CN106086562B - Biological degradable in vivo anastomosis staple and its production technology - Google Patents

Biological degradable in vivo anastomosis staple and its production technology Download PDF

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Publication number
CN106086562B
CN106086562B CN201610592979.5A CN201610592979A CN106086562B CN 106086562 B CN106086562 B CN 106086562B CN 201610592979 A CN201610592979 A CN 201610592979A CN 106086562 B CN106086562 B CN 106086562B
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anastomosis staple
vivo
magnesium alloy
biological degradable
purity
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CN106086562A (en
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周建良
吴伟敏
戴明凯
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Changzhou Huasen Medical Instrument Co.,Ltd.
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Changzhou Waston Medical Appliance Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • C22C23/04Alloys based on magnesium with zinc or cadmium as the next major constituent
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials 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
    • A61L31/02Inorganic materials
    • A61L31/022Metals or alloys
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials 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
    • A61L31/02Inorganic materials
    • A61L31/028Other inorganic materials not covered by A61L31/022 - A61L31/026
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials 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
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/148Materials at least partially resorbable by the body
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/06Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon

Abstract

The present invention relates to tissue engineering technique field more particularly to a kind of biological degradable in vivo anastomosis staple and its production technology, anastomosis staple are composed of the following components by mass percentage:Zn 2 6%, Mn 2 5%, Sn 0.1 1%, Ag 1.5 2%, HA powder 0.5 2%, surplus Mg.A kind of biological degradable in vivo anastomosis staple of the present invention can natural degradation in vivo, can be avoided second operation from internal degradation and cause economy and the burden of body to patient within the regular hour after reaching medical effect;It is avoided in composition design using Al and rare earth metal, the biological safety of material is ensure that from the selection of material;With high corrosion-resistant, good plastic deformation ability and good biocompatibility, meet requirement of the inner implantation material to corrosion rate, and the material, without apparent cytotoxicity, blood compatibility is good, can meet requirement of the inner implantation material to biocompatibility.

Description

Biological degradable in vivo anastomosis staple and its production technology
Technical field
The present invention relates to tissue engineering technique field more particularly to a kind of biological degradable in vivo anastomosis staple and its production works Skill.
Background technology
Medical metal material future will occupy an important position in technical field of biological material, this is because medical metal material has Standby excellent mechanical performance.316L stainless steels, titanium or titanium alloy and Co-Cr alloys etc. have been obtained extensively with excellent mechanical property General application.But it is the power with biological bone there are a common problem in the existing metal implant material such as stainless steel and titanium alloy Learn poor compatibility.5 times higher than nature bone of tensile strength of stainless steel, titanium alloy etc. or more, elasticity modulus be even more high 10 times with On.Very big " stress shielding " effect can be generated to local bone tissue after such material implantation human body.Due to suffered by matrix bone Stress stimulation declines, and bone remodeling negative balance occurs, bone information is caused to increase, and bon e formation is reduced, and induces blocking property bone loss.Together When these materials taken, it is necessary to carry out second operation when as provisional implantation material such as intravascular stent, nail, bone plate, spicule Go out, economy and the burden of body are caused to patient.
To solve the above-mentioned problems, related technical staff researches and develops biodegradable absorbing material, with regard to current Speech, biodegradable absorbing material are mainly polymer and some ceramic materials, such as polylactic acid, calcium phosphate, but due to mesh The property of preceding polymer material used in itself influences, as mechanical property is relatively low, processing difficulties, the more acid of decomposition generation in vivo And easily trigger the problem of inflammation and swelling, limit its application;The plasticity and toughness of ceramic material are poor, and volume is made very with this material Small vascular stent material is extremely difficult, and rejection rate is high.
Magnesium is biomechanical property and the immediate metal material of human body bone in current all metal materials.The bullet of magnesium alloy Property be about 45GPa, than the biomaterial titanium alloy (100GPa) that is widely used at present closer to the elasticity modulus of people's bone (20GPa) can be reduced effectively " stress-shielding effect ", promote symphysis.Magnesium alloy has higher yield strength simultaneously, can To bear larger load, applied to bone tissue carrying position, endovascular stent can also be applied to, play the work of support blood vessels With.But there are corrosion resistance is poor, plastic deformation ability force difference for traditional magnesium alloy.Therefore, it is strong, high resistance to develop plastic deformation ability The biological medical magnesium alloy of corrosion is effectively to reduce its corrosion degradation rate in human body for magnesium alloy is promoted to be cured in biology The application in field is most important.
Alloying is to improve magnesium alloy plastic deformation ability, improve corrosion stability of magnesium alloy energy, solve its corrosion degradation rate The effective way of too fast problem.The study found that aluminium, which is added in magnesium alloy, can improve the corrosion resisting property of alloy, play solution strengthening and Precipitation enhancement, but Al elements can generate health harm, should not be used in biological medical magnesium alloy material.It is in addition, dilute The addition of earth elements can also significantly improve the corrosion resistance of magnesium alloy, and stress-free corrosion is inclined to, but have been reported that show it is dilute Earth elements are easily enriched in brain, lack certain biological safety.At present, the more biocompatibility requirement that meets is studied Complex magnesium alloy has Mg-Mn-Sr-Ca, Mg-Zn-Ca, Mg-Zn-Mn-Ca etc., but the comprehensive performance of these above-mentioned materials is still Have much room for improvement.
The content of the invention
The purpose of the present invention is be directed to current anastomosis staple material to take into account good plastic deformation ability and higher anti-corrosion It the problem of property, provides in a kind of organism with high corrosion-resistant, good plastic deformation ability and good biocompatibility Degradable anastomosis staple and its production technology.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of biology degradable in vivo anastomosis staple, it is composed of the following components by mass percentage:
Zn 2-6%, Mn 2-5%, Sn 0.1-1%, Ag 1.5-2%, HA powder 0.5-2%, surplus Mg.
Preferably, the HA powder is nano bar-shape HA powder, grain size 20-60nm.
Hydroxyapatite(HA)As a kind of ingredient of nature bone, the solubility in human body environment is very low, is closed in magnesium On the one hand addition in gold can adjust the mechanical performance of magnesium alloy bracket, make the mechanical performance of stent and organism difference portion The mechanical property of the bone of position matches, and alleviates or avoids stress-shielding effect, the addition of another aspect hydroxyapatite is conducive to The growth of osteocyte and multiplication can improve the corrosion resisting property of magnesium alloy bracket to a certain extent.The HA selected in the present invention The HA that the article No. provided for Nanjing Ai Purui nano materials Co., Ltd is MH01.
Preferably, the degree of purity of the Zn is more than 99.99%.
Zinc(Zn)It is alloying element relatively common in a kind of magnesium alloy, the creep-resistant property of casting can be improved, it can be with Increase the mobility of melt, weak grain refiner to form Micro shrinkage tendency, there is precipitation enhancement.
Preferably, the degree of purity of the Sn is more than 99.99%.
Tin(Sn)The corrosion resistance and intensity of magnesium alloy can be improved.
Preferably, the degree of purity of the Ag is more than 99.99%.
Silver(Ag)Solid solubility maximum in Mg can reach 15%, and after Ag is dissolved in Mg, clearance-type solid solution atom causes non- Spherical symmetric distorts, so as to generate very strong solid solution strengthening effect and ageing strengthening effect, in magnesium alloy the addition of Ag can compare The tensile strength and yield strength of alloy are improved more significantly.
Preferably, the degree of purity of the Mg is more than 99.99%.
Preferably, the degree of purity of the Mn is more than 99.99%.
Manganese(Mn)Solid solubility in Mg is small, does not form compound with Mg.Mn with crystal grain thinning, can improve the weldering of alloy Connect performance.It is but smaller to the invigoration effect of alloy.In other cast magnesium alloys or wrought magnesium alloy, often add in a small amount of Mn, improve the corrosion resisting property of magnesium alloy.Mn can form high-melting-point chemical combination with the impurity F e of serious damage corrosion stability of magnesium alloy energy Object and be precipitated out, refine precipitated product, increase creep resistance, improve the corrosion resisting property of alloy.
A kind of production technology of above-mentioned biological degradable in vivo anastomosis staple, comprises the following steps:
1. the preparation process of magnesium alloy:
1)Each component is weighed in proportion;
2)The above-mentioned each component weighed is dried in 100 DEG C of baking oven 1-2 it is small when;
3)Zn, Mn, Sn, Ag and Mg for weighing are added in graphite crucible, after vacuumizing, are passed through BF3And CO2Gaseous mixture Body after being completely dissolved each component under conditions of 700-800 DEG C, keeps 10-20min as protective gas;
4)HA powder is added to melting has in the graphite crucible of Zn, Mn, Sn, Ag and Mg, and stirs evenly, and it is molten to obtain melting Liquid;
5)Melting solution is poured into the graphite jig dried in advance, obtains magnesium alloy ingot;
2. the heat treatment process of magnesium alloy:
1)By the magnesium alloy ingot obtained in the preparation process of magnesium alloy when solid solution 10 is small under conditions of 540 DEG C;
2)Magnesium alloy ingot after solid solution is put into the mold preheated in advance, preheating temperature is 220-480 DEG C, in 300- Section bar, i.e. anastomosis staple are squeezed at a temperature of 500 DEG C;
3)By step 2)In section bar made annealing treatment under conditions of 500 DEG C;
4)To step 3)The section bar of the processing of middle annealing carries out alkali heat-treatment.
Preferably, the base extraction includes the following steps:
1)In NaHCO3-NaOH-Mg(OH)2Solution(pH9.3)It is middle impregnate 24 it is small when, take out natural air drying;
2)10h is kept the temperature in 773K, it is air-cooled.
Advantages of the present invention and advantageous effect are:
(1) a kind of biological degradable in vivo anastomosis staple of the present invention can natural degradation in vivo, reach medical effect It can be avoided second operation from internal degradation and cause economy and the burden of body to patient within the regular hour after fruit.
(2) a kind of biological degradable in vivo anastomosis staple of the present invention is avoided in composition design using Al and rare earth gold Belong to, the biological safety of material is ensure that from the selection of material.
(3) a kind of biological degradable in vivo anastomosis staple of the present invention have high corrosion-resistant, good plastic deformation ability and Good biocompatibility meets requirement of the inner implantation material to corrosion rate, and the material is without apparent cytotoxicity, blood Liquid phase capacitive is good, can meet requirement of the inner implantation material to biocompatibility.
(4)A kind of biological degradable in vivo anastomosis staple of the present invention uses hydroxyapatite(HA), on the one hand can adjust magnesium The mechanical performance of alloy bracket, the mechanical performance and the mechanical property of the bone of organism different parts for making stent match, and alleviate Or stress-shielding effect is avoided, the opposing party is conducive to growth and the multiplication of osteocyte, can improve magnesium alloy to a certain extent The corrosion resisting property of stent.
(5)A kind of production technology of biological degradable in vivo anastomosis staple of the present invention, in heat treatment process, is squeezed in section bar After molded, section bar at 500 DEG C is made annealing treatment, the corrosion resistance of magnesium alloy is improved from inside;At subsequent alkali heat Manage the corrosion resistance that magnesium alloy is improved from outside.
Specific embodiment
The present invention is described in further detail now.
A kind of biology degradable in vivo anastomosis staple, by mass percentage its component composition see the table below:
A kind of production technology of biology degradable in vivo anastomosis staple, comprises the following steps:
1)Each component is weighed in proportion;
2)The above-mentioned each component weighed is dried in 100 DEG C of baking oven 1-2 it is small when;
3)Zn, Mn, Sn, Ag and Mg for weighing are added in graphite crucible, after vacuumizing, are passed through BF3And CO2Gaseous mixture Body after being completely dissolved each component under conditions of 700-800 DEG C, keeps 10-20min as protective gas;
4)HA powder is added to melting has in the graphite crucible of Zn, Mn, Sn, Ag and Mg, and stirs evenly, and it is molten to obtain melting Liquid;
5)Melting solution is poured into the graphite jig dried in advance, obtains magnesium alloy ingot;
2. the heat treatment process of magnesium alloy:
1)By the magnesium alloy ingot obtained in the preparation process of magnesium alloy when solid solution 10 is small under conditions of 540 DEG C;
2)Magnesium alloy ingot after solid solution is put into the mold preheated in advance, preheating temperature is 220-480 DEG C, in 300- Section bar, i.e. anastomosis staple are squeezed at a temperature of 500 DEG C;
3)By step 2)In section bar made annealing treatment under conditions of 500 DEG C;
4)To step 3)The section bar of the processing of middle annealing is in NaHCO3-NaOH-Mg(OH)2Solution(pH9.3)Middle immersion 24 is small When, take out natural air drying;
5)By step 4)Obtained section bar keeps the temperature 10h in 773K, air-cooled, obtains biological degradable in vivo anastomosis staple.
Mechanical property, corrosion resistance and cytotoxicity are carried out to the anastomosis staple section bar that each embodiment obtains to test, Its structure such as following table:
Anastomosis staple provided by the invention not only has good mechanical property, with more excellent corrosion resisting property, solves Anastomosis staple material cannot take into account good plastic deformation ability and the problem of compared with high corrosion-resistant at present, and catabolite is nontoxic, Good biocompatibility has larger potential application in biomedical sector.
Using above-mentioned desirable embodiment according to the invention as enlightenment, by above-mentioned description, relevant staff is complete Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention Property scope is not limited to the content on specification, it is necessary to determine its technical scope according to right.

Claims (7)

1. a kind of biology degradable in vivo anastomosis staple, composed of the following components by mass percentage:
Zn 2-6%
Mn 2-5%
Sn 0.1-1%
Ag 1.5-2%
HA powder 0.5-2%
Surplus is Mg;
The production technology of the biological degradable in vivo anastomosis staple, comprises the following steps:
First, the preparation process of magnesium alloy:
1)Each component is weighed in proportion;
2)The above-mentioned each component weighed is dried in 100 DEG C of baking oven 1-2 it is small when;
3)Zn, Mn, Sn, Ag and Mg for weighing are added in graphite crucible, after vacuumizing, are passed through BF3And CO2Mixed gas make For protective gas, after being completely dissolved each component under conditions of 700-800 DEG C, 10-20min is kept;
4)HA powder is added to melting has in the graphite crucible of Zn, Mn, Sn, Ag and Mg, and stirs evenly, and obtains melting melt;
5)Melting melt is poured into the graphite jig dried in advance, obtains magnesium alloy ingot;
2nd, the heat treatment process of magnesium alloy:
1)By the magnesium alloy ingot obtained in the preparation process of magnesium alloy when solid solution 10 is small under conditions of 540 DEG C;
2)Magnesium alloy ingot after solid solution is put into the mold preheated in advance, preheating temperature is 220-480 DEG C, at 300-500 DEG C At a temperature of be squeezed into section bar, i.e. anastomosis staple;
3)By step 2)In section bar made annealing treatment under conditions of 500 DEG C;
4)To step 3)The section bar of middle annealing carries out alkali heat-treatment.
2. a kind of biological degradable in vivo anastomosis staple as described in claim 1, it is characterised in that:The HA powder is nano bar-shape HA powder, grain size 20-60nm.
3. a kind of biological degradable in vivo anastomosis staple as described in claim 1, it is characterised in that:The degree of purity of the Zn exists More than 99.99%.
4. a kind of biological degradable in vivo anastomosis staple as described in claim 1, it is characterised in that:The degree of purity of the Sn exists More than 99.99%.
5. a kind of biological degradable in vivo anastomosis staple as described in claim 1, it is characterised in that:The degree of purity of the Ag exists More than 99.99%.
6. a kind of biological degradable in vivo anastomosis staple as described in claim 1, it is characterised in that:The degree of purity of the Mg exists More than 99.99%.
7. a kind of biological degradable in vivo anastomosis staple as described in claim 1, it is characterised in that:The degree of purity of the Mn exists More than 99.99%.
CN201610592979.5A 2016-07-26 2016-07-26 Biological degradable in vivo anastomosis staple and its production technology Active CN106086562B (en)

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CN109280827A (en) * 2017-07-19 2019-01-29 北京普润医疗器械有限公司 Anastomosis staple and its preparation method and application
CN110257678B (en) * 2019-07-29 2021-07-16 湘潭大学 High-strength heat-deformation-resistant magnesium alloy material and preparation method thereof
CN110343922A (en) * 2019-08-14 2019-10-18 西京学院 A kind of magnesium tin alloy and its preparation method and application that human body is degradable
CN111388764A (en) * 2020-04-03 2020-07-10 北京联合大学 Degradable metal anastomosis nail and preparation method thereof
EP4163408A4 (en) 2020-06-05 2023-07-26 Sichuan Megall Medical Devices Co., Ltd Degradable magnesium alloy in-situ composite staple and preparation method therefor
CN112245665A (en) * 2020-09-28 2021-01-22 兰州理工大学 Degradable magnesium alloy anastomosis nail and preparation method thereof
CN113476668A (en) * 2021-07-12 2021-10-08 中山大学附属第六医院 Biodegradable anastomosis nail and preparation method thereof
CN114086011B (en) * 2021-10-25 2022-07-08 江苏理工学院 Preparation method of component gradient magnesium-based implant material with controllable degradation

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