CN112608140A - Preparation method of zinc oxide-magnesium oxide/hydroxyapatite porous composite material - Google Patents
Preparation method of zinc oxide-magnesium oxide/hydroxyapatite porous composite material Download PDFInfo
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- CN112608140A CN112608140A CN202011492936.2A CN202011492936A CN112608140A CN 112608140 A CN112608140 A CN 112608140A CN 202011492936 A CN202011492936 A CN 202011492936A CN 112608140 A CN112608140 A CN 112608140A
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- zinc oxide
- magnesium oxide
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- hydroxyapatite
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- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 58
- 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 56
- PNHVEGMHOXTHMW-UHFFFAOYSA-N magnesium;zinc;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Zn+2] PNHVEGMHOXTHMW-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000843 powder Substances 0.000 claims abstract description 44
- 238000000227 grinding Methods 0.000 claims abstract description 31
- 238000000498 ball milling Methods 0.000 claims abstract description 29
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 25
- 239000011787 zinc oxide Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 17
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 17
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 26
- 238000005245 sintering Methods 0.000 claims description 25
- 239000002270 dispersing agent Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 229910002804 graphite Inorganic materials 0.000 claims description 21
- 239000010439 graphite Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 14
- 239000010935 stainless steel Substances 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 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
- 229940099259 vaseline Drugs 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 4
- 238000003801 milling Methods 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 239000011148 porous material Substances 0.000 abstract description 12
- 210000000988 bone and bone Anatomy 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 7
- 210000001519 tissue Anatomy 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 238000002490 spark plasma sintering Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 9
- 229910000861 Mg alloy Inorganic materials 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 5
- 210000001124 body fluid Anatomy 0.000 description 5
- 239000010839 body fluid Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000033558 biomineral tissue development Effects 0.000 description 4
- 230000007541 cellular toxicity Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- 229910052586 apatite Inorganic materials 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
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 206010061218 Inflammation Diseases 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003519 biomedical and dental material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000004069 differentiation Effects 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 230000004054 inflammatory process Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 210000000963 osteoblast Anatomy 0.000 description 2
- 230000035755 proliferation Effects 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 210000002449 bone cell Anatomy 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011068 loading method Methods 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
- 230000003014 reinforcing effect Effects 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 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 description 1
- 230000002792 vascular Effects 0.000 description 1
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Abstract
本发明公开一种氧化锌‑氧化镁/羟基磷灰石多孔复合材料的制备方法，属于生物医用材料技术领域。本发明所述方法：以纳米氧化锌、氧化镁和纳米羟基磷灰石粉末为原料，其中氧化锌与氧化镁粉末和羟基磷灰石按质量比1％～10％:99％～90％进行配比，称取，球磨，烘干，研磨后得到复合粉末；将复合粉末与医用级碳酸氢铵按体积百分比40％～80％:60％～20％进行混合，混合均匀压制得到长条状坯体；采用放电等离子烧结制备出氧化锌‑氧化镁/羟基磷灰石多孔复合材料。本发明所制备出的复合材料孔隙率在20％～60％，孔径尺寸在100～500μm且可控，可根据实际的需求，制备出满足各种不同需求的复合材料，如骨支架、骨填充及硬组织缺损部分的修复材料等。The invention discloses a preparation method of a zinc oxide-magnesium oxide/hydroxyapatite porous composite material, and belongs to the technical field of biomedical materials. The method of the invention: using nano-zinc oxide, magnesium oxide and nano-hydroxyapatite powder as raw materials, wherein zinc oxide, magnesium oxide powder and hydroxyapatite are carried out in a mass ratio of 1% to 10%: 99% to 90% Proportion, weighing, ball milling, drying, and grinding to obtain composite powder; the composite powder and medical grade ammonium bicarbonate are mixed by volume percentage of 40%-80%: 60%-20%, and the mixture is uniformly pressed to obtain a long strip. The green body; the zinc oxide-magnesium oxide/hydroxyapatite porous composite material is prepared by spark plasma sintering. The porosity of the composite material prepared by the invention is 20%-60%, and the pore size is 100-500 μm and controllable. According to actual needs, composite materials that meet various needs can be prepared, such as bone scaffolds and bone fillings. and repair materials for hard tissue defects.
Description
Technical Field
The invention relates to a preparation method of a zinc oxide-magnesium oxide/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. Hydroxyapatite is taken as an additive phase, and the zinc-magnesium alloy isThe zinc is a metal element with a narrow safety range, zinc ions are quickly released after implantation to cause cell toxicity, and the zinc-magnesium alloy is easy to generate gas in body fluid to induce inflammation; NaCl is used as a pore forming agent, and HA is easy to react to generate Ca in the sintering process5(PO4)3Cl, etc., resulting in impure composite components. In a body fluid environment, zinc oxide and magnesium oxide can slowly release zinc ions and magnesium ions, the problem of rapid degradation of zinc-magnesium alloy can be effectively avoided, the proliferation and differentiation of osteoblasts can be continuously stimulated, and the synthesis of related proteins is induced.
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-magnesium alloy serving 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 amount is 80-400 mg/d, and most of the zinc is acute symptoms, zinc ions are rapidly released after implantation to cause cell toxicity, and the zinc-magnesium alloy is easy to generate gas in body fluid to induce inflammation.
In order to achieve the purpose, the invention adopts a preparation method of a zinc oxide-magnesium oxide/hydroxyapatite porous composite material, which mainly comprises the following steps:
(1) the preparation method comprises the following steps of selecting nano zinc oxide, magnesium oxide and nano hydroxyapatite as raw materials, wherein the mass percent of the zinc oxide is 1-10%, the mass percent of the magnesium oxide powder is 1-10%, and the mass percent of the hydroxyapatite is 98-80%.
(2) Putting the powder weighed in the step (1) into an agate ball milling tank, putting agate milling balls, and adding absolute ethyl alcohol and a dispersing agent; and after the ball milling is finished, drying and grinding to obtain composite powder.
(3) Mixing the composite powder obtained in the step (2) with medical ammonium bicarbonate powder according to the volume percentage of 40-80% to 60-20%, uniformly coating a proper amount of vaseline on the inner wall of a self-made stainless steel die, adding the mixed powder into the die, placing the die on a press machine for prepressing, and pressing the die into a long-strip-shaped prepressing blank.
(4) Putting the long-strip-shaped prepressing blank obtained in the step (3) into a self-made graphite mold, and vacuumizing to enable the internal vacuum degree of the sintering furnace to be 6-8 Pa; heating to 800-900 ℃ at a heating rate of 100-150 ℃/min, and keeping the temperature for 2-3 min; then heating to 950-1050 ℃ at a heating rate of 25-50 ℃/min, and preserving heat for 5-10 min; and cooling the sintered product to room temperature along with the furnace to obtain the zinc oxide-magnesium oxide/hydroxyapatite porous composite material.
Preferably, the purity of the nano-hydroxyapatite in the step (1) is more than or equal to 99.9%, the particle size is 150-300 nm, the purity of the nano-zinc oxide is more than or equal to 99.7%, the particle size is 200-300 nm, the purity of the nano-magnesium oxide is 99.9%, and the particle size is 100-200 nm.
Preferably, the ball milling conditions in step (2) of the present invention are: the rotating speed is 200-400 r/min, and the ball milling time is 8-10 h.
Preferably, in the step (2), the ratio of the agate grinding balls to the raw materials is 4: 1-3: 1, wherein the mass ratio of the agate grinding balls to the raw materials is as follows: a middle ball: the pellet is 1:4:5 to 2:7: 9.
Preferably, the dispersant in step (2) of the present invention is span 80, and the chemical formula thereof is C24H44O6And the addition amount of the medicinal grade is 0.3-0.5% of the mass of the original powder.
Preferably, the temperature of the oven is 30-40 ℃.
Preferably, the purity of the ammonium bicarbonate powder in the step (3) is analytical purity, the particle size is 100-300 μm, and the ammonium bicarbonate powder is mixed by a mixer at a rotating speed of 50-100 r/min for 20-30 min.
Preferably, the pre-pressing process in the step (3) is one-way pressurization, 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 mold has the following structure: a cylindrical outer body: phi 75mm multiplied by H30 mm; a rectangular inner cavity: a15mm xb 5mm xc 30mm, the prepared strip-like size is in accordance with the bone repair material currently used in clinic.
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.
The invention has the advantages of
(1) The invention selects zinc oxide and magnesium oxide as the second phase, can be prepared at normal temperature and normal pressure, effectively avoids the experimental risks in the vacuum environment and sintering process required by using simple substances of zinc and magnesium, and has simple process and convenient operation.
(2) According to the invention, ammonium bicarbonate is selected as a pore-forming agent, the ammonium bicarbonate can be quickly decomposed at about 60 ℃, and the ammonium bicarbonate 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 (20-80%) 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) According to the invention, hydroxyapatite is selected as a matrix, and nano zinc oxide and nano magnesium oxide are added into the matrix to prepare the zinc oxide-magnesium oxide/hydroxyapatite porous composite material, and after the zinc oxide-magnesium oxide/hydroxyapatite porous composite material is implanted, zinc ions and magnesium ions can be slowly and long-term released along with the degradation of the hydroxyapatite, so that cell toxicity caused by quick release is avoided.
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 an X-ray diffraction pattern of a zinc oxide-magnesium oxide/hydroxyapatite porous composite prepared in example 2 of the present invention;
FIG. 4 is a surface topography of a zinc oxide-magnesium oxide/hydroxyapatite porous composite prepared according to example 2 of the present invention;
FIG. 5 is a 7d mineralization profile of a zinc oxide-magnesium oxide/hydroxyapatite porous composite prepared in example 2 of the present invention;
FIG. 6 degradation performance of the zinc oxide-magnesium oxide/hydroxyapatite porous composite 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 used in 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, the strip-like dimensions prepared correspond to those of the bone repair materials currently used in the clinic, 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
A preparation method of a zinc oxide-magnesium oxide/hydroxyapatite porous composite material specifically comprises the following steps:
(1) the method is characterized in that the zinc oxide powder is prepared from 1% by mass of zinc oxide, 1% by mass of magnesium oxide powder and 98% by mass of hydroxyapatite, wherein the zinc oxide has a purity of not less than 99.7% and a particle size of 200-300 nm, the magnesium oxide has a purity of not less than 99.9% and a particle size of 100-200 nm, and the hydroxyapatite has a purity of not less than 99.9% and a particle size of 150-300 nm.
(2) Putting the powder weighed in the step (1) into an agate ball milling tank, adding a proper amount of agate grinding balls (the mass ratio of the agate grinding balls to the raw materials is 3:1, wherein the mass ratio of the agate grinding balls to the large balls to the medium balls to the small balls is 1:4:5), and adding a proper amount of anhydrous ethanol and a dispersing agent (the dispersing agent is span 80, and the chemical formula of the dispersing agent is C24H44O6Medicinal grade, the addition amount is 0.3 percent of the mass of the original powder); ball milling is carried out for 8 hours at the rotating speed of 300 r/min. After ball milling, drying (drying temperature is 30 ℃) and grinding are carried out.
(3) Pouring the slurry obtained in the step (1) into a culture dish, and putting the culture dish into a vacuum drying oven, wherein the drying temperature in the oven is 35 ℃; and mixing the composite powder with 50 percent of ammonium bicarbonate by volume percentage, and putting the mixture into a mixer for mixing for 30 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 20min, 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, vacuumizing to enable the internal vacuum degree of the sintering furnace to be 6-8 Pa, heating to 800 ℃ at the heating rate of 150 ℃/min, and keeping the temperature for 2 min; then heating to 1000 ℃ at the heating rate of 25 ℃/min, and keeping the temperature for 5 min; and after sintering, introducing air, cooling to room temperature along with the furnace, and obtaining the zinc oxide-magnesium oxide/hydroxyapatite porous composite material.
Example 2
(1) The method is characterized in that the zinc oxide powder is prepared from 3% by mass of zinc oxide, 3% by mass of magnesium oxide powder and 94% by mass of hydroxyapatite, wherein the zinc oxide has a purity of not less than 99.7% and a particle size of 200-300 nm, the magnesium oxide has a purity of not less than 99.9% and a particle size of 100-200 nm, and the hydroxyapatite has a purity of not less than 99.9% and a particle size of 150-300 nm.
(2) Putting the powder weighed in the step (1) into an agate ball milling tank, adding a proper amount of agate grinding balls (the mass ratio of the agate grinding balls to the raw materials is 4:1, wherein the mass ratio of the agate grinding balls to the large balls to the medium balls to the small balls is 2:7:9), and adding a proper amount of anhydrous ethanol and a dispersing agent (the dispersing agent is span 80, and the chemical formula of the dispersing agent is C24H44O6Medicinal grade, the addition amount is 0.5 percent of the mass of the original powder); ball milling is carried out for 8 hours at the rotating speed of 300 r/min. After ball milling, drying (drying temperature 40 ℃) and grinding are carried out.
(3) Pouring the slurry obtained in the step (1) into a culture dish, and putting the culture dish into a vacuum drying oven, wherein the drying temperature in the oven is 35 ℃; and mixing the composite powder with 50 percent of ammonium bicarbonate by volume percentage, and putting the mixture into a mixer to mix for 20 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 20min, 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, vacuumizing to enable the internal vacuum degree of the sintering furnace to be 6-8 Pa, heating to 800 ℃ at the heating rate of 150 ℃/min, and keeping the temperature for 2 min; then heating to 1000 ℃ at the heating rate of 25 ℃/min, and keeping the temperature for 5 min; and after sintering, introducing air, cooling to room temperature along with the furnace, and obtaining the zinc oxide-magnesium oxide/hydroxyapatite porous composite material.
Example 3
(1) The method is characterized in that the zinc oxide powder is prepared from 5% by mass of zinc oxide, 5% by mass of magnesium oxide powder and 90% by mass of hydroxyapatite, wherein the zinc oxide has a purity of not less than 99.7% and a particle size of 200-300 nm, the magnesium oxide has a purity of not less than 99.9% and a particle size of 100-200 nm, and the hydroxyapatite has a purity of not less than 99.9% and a particle size of 150-300 nm.
(2) Putting the powder weighed in the step (1) into an agate ball milling tank, adding a proper amount of agate grinding balls (the mass ratio of the agate grinding balls to the raw materials is 3:1, wherein the mass ratio of the agate grinding balls to the large balls to the medium balls to the small balls is 1:4:9), and adding a proper amount of anhydrous ethanol and a dispersing agent (the dispersing agent is span 80, and the chemical formula of the dispersing agent is C24H44O6Medicinal grade, the addition amount is 0.4 percent of the mass of the original powder); ball milling is carried out for 10 hours at the rotating speed of 400 r/min. And (4) drying and grinding after ball milling.
(3) Pouring the slurry obtained in the step (1) into a culture dish, and putting the culture dish into a vacuum drying oven, wherein the drying temperature in the oven is 35 ℃; and mixing the composite powder with 50 percent of ammonium bicarbonate by volume percentage, and putting the mixture into a mixer for mixing for 30 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 450MPa at a pressurizing rate of 3KN/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, vacuumizing to enable the internal vacuum degree of the sintering furnace to be 6-8 Pa, heating to 800 ℃ at the heating rate of 150 ℃/min, and keeping the temperature for 2 min; then heating to 1000 ℃ at the heating rate of 25 ℃/min, and keeping the temperature for 5 min; and after sintering, introducing air, cooling to room temperature along with the furnace, and obtaining the zinc oxide-magnesium oxide/hydroxyapatite porous composite material.
Example 4
(1) The method is characterized in that the zinc oxide powder is prepared from raw materials including nano zinc oxide with the purity of more than or equal to 99.7% and the particle size of 200-300 nm, nano magnesium oxide with the purity of more than or equal to 99.9% and nano hydroxyapatite with the purity of more than or equal to 99.9% and the particle size of 150-300 nm, wherein the mass percent of the zinc oxide is 7%, the mass percent of the magnesium oxide powder is 7%, and the mass percent of the hydroxyapatite is 86%.
(2) Putting the powder weighed in the step (1) into an agate ball milling tank, adding a proper amount of agate grinding balls (the mass ratio of the agate grinding balls to the raw materials is 4:1, wherein the mass ratio of the agate grinding balls to the large balls to the medium balls to the small balls is 1:7:9), and adding a proper amount of anhydrous ethanol and a dispersing agent (the dispersing agent is span 80, and the chemical formula of the dispersing agent is C24H44O6Medicinal grade, the addition amount is 0.4 percent of the mass of the original powder); ball milling for 10 hours at the rotating speed of 400 r/min; after ball milling, drying (drying temperature 40 ℃) and grinding are carried out.
(3) Pouring the slurry obtained in the step (1) into a culture dish, and putting the culture dish into a vacuum drying oven, wherein the drying temperature in the oven is 35 ℃; and mixing the composite powder with 50 percent of ammonium bicarbonate by volume percentage, and putting the mixture into a mixer for mixing for 30 min.
(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 (3) into the mold, placing the mold in a press machine, pressurizing to 450MPa at a pressurizing rate of 3KN/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, vacuumizing to enable the internal vacuum degree of the sintering furnace to be 6-8 Pa, heating to 800 ℃ at the heating rate of 150 ℃/min, and keeping the temperature for 2 min; then heating to 1000 ℃ at the heating rate of 25 ℃/min, and keeping the temperature for 5 min; and after sintering, introducing air, cooling to room temperature along with the furnace, and obtaining the zinc oxide-magnesium oxide/hydroxyapatite porous composite material.
Example 5
(1) The method is characterized in that the zinc oxide powder is prepared from 10 mass percent of zinc oxide, 10 mass percent of magnesium oxide powder and 98 mass percent of hydroxyapatite, wherein the zinc oxide has the purity of more than or equal to 99.7 percent and the particle size of 200-300 nm, the magnesium oxide has the purity of more than or equal to 99.9 percent and the particle size of 100-200 nm, and the hydroxyapatite has the purity of more than or equal to 99.9 percent and the particle size of 150-300 nm.
(2) Putting the powder weighed in the step (1) into an agate ball milling tank, adding a proper amount of agate grinding balls (the mass ratio of the agate grinding balls to the raw materials is 3:1, wherein the mass ratio of the agate grinding balls to the large balls to the medium balls to the small balls is 1:5:8), and adding a proper amount of anhydrous ethanol and a dispersing agent (the dispersing agent is span 80, and the chemical formula of the dispersing agent is C24H44O6Medicinal grade, the addition amount is 0.4 percent of the mass of the original powder); ball milling for 10 hours at the rotating speed of 400 r/min; after ball milling, drying (drying temperature 40 ℃) and grinding are carried out.
(3) Pouring the slurry obtained in the step (1) into a culture dish, and putting the culture dish into a vacuum drying oven, wherein the drying temperature in the oven is 35 ℃; and mixing the composite powder with 50 percent of ammonium bicarbonate by volume percentage, and putting the mixture into a mixer for mixing for 30 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 450MPa at a pressurizing rate of 3KN/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, vacuumizing to enable the internal vacuum degree of the sintering furnace to be 6-8 Pa, heating to 800 ℃ at the heating rate of 150 ℃/min, and keeping the temperature for 2 min; then raising the temperature to 1000 ℃ at the heating rate of 25 ℃/min, and preserving the temperature for 5 min. And after sintering, introducing air, cooling to room temperature along with the furnace, and obtaining the zinc oxide-magnesium oxide/hydroxyapatite porous composite material.
Example 6
(1) The method is characterized in that the zinc oxide powder is prepared from 5% by mass of zinc oxide, 5% by mass of magnesium oxide powder and 90% by mass of hydroxyapatite, wherein the zinc oxide has a purity of not less than 99.7% and a particle size of 200-300 nm, the magnesium oxide has a purity of not less than 99.9% and a particle size of 100-200 nm, and the hydroxyapatite has a purity of not less than 99.9% and a particle size of 150-300 nm.
(2) Putting the powder weighed in the step (1) into an agate ball milling tank, adding a proper amount of agate grinding balls (the mass ratio of the agate grinding balls to the raw materials is 4:1, wherein the mass ratio of the agate grinding balls to the large balls to the medium balls to the small balls is 1:6:8), and adding a proper amount of anhydrous ethanol and a dispersing agent (the dispersing agent is span 80, and the chemical formula of the dispersing agent is C24H44O6Medicinal grade, the addition amount is 0.4 percent of the mass of the original powder); ball milling for 10 hours at the rotating speed of 400 r/min; after ball milling, drying (drying temperature 35 ℃) and grinding are carried out.
(3) Pouring the slurry obtained in the step (1) into a culture dish, and putting the culture dish into a vacuum drying oven, wherein the drying temperature in the oven is 35 ℃; and mixing the composite powder with ammonium bicarbonate according to the volume percentage of 40 percent to 60 percent, and putting the mixture into a mixer for mixing for 30 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 450MPa at a pressurizing rate of 3KN/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, vacuumizing to enable the internal vacuum degree of the sintering furnace to be 6-8 Pa, heating to 800 ℃ at the heating rate of 150 ℃/min, and keeping the temperature for 2 min; then raising the temperature to 1000 ℃ at the heating rate of 25 ℃/min, and preserving the temperature for 5 min. And after sintering, introducing air, cooling to room temperature along with the furnace, and obtaining the zinc oxide-magnesium oxide/hydroxyapatite porous composite material.
The prepared composite material is analyzed by an X-ray diffractometer, and the X-ray diffraction pattern (figure 3) shows that the composite material consists of a main phase HA and reinforcing phases MgO and ZnO, and CaO, beta-TCP and NH are not found4HCO3Characteristic peaks of (2)At the temperature, the main body HA is not decomposed, and simultaneously, the ammonium bicarbonate and the dispersing agent are completely volatilized in the sintering process, so that the purity of the composite material is ensured; the peak intensity of the HA phase is slightly reduced, which may be caused by grain refinement after ball milling.
Testing the porosity of the composite material by adopting an Archimedes drainage method; the mechanical properties (compressive strength) of the material are tested in a mechanical testing machine according to the GB/T4740-. To ensure that the results are statistically significant, the average is taken over multiple tests. The test results are detailed in table 1.
TABLE 1 porosity and compressive Strength of the composites
| Examples | 1 | 2 | 3 | 4 | 5 | 6 |
| Porosity (%) | 52.50 | 54.88 | 54.58 | 52.48 | 55.96 | 62.71 |
| Compressive strength (MPa) | 165.6 | 165.2 | 169.6 | 160.8 | 165.76 | 144.42 |
The surface topography of the composite material before and after mineralization is analyzed by a scanning electron microscope, and fig. 4 is a surface topography graph 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 46%, the pore size of the large pores is 200-300 mu m, the pore size of the micropores is less than 5 mu m, and the large pores and the small pores are crossed and uniformly distributed. The pore structure can increase the specific surface area of the material and is also beneficial to the flow of body fluid among the materials; and also provides space and channels for adhesion of bone cells, ingrowth of blood vessels and formation of a vascular network, and ingrowth of bone tissue. FIG. 5 is a surface topography after mineralization for 14 days, after simulated artificial body fluid (SBF) soaking for 14 days, a large amount of bone-like apatite is deposited on the surface of the composite material, most of the matrix of the composite material is covered by apatite, and the fact that the addition of zinc oxide and magnesium oxide can improve the bone-like apatite promotion capability of the composite material is illustrated. Fig. 6 is a graph of the degradation rate of the composite material after being soaked in SBF for 6 weeks, and it can be seen from the graph that the degradation rate of the composite material is obviously accelerated along with the increase of the soaking time, and the long-acting and slow release of zinc ions and magnesium ions can be achieved along with the degradation of the composite material, so as to continuously stimulate the proliferation, differentiation and the like of osteoblasts.
Claims (9)
1. A preparation method of a zinc oxide-magnesium oxide/hydroxyapatite porous composite material is characterized by comprising the following steps:
(1) selecting nano zinc oxide, magnesium oxide and nano hydroxyapatite as raw materials, wherein the mass percent of the zinc oxide is 1-10%, the mass percent of the magnesium oxide powder is 1-10%, and the mass percent of the hydroxyapatite is 98-80%;
(2) putting the powder weighed in the step (1) into an agate ball milling tank, putting agate milling balls, and adding absolute ethyl alcohol and a dispersing agent; after the ball milling is finished, drying and grinding are carried out;
(3) mixing the composite powder obtained in the step (2) with medical ammonium bicarbonate powder according to the volume percentage of 40-80% to 60-20%, uniformly coating a proper amount of vaseline on the inner wall of a self-made stainless steel mold, adding the mixed powder into the mold, placing the mold on a pressure testing machine, and pressing the mold into a strip-shaped pre-pressing blank;
(4) putting the long-strip-shaped prepressing blank obtained in the step (3) into a self-made graphite mold, and vacuumizing to enable the internal vacuum degree of the sintering furnace to be 6-8 Pa; heating to 800-1000 ℃ at a heating rate of 100-150 ℃/min, and keeping the temperature for 1-2 min; then heating to 900-1050 ℃ at a heating rate of 25-50 ℃/min, and preserving heat for 5-10 min; and cooling the sintered product to room temperature along with the furnace to obtain the zinc oxide-magnesium oxide/hydroxyapatite porous composite material.
2. The method for preparing the zinc oxide-magnesium oxide/hydroxyapatite porous composite material according to claim 1, characterized in that: in the step (1), the purity of the nano-hydroxyapatite is not less than 99.9%, the particle size is 150-300 nm, the purity of the nano-zinc oxide is not less than 99.7%, the particle size is 200-300 nm, the purity of the nano-magnesium oxide is not less than 99.9%, and the particle size is 100-200 nm.
3. The method for preparing the zinc oxide-magnesium oxide/hydroxyapatite porous composite material according to claim 1, characterized in that: the ball milling conditions in the step (2) are as follows: the rotating speed is 200-400 r/min, and the ball milling time is 8-10 h.
4. The method for preparing the zinc oxide-magnesium oxide/hydroxyapatite porous composite material according to claim 3, characterized in that: in the step (2), the ratio of the agate grinding balls to the raw materials is 4: 1-3: 1, wherein the mass ratio of the agate grinding balls to the raw materials is as follows: a middle ball: the pellet is 1:4:5 to 2:7: 9.
5. The method for preparing the zinc oxide-magnesium oxide/hydroxyapatite porous composite material according to claim 1, characterized in that: the dispersant used in the step (2) is span 80, and the chemical formula of the dispersant is C24H44O6And the addition amount of the medicinal grade is 0.3-0.5% of the mass of the original powder.
6. The method for preparing the zinc oxide-magnesium oxide/hydroxyapatite porous composite material according to claim 1, characterized in that: and (3) drying at the temperature of 30-40 ℃ in the step (2).
7. The method for preparing the zinc oxide-magnesium oxide/hydroxyapatite porous composite material according to claim 1, characterized in that: the purity of the ammonium bicarbonate powder in the step (2) is analytically pure, the particle size is 100-300 mu m, and the ammonium bicarbonate powder is mixed by a mixer at a rotating speed of 50-100 r/min for 20-30 min.
8. The method for preparing the zinc oxide-magnesium oxide/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 the zinc oxide-magnesium oxide/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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| US5605713A (en) * | 1991-11-22 | 1997-02-25 | Boltong; Maria G. | Process for the preparation of calcium phosphate cements and its application as bio-materials |
| CN105712735A (en) * | 2016-01-29 | 2016-06-29 | 云南省第一人民医院 | Preparation method for porous hydroxyapatite material for bone repairing |
| CN109432507A (en) * | 2018-11-08 | 2019-03-08 | 中南大学 | The antibacterial hydroxylapatite composite material and preparation method of containing metal oxide |
| CN110054491A (en) * | 2019-03-27 | 2019-07-26 | 昆明理工大学 | A kind of preparation method of nano-zinc oxide doped hydroxyapatite porous bio-ceramic |
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2020
- 2020-12-16 CN CN202011492936.2A patent/CN112608140A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5605713A (en) * | 1991-11-22 | 1997-02-25 | Boltong; Maria G. | Process for the preparation of calcium phosphate cements and its application as bio-materials |
| CN105712735A (en) * | 2016-01-29 | 2016-06-29 | 云南省第一人民医院 | Preparation method for porous hydroxyapatite material for bone repairing |
| CN109432507A (en) * | 2018-11-08 | 2019-03-08 | 中南大学 | The antibacterial hydroxylapatite composite material and preparation method of containing metal oxide |
| CN110054491A (en) * | 2019-03-27 | 2019-07-26 | 昆明理工大学 | A kind of preparation method of nano-zinc oxide doped hydroxyapatite porous bio-ceramic |
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