CN112620630B - Preparation method of zinc-magnesium/hydroxyapatite porous composite material - Google Patents
Preparation method of zinc-magnesium/hydroxyapatite porous composite material Download PDFInfo
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- CN112620630B CN112620630B CN202011475255.5A CN202011475255A CN112620630B CN 112620630 B CN112620630 B CN 112620630B CN 202011475255 A CN202011475255 A CN 202011475255A CN 112620630 B CN112620630 B CN 112620630B
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- hydroxyapatite
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- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 62
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 34
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000000227 grinding Methods 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 238000000498 ball milling Methods 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 15
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 13
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 13
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 239000010935 stainless steel Substances 0.000 claims description 36
- 229910001220 stainless steel Inorganic materials 0.000 claims description 36
- 238000005245 sintering Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000010439 graphite Substances 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 15
- 230000036760 body temperature Effects 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
- 239000008188 pellet Substances 0.000 claims description 8
- 238000005086 pumping Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 229940099259 vaseline Drugs 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 7
- 210000000988 bone and bone Anatomy 0.000 abstract description 6
- 210000001519 tissue Anatomy 0.000 abstract description 5
- 238000002490 spark plasma sintering Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 description 14
- 229910052749 magnesium Inorganic materials 0.000 description 14
- 229910052725 zinc Inorganic materials 0.000 description 14
- 239000011701 zinc Substances 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 229910000861 Mg alloy Inorganic materials 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 230000007541 cellular toxicity Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 230000033558 biomineral tissue development Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 229910052586 apatite Inorganic materials 0.000 description 3
- 210000001124 body fluid Anatomy 0.000 description 3
- 239000010839 body fluid Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000002513 implantation Methods 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 206010061218 Inflammation Diseases 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003519 biomedical and dental material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004054 inflammatory process Effects 0.000 description 2
- 230000011164 ossification Effects 0.000 description 2
- 210000000963 osteoblast Anatomy 0.000 description 2
- 230000002138 osteoinductive effect Effects 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 208000006386 Bone Resorption Diseases 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 206010072064 Exposure to body fluid Diseases 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000018678 bone mineralization Effects 0.000 description 1
- 230000024279 bone resorption Effects 0.000 description 1
- 230000002308 calcification Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 210000002997 osteoclast Anatomy 0.000 description 1
- 230000000278 osteoconductive effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
-
- 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
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
- A61L27/425—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of phosphorus containing material, 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
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/12—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides
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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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
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- Optics & Photonics (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a preparation method of a zinc-magnesium/hydroxyapatite porous composite material, belonging to the technical field of biomedical materials. The method of the invention comprises the following steps: taking metal zinc powder, magnesium powder and nano hydroxyapatite powder as raw materials, proportioning 1-10% of zinc powder, 1-10% of magnesium powder and 98-80% of nano hydroxyapatite according to the mass ratio, weighing, ball milling, drying and grinding to obtain composite powder; mixing the composite powder with medical ammonium bicarbonate according to the volume percentage of 40-60% to 60-40%, uniformly mixing and pressing to obtain a strip-shaped green body; the zinc-magnesium/hydroxyapatite porous composite material is prepared by spark plasma sintering. The porosity of the composite material prepared by the invention is 40-60 percent, the pore size is 100-500 mu m and is controllable, and the composite material meeting different requirements, such as a bone scaffold, a bone filling and repairing material of a hard tissue defect part and the like, can be prepared according to actual requirements.
Description
Technical Field
The invention relates to a preparation method of a zinc-magnesium/hydroxyapatite porous composite material, belonging to the preparation technology in the field of biomedical materials.
Background
The biomedical composite material is a biomedical material compounded by two or more different biomedical materials, and is mainly used for repairing and replacing human tissues and manufacturing artificial organs. Many of the natural and human tissues are natural composites, for example, human bones are a fiber reinforced composite of collagen, protein and minerals. Traditional biomedical materials of a single kind can well meet biomedical applications in certain aspects, but can not meet standards in other aspects, even react, and can not meet clinical applications. The biomedical material compounded by materials with different properties not only has the properties of component materials, but also can obtain new characteristics which are not possessed by single-component materials.
The Chinese patent with application number 201711047520.8 discloses a preparation method of a porous zinc-magnesium alloy/hydroxyapatite composite material. The method adopts hydroxyapatite, magnesium and zinc as raw materials, sodium chloride crystal as pore-forming agent, and prepares porous zinc-magnesium alloy/hydroxyapatite composite material block with the density of 2.94g/cm by powder mixing, ball milling powder mixing, spark plasma sintering and pore-forming agent removal 3 The porosity is 53%, the pore diameter is less than or equal to 450 mu m, the yield strength is 60MPa, and the elastic modulus is 4GPa. At present, zinc is used as a matrix and added with hydroxyapatite and magnesium to improve biocompatibility, and is a metal element with a narrower safety range, and zinc ions are quickly released after implantation, so that cell toxicity is caused; in addition, naCl is used as pore-forming agent, and HA is easy to react to generate Ca in the sintering process 5 (PO 4 ) 3 Cl, etc., which results in impure composite materials.
Disclosure of Invention
The invention aims to solve the technical problems that: the zinc-magnesium/hydroxyapatite porous composite material prepared by taking zinc as a matrix and adding hydroxyapatite in the prior art has the problem of cell toxicity, because zinc is a metal element with a narrower safety range, the requirement of adult men is 10-20 mg/d, the poisoning amount is 80-400 mg/d and is mainly an acute symptom, zinc ions are rapidly released after implantation, and the cell toxicity is caused.
In order to achieve the above purpose, the invention adopts a preparation method of zinc-magnesium/hydroxyapatite porous composite material, which mainly comprises the following steps:
(1) Selecting metal zinc powder, magnesium powder and nano hydroxyapatite as raw materials, wherein the zinc powder comprises the following components in percentage by mass: 1 to 10 percent of magnesium powder, which comprises the following components in percentage by mass: 1 to 10 percent of nano hydroxyapatite with the mass percentage of 98 to 80 percent.
(2) Placing the powder weighed in the step (1) into a stainless steel ball milling tank, placing a proper amount of stainless steel balls, and vacuumizing the stainless steel balls, wherein the processes are completed in a vacuum glove box; and (5) after ball milling, drying and grinding.
(3) Mixing the composite powder obtained in the step (2) with medical ammonium bicarbonate powder according to the volume percentage of 40-60 percent, namely 40-60 percent.
(4) Uniformly coating proper amount of vaseline on the inner wall of a self-made stainless steel die, adding the mixed powder obtained in the step (2) into the die, and placing the die on a press for prepressing, so as to press the die into a long strip-shaped pre-pressed blank.
(5) Placing the long-strip-shaped pre-blank obtained in the step (4) into a self-made graphite die, placing into a discharge plasma sintering furnace, and pumping the vacuum degree in the sintering furnace to 10 -3 ～10 -4 After Pa, heating to 600-800 ℃ at a heating rate of 100-150 ℃/min, preserving heat for 2-3 min, heating to 700-900 ℃ at a heating rate of 25-50 ℃/min, and preserving heat for 5-10 min; after sintering, cooling to room temperature along with a furnace to obtain the zinc-magnesium/hydroxyapatite porous composite material.
Preferably, the purity of the nano hydroxyapatite in the step (1) is more than or equal to 99.9%, and the particle size is 150-300 nm; the purity of the metal magnesium powder is 99.95-99.99%, and the grain diameter is 10-20 mu m; the purity of the metal zinc powder is 99.95 percent, and the grain diameter is 1-10 mu m.
Preferably, the ball milling process in step (2) of the present invention is carried out under the following conditions: the vacuum degree in the stainless steel ball grinding tank is 8-10 Pa, the stainless steel ball grinding tank is fixed on a planetary ball mill, and ball milling is carried out for 2 hours at the rotating speed of 200-300 r/min; after the tank body temperature is reduced to room temperature, vacuumizing the tank body to 8-10 Pa again, and ball milling for 6-8 hours at the rotating speed of 300-400 r/min.
Preferably, the ball-to-material ratio of the stainless steel grinding ball and the raw materials is 4:1-3:1, wherein the mass ratio of the grinding ball is a big ball: medium ball: pellets = 2:8:15 to 3:10:20.
Preferably, the drying process in the step (1) is carried out in a vacuum drying oven, the vacuum degree of the drying oven is 8-10 Pa, and the drying temperature is 30-40 ℃.
Preferably, the purity of the ammonium bicarbonate powder in the step (3) is analytically pure, and the particle size is 100-300 mu m; the mixing process is carried out in an argon atmosphere, and the mixer is used for mixing for 20-30 min at the rotating speed of 50-100 r/min.
Preferably, the pre-pressing process in the step (4) of the present invention is as follows: one-way pressurization is carried out, the loading rate is 1-3 KN/min, the pressure is 400-450 MPa, and the pressure is maintained for 20-30 min.
Preferably, the self-made stainless steel die has the structure that: cylindrical outer body: phi 75mm x H30mm; rectangular inner cavity: a15mm×b5mm×c30mm.
Preferably, the self-made graphite mold of the invention has the structure that: cylindrical outer body: phi 15.5mm×H17.5mm; rectangular inner cavity: a5.5mmXb5.5mmX17.5 mm; and (3) plug: phi 10mm is multiplied by 10mm, and is matched with the rectangular inner cavity of the graphite die.
Except for the special descriptions, all mass percentages in the invention are mass percentages.
The invention has the beneficial effects that:
(1) The zinc-magnesium alloy can be used as a hard tissue substitute product, and although zinc and magnesium have excellent biocompatibility and osteoinductive property, zinc has antibacterial property, zinc and magnesium are not corrosion-resistant, are easy to degrade in a body fluid environment, have high degradation rate, cause local zinc and magnesium ion concentration to be too high, cause cell toxicity and induce inflammation. The zinc-magnesium/hydroxyapatite porous composite material is prepared by adding zinc and magnesium serving as activity enhancing phases into hydroxyapatite. Under the body fluid environment, zinc ions and magnesium ions can be released slowly and for a long time along with the degradation of the hydroxyapatite, so that the cell toxicity caused by quick release is avoided. The sintering temperature can be reduced by adopting the spark plasma sintering technology, the zinc and magnesium loss caused by overhigh temperature can be avoided, the heat preservation time can be reduced, the decomposition of hydroxyapatite caused by overlong calcination time can be avoided, and the coarsening phenomenon of crystal grains can be effectively avoided.
(2) The invention selects ammonium bicarbonate as pore-forming agent, which has the following advantages: the ammonium bicarbonate can be quickly decomposed at about 60 ℃, is completely volatilized in the sintering process and cannot react with HA, so that the purity of the components of the composite material is ensured; the porosity (40% -60%) and the pore size (100-500 μm) of the composite material can be controlled by adjusting the particle size and the addition amount of the pore-forming agent according to actual demands, and the demands of bone scaffolds, bone filling, repairing materials of hard tissue defect parts and the like can be met.
(3) The experimental result shows that the zinc-magnesium/hydroxyapatite porous composite material prepared by the invention: the addition of magnesium significantly improves the osteoinductive, osteoconductive and absorbable properties of the composite material; zinc has direct stimulation to osteoblast, can promote bone formation and mineralization, has selective inhibition to bone resorption of osteoclast, and has certain antibacterial property; under the continuous stimulation of zinc and magnesium, the osteogenesis process is quickened, and the treatment speed is improved.
Drawings
FIG. 1 is a schematic diagram of a self-made stainless steel mold according to the present invention;
FIG. 2 is a schematic diagram of a self-made graphite mold according to the present invention;
FIG. 3 is a surface topography of a porous zinc-magnesium/hydroxyapatite composite material prepared in example 2 of the present invention;
FIG. 4 is a graph showing the 7d mineralization morphology of the porous zinc-magnesium/hydroxyapatite composite material prepared in example 2 of the present invention.
Detailed Description
The invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to the description.
The self-made stainless steel die provided by the embodiment of the invention has the structure that: cylindrical outer body: phi 75mm x H30mm; rectangular inner cavity: a15 mm. Times.b 5 mm. Times.c 30mm, as shown in FIG. 1. The self-made graphite mold has the structure that: cylindrical outer body: phi 15.5mm×H17.5mm; rectangular inner cavity: a5.5mmXb5.5mmX17.5 mm; and (3) plug: phi 10mm x 10mm is matched with the rectangular inner cavity of the graphite mould, as shown in figure 2.
Example 1
(1) The method is characterized in that metal zinc powder with the purity of 99.5 percent and the grain diameter of 1-10 mu m, metal magnesium powder with the purity of 99.95-99.99 percent and the grain diameter of 10-20 mu m and nano hydroxyapatite with the purity of more than or equal to 99.9 percent and the grain diameter of 150-300 mu m are used as raw materials, wherein the zinc powder, the magnesium powder and the nano hydroxyapatite are proportioned according to the mass ratio of 1 percent to 98 percent.
(2) Putting the powder weighed in the step (1) into a stainless steel ball grinding tank, and putting a proper amount of stainless steel grinding balls according to the ball-to-material ratio of 4:1, wherein the mass ratio of the grinding balls is large balls: medium ball: pellets = 2:8:15, and evacuated to 10Pa, all in a vacuum glove box; fixing on a planetary ball mill, and ball milling for 2 hours at a rotating speed of 200 r/min; after the tank body temperature is reduced to room temperature, vacuumizing the tank body to 10Pa again, and ball milling for 8 hours at the rotating speed of 300/min.
(3) Pouring the slurry obtained in the step (2) into a culture dish in a vacuum glove box, and placing the culture dish into a vacuum drying box, wherein the drying temperature in the box is 35 ℃; the vacuum degree is 8Pa; mixing the composite powder with 50% by volume of ammonium bicarbonate in an argon environment in the mixing process, and mixing the mixture for 20min at a rotating speed of 50r/min by a mixer.
(4) Uniformly coating proper amount of vaseline on the inner wall of a self-made stainless steel die, adding the mixed powder obtained in the step (3) into the die, placing the die in a press machine, pressurizing to 400MPa at a pressurizing rate of 1KN/min, maintaining the pressure for 30min, and unloading to obtain a strip-shaped pre-cast.
(5) Placing the long-strip-shaped pre-blank obtained in the step (4) into a self-made graphite die, placing into a discharge plasma sintering furnace, and pumping the vacuum degree in the sintering furnace to 10 -3 a, then; heating to 600 ℃ at a heating rate of 100 ℃/min, and preserving heat for 1min; then the temperature is raised to 700 ℃ at the heating rate of 50 ℃/min, and the temperature is kept for 5min. And after sintering, cooling to room temperature along with a furnace to obtain the zinc-magnesium/hydroxyapatite porous composite material.
Example 2
(1) The method is characterized in that metal zinc powder with the purity of 99.5 percent and the grain diameter of 1-10 mu m, metal magnesium powder with the purity of 99.95-99.99 percent and the grain diameter of 10-20 mu m and nano hydroxyapatite with the purity of more than or equal to 99.9 percent and the grain diameter of 150-300 mu m are used as raw materials, wherein the zinc powder, the magnesium powder and the nano hydroxyapatite are proportioned according to the mass ratio of 3 percent to 94 percent.
(2) Putting the powder weighed in the step (1) into a stainless steel ball grinding tank, and putting a proper amount of stainless steel grinding balls according to the ball-to-material ratio of 4:1, wherein the mass ratio of the grinding balls is large balls: medium ball: pellets = 2:8:15, and evacuated to 10Pa, all in a vacuum glove box; fixing on a planetary ball mill, and ball milling for 2 hours at a rotating speed of 200 r/min; after the tank body temperature is reduced to room temperature, vacuumizing the tank body to 10Pa again, and ball milling for 8 hours at the rotating speed of 300/min.
(3) Pouring the slurry obtained in the step (2) into a culture dish in a vacuum glove box, and placing the culture dish into a vacuum drying box, wherein the drying temperature in the box is 35 ℃; the vacuum degree is 8Pa; mixing the composite powder with 50% by volume of ammonium bicarbonate in an argon environment in the mixing process, and mixing the mixture for 20min at a rotating speed of 50r/min by a mixer.
(4) Uniformly coating proper amount of vaseline on the inner wall of a self-made stainless steel die, adding the mixed powder obtained in the step (3) into the die, placing the die in a press machine, pressurizing to 400MPa at a pressurizing rate of 1KN/min, maintaining the pressure for 30min, and unloading to obtain a strip-shaped pre-cast.
(5) Placing the long-strip-shaped pre-blank obtained in the step (4) into a self-made graphite die, placing into a discharge plasma sintering furnace, and pumping the vacuum degree in the sintering furnace to 10 -3 a, then; heating to 600 ℃ at a heating rate of 100 ℃/min, and preserving heat for 1min; then the temperature is raised to 700 ℃ at the heating rate of 50 ℃/min, and the temperature is kept for 5min. And after sintering, cooling to room temperature along with a furnace to obtain the zinc-magnesium/hydroxyapatite porous composite material.
Example 3
(1) The method is characterized in that metal zinc powder with the purity of 99.5 percent and the grain diameter of 1-10 mu m, metal magnesium powder with the purity of 99.95-99.99 percent and the grain diameter of 10-20 mu m and nano hydroxyapatite with the purity of more than or equal to 99.9 percent and the grain diameter of 150-300 mu m are used as raw materials, wherein the zinc powder, the magnesium powder and the nano hydroxyapatite are proportioned according to the mass ratio of 3 percent to 94 percent.
(2) Putting the powder weighed in the step (1) into a stainless steel ball grinding tank, and putting a proper amount of stainless steel grinding balls according to the ball-to-material ratio of 4:1, wherein the mass ratio of the grinding balls is large balls: medium ball: pellets = 2:8:15, and evacuated to 10Pa, all in a vacuum glove box; fixing on a planetary ball mill, and ball milling for 2 hours at a rotating speed of 200 r/min; after the tank body temperature is reduced to room temperature, vacuumizing the tank body to 10Pa again, and ball milling for 8 hours at the rotating speed of 300/min.
(3) Pouring the slurry obtained in the step (2) into a culture dish in a vacuum glove box, and placing the culture dish into a vacuum drying box, wherein the drying temperature in the box is 35 ℃; the vacuum degree is 8Pa; mixing the composite powder with ammonium bicarbonate according to the volume percentage of 60-40%, wherein the mixing process is carried out under an argon environment, and the mixer is used for mixing for 20min at the rotating speed of 50 r/min.
(4) Uniformly coating proper amount of vaseline on the inner wall of a self-made stainless steel die, adding the mixed powder obtained in the step (3) into the die, placing the die in a press machine, pressurizing to 400MPa at a pressurizing rate of 1KN/min, maintaining the pressure for 30min, and unloading to obtain a strip-shaped pre-cast.
(5) Placing the long-strip-shaped pre-blank obtained in the step (4) into a self-made graphite die, placing into a discharge plasma sintering furnace, and pumping the vacuum degree in the sintering furnace to 10 -3 a, then; heating to 600 ℃ at a heating rate of 100 ℃/min, and preserving heat for 1min; then the temperature is raised to 700 ℃ at the heating rate of 50 ℃/min, and the temperature is kept for 5min. And after sintering, cooling to room temperature along with a furnace to obtain the zinc-magnesium/hydroxyapatite porous composite material.
Example 4
(1) The method is characterized in that metal zinc powder with the purity of 99.5 percent and the grain diameter of 1-10 mu m, metal magnesium powder with the purity of 99.95-99.99 percent and the grain diameter of 10-20 mu m and nano hydroxyapatite with the purity of more than or equal to 99.9 percent and the grain diameter of 150-300 mu m are used as raw materials, wherein the zinc powder, the magnesium powder and the nano hydroxyapatite are proportioned according to the mass ratio of 3 percent to 94 percent.
(2) Putting the powder weighed in the step (1) into a stainless steel ball grinding tank, and putting a proper amount of stainless steel grinding balls according to the ball-to-material ratio of 4:1, wherein the mass ratio of the grinding balls is large balls: medium ball: pellets = 2:8:15, and evacuated to 10Pa, all in a vacuum glove box; fixing on a planetary ball mill, and ball milling for 2 hours at a rotating speed of 200 r/min; after the tank body temperature is reduced to room temperature, vacuumizing the tank body to 10Pa again, and ball milling for 8 hours at the rotating speed of 300/min.
(3) Pouring the slurry obtained in the step (2) into a culture dish in a vacuum glove box, and placing the culture dish into a vacuum drying box, wherein the drying temperature in the box is 35 ℃; the vacuum degree is 8Pa; mixing the composite powder with ammonium bicarbonate according to the volume percentage of 40-60%, wherein the mixing process is carried out under an argon environment, and the mixer is used for mixing for 20min at the rotating speed of 50 r/min.
(4) Uniformly coating proper amount of vaseline on the inner wall of a self-made stainless steel die, adding the mixed powder obtained in the step (3) into the die, placing the die in a press machine, pressurizing to 400MPa at a pressurizing rate of 1KN/min, maintaining the pressure for 30min, and unloading to obtain a strip-shaped pre-cast.
(5) Placing the long-strip-shaped pre-blank obtained in the step (4) into a self-made graphite die, placing into a discharge plasma sintering furnace, and pumping the vacuum degree in the sintering furnace to 10 -3 a, then; heating to 600 ℃ at a heating rate of 100 ℃/min, and preserving heat for 1min; then the temperature is raised to 700 ℃ at the heating rate of 50 ℃/min, and the temperature is kept for 5min. And after sintering, cooling to room temperature along with a furnace to obtain the zinc-magnesium/hydroxyapatite porous composite material.
Example 5
(1) The method is characterized in that metal zinc powder with the purity of 99.5 percent and the grain diameter of 1-10 mu m, metal magnesium powder with the purity of 99.95-99.99 percent and the grain diameter of 10-20 mu m and nano hydroxyapatite with the purity of more than or equal to 99.9 percent and the grain diameter of 150-300 mu m are used as raw materials, wherein the zinc powder, the magnesium powder and the nano hydroxyapatite are proportioned according to the mass ratio of 5 percent to 90 percent.
(2) Putting the powder weighed in the step (1) into a stainless steel ball grinding tank, and putting a proper amount of stainless steel grinding balls according to the ball-to-material ratio of 4:1, wherein the mass ratio of the grinding balls is large balls: medium ball: pellets = 2:8:15, and evacuated to 8Pa, all in a vacuum glove box; fixing on a planetary ball mill, and ball milling for 2 hours at a rotating speed of 300 r/min; after the tank body temperature is reduced to room temperature, vacuumizing the tank body to 10Pa again, and ball milling for 8 hours at a rotating speed of 400/min.
(3) Pouring the slurry obtained in the step (2) into a culture dish in a vacuum glove box, and placing the culture dish into a vacuum drying box, wherein the drying temperature in the box is 35 ℃; the vacuum degree is 8Pa; mixing the composite powder with 50% by volume of ammonium bicarbonate in an argon environment in the mixing process, and mixing the mixture for 20min at a rotating speed of 50r/min by a mixer.
(4) Uniformly coating proper amount of vaseline on the inner wall of a self-made stainless steel die, adding the mixed powder obtained in the step (3) into the die, placing the die in a press machine, pressurizing to 400MPa at a pressurizing rate of 1KN/min, maintaining the pressure for 30min, and unloading to obtain a strip-shaped pre-cast.
(5) Placing the long-strip-shaped pre-blank obtained in the step (4) into a self-made graphite die, placing into a discharge plasma sintering furnace, and pumping the vacuum degree in the sintering furnace to 10 -3 a, then; heating to 600 ℃ at a heating rate of 100 ℃/min, and preserving heat for 1min; then the temperature is raised to 700 ℃ at the heating rate of 50 ℃/min, and the temperature is kept for 5min. And after sintering, cooling to room temperature along with a furnace to obtain the zinc-magnesium/hydroxyapatite porous composite material.
Example 6
(1) The method is characterized in that metal zinc powder with the purity of 99.5 percent and the grain diameter of 1-10 mu m, metal magnesium powder with the purity of 99.95-99.99 percent and the grain diameter of 10-20 mu m and nano hydroxyapatite with the purity of more than or equal to 99.9 percent and the grain diameter of 150-300 mu m are used as raw materials, wherein the zinc powder, the magnesium powder and the nano hydroxyapatite are proportioned according to the mass ratio of 10 percent to 80 percent.
(2) Putting the powder weighed in the step (1) into a stainless steel ball grinding tank, and putting a proper amount of stainless steel grinding balls according to the ball-to-material ratio of 4:1, wherein the mass ratio of the grinding balls is large balls: medium ball: pellets = 2:8:15, and evacuated to 8Pa, all in a vacuum glove box; fixing on a planetary ball mill, and ball milling for 2 hours at a rotating speed of 300 r/min; after the tank body temperature is reduced to room temperature, vacuumizing the tank body to 10Pa again, and ball milling for 8 hours at a rotating speed of 400/min.
(3) Pouring the slurry obtained in the step (2) into a culture dish in a vacuum glove box, and placing the culture dish into a vacuum drying box, wherein the drying temperature in the box is 35 ℃; the vacuum degree is 8Pa; mixing the composite powder with 50% by volume of ammonium bicarbonate in an argon environment in the mixing process, and mixing the mixture for 20min at a rotating speed of 50r/min by a mixer.
(4) Uniformly coating proper amount of vaseline on the inner wall of a self-made stainless steel die, adding the mixed powder obtained in the step (3) into the die, placing the die in a press machine, pressurizing to 400MPa at a pressurizing rate of 1KN/min, maintaining the pressure for 30min, and unloading to obtain a strip-shaped pre-cast.
(5) Placing the long-strip-shaped pre-blank obtained in the step (4) into a self-made graphite die, placing into a discharge plasma sintering furnace, and pumping the vacuum degree in the sintering furnace to 10 -4 a, then; heating to 600 ℃ at a heating rate of 100 ℃/min, and preserving heat for 1min; then the temperature is raised to 700 ℃ at the heating rate of 50 ℃/min, and the temperature is kept for 5min. And after sintering, cooling to room temperature along with a furnace to obtain the zinc-magnesium/hydroxyapatite porous composite material.
ICP-OES detection is carried out on the magnesium element in the magnesium/hydroxyapatite porous composite material prepared by the method, the difference between the sintered magnesium content and the preset content is not large, and the magnesium element meets the expectation, and the specific result is shown in Table 1.
TABLE 1 content of zinc and magnesium elements in Zinc-magnesium/hydroxyapatite porous composite materials
Measuring the porosity of the composite material prepared by the implementation by adopting an Archimedes drainage method; the mechanical properties (compressive strength) of the materials are tested in a mechanical testing machine according to the GB/T4740-1999 standard; in order to ensure that the result has statistical significance, taking an average value through multiple tests; the test results are shown in Table 2.
TABLE 2 porosity and compressive Strength of Zinc-magnesium/hydroxyapatite porous composites
The surface morphology of the composite material before and after mineralization was analyzed by using a scanning electron microscope, and fig. 3 is a graph of the surface morphology of the composite material prepared in example 2 before mineralization, and it can be seen from the graph: the composite material has a porous structure with three-dimensional interconnection and concurrent big and small holes, the pore content is about 53%, the pore size of the big holes is 200-300 mu m, the pore size of the micro holes is less than 10 mu m, and the big holes and the small holes are crossed and uniformly distributed; compared with the porous zinc-magnesium alloy/hydroxyapatite composite material prepared in the application number 201711047520.8, the porous zinc-magnesium alloy/hydroxyapatite composite material can obtain a material with more porous rate or pore diameter by controlling the proportion and the particle size of the pore-forming agent, and can be used in different directions; because the hydroxyapatite is used as a matrix, zinc and magnesium can be coated, and direct exposure to body fluid is avoided, so that cell toxicity, inflammation and the like are avoided, zinc ions and magnesium ions are slowly released along with degradation of the hydroxyapatite, and osteoblast proliferation and differentiation are continuously stimulated.
FIG. 4 is a surface topography of the composite material prepared in example 2 after mineralization for 14 days, after soaking in simulated artificial body fluid (SBF) for 14 days, a large amount of bone-like apatite is deposited on the surface of the composite material, and most of the matrix is covered by apatite. Compared with the porous zinc-magnesium alloy/hydroxyapatite composite material prepared in the application number 201711047520.8, the hydroxyapatite is adopted as a matrix, so that the bone-like apatite deposition capability can be improved, and the calcification of bones is facilitated after implantation.
Claims (7)
1. The preparation method of the zinc-magnesium/hydroxyapatite porous composite material is characterized by comprising the following steps of:
(1) Selecting metal zinc powder, magnesium powder and nano hydroxyapatite as raw materials, wherein the zinc powder comprises the following components in percentage by mass: 1 to 10 percent of magnesium powder, which comprises the following components in percentage by mass: 1 to 10 percent of nano hydroxyapatite with the mass percentage of 98 to 80 percent;
(2) Placing the powder weighed in the step (1) into a stainless steel ball milling tank, placing a proper amount of stainless steel balls, and vacuumizing the stainless steel balls, wherein the processes are completed in a vacuum glove box; drying and grinding after ball milling;
(3) Mixing the composite powder obtained in the step (2) with medical ammonium bicarbonate powder according to the volume percentage of 40-60% to 40-60%;
(4) Uniformly coating proper amount of vaseline on the inner wall of a self-made stainless steel die, adding the mixed powder obtained in the step (3) into the die, and pre-pressing the die on a press to form a long strip-shaped pre-pressed blank;
(5) Placing the long-strip-shaped pre-blank obtained in the step (4) into a self-made graphite die, placing into a discharge plasma sintering furnace, and pumping the vacuum degree in the sintering furnace to 10 -3 ~10 -4 After Pa, heating to 600-800 ℃ at a heating rate of 100-150 ℃/min, preserving heat for 2-3 min, heating to 700-900 ℃ at a heating rate of 25-50 ℃/min, and preserving heat for 5-10 min; after sintering, cooling to room temperature along with a furnace to obtain a zinc-magnesium/hydroxyapatite porous composite material;
the self-made stainless steel die has the structure that: cylindrical outer body: phi 75mm x H30mm; rectangular inner cavity: a15mm b5mm c30mm;
the self-made graphite mold has the structure that: cylindrical outer body: phi 15.5mm×H17.5mm; rectangular inner cavity: a5.5mmXb5.5mmX17.5 mm; and (3) plug: phi 10mm is multiplied by 10mm, and is matched with the rectangular inner cavity of the graphite die.
2. The method for preparing the zinc-magnesium/hydroxyapatite porous composite material according to claim 1, wherein: the purity of the nano hydroxyapatite in the step (1) is more than or equal to 99.9%, and the particle size is 150-300 nm; the purity of the metal magnesium powder is 99.95-99.99%, and the grain diameter is 10-20 mu m; the purity of the metal zinc powder is 99.95 percent, and the grain diameter is 1-10 mu m.
3. The method for preparing the zinc-magnesium/hydroxyapatite porous composite material according to claim 1, wherein: the ball milling process in the step (2) is carried out under the following conditions: the vacuum degree in the stainless steel ball grinding tank is 8-10 Pa, the stainless steel ball grinding tank is fixed on a planetary ball mill, and ball milling is carried out for 2 hours at the rotating speed of 200-300 r/min; after the tank body temperature is reduced to room temperature, vacuumizing the tank body to 8-10 Pa again, and ball milling for 6-8 hours at the rotating speed of 300-400 r/min.
4. A method for preparing a zinc-magnesium/hydroxyapatite porous composite material according to claim 3, wherein: the ball-to-material ratio of the stainless steel grinding ball to the raw materials is 4:1-3:1, wherein the mass ratio of the grinding ball is a big ball: medium ball: pellets = 2:8:15 to 3:10:20.
5. The method for preparing the zinc-magnesium/hydroxyapatite porous composite material according to claim 1, wherein: the drying process in the step (1) is carried out in a vacuum drying oven, the vacuum degree of the drying oven is 8-10 Pa, and the drying temperature is 30-40 ℃.
6. The method for preparing the zinc-magnesium/hydroxyapatite porous composite material according to claim 1, wherein: the purity of the ammonium bicarbonate powder in the step (3) is analytically pure, and the particle size is 100-300 mu m; the mixing process is carried out in an argon atmosphere, and the mixer is used for mixing for 20-30 min at the rotating speed of 50-100 r/min.
7. The method for preparing the zinc-magnesium/hydroxyapatite porous composite material according to claim 1, wherein: the pre-pressing process in the step (4) is as follows: one-way pressurization is carried out, the loading rate is 1-3 KN/min, the pressure is 400-450 MPa, and the pressure is maintained for 20-30 min.
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