CN114177349A - 一种生物可降解的医用金属镁及镁合金补片的制备方法 - Google Patents
一种生物可降解的医用金属镁及镁合金补片的制备方法 Download PDFInfo
- Publication number
- CN114177349A CN114177349A CN202111536726.3A CN202111536726A CN114177349A CN 114177349 A CN114177349 A CN 114177349A CN 202111536726 A CN202111536726 A CN 202111536726A CN 114177349 A CN114177349 A CN 114177349A
- Authority
- CN
- China
- Prior art keywords
- magnesium
- metal
- coating
- patch
- biodegradable medical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 239000011777 magnesium Substances 0.000 title claims abstract description 118
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 118
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 44
- 239000002184 metal Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910000861 Mg alloy Inorganic materials 0.000 title abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims description 50
- 238000000576 coating method Methods 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000005096 rolling process Methods 0.000 claims description 14
- 238000011282 treatment Methods 0.000 claims description 11
- 238000005520 cutting process Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 230000001954 sterilising effect Effects 0.000 claims description 7
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 6
- ZQBZAOZWBKABNC-UHFFFAOYSA-N [P].[Ca] Chemical compound [P].[Ca] ZQBZAOZWBKABNC-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 230000007547 defect Effects 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 229940068041 phytic acid Drugs 0.000 claims description 6
- 235000002949 phytic acid Nutrition 0.000 claims description 6
- 239000000467 phytic acid Substances 0.000 claims description 6
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 6
- 239000004632 polycaprolactone Substances 0.000 claims description 6
- 239000004626 polylactic acid Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004659 sterilization and disinfection Methods 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 3
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 230000002035 prolonged effect Effects 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 208000027418 Wounds and injury Diseases 0.000 abstract description 9
- 230000004060 metabolic process Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000008439 repair process Effects 0.000 abstract description 6
- 235000015097 nutrients Nutrition 0.000 abstract description 5
- 206010019909 Hernia Diseases 0.000 abstract description 4
- 210000000056 organ Anatomy 0.000 abstract description 4
- 208000007913 Pituitary Neoplasms Diseases 0.000 abstract description 3
- 201000005746 Pituitary adenoma Diseases 0.000 abstract description 3
- 206010061538 Pituitary tumour benign Diseases 0.000 abstract description 3
- 238000002316 cosmetic surgery Methods 0.000 abstract description 3
- 230000006378 damage Effects 0.000 abstract description 3
- 208000014674 injury Diseases 0.000 abstract description 3
- 208000013823 pelvic organ prolapse Diseases 0.000 abstract description 3
- 208000021310 pituitary gland adenoma Diseases 0.000 abstract description 3
- 238000004080 punching Methods 0.000 abstract description 3
- 230000007281 self degradation Effects 0.000 abstract description 3
- 210000000779 thoracic wall Anatomy 0.000 abstract description 3
- 230000017423 tissue regeneration Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 210000001519 tissue Anatomy 0.000 description 7
- 206010052428 Wound Diseases 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 208000029836 Inguinal Hernia Diseases 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 206010061218 Inflammation Diseases 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 239000010839 body fluid Substances 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003467 diminishing effect Effects 0.000 description 2
- 235000020774 essential nutrients Nutrition 0.000 description 2
- 210000003722 extracellular fluid Anatomy 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000035876 healing Effects 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 230000004054 inflammatory process Effects 0.000 description 2
- 238000003698 laser cutting Methods 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 210000002381 plasma Anatomy 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 210000002027 skeletal muscle Anatomy 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 210000002700 urine Anatomy 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 206010048038 Wound infection Diseases 0.000 description 1
- IXHOXXFTTQTNQS-UHFFFAOYSA-N [Ca].[Na].[K] Chemical compound [Ca].[Na].[K] IXHOXXFTTQTNQS-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
Classifications
-
- 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
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
-
- 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
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
-
- 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
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/32—Phosphorus-containing materials, e.g. apatite
-
- 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
- A61L27/28—Materials for coating prostheses
- A61L27/34—Macromolecular materials
-
- 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
-
- 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
- A61L27/54—Biologically active materials, e.g. therapeutic substances
-
- 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
- A61L27/56—Porous materials, e.g. foams or sponges
-
- 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
- A61L27/58—Materials at least partially resorbable by the body
-
- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0242—Flattening; Dressing; Flexing
-
- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0268—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment between cold rolling steps
-
- 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
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/41—Anti-inflammatory agents, e.g. NSAIDs
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/412—Tissue-regenerating or healing or proliferative agents
-
- 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
-
- 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
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Engineering & Computer Science (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Dispersion Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
本发明公开了一种生物可降解的医用金属镁及镁合金补片的制备方法，所述所选补片是金属镁板材由激光或者冲压等其他达到一致目的的加工方式而成的多孔网状结构。本发明金属镁补片可实现自我降解，降解的镁可作为营养元素被人体吸收，余量镁参与人体新陈代谢而不会对人体有害，现有补片大多需要二次取出而造成患者的二次伤害，金属镁补片的镁元素是人体必需元素，与人体组织可达到生物相容性，不会出现排异现象而出现并发症等现象，能够较有利的挡住已攻破人体薄弱点而进入到另一部分的脏器官，易实现量产，品质稳定可控，生产效率高，在作为疝修复手术，盆腔脏器脱垂手术，胸壁修复手术，脑垂体腺瘤手术，或整形外科手术用组织修复补片的用途。
Description
技术领域
本发明涉及生物医用相关技术领域，更具体地说，本发明涉及一种生物可降解的医用金属镁及镁合金补片的制备方法。
背景技术
疝是指体内某个组织或脏器离开正常解刨位置，通过先天或后天形成的薄弱点，缺损和空隙进入另一部位，其中以腹股沟疝发生率最高，占90％以上，股疝次之，占5％左右，有调查显示，国内60岁以上老年人腹股沟疝的发病率可高达11.8％，而患腹股沟疝的概率，男性可为27％，女性为3％。
目前应用的补片大多是高分子材料包括聚丙烯网，聚四氟乙烯补片，聚酯网片等，其缺点非常明显，表现为因为是不能降解材料，植入体内会使得伤口感染的可能，甚至可能导致严重的并发症，需要二次手术取出，增加患者的痛苦的经济负担，因此开发一种能够避免上述缺陷的高性能补片是非常有必要的。
针对上述问题，制定本制备方法，因镁元素是人体必需的营养元素，成人体内约有25g镁其中约一半储存在人体的骨组织中，镁还会参与人体一系列的新陈代谢过程，是人体内很多酶的辅助因子，并对稳定体内K+的平衡取这至关重要的作用，可以调节DNA和RNA的结构，镁的标准电极电位很低(-2.37Vvs.SHE)，在水溶液中容易发生降解反应，生成可溶性镁离子和气体(H2)，进而通过周边的组织吸收和新陈代谢排除体外，并且镁是人体必需营养元素，排第四重要，仅次于钙钾钠，同时镁分布在人体的骨骼肌，肌肉，血浆，细胞外液；可降解性：镁的腐蚀电位低，在含有氯离子的体液中便可腐蚀溶解；至伤口完全康复后，植入体内的金属镁网板无需二次手术取出，同时生物安全性中镁元素即使在体内含量偏高，会通过尿液形式排出体外，不会明显提高体内组织的镁元素含量，不会对人体有负面影响。
发明内容
为了克服现有技术的上述缺陷，本发明的实施例提供一种生物可降解的医用金属镁及镁合金补片的制备方法，因镁元素是人体必需的营养元素，成人体内约有25g镁其中约一半储存在人体的骨组织中，镁还会参与人体一系列的新陈代谢过程，是人体内很多酶的辅助因子，并对稳定体内K+的平衡取这至关重要的作用，可以调节DNA和RNA的结构，镁的标准电极电位很低，在水溶液中容易发生降解反应，生成可溶性镁离子和气体，进而通过周边的组织吸收和新陈代谢排除体外，并且镁是人体必需营养元素，排第四重要，仅次于钙钾钠，同时镁分布在人体的骨骼肌，肌肉，血浆，细胞外液；可降解性：镁的腐蚀电位低，在含有氯离子的体液中便可腐蚀溶解；至伤口完全康复后，植入体内的金属镁网板无需二次手术取出，同时生物安全性中镁元素即使在体内含量偏高，会通过尿液形式排出体外，不会明显提高体内组织的镁元素含量，不会对人体有负面影响，以解决上述背景技术中提出的问题。
为实现上述目的，本发明提供如下技术方案：一种生物可降解的医用金属镁补片，所述所选补片是金属镁板材由激光或者冲压等其他达到一致目的的加工方式而成的多孔网状结构。
优选的，所述金属镁包括纯度为大于99％的纯镁，其中金属镁纯度为99.98％，或者是镁锌合金，其锌含量为2％-6％。
优选的，所述金属镁网状结构由板材通过激光或者冲压等其他达到一致目的的加工方式而成。
优选的，所述金属镁的网状结构为所有规则形状。
优选的，所述金属镁网状结构的孔隙率为20％-80％，所述金属镁网状结构中激光切割的孔的直径为0.5-5mm，所述金属镁网状结构中的孔间距为1.5-8mm。
优选的，所述金属镁网状结构的板厚为0.05-0.5mm。
优选的，所述金属镁网状结构上涂布有可吸收膜层。
优选的、所述金属镁网状结构上涂布的可吸收膜层为化学转化膜或者沉积涂层，且可吸收膜层包含氟化膜、磷酸盐转化膜、植酸转化膜层、微弧氧化膜层、聚乳酸涂层、聚己内酯涂层或钙磷涂层等。
一种生物可降解的医用金属镁补片的制备方法，所述制备方法包括如下步骤：
S1：将镁锭通过线切割成方形的镁块，如有氧化层需用铣床去除氧化层；
S2：将方形镁块运用轧辊机多道次轧制成不同厚度的镁板；
S3：每道次轧制前需进行热处理，达到减少缺陷和完全再结晶的作用；
S4：将得到的镁板在整平机上整平处理，得到所需平整度的镁板；
S5：再将镁板激光切割出各种不同形状，不同大小，不同孔隙率的网状结构；
S6：将所得网状结构的镁板电解抛光，清洗，涂层处理，干燥，灭菌处理，即可完成，其中涂层处理为化学转化膜或者沉积涂层，包含氟化膜、磷酸盐转化膜、植酸转化膜层、微弧氧化膜层、聚乳酸涂层、聚己内酯涂层或钙磷涂层等、延长其溶解的时间及提高与人体内部环境的相容性。
本发明的技术效果和优点：
金属镁补片可实现自我降解，降解的镁可作为营养元素被人体吸收，余量镁参与人体新陈代谢而不会对人体有害，现有补片大多需要二次取出而造成患者的二次伤害，金属镁补片的镁元素是人体必需元素，与人体组织可达到生物相容性，不会出现排异现象而出现并发症等现象，植入初期具有较好的强度，能够较有利的挡住已攻破人体薄弱点而进入到另一部分的脏器官，通过激光切割工艺方式可制备不同孔径，不同形状孔，不同孔隙率的补片，而运用于不同部位，镁的密度小，制备出来的补片较轻，且植入的金属镁在体内降解的部位呈碱性微环境，此环境可在伤口处起到抗菌消炎的作用，有利于伤口的愈合，在制得的网状结构上制备一层涂层，一方面可大大降低金属镁的降解速率，起到了抗腐蚀作用，另一方面可大大提高产品的生物活性，易实现量产，品质稳定可控，生产效率高，在作为疝修复手术，盆腔脏器脱垂手术，胸壁修复手术，脑垂体腺瘤手术，或整形外科手术用组织修复补片的用途。
具体实施方式
下面将结合本发明的实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
一种生物可降解的医用金属镁补片，所述所选补片是金属镁板材由激光或者冲压等其他达到一致目的的加工方式而成的多孔网状结构。
进一步的，所述金属镁包括纯度为大于99％的纯镁，或者是镁锌合金，其锌含量为2％-6％。
进一步的，所述金属镁网状结构由板材通过激光或者冲压等其他达到一致目的的加工方式而成。
进一步的，所述金属镁的网状结构为所有规则形状，比如圆形或方形或菱形等。
进一步的，所述金属镁网状结构的孔隙率为20％-80％，所述金属镁网状结构中激光切割的孔的直径为0.5-5mm，所述金属镁网状结构中的孔间距为1.5-8mm。
进一步的，所述金属镁网状结构的板厚为0.05-0.5mm。
进一步的，所述金属镁网状结构上涂布有可吸收膜层。
进一步的，所述金属镁网状结构上涂布的可吸收膜层为化学转化膜或者沉积涂层，且可吸收膜层包含氟化膜、磷酸盐转化膜、植酸转化膜层、微弧氧化膜层、聚乳酸涂层、聚己内酯涂层或钙磷涂层等。
一种生物可降解的医用金属镁补片的制备方法，所述制备方法包括如下步骤：
S1：将镁锭通过线切割成方形的镁块，如有氧化层需用铣床去除氧化层；
S2：将方形镁块运用轧辊机多道次轧制成不同厚度的镁板；
S3：每道次轧制前需进行热处理，达到减少缺陷和完全再结晶的作用；
S4：将得到的镁板在整平机上整平处理，得到所需平整度的镁板；
S5：再将镁板激光切割出各种不同形状，不同大小，不同孔隙率的网状结构；
S6：将所得网状结构的镁板电解抛光，清洗，涂层处理，干燥，灭菌处理，即可完成，其中涂层处理为化学转化膜或者沉积涂层，包含氟化膜、磷酸盐转化膜、植酸转化膜层、微弧氧化膜层、聚乳酸涂层、聚己内酯涂层或钙磷涂层等、延长其溶解的时间及提高与人体内部环境的相容性。
S7：以上方法得出结果如下：
通过线切割制得90*70*20mm大小的纯镁块，按照以下表格内变形量进行轧制，每轧制之前就需要经一次热处理，温度为200-400℃，保温时间为10-60Min；
实施例一：
制得有效镁板300*60*0.5mm，通过激光器切割成直径为6mm，间距为8mm的小孔，整体外观较好，无裂边，进一步的表面抛光，最后以Ca-P涂层溶液为防腐蚀涂层溶液对补片进行涂层处理，干燥，灭菌处理，激光器的加工参数是：能量为1200W，脉宽为120ms，频率为800HZ，速率10mm/s，高度为71mm，焦点45mm。
实施例二：
先通过实例1的轧制工艺制得300*60*0.5mm，进一步的通过表格二工艺继续轧制，制得厚度为0.2mm的镁板，通过激光器切割成直径6mm，间距为7mm的小孔，整体外观较好，无裂边。进一步的表面抛光，清洗，最后以Ca-P涂层溶液为防腐蚀涂层溶液对补片进行涂层处理，干燥，灭菌处理；激光器的加工参数是：能量为1200W，脉宽为120ms，频率为800HZ，速率10mm/s，高度为71mm，焦点45mm。
实施例三：
先通过实例1和实例2的轧制工艺制得0.2mm厚度的镁板，进一步的通过表格三工艺继续轧制，制得厚度为0.1mm的镁板，通过激光器切割成直径6mm，间距为6.5mm的小孔，整体外观较好，无裂边；进一步的表面抛光，清洗，最后以Ca-P涂层溶液为防腐蚀涂层溶液对补片进行涂层处理，干燥，灭菌处理；激光器的加工参数是：能量为1200W，脉宽为120ms，频率为800HZ，速率10mm/s，高度为71mm，焦点45mm。
实施例四：
先通过实例1，实例2和实例3的轧制工艺制得0.1mm厚度的镁板，进一步的通过表格三工艺继续轧制，制得厚度为0.05mm的镁板，通过激光器切割成直径6mm，间距为6.5mm的小孔，整体外观较好，无裂边，进一步的表面抛光，清洗，最后以Ca-P涂层溶液为防腐蚀涂层溶液对补片进行涂层处理，干燥，灭菌处理；激光器的加工参数是：能量为1200W，脉宽为120ms，频率为800HZ，速率10mm/s，高度为71mm，焦点45mm。
本发明工作原理：
本生物可降解的医用金属镁补片，可实现自我降解，降解的镁可作为营养元素被人体吸收，余量镁参与人体新陈代谢而不会对人体有害，现有补片大多需要二次取出而造成患者的二次伤害，金属镁补片的镁元素是人体必需元素，与人体组织可达到生物相容性，不会出现排异现象而出现并发症等现象，植入初期具有较好的强度，能够较有利的挡住已攻破人体薄弱点而进入到另一部分的脏器官，通过激光切割工艺方式可制备不同孔径，不同形状孔，不同孔隙率的补片，而运用于不同部位，镁的密度小，制备出来的补片较轻，且植入的金属镁在体内降解的部位呈碱性微环境，此环境可在伤口处起到抗菌消炎的作用，有利于伤口的愈合，在制得的网状结构上制备一层涂层，一方面可大大降低金属镁的降解速率，起到了抗腐蚀作用，另一方面可大大提高产品的生物活性，易实现量产，品质稳定可控，生产效率高，在作为疝修复手术，盆腔脏器脱垂手术，胸壁修复手术，脑垂体腺瘤手术，或整形外科手术用组织修复补片的用途。
其次应说明的几点是：首先，在本申请的描述中，需要说明的是，除非另有规定和限定，术语“安装”、“相连”、“连接”应做广义理解，可以是机械连接或电连接，也可以是两个元件内部的连通，可以是直接相连，“上”、“下”、“左”、“右”等仅用于表示相对位置关系，当被描述对象的绝对位置改变，则相对位置关系可能发生改变；
最后：以上所述仅为本发明的优选实施例而已，并不用于限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (9)
1.一种生物可降解的医用金属镁补片，其特征在于：所述所选补片是金属镁板材由激光或者冲压等其他达到一致目的的加工方式而成的多孔网状结构。
2.根据权利要求1所述的一种生物可降解的医用金属镁补片，其特征在于：所述金属镁包括纯度为大于99％的纯镁，或者是镁锌合金，其锌含量为2％-6％。
3.根据权利要求1所述的一种生物可降解的医用金属镁补片，其特征在于：所述金属镁网状结构由板材通过激光或者冲压等其他达到一致目的的加工方式而成。
4.根据权利要求3所述的一种生物可降解的医用金属镁补片，其特征在于：所述金属镁的网状结构为所有规则形状。
5.根据权利要求3所述的一种生物可降解的医用金属镁补片，其特征在于：所述金属镁网状结构的孔隙率为20％-80％，所述金属镁网状结构中激光切割的孔的直径为0.5-5mm，所述金属镁网状结构中的孔间距为1.5-8mm。
6.根据权利要求3所述的一种生物可降解的医用金属镁补片，其特征在于：所述金属镁网状结构的板厚为0.05-0.5mm。
7.根据权利要求3所述的一种生物可降解的医用金属镁补片，其特征在于：所述金属镁网状结构上涂布有可吸收膜层。
8.根据权利要求7所述的一种生物可降解的医用金属镁补片，其特征在于：所述金属镁网状结构上涂布的可吸收膜层为化学转化膜或者沉积涂层，且可吸收膜层包含氟化膜、磷酸盐转化膜、植酸转化膜层、微弧氧化膜层、聚乳酸涂层、聚己内酯涂层或钙磷涂层等。
9.一种生物可降解的医用金属镁补片的制备方法，其特征在于：所述制备方法包括如下步骤：
S1：将镁锭通过线切割成方形的镁块，如有氧化层需用铣床去除氧化层；
S2：将方形镁块运用轧辊机多道次轧制成不同厚度的镁板；
S3：每道次轧制前需进行热处理，达到减少缺陷和完全再结晶的作用；
S4：将得到的镁板在整平机上整平处理，得到所需平整度的镁板；
S5：再将镁板激光切割出各种不同形状，不同大小，不同孔隙率的网状结构；
S6：将所得网状结构的镁板电解抛光，清洗，涂层处理，干燥，灭菌处理，即可完成，其中涂层处理为化学转化膜或者沉积涂层，包含氟化膜、磷酸盐转化膜、植酸转化膜层、微弧氧化膜层、聚乳酸涂层、聚己内酯涂层或钙磷涂层等、延长其溶解的时间及提高与人体内部环境的相容性。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111536726.3A CN114177349A (zh) | 2021-12-15 | 2021-12-15 | 一种生物可降解的医用金属镁及镁合金补片的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111536726.3A CN114177349A (zh) | 2021-12-15 | 2021-12-15 | 一种生物可降解的医用金属镁及镁合金补片的制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114177349A true CN114177349A (zh) | 2022-03-15 |
Family
ID=80544007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111536726.3A Pending CN114177349A (zh) | 2021-12-15 | 2021-12-15 | 一种生物可降解的医用金属镁及镁合金补片的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114177349A (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115531606A (zh) * | 2022-09-30 | 2022-12-30 | 珠海奥华复维医疗技术有限公司 | 一种梯度降解的网状植入物、其制备方法及其用途 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274332A (zh) * | 2008-02-22 | 2008-10-01 | 中南大学 | 镁合金超薄板材的成型方法 |
| CN101385660A (zh) * | 2007-09-12 | 2009-03-18 | 中国科学院金属研究所 | 一种可生物降解的颅骨修补体 |
| CN108159506A (zh) * | 2017-11-28 | 2018-06-15 | 浙江理工大学 | 一种基于镁合金的可吸收引导组织再生膜及其制备方法 |
| CN109847108A (zh) * | 2019-03-13 | 2019-06-07 | 北京大学口腔医学院 | 一种锌基合金引导性骨组织再生膜 |
| US20190240374A1 (en) * | 2016-10-21 | 2019-08-08 | University Of Pittsburgh-Of The Commonwealth System Of Higher Education | Degradable bulk metallic magnesium/polymer composite barrier membranes for dental, craniomaxillofacial and orthopedic applications and manufacturing methods |
| US20200179084A1 (en) * | 2017-08-14 | 2020-06-11 | University Of Florida Research Foundation, Inc. | Bioresorbable metal alloy membranes, methods of making, and methods of use |
| CN212853732U (zh) * | 2020-08-27 | 2021-04-02 | 上海交通大学 | 个性化牙槽骨缺损重建用可降解镁网 |
| CN113384755A (zh) * | 2021-05-12 | 2021-09-14 | 北京大学口腔医学院 | 一种生物活性可降解镁合金引导骨再生膜及其密集孔的加工方法 |
-
2021
- 2021-12-15 CN CN202111536726.3A patent/CN114177349A/zh active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101385660A (zh) * | 2007-09-12 | 2009-03-18 | 中国科学院金属研究所 | 一种可生物降解的颅骨修补体 |
| CN101274332A (zh) * | 2008-02-22 | 2008-10-01 | 中南大学 | 镁合金超薄板材的成型方法 |
| US20190240374A1 (en) * | 2016-10-21 | 2019-08-08 | University Of Pittsburgh-Of The Commonwealth System Of Higher Education | Degradable bulk metallic magnesium/polymer composite barrier membranes for dental, craniomaxillofacial and orthopedic applications and manufacturing methods |
| US20200179084A1 (en) * | 2017-08-14 | 2020-06-11 | University Of Florida Research Foundation, Inc. | Bioresorbable metal alloy membranes, methods of making, and methods of use |
| CN108159506A (zh) * | 2017-11-28 | 2018-06-15 | 浙江理工大学 | 一种基于镁合金的可吸收引导组织再生膜及其制备方法 |
| CN109847108A (zh) * | 2019-03-13 | 2019-06-07 | 北京大学口腔医学院 | 一种锌基合金引导性骨组织再生膜 |
| CN212853732U (zh) * | 2020-08-27 | 2021-04-02 | 上海交通大学 | 个性化牙槽骨缺损重建用可降解镁网 |
| CN113384755A (zh) * | 2021-05-12 | 2021-09-14 | 北京大学口腔医学院 | 一种生物活性可降解镁合金引导骨再生膜及其密集孔的加工方法 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115531606A (zh) * | 2022-09-30 | 2022-12-30 | 珠海奥华复维医疗技术有限公司 | 一种梯度降解的网状植入物、其制备方法及其用途 |
| CN115531606B (zh) * | 2022-09-30 | 2024-03-26 | 珠海奥华复维医疗技术有限公司 | 一种梯度降解的网状植入物、其制备方法及其用途 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101015711B (zh) | 一种可体液降解的医用植入体及其制备方法 | |
| CN101461964B (zh) | 一种生物医用可降解镁合金的生物活性表面改性方法 | |
| CN101709496B (zh) | 一种镁基生物活性涂层的微弧氧化-电沉积制备方法 | |
| CN107456610B (zh) | 一种Zn-Ag系锌合金及其制备方法与应用 | |
| CN106676604B (zh) | 具有点阵结构多孔的钛或钛合金表面抑菌生物活性陶瓷膜的制备方法及其应用 | |
| CN102580143A (zh) | 医用可降解吸收Mg-Sr系镁合金植入体及其制备方法 | |
| CN108297500B (zh) | 颅颌面骨修复用可降解金属复合板的制备方法 | |
| CN105671612A (zh) | 具有微弧氧化涂层的多孔金属植入物及制备方法 | |
| CN102552973A (zh) | 医用可降解吸收Mg-Sr-Ca系镁合金植入体及其制备方法 | |
| EA029095B1 (ru) | Имплантируемое изделие медицинского назначения, поддающееся биологическому разложению, которое сформовано из материала на основе сверхчистого магния | |
| CN110029383B (zh) | 一种可降解锌铜泡沫生物材料 | |
| CN102978495A (zh) | 一种Mg-Sr-Zn系合金及其制备方法 | |
| CN111826564A (zh) | 一种可吸收镁合金美容线及其制备方法 | |
| CN114177349A (zh) | 一种生物可降解的医用金属镁及镁合金补片的制备方法 | |
| US20220031916A1 (en) | Zn-ga series alloy and its preparation method and application | |
| CN101560685B (zh) | 一种钛合金表面制备生物活性涂层的方法 | |
| AU2020104227A4 (en) | Zinc-Calcium alloy series and preparation method and application thereof | |
| RU2508130C1 (ru) | Способ изготовления кардиоимплантата из сплава на основе никелида титана с модифицированным ионно-плазменной обработкой поверхностным слоем | |
| CN102978494A (zh) | 一种Mg-Ge系镁合金及其制备方法 | |
| CN108714252B (zh) | 体内可控降解的镁合金固定螺钉的制备方法 | |
| US20100145432A1 (en) | Implant and method for producing the same | |
| CN114392398A (zh) | 一种生物可降解的医用金属镁补片及其制备方法 | |
| CN108853608B (zh) | 一种生物可降解的医用镁合金补片及其制备方法和用途 | |
| CN108853574B (zh) | 镁合金与锌合金丝材混编复合补片及其用途 | |
| CN103272284B (zh) | 生物医用可控全降解材料及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220315 |
|
| RJ01 | Rejection of invention patent application after publication |