restenosis has a very important significance after implantation.With the biological safety and mechanical property etc. to nickelles stainless steel
Deepen continuously progress and the successive optimization of relevant rudimentary Journal of Sex Research, it is stainless that medical free nickel stainless steel is gradually replacing conventional medical
Steel.
The sterilization mechanism of different types of anti-bacteria stainless steel will be different.According to the difference of antibacterial agent, Antibacterial Mechanism master
Will there are two types of: ionic sterilization and photo-catalyst.The surface modified version for being coated with antibacterial metal for alloy-type and surface is stainless
Steel, main Antibacterial Mechanism are ionic sterilization.By taking copper-bearing antibacterial stainless steel as an example, anti-bacteria stainless steel during military service due to
Inevitably corrosiveness can micro and constantly release the antibacterial ion with strong bactericidal effect on its surface.No
The copper ion of rust steel surface dissolution can destroy bacterium internal protein structure, inhibit duplication and the related protein/enzyme of DNA of bacteria
Synthesis, destroy bacterium in metabolic activity, so that bacterium is lost activity, lead to bacterial death.
Surface modification is the corrosion resistance for improving medical metal material and the effective ways of blood compatibility, main method
Two classes can be divided into: one kind is to prepare the good bioceramic film (or coating) of biocompatibility in stainless steel surface, but exist
The poor problem of the stability that substrate-film (or coating) interface bond strength is not high, is implanted into for a long time in physiological environment；Separately
One kind is such as mechanically polished, particle beams injection, laser modified, surface using in-situ-surface modifying is either physically or chemically carried out
Chemical treatment and Surface heat-treatent etc., these methods can change material surface while retaining metal material performance itself
Ingredient and structure.Biomedical metallic material is easy to wear and corrodes, therefore medical material can be improved using process for modifying surface
Biocompatibility.It is especially modified to the surface of bone, Chi Deng sclerous tissues implantation material and cardiovascular metallic support, it can be improved implantation material
Corrosion resistance and blood compatibility.
The manufacture craft of medical free nickel stainless steel material of the present invention has abandoned nickel element completely, strengthens Austria using nitrogen
Family name's body matrix, suitable heat treatment make stainless steel ensure that single, stable microcosmic grain structure, even if severely deformed in generation
It is still able to maintain rock-steady structure afterwards.Also, stainless steel product of the present invention is in 0.9wt% NaCl physiological saline and simulating blood plasma solution
With excellent corrosion resistance, while its intensity improves, elongation, the contraction percentage of area still maintain higher level.
Below with reference to embodiment and comparative example, the present invention is described in more detail.
Embodiment 1:
A kind of the step for the treatment of process of medical free nickel stainless steel, the technique are as follows:
(1), hot forging is carried out according to the stainless steel billet size of medical material product design and prepares the blank, then to the base
Material is rolled.
(2), the stainless steel after cold rolling is managed in some tension tripping in furnace treatment, the tension can ensure that control stainless steel
Elongation percentage is first warming up to 550 DEG C 1.0% with the heating speed of 120 DEG C/h, keeps the temperature 2h, then with the heating speed of 850 DEG C/min
Degree is warming up to 880 DEG C and keeps the temperature 1h.
(3), it is quenched in quenching oil, and takes out heat preservation 0.5h after stainless steel is cooled to 180 DEG C.
(4), stainless steel is heated to 360 DEG C of tempering heat preservation 2h again, be cooled to room temperature.
(5), the stainless steel material after tempering is cleaned, is put on the nitridation workbench in ionic nitriding equipment, if
Standby to vacuumize, keeping facility environment temperature is 400 DEG C or so, and when being evacuated to 10Pa, ammonia is added to 410Pa.
(6), ionic nitriding equipment is warming up to 480 DEG C of holding 10h, then is adjusted to 420 DEG C, be passed through 25%N2+75% H2It is mixed
It closes gas and keeps 8h, be finally cooled to room temperature, obtain medical free nickel stainless steel.
The ingredient of the stainless steel blank is C 0.05wt%, Cr 21.0wt%, Mn 8.0wt%, V 0.50wt%, Sn
0.30wt%, Cu 0.25wt%, surplus are iron and inevitable impurity.
The yield strength of the medical free nickel stainless steel finished product is 550MPa, tensile strength 950MPa, elongation are
56%。
The medical free nickel stainless steel finished product is used for surgical implantation metal material.
Embodiment 2:
A kind of the step for the treatment of process of medical free nickel stainless steel, the technique are as follows:
(1), hot forging is carried out according to the stainless steel billet size of medical material product design and prepares the blank, then to the base
Material is rolled.
(2), the stainless steel after cold rolling is managed in some tension tripping in furnace treatment, the tension can ensure that control stainless steel
Elongation percentage is first warming up to 600 DEG C 4.0% with the heating speed of 150 DEG C/h, keeps the temperature 2h, then with the heating speed of 450 DEG C/min
Degree is warming up to 860 DEG C and keeps the temperature 0.5h.
(3), it is quenched in quenching oil, and takes out heat preservation 0.5h after stainless steel is cooled to 190 DEG C.
(4), stainless steel is heated to 380 DEG C of tempering heat preservation 3h again, be cooled to room temperature.
(5), the stainless steel material after tempering is cleaned, is put on the nitridation workbench in ionic nitriding equipment, if
Standby to vacuumize, keeping facility environment temperature is 400 DEG C or so, and when being evacuated to 10Pa, ammonia is added to 420Pa.
(6), ionic nitriding equipment is warming up to 500 DEG C of holding 6h, then is adjusted to 420 DEG C, be passed through 25%N2+75% H2Mixing
Gas simultaneously keeps 5h, is finally cooled to room temperature, obtains medical free nickel stainless steel.
The ingredient of the stainless steel blank is C 0.05wt%, Cr 21.0wt%, Mn 8.0wt%, V 0.50wt%, Sn
0.30wt%, Cu 0.25wt%, surplus are iron and inevitable impurity.
The yield strength of the medical free nickel stainless steel finished product is 600MPa, tensile strength 1000MPa, elongation are
55%。
The medical free nickel stainless steel finished product is the product steel of stainless steel bone fixation instrument.
Embodiment 3:
A kind of the step for the treatment of process of medical free nickel stainless steel, the technique are as follows:
(1), hot forging is carried out according to the stainless steel billet size of medical material product design and prepares the blank, then to the base
Material is rolled.
(2), the stainless steel after cold rolling is managed in some tension tripping in furnace treatment, the tension can ensure that control stainless steel
Elongation percentage is first warming up to 700 DEG C 3.5% with the heating speed of 130 DEG C/h, 1.5h is kept the temperature, then with the heating of 650 DEG C/min
Speed is warming up to 850 DEG C and keeps the temperature 0.5h.
(3), it is quenched in quenching oil, and takes out heat preservation 1h after stainless steel is cooled to 160 DEG C.
(4), stainless steel is heated to 380 DEG C of tempering heat preservation 3h again, be cooled to room temperature.
(5), the stainless steel material after tempering is cleaned, is put on the nitridation workbench in ionic nitriding equipment, if
Standby to vacuumize, keeping facility environment temperature is 400 DEG C or so, and when being evacuated to 10Pa, ammonia is added to 450Pa.
(6), ionic nitriding equipment is warming up to 490 DEG C of holding 10h, then is adjusted to 440 DEG C, be passed through 25%N2+75% H2It is mixed
It closes gas and keeps 6h, be finally cooled to room temperature, obtain medical free nickel stainless steel.
The ingredient of the stainless steel blank is C 0.05wt%, Cr 21.0wt%, Mn 8.0wt%, V 0.50wt%, Sn
0.30wt%, Cu 0.25wt%, surplus are iron and inevitable impurity.
The yield strength of the medical free nickel stainless steel finished product is 650MPa, tensile strength 1050MPa, elongation are
52%。
The medical free nickel stainless steel finished product is the product steel of anti-coagulation stainless steel angiocarpy bracket.
Comparative example 1:
When system of heat treatment process changes, the microstructure change of stainless steel will lead to.Such as heating cycle is not segmented
It carries out, will lead to stainless steel, there are cold rolling residual stress, and austenitization stage coarse grains, local part are uneven.And
Element ratio of the invention is the balanced mechanical property and corrosion-resistant, biocompatibility comprehensive performance considered, works as element species
Or content deteriorates the mechanical property for making final stainless steel product, biological sensitization and cytotoxicity, together when changing
When also make heat treating regime incompatible therewith, excellent comprehensive performance can not be obtained.
Comparative example 2:
In the manufacturing method of the present invention, when changing process of surface treatment, especially the technological parameters such as nitriding atmosphere and temperature are sent out
It is raw to change, it will affect the effect of surface treatment, cause the coating quality of medical stainless steel final products bad, height is answered in human body
Reduced service life under power high corrosion environment.
The results showed that the present invention is in the prior art medical it can be seen from embodiment 1-3 and comparative example 1 and 2
Stainless steel preparation process improves, the heat treatment step for quenching and being tempered after taking segmentally heating, then using at nitrided surface
Science and engineering sequence passes through the modified parameter area of strict control heat treating regime and surface, it is ensured that the surface covering of stainless steel product
Performance obtains excellent biocompatibility, Neng Gouman while so that it is had both the requirement of mechanical property and corrosion resistance
The application demand of podiatrist's surgical implantation metal material.
Although an embodiment of the present invention has been shown and described, it will be understood by those skilled in the art that: not
A variety of change, modification, replacement and modification can be carried out to these embodiments in the case where being detached from the principle of the present invention and objective, this
The range of invention is defined by the claims and their equivalents.
Claims (10)
1. a kind for the treatment of process of medical free nickel stainless steel, which is characterized in that the step of the technique are as follows:
(1), hot forging is carried out according to the stainless steel billet size of medical material product design and prepares the blank, then to the base
Material is rolled；
(2), the stainless steel after rolling is managed in some tension tripping in furnace treatment, is first heated up with the heating speed of 100~150 DEG C/h
To 500~700 DEG C, 1~2h is kept the temperature, austenitizing temperature is then warming up to the heating speed of 400~850 DEG C/min and is kept the temperature
0.5~1h；
(3), it is quenched in quenching oil, and takes out 0.5~1h of heat preservation after stainless steel is cooled to 160~220 DEG C；
(4), stainless steel is heated to certain temperature tempering 2~3h of heat preservation again, be cooled to room temperature；
(5), the stainless steel material after tempering is cleaned, is put on the nitridation workbench in ionic nitriding equipment, equipment is taken out
Ammonia is added to 400~450Pa when being evacuated to 10Pa in vacuum；
(6), ionic nitriding equipment is warming up to 480~500 DEG C of 5~10h of holding, then is adjusted to 420~440 DEG C, be passed through 25%N2+
75% H2Mixed gas simultaneously keeps 5~10h, is finally cooled to room temperature, obtains medical free nickel stainless steel.
2. treatment process according to claim 1, which is characterized in that the ingredient of the stainless steel blank is C 0.05wt%,
Cr 21.0wt%, Mn 8.0wt%, V 0.50wt%, Sn 0.30wt%, Cu 0.25wt%, surplus be iron and inevitably it is miscellaneous
Matter.
3. treatment process according to claim 1 or 2, which is characterized in that in step (1), the rolling is cold rolling.
4. manufacturing method according to claim 1 or 2, which is characterized in that in step (2), the tension can ensure that control
The elongation percentage of stainless steel is 1.0%~5.0%.
5. manufacturing method according to claim 1 or 2, which is characterized in that in step (3), the austenitizing temperature is
850~880 DEG C.
6. treatment process according to claim 1 or 2, which is characterized in that in step (4), the tempering temperature be 350~
380℃。
7. treatment process according to claim 1 or 2, which is characterized in that in step (5), keep setting when equipment vacuumizes
Standby environment temperature is 400 DEG C or so.
8. according to claim 1 to treatment process described in 7, which is characterized in that the medical free nickel stainless steel finished product is bent
Take that intensity is 550~650MPa, tensile strength is 950~1050MPa, elongation is 52~56%.
9. according to claim 1 to treatment process described in 8, which is characterized in that the medical free nickel stainless steel finished product is used for
Surgical implantation metal material.
10. treatment process according to claim 9, which is characterized in that the medical free nickel stainless steel finished product is stainless
The product steel of reinforcing bar fixed instrument and anti-coagulation stainless steel angiocarpy bracket.
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| CN111840659A (en) * | 2020-04-30 | 2020-10-30 | 中科益安医疗科技（北京）股份有限公司 | High-safety blood vessel support without nickel metal medicine elution and its making method |
| CN111850422A (en) * | 2020-04-30 | 2020-10-30 | 中科益安医疗科技（北京）股份有限公司 | High-nitrogen nickel-free austenitic stainless steel seamless thin-walled tube and preparation method thereof |
| WO2021218089A1 (en) * | 2020-04-30 | 2021-11-04 | 中科益安医疗科技（北京）股份有限公司 | High-nitrogen nickel-free austenitic stainless steel seamless thin-walled tube |
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|---|---|---|---|---|
| CN111840659A (en) * | 2020-04-30 | 2020-10-30 | 中科益安医疗科技（北京）股份有限公司 | High-safety blood vessel support without nickel metal medicine elution and its making method |
| CN111850422A (en) * | 2020-04-30 | 2020-10-30 | 中科益安医疗科技（北京）股份有限公司 | High-nitrogen nickel-free austenitic stainless steel seamless thin-walled tube and preparation method thereof |
| WO2021218089A1 (en) * | 2020-04-30 | 2021-11-04 | 中科益安医疗科技（北京）股份有限公司 | High-nitrogen nickel-free austenitic stainless steel seamless thin-walled tube |
| CN111840659B (en) * | 2020-04-30 | 2022-02-08 | 中科益安医疗科技（北京）股份有限公司 | High-safety blood vessel support without nickel metal medicine elution and its making method |
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