CN112620630A - 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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- CN112620630A CN112620630A CN202011475255.5A CN202011475255A CN112620630A CN 112620630 A CN112620630 A CN 112620630A CN 202011475255 A CN202011475255 A CN 202011475255A CN 112620630 A CN112620630 A CN 112620630A
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- hydroxyapatite
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- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 66
- 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 51
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 43
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000498 ball milling Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000000227 grinding Methods 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
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 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
- 239000002245 particle Substances 0.000 claims description 28
- 238000005245 sintering Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 229910002804 graphite Inorganic materials 0.000 claims description 24
- 239000010439 graphite Substances 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 229910052786 argon Inorganic materials 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
- 238000011068 loading method Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 12
- 210000000988 bone and bone Anatomy 0.000 abstract description 6
- 210000001519 tissue Anatomy 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract description 2
- 238000002490 spark plasma sintering Methods 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 description 16
- 239000011701 zinc Substances 0.000 description 16
- 239000011777 magnesium Substances 0.000 description 15
- 229910052749 magnesium Inorganic materials 0.000 description 15
- 229910000861 Mg alloy Inorganic materials 0.000 description 6
- 230000007541 cellular toxicity Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052586 apatite Inorganic materials 0.000 description 4
- 230000033558 biomineral tissue development Effects 0.000 description 4
- 210000001124 body fluid Anatomy 0.000 description 4
- 239000010839 body fluid Substances 0.000 description 4
- 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 4
- 238000012876 topography Methods 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 206010061218 Inflammation Diseases 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003519 biomedical and dental material Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 230000004054 inflammatory process Effects 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 230000011164 ossification Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 230000000638 stimulation Effects 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
- 230000001154 acute effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000018678 bone mineralization 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
- 238000001514 detection method Methods 0.000 description 1
- 230000004821 effect on bone 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
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 210000000963 osteoblast Anatomy 0.000 description 1
- 210000002997 osteoclast Anatomy 0.000 description 1
- 230000004819 osteoinduction Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
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- 208000024891 symptom Diseases 0.000 description 1
- 231100000816 toxic dose Toxicity 0.000 description 1
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- 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
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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
- A61L27/40—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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- 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
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- 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
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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 comprises the following steps: taking metal zinc powder, magnesium powder and nano-hydroxyapatite powder as raw materials, proportioning the zinc powder, the magnesium powder and the nano-hydroxyapatite according to the mass ratio of 1-10 percent to 1-10 percent and 98-80 percent, 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 percent to 60-40 percent, and uniformly mixing and pressing to obtain a strip-shaped blank; the zinc-magnesium/hydroxyapatite porous composite material is prepared by adopting spark plasma sintering. The porosity of the composite material prepared by the invention is 40-60%, the pore size is 100-500 mu m and is controllable, and the composite material meeting various different requirements, such as a bone scaffold, bone filling, a repair 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 composites are found in nature and in human tissues, for example, human bone is a fiber-reinforced composite of collagen, protein and inorganic substances. The traditional single-kind biomedical materials can well meet the biomedical requirements in some aspects, but can not meet the standards in other aspects, even can generate adverse effects, and can not meet the clinical application. 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 a pore-forming agent, and prepares a porous zinc-magnesium alloy/hydroxyapatite composite material block by powder preparation, ball milling and powder mixing, discharge plasma sintering and pore-forming agent removal, wherein the density of the porous zinc-magnesium alloy/hydroxyapatite composite material block is 2.94g/cm3The porosity is 53 percent, the aperture is less than or equal to 450 mu m, the yield strength is 60MPa, and the elastic modulus is 4 GPa. At present, zinc is adopted as a matrix, hydroxyapatite and magnesium are added to improve biocompatibility, and the zinc is narrow in safety rangeMetal elements, and zinc ions are quickly released after implantation to cause cell toxicity; and NaCl is used as a pore forming agent, so that HA is easy to react to generate Ca in the sintering process5(PO4)3Cl, etc., resulting in impure composite components.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the zinc-magnesium/hydroxyapatite porous composite material prepared by adding hydroxyapatite into zinc as a matrix in the prior art has the problem of cell toxicity, since zinc is a metal element with a narrow safety range, the requirement of adult men is 10-20 mg/d, the toxic dose is 80-400 mg/d, and most of the zinc elements are acute symptoms, and zinc ions are rapidly released after implantation to cause cell toxicity.
In order to achieve the purpose, the invention adopts a preparation method of a 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: 1-10 percent of magnesium powder, and the mass percent of the magnesium powder is as follows: 1-10 percent of nano hydroxyapatite, and the mass percentage of the nano hydroxyapatite is 98-80 percent.
(2) Putting the powder weighed in the step (1) into a stainless steel ball milling tank, putting a proper amount of stainless steel balls, and vacuumizing the stainless steel balls, wherein the processes are all finished in a vacuum glove box; and (4) 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 percent to 40-60 percent.
(4) Uniformly coating a 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, placing the die on a press machine for prepressing, and pressing the die into a long-strip-shaped prepressing blank.
(5) Putting the strip-shaped prepressing blank obtained in the step (4) into a self-made graphite mold, putting the self-made graphite mold into a discharge plasma sintering furnace, and pumping the vacuum degree in the sintering furnace to 10-3～10-4After Pa, heating to 600-800 ℃ at a heating rate of 100-150 ℃/min, keeping the temperature for 2-3 min, and then heating to 25 ∞Heating to 700-900 ℃ at a heating rate of 50 ℃/min, and keeping the temperature for 5-10 min; after sintering, furnace cooling is carried out to room temperature, and the zinc-magnesium/hydroxyapatite porous composite material is obtained.
Preferably, in the step (1), the purity of the nano-hydroxyapatite 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 particle size is 10-20 mu m; the purity of the metallic zinc powder is 99.95%, and the particle size is 1-10 mu m.
Preferably, the conditions of the ball milling process in step (2) of the present invention are: the vacuum degree in the stainless steel ball milling tank is 8-10 Pa, the stainless steel ball milling 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; and after the temperature of the tank body is reduced to room temperature, vacuumizing the tank body again to 8-10 Pa, and then ball-milling for 6-8 h at the rotating speed of 300-400 r/min.
Preferably, the ball material ratio of the stainless steel grinding ball to the raw materials is 4: 1-3: 1, wherein the grinding ball mass ratio is as follows: a middle ball: the pellet is 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, in the step (3), the purity of the ammonium bicarbonate powder is analytical purity, and the particle size is 100-300 μm; the mixing process is carried out in an argon environment, and the mixer is used for mixing for 20-30 min at a rotating speed of 50-100 r/min.
Preferably, the pre-pressing process in step (4) of the present invention is: unidirectional pressurization, the loading rate of 1-3 KN/min, the pressure of 400-450 MPa, and pressure maintaining for 20-30 min.
Preferably, the self-made stainless steel mold has the following structure: a cylindrical outer body: phi 75mm multiplied by H30 mm; a rectangular inner cavity: a15mm × b5mm × c30 mm.
Preferably, the self-made graphite mold provided by the invention has the following structure: a cylindrical outer body: phi 15.5mm multiplied by H17.5mm; a rectangular inner cavity: a5.5mm. times.b5.5mm. times.17.5 mm; and (3) plugging: phi 10mm multiplied by 10mm is matched with the rectangular inner cavity of the graphite mould.
All mass percentages in the present invention are mass percentages unless otherwise specified.
The invention has the beneficial effects that:
(1) the zinc-magnesium alloy can be used as a substitute product of hard tissues, and although zinc and magnesium have excellent biocompatibility and osteoinduction and antibacterial property, zinc and magnesium are not corrosion-resistant and are easy to degrade in a body fluid environment, and the degradation rate is high, so that the local zinc and magnesium ion concentration is too high, cell toxicity is caused, and inflammation is induced. According to the invention, zinc and magnesium are used as activity enhancement phases and added into hydroxyapatite to prepare the zinc-magnesium/hydroxyapatite porous composite material. Under the environment of body fluid, zinc ions and magnesium ions can be slowly and long-term released along with the degradation of hydroxyapatite, so that the cell toxicity caused by quick release is avoided. The adoption of the spark plasma sintering technology can reduce the sintering temperature, avoid the loss of zinc and magnesium caused by overhigh temperature, reduce the heat preservation time, avoid the decomposition of hydroxyapatite caused by overlong calcination time and effectively avoid the occurrence of the phenomenon of coarsening of crystal grains.
(2) The invention selects ammonium bicarbonate as pore-forming agent and 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 mu m) of the composite material can be controlled by adjusting the particle size and the addition amount of the pore-forming agent according to actual requirements, and the requirements of bone scaffolds, bone filling materials, repair materials of hard tissue defect parts and the like can be met.
(3) Experimental results of the zinc-magnesium/hydroxyapatite porous composite material prepared by the invention show that: the addition of magnesium obviously improves the osteoinductivity, the osteoconductivity and the absorbability of the composite material; the zinc has direct stimulation effect on osteoblasts, can promote bone formation and mineralization, has selective inhibition effect on bone resorption of osteoclasts, and also has certain antibacterial property; under the continuous stimulation of zinc and magnesium, the osteogenesis process is accelerated, and the treatment speed is improved.
Drawings
FIG. 1 is a schematic view of a self-made stainless steel mold according to the present invention;
FIG. 2 is a schematic view of a self-made graphite mold according to the present invention;
FIG. 3 is a surface topography of a zinc-magnesium/hydroxyapatite porous composite prepared according to example 2 of the present invention;
FIG. 4 is a 7d mineralization profile of a zinc-magnesium/hydroxyapatite porous composite material prepared in example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
The self-made stainless steel die provided by the embodiment of the invention has the following structure: a cylindrical outer body: phi 75mm multiplied by H30 mm; a rectangular inner cavity: a15mm xb 5mm xc 30mm, as shown in fig. 1. The self-made graphite mold has the structure that: a cylindrical outer body: phi 15.5mm multiplied by H17.5mm; a rectangular inner cavity: a5.5mm. times.b5.5mm. times.17.5 mm; and (3) plugging: phi 10mm multiplied by 10mm, which is matched with the rectangular inner cavity of the graphite mold, as shown in figure 2.
Example 1
(1) The zinc powder and magnesium powder composite material is prepared from 99.5% of metallic zinc powder with the particle size of 1-10 mu m, 99.95-99.99% of metallic magnesium powder with the particle size of 10-20 mu m and nano-hydroxyapatite with the particle size of 150-300 mu m, wherein the zinc powder, the magnesium powder and the nano-hydroxyapatite are mixed according to the mass ratio of 1% to 98%.
(2) Putting the powder weighed in the step (1) into a stainless steel ball milling tank, and putting a proper amount of stainless steel grinding balls according to a ball-to-material ratio of 4:1, wherein the grinding balls are large balls in mass ratio: a middle ball: the pellets are 2:8:15, and are vacuumized to 10Pa, and the processes are all finished in a vacuum glove box; fixing the mixture on a planetary ball mill, and carrying out ball milling for 2 hours at the rotating speed of 200 r/min; and after the temperature of the tank body is reduced to room temperature, vacuumizing the tank body again to 10Pa, and then performing 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 putting the culture dish into a vacuum drying box, wherein the drying temperature in the box is 35 ℃; the vacuum degree is 8 Pa; and mixing the composite powder and 50 percent of ammonium bicarbonate according to the volume percentage, wherein the mixing process is carried out in an argon environment, and a mixer is used for mixing for 20min at the rotating speed of 50 r/min.
(4) Uniformly coating a 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 long-strip-shaped prepressing blank.
(5) Putting the strip-shaped prepressing blank obtained in the step (4) into a self-made graphite mold, putting the self-made graphite mold into a discharge plasma sintering furnace, and pumping the vacuum degree in the sintering furnace to 10-3a, then; heating to 600 deg.C at a heating rate of 100 deg.C/min, and maintaining for 1 min; then the temperature is raised to 700 ℃ at the heating rate of 50 ℃/min, and the temperature is kept for 5 min. And after sintering, cooling to room temperature along with the furnace to obtain the zinc-magnesium/hydroxyapatite porous composite material.
Example 2
(1) The zinc powder and magnesium powder composite material is prepared from 99.5% of metallic zinc powder with the particle size of 1-10 mu m, 99.95-99.99% of metallic magnesium powder with the particle size of 10-20 mu m and nano-hydroxyapatite with the particle size of 150-300 mu m, wherein the zinc powder, the magnesium powder and the nano-hydroxyapatite are mixed according to the mass ratio of 3% to 94%.
(2) Putting the powder weighed in the step (1) into a stainless steel ball milling tank, and putting a proper amount of stainless steel grinding balls according to a ball-to-material ratio of 4:1, wherein the grinding balls are large balls in mass ratio: a middle ball: the pellets are 2:8:15, and are vacuumized to 10Pa, and the processes are all finished in a vacuum glove box; fixing the mixture on a planetary ball mill, and carrying out ball milling for 2 hours at the rotating speed of 200 r/min; and after the temperature of the tank body is reduced to room temperature, vacuumizing the tank body again to 10Pa, and then performing 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 putting the culture dish into a vacuum drying box, wherein the drying temperature in the box is 35 ℃; the vacuum degree is 8 Pa; and mixing the composite powder and 50 percent of ammonium bicarbonate according to the volume percentage, wherein the mixing process is carried out in an argon environment, and a mixer is used for mixing for 20min at the rotating speed of 50 r/min.
(4) Uniformly coating a 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 long-strip-shaped prepressing blank.
(5) Putting the strip-shaped prepressing blank obtained in the step (4) into a self-made graphite mold, putting the self-made graphite mold into a discharge plasma sintering furnace, and pumping the vacuum degree in the sintering furnace to 10-3a, then; heating to 600 deg.C at a heating rate of 100 deg.C/min, and maintaining for 1 min; then the temperature is raised to 700 ℃ at the heating rate of 50 ℃/min, and the temperature is kept for 5 min. And after sintering, cooling to room temperature along with the furnace to obtain the zinc-magnesium/hydroxyapatite porous composite material.
Example 3
(1) The zinc powder and magnesium powder composite material is prepared from 99.5% of metallic zinc powder with the particle size of 1-10 mu m, 99.95-99.99% of metallic magnesium powder with the particle size of 10-20 mu m and nano-hydroxyapatite with the particle size of 150-300 mu m, wherein the zinc powder, the magnesium powder and the nano-hydroxyapatite are mixed according to the mass ratio of 3% to 94%.
(2) Putting the powder weighed in the step (1) into a stainless steel ball milling tank, and putting a proper amount of stainless steel grinding balls according to a ball-to-material ratio of 4:1, wherein the grinding balls are large balls in mass ratio: a middle ball: the pellets are 2:8:15, and are vacuumized to 10Pa, and the processes are all finished in a vacuum glove box; fixing the mixture on a planetary ball mill, and carrying out ball milling for 2 hours at the rotating speed of 200 r/min; and after the temperature of the tank body is reduced to room temperature, vacuumizing the tank body again to 10Pa, and then performing 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 putting the culture dish into a vacuum drying box, wherein the drying temperature in the box is 35 ℃; the vacuum degree is 8 Pa; and mixing the composite powder and ammonium bicarbonate according to the volume percentage of 60 percent to 40 percent under the argon environment in the mixing process, and mixing for 20min by a mixer at the rotating speed of 50 r/min.
(4) Uniformly coating a 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 long-strip-shaped prepressing blank.
(5) In self-madePutting the graphite die into the strip-shaped prepressing blank obtained in the step (4), putting the graphite die into a discharge plasma sintering furnace, and pumping the graphite die to 10 degrees of vacuum inside the sintering furnace-3a, then; heating to 600 deg.C at a heating rate of 100 deg.C/min, and maintaining for 1 min; then the temperature is raised to 700 ℃ at the heating rate of 50 ℃/min, and the temperature is kept for 5 min. And after sintering, cooling to room temperature along with the furnace to obtain the zinc-magnesium/hydroxyapatite porous composite material.
Example 4
(1) The zinc powder and magnesium powder composite material is prepared from 99.5% of metallic zinc powder with the particle size of 1-10 mu m, 99.95-99.99% of metallic magnesium powder with the particle size of 10-20 mu m and nano-hydroxyapatite with the particle size of 150-300 mu m, wherein the zinc powder, the magnesium powder and the nano-hydroxyapatite are mixed according to the mass ratio of 3% to 94%.
(2) Putting the powder weighed in the step (1) into a stainless steel ball milling tank, and putting a proper amount of stainless steel grinding balls according to a ball-to-material ratio of 4:1, wherein the grinding balls are large balls in mass ratio: a middle ball: the pellets are 2:8:15, and are vacuumized to 10Pa, and the processes are all finished in a vacuum glove box; fixing the mixture on a planetary ball mill, and carrying out ball milling for 2 hours at the rotating speed of 200 r/min; and after the temperature of the tank body is reduced to room temperature, vacuumizing the tank body again to 10Pa, and then performing 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 putting the culture dish into a vacuum drying box, wherein the drying temperature in the box is 35 ℃; the vacuum degree is 8 Pa; and mixing the composite powder and ammonium bicarbonate according to the volume percentage of 40 percent to 60 percent under the argon environment in the mixing process, and mixing for 20min by a mixer at the rotating speed of 50 r/min.
(4) Uniformly coating a 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 long-strip-shaped prepressing blank.
(5) Putting the strip-shaped prepressing blank obtained in the step (4) into a self-made graphite mold, putting the self-made graphite mold into a discharge plasma sintering furnace, and pumping the vacuum degree in the sintering furnace to 10-3a, then; heating to the temperature of 100 ℃/minKeeping the temperature at 600 ℃ for 1 min; then the temperature is raised to 700 ℃ at the heating rate of 50 ℃/min, and the temperature is kept for 5 min. And after sintering, cooling to room temperature along with the furnace to obtain the zinc-magnesium/hydroxyapatite porous composite material.
Example 5
(1) The zinc powder and magnesium powder composite material is prepared from 99.5% of metallic zinc powder with the particle size of 1-10 mu m, 99.95-99.99% of metallic magnesium powder with the particle size of 10-20 mu m and nano-hydroxyapatite with the particle size of 150-300 mu m, wherein the zinc powder, the magnesium powder and the nano-hydroxyapatite are mixed according to the mass ratio of 5% to 90%.
(2) Putting the powder weighed in the step (1) into a stainless steel ball milling tank, and putting a proper amount of stainless steel grinding balls according to a ball-to-material ratio of 4:1, wherein the grinding balls are large balls in mass ratio: a middle ball: the pellets are 2:8:15, and are vacuumized to 8Pa, and the processes are finished in a vacuum glove box; fixing the mixture on a planetary ball mill, and carrying out ball milling for 2 hours at the rotating speed of 300 r/min; and after the temperature of the tank body is reduced to room temperature, vacuumizing the tank body again to 10Pa, and then performing ball milling for 8 hours at the rotating speed of 400/min.
(3) Pouring the slurry obtained in the step (2) into a culture dish in a vacuum glove box, and putting the culture dish into a vacuum drying box, wherein the drying temperature in the box is 35 ℃; the vacuum degree is 8 Pa; and mixing the composite powder and 50 percent of ammonium bicarbonate according to the volume percentage, wherein the mixing process is carried out in an argon environment, and a mixer is used for mixing for 20min at the rotating speed of 50 r/min.
(4) Uniformly coating a 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 long-strip-shaped prepressing blank.
(5) Putting the strip-shaped prepressing blank obtained in the step (4) into a self-made graphite mold, putting the self-made graphite mold into a discharge plasma sintering furnace, and pumping the vacuum degree in the sintering furnace to 10-3a, then; heating to 600 deg.C at a heating rate of 100 deg.C/min, and maintaining for 1 min; then the temperature is raised to 700 ℃ at the heating rate of 50 ℃/min, and the temperature is kept for 5 min. And after sintering, cooling to room temperature along with the furnace to obtain the zinc-magnesium/hydroxyapatite porous composite material.
Example 6
(1) The zinc powder and magnesium powder composite material is prepared from 99.5% of metallic zinc powder with the particle size of 1-10 mu m, 99.95-99.99% of metallic magnesium powder with the particle size of 10-20 mu m and nano-hydroxyapatite with the particle size of 150-300 mu m, wherein the zinc powder, the magnesium powder and the nano-hydroxyapatite are mixed according to the mass ratio of 10% to 80%.
(2) Putting the powder weighed in the step (1) into a stainless steel ball milling tank, and putting a proper amount of stainless steel grinding balls according to a ball-to-material ratio of 4:1, wherein the grinding balls are large balls in mass ratio: a middle ball: the pellets are 2:8:15, and are vacuumized to 8Pa, and the processes are finished in a vacuum glove box; fixing the mixture on a planetary ball mill, and carrying out ball milling for 2 hours at the rotating speed of 300 r/min; and after the temperature of the tank body is reduced to room temperature, vacuumizing the tank body again to 10Pa, and then performing ball milling for 8 hours at the rotating speed of 400/min.
(3) Pouring the slurry obtained in the step (2) into a culture dish in a vacuum glove box, and putting the culture dish into a vacuum drying box, wherein the drying temperature in the box is 35 ℃; the vacuum degree is 8 Pa; and mixing the composite powder and 50 percent of ammonium bicarbonate according to the volume percentage, wherein the mixing process is carried out in an argon environment, and a mixer is used for mixing for 20min at the rotating speed of 50 r/min.
(4) Uniformly coating a 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 long-strip-shaped prepressing blank.
(5) Putting the strip-shaped prepressing blank obtained in the step (4) into a self-made graphite mold, putting the self-made graphite mold into a discharge plasma sintering furnace, and pumping the vacuum degree in the sintering furnace to 10-4a, then; heating to 600 deg.C at a heating rate of 100 deg.C/min, and maintaining for 1 min; then the temperature is raised to 700 ℃ at the heating rate of 50 ℃/min, and the temperature is kept for 5 min. And after sintering, cooling to room temperature along with the 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 invention, the difference between the sintered magnesium content and the preset content is not large, and the magnesium/hydroxyapatite porous composite material accords with the expectation, and the specific result is shown in Table 1.
TABLE 1 Zinc and magnesium contents in Zinc-magnesium/hydroxyapatite porous composites
Measuring the porosity of the composite material prepared by the implementation by adopting an Archimedes drainage method; the mechanical property (compressive strength) of the material is tested in a mechanical testing machine according to the GB/T4740-; in order to ensure that the result has statistical significance, the average value of the result is obtained through multiple tests; the test results are detailed in table 2.
TABLE 2 porosity and compressive strength of Zinc-magnesium/hydroxyapatite porous composites
The surface topography of the composite material before and after mineralization is analyzed by a scanning electron microscope, and fig. 3 is a surface topography map of the composite material prepared in example 2 before mineralization, which can be seen as follows: the composite material has a porous structure with three-dimensional interconnection and coexistence of large pores and small pores, the content of the pores is about 53%, the pore size of the large pores is 200-300 mu m, the pore size of the micropores is less than 10 mu m, and the large pores and the small pores are crossed and uniformly distributed; compared with the porous zinc-magnesium alloy/hydroxyapatite composite material prepared in the application number of 201711047520.8, the material with more porosity or pore size can be obtained by controlling the proportion and the particle size of the pore-forming agent, and can be used in different directions; the hydroxyapatite is adopted as a matrix, so that zinc and magnesium can be coated, and the zinc and magnesium are prevented from being directly exposed in body fluid, thereby avoiding cell toxicity, inflammation and the like.
FIG. 4 is a surface topography of the composite material prepared in example 2 after 14 days of mineralization, and after 14 days of simulated artificial body fluid (SBF) soaking, 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 of 201711047520.8, the hydroxyapatite is adopted as the matrix, so that the sedimentation capability of the bone-like apatite can be improved, and the bone-like apatite composite material is beneficial to calcification of bones after being implanted.
Claims (9)
1. A preparation method of a zinc-magnesium/hydroxyapatite porous composite material is characterized by comprising 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: 1-10 percent of magnesium powder, and the mass percent of the magnesium powder is as follows: 1-10 percent of nano hydroxyapatite, and the mass percent of the nano hydroxyapatite is 98-80 percent;
(2) putting the powder weighed in the step (1) into a stainless steel ball milling tank, putting a proper amount of stainless steel balls, and vacuumizing the stainless steel balls, wherein the processes are all finished in a vacuum glove box; 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 to 40-60 percent;
(4) uniformly coating a proper amount of vaseline on the inner wall of a self-made stainless steel mold, adding the mixed powder obtained in the step (2) into the mold, placing the mold on a press machine for prepressing, and pressing the mold into a long-strip-shaped prepressing blank;
(5) putting the strip-shaped prepressing blank obtained in the step (4) into a self-made graphite mold, putting the self-made graphite mold into a discharge plasma sintering furnace, and pumping the vacuum degree in the sintering furnace to 10-3～10-4After Pa, heating to 600-800 ℃ at a heating rate of 100-150 ℃/min, preserving heat for 2-3 min, then heating to 700-900 ℃ at a heating rate of 25-50 ℃/min, and preserving heat for 5-10 min; after sintering, furnace cooling is carried out to room temperature, and the zinc-magnesium/hydroxyapatite porous composite material is obtained.
2. The method for preparing a zinc-magnesium/hydroxyapatite porous composite material according to claim 1, characterized in that: in the step (1), the purity of the nano-hydroxyapatite 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 particle size is 10-20 mu m; the purity of the metallic zinc powder is 99.95%, and the particle size is 1-10 mu m.
3. The method for preparing a zinc-magnesium/hydroxyapatite porous composite material according to claim 1, characterized in that: the conditions of the ball milling process in the step (2) are as follows: the vacuum degree in the stainless steel ball milling tank is 8-10 Pa, the stainless steel ball milling 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; and after the temperature of the tank body is reduced to room temperature, vacuumizing the tank body again to 8-10 Pa, and then ball-milling for 6-8 h at the rotating speed of 300-400 r/min.
4. The method for preparing a zinc-magnesium/hydroxyapatite porous composite material according to claim 3, characterized in that: the ball material ratio of the stainless steel grinding balls to the raw materials is 4: 1-3: 1, wherein the grinding balls are large balls in mass ratio: a middle ball: the pellet is 2:8:15 to 3:10: 20.
5. The method for preparing a zinc-magnesium/hydroxyapatite porous composite material according to claim 1, characterized in that: 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 a zinc-magnesium/hydroxyapatite porous composite material according to claim 1, characterized in that: the purity of the ammonium bicarbonate powder in the step (3) is analytical purity, and the particle size is 100-300 mu m; the mixing process is carried out in an argon environment, and the mixer is used for mixing for 20-30 min at a rotating speed of 50-100 r/min.
7. The method for preparing a zinc-magnesium/hydroxyapatite porous composite material according to claim 1, characterized in that: the prepressing process in the step (4) is as follows: unidirectional pressurization, the loading rate of 1-3 KN/min, the pressure of 400-450 MPa, and pressure maintaining for 20-30 min.
8. The method for preparing a zinc-magnesium/hydroxyapatite porous composite material according to claim 1, characterized in that: the self-made stainless steel die has the structure that: a cylindrical outer body: phi 75mm multiplied by H30 mm; a rectangular inner cavity: a15mm × b5mm × c30 mm.
9. The method for preparing a zinc-magnesium/hydroxyapatite porous composite material according to claim 1, characterized in that: the self-made graphite mold has the structure that: a cylindrical outer body: phi 15.5mm multiplied by H17.5mm; a rectangular inner cavity: a5.5mm. times.b5.5mm. times.17.5 mm; and (3) plugging: phi 10mm multiplied by 10mm is matched with the rectangular inner cavity of the graphite mould.
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