CN104415400A - Hard tissue substitute material and preparation method thereof - Google Patents
Hard tissue substitute material and preparation method thereof Download PDFInfo
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- CN104415400A CN104415400A CN201310375561.5A CN201310375561A CN104415400A CN 104415400 A CN104415400 A CN 104415400A CN 201310375561 A CN201310375561 A CN 201310375561A CN 104415400 A CN104415400 A CN 104415400A
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- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000011248 coating agent Substances 0.000 claims abstract description 59
- 238000000576 coating method Methods 0.000 claims abstract description 59
- 239000011787 zinc oxide Substances 0.000 claims abstract description 49
- 239000002131 composite material Substances 0.000 claims abstract description 48
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 22
- 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 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims description 44
- 239000000843 powder Substances 0.000 claims description 35
- 238000001652 electrophoretic deposition Methods 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 239000011159 matrix material Substances 0.000 claims description 25
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- 238000004070 electrodeposition Methods 0.000 claims description 18
- 230000032683 aging Effects 0.000 claims description 17
- 238000001962 electrophoresis Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 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 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 235000013877 carbamide Nutrition 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 9
- 230000010355 oscillation Effects 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 230000029087 digestion Effects 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 210000001519 tissue Anatomy 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 244000137852 Petrea volubilis Species 0.000 description 5
- 241000292525 Titanio Species 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 238000009388 chemical precipitation Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 210000000988 bone and bone Anatomy 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052586 apatite Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- -1 carboxy apatite Chemical compound 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 102000002260 Alkaline Phosphatase Human genes 0.000 description 1
- 108020004774 Alkaline Phosphatase Proteins 0.000 description 1
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 210000000963 osteoblast Anatomy 0.000 description 1
- 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 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012890 simulated body fluid Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Materials For Medical Uses (AREA)
Abstract
The invention provides a hard tissue substitute material which comprises a substrate and a composite coating; the composite coating is a hydroxyapatite/zinc oxide composite coating, wherein the weight ratio of hydroxyapatite to zinc oxide is 1-10:1. The invention also provides a preparation method of the hard tissue substitute material. The hard tissue substitute material of the invention has interface bonding strength of more than 35 MPa, which shows that the interface bonding strength of the hard tissue substitute material of the invention is very good.
Description
Technical field
The invention belongs to biomaterial for medical purpose field, particularly relate to a kind of hard tissue substituting material and preparation method thereof.
Background technology
Hydroxyapatite (HA, Ca
10(PO4)
6(OH)
2) similar to the mineralizer of natural sclerous tissues, be considered to a kind of bioactive materials.Osseous tissue can be counted as in organic matrix and be filled with the nanometer of 70% and the mineralizer of sub-micro rice hydroxyapatite structure.Hydroxylapatite ceramic obtains application clinically as bone substitution material.But the mechanical property of hydroxyapatite and fatigue performance poor, the osseous tissue that can not be used for carrying position is replaced.Japanese scholars proposes the imagination of hydroxyapatite coating layer in plasma spraying the earliest, and hydroxyapatite coating layer implant into body can form strong bonded with osseous tissue at short notice, its major defect be hydroxyapatite coating layer with Titanium base in conjunction with insecure.The main cause that hydroxyapatite coating layer is low with Titanium base bond strength is that their thermal coefficient of expansion differs and (is respectively 13.3 × 10 comparatively greatly
-6/ K and (8.4 ~ 8.8) × 10
-6/ K), cause residual stress higher.
Adopting high mechanical properties and have the pottery of good biocompatibility or metal and HA compound and prepare composite coating, is improve a kind of better method that coating is combined with matrix.
Publication number is that the Chinese patent of CN101385873A discloses a kind of preparation method at nano-hydroxyapatite biological composite coating, the method prepares the method for nano-hydroxyapatite biological composite coating, and obtained coating and the interface bond strength of matrix are 10-23MPa.
Publication number is that the Chinese patent of CN177969A discloses a kind of process for producing nan-hydroxyl kietyoite/carbon nano-pipe compound coating, the method is the method adopting electrophoretic deposition to prepare New Type of Carbon nanotube/nanometer hydroxyapatite composite coating, and obtained coating and the interface bond strength of matrix are only 20-35MPa.
Above-mentioned composite coating has the following disadvantages: the bond strength of HA composite coating and matrix is not high, needs to be improved further.
Summary of the invention
The present invention is the technical problem of the poor bonding strength solving carboxy apatite composite coating and matrix in existing hard tissue substituting material, provides hard tissue substituting material that the bond strength of a kind of carboxy apatite composite coating and matrix is good and preparation method thereof.
The invention provides a kind of hard tissue substituting material,
Described material comprises matrix and composite coating, and described composite coating is hydroxyapatite/zinc oxide composite coating, and in described composite coating, the weight ratio of hydroxyapatite and zinc oxide is 1-10:1.
Present invention also offers a kind of preparation method of hard tissue substituting material, the method comprises the following steps:
Prepared by S1, nano hydroxyapatite powder;
S2, substrate pretreated;
S3, electrophoretic deposition suspension configure: first by hydroxy apatite powder, ZnO powder body and Mg (NO
3)
26H
2o powder body joins in isopropyl alcohol by the mass percent of (1-10): 1:1-2, makes the total concentration of electrophoretic deposition suspension be 6-12g/L; Then obtained nano HA/ZnO electrophoretic deposition suspension after supersonic oscillations, magnetic agitation and ageing;
S4, electrophoretic deposition process, poured in hydro-thermal electrophoresis reactor by nano HA/ZnO electrophoretic deposition suspension, compactedness controls at 60-80%; Then pretreated for step S2 matrix is fixed on the negative electrode of hydro-thermal electrophoresis reactor, platinum or rustless steel are anode, and are dipped in suspension by negative electrode and anode; Sealed reactor, carries out electro-deposition, and after electro-deposition, namely cool drying obtains the substitution material with HA/ZnO composite coating.
Hard tissue substituting material of the present invention, its composite coating is HA/ZnO composite coating, and this composite coating and matrix have stronger bond strength, interface bond strength 35-45MPa.This hard stops the preparation method of substitution material not need the crystallization and thermal treatment in later stage, thus avoids the phase transformation Sum decomposition of biological coating in high-temperature heat treatment process.And the present invention operation is simple, gained coating product cost is low.
Detailed description of the invention
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The invention provides a kind of hard tissue substituting material, described material comprises matrix and composite coating, and described composite coating is hydroxyapatite/zinc oxide composite coating, and in described composite coating, the weight ratio of hydroxyapatite and zinc oxide is 1-10:1.
In hard tissue substituting material of the present invention, owing to adding the ZnO of low thermal coefficient of expansion, reduce the coefficient of expansion of coating, relax the thermal expansion coefficient difference between coating and matrix, weaken concentrated at coating and basal body interface place of residual thermal stress.Meanwhile, the Zn of HA/ZnO composite coating can infiltrate part in the structure cell of HA and replace Ca, thus improves the bond strength of HA and ZnO.Nano-ZnO in composite coating is a kind of good catalysis material, can strengthen the photocatalysis effect of HA, promotes the molecule assembling ability of HA, can further improve the bond strength of composite coating and matrix.After ZnO nanoparticle is subject to being greater than the photon irradiation of energy gap energy, electronics transits to conduction band from valence band, create electron-hole pair, electronics has reproducibility, hole has oxidisability,-OH the reaction of hole and nanoparticle surface generates the very high OH free radical of oxidisability, and active OH free radical and substrate surface material occur automatically, continuous print chemical reaction, substrate surface formation chemical bond linkage, sequential 2 D self-composed monomolecular (SAM) film closely.In addition, the bond strength of ZnO itself is higher is also one of the reason that HA/ZnO composite coating has compared with high bond strength.And appropriate ZnO adds and does not make significant difference to the biological activity of hydroxyapatite coating layer and biocompatibility, and after simulated body fluid soaks 1d, each composite coating surface can form osteoid apatite.Cell assay in vitro shows, osteoblast normally can seek connections with growth on above-mentioned composite coating surface, and its alkaline phosphatase activities is also normal.
In order to improve the intensity of composite coating and matrix further, preferably, the mean diameter of described hydroxyapatite is 10-80nm, and the thickness of described composite coating is 30-150 μm.
In the present invention, described matrix has no particular limits, as long as can meet medical, in an embodiment of the present invention, matrix is medical titanium or titanium alloy.
Present invention also offers a kind of preparation method of hard tissue substituting material, the method comprises the following steps:
Prepared by S1, nano hydroxyapatite powder;
S2, substrate pretreated;
S3, electrophoretic deposition suspension configure: first by hydroxy apatite powder, ZnO powder body and Mg (NO
3)
26H
2o powder body joins in isopropyl alcohol by the mass percent of (1-10): 1:1-2, makes the total concentration of electrophoretic deposition suspension be 6-12g/L; Then obtained nano HA/ZnO electrophoretic deposition suspension after supersonic oscillations, magnetic agitation and ageing;
S4, electrophoretic deposition process, poured in hydro-thermal electrophoresis reactor by nano HA/ZnO electrophoretic deposition suspension, compactedness controls at 60-80%; Then pretreated for step S2 matrix is fixed on the negative electrode of hydro-thermal electrophoresis reactor, platinum or rustless steel are anode, and are dipped in suspension by negative electrode and anode; Sealed reactor, carries out electro-deposition, and after electro-deposition, namely cool drying obtains the substitution material with HA/ZnO composite coating.
Preferably, in step S3, described supersonic oscillations power is 200W, and the time is 30-60min; The time of magnetic agitation is 2-5h, and digestion time is 1-3h.
Preferably, in step S4, before electro-deposition, after nano HA/ZnO electrophoretic deposition suspension is heated to 80-100 DEG C, be incubated 40-60min.The voltage of described electro-deposition is 15-50V, and keeps constant, and the time of electro-deposition is 30-120s.
Drying means in step S4 has no particular limits, and can be various conventional drying means in this area, and in the present invention, drying means is the matrix after electro-deposition is placed in electric heating ancient customs drying baker dry 10-20min at 40-60 DEG C.
In the present invention, described step S1 nano hydroxyapatite powder can be purchased also can oneself preparation, and the present invention adopts and prepares with the following method: first according to the mol ratio of Ca/P=1.4-2.0 by analytical pure Ca (NO
3)
24H
2o and (NH
2)
2hPO
4mixing, adds distilled water and dissolves, ensure the Ca in solution
2+ion concentration is 0.03-0.4mol/L; Ca (NO in mass ratio
3)
24H
2o and (NH
2)
2hPO
4gross mass/carbamide=1:5-10 adds carbamide powder body, adds dispersant Polyethylene Glycol simultaneously, and Polyethylene Glycol addition is the 3-5% of gross mass, then stirs and makes it fully react, carry out water-bath ageing after reaction; Finally by the suspension filtered after ageing, wash, be drying to obtain nano hydroxyapatite powder.
In the preparation method of hydroxy apatite powder, preferably, described reaction temperature is 40-60 DEG C, and the time is 2-3h.The temperature of described water-bath is 50-60 DEG C, and digestion time is 12-18h.
The detailed process of filtration described above, washing, drying is as follows: adopt filtered on buchner funnel, the method for described washing, for first to clean 3 times with distilled water, then uses washes of absolute alcohol 3 times; Described hothouse is dry 12-24h in the freezer dryer of 40-60 DEG C.
Described nano ZnO powder is a kind of conventional commercial goods in industry, and its particle diameter is at below 100nm.
Described Mg (NO
3)
26H
2o powder body is a kind of conventional commercial goods in industry, and its effect prevents from reuniting between ZnO particle in electrophoresis process to make.
Preferably, the method for described substrate pretreated is: after matrix is carried out surperficial mechanical sanding and polishing, use at least one ultrasonic cleaning in water, acetone, an ethanol etc. successively; Then soaked by matrix in 6-12mol/L alkali liquor, at 60-100 DEG C, insulation 5-8h, dries up with deionized water washings after cooling again.
The crystallization and thermal treatment that hard tissue substituting material of the present invention has high interface bond strength, this preparation method does not need the later stage, avoid the phase transformation Sum decomposition of composite coating in high-temperature heat treatment process, operation is simple, product cost is low.
Apply specific embodiment to be below further described the present invention.
Embodiment 1
1) commercially available analytically pure Ca (NO is selected
3)
24H
2o, (NH
2)
2hPO
4, CO (NH2) 2 is raw material, adopts the hydroxy apatite powder of chemical precipitation method synthesis of nano size.Concrete technology is as follows: first according to the mol ratio of Ca/P=1.67 by analytical pure Ca (NO
3)
24H
2o and (NH
2)
2hPO
4mixing, adds distilled water and dissolves, ensure the Ca in solution
2+ion concentration is 0.05mol/L; Ca (NO in mass ratio
3)
24H
2o and (NH
2)
2hPO
4gross mass/carbamide=1:5 adds carbamide powder body, adds dispersant Polyethylene Glycol simultaneously, and Polyethylene Glycol addition is 3% of gross mass, and then rapid stirring makes abundant reaction, and reaction temperature remains on 50 DEG C; Note sealed container, prevent Ammonia valatilization; Water-bath is put into, 50 DEG C of ageing 12h after abundant stirring 2h; Suspension filtered is washed, first cleans 3 times with distilled water, then use washes of absolute alcohol 3 times, the soluble impurity (PO that removing is residual
3 4-and Ca
2+ion etc.), filtered on buchner funnel is placed on dry 24h in the freezer dryer of 40 DEG C, namely obtains the nano HA powder body that mean diameter is 40nm.
2) select commercial pure titanium TA1 as base material, sample size is 10mm × 20mm × 3mm, adopts the cleaning of water, acetone, EtOH Sonicate with sand paper machinery sanding and polishing.And then immerse in 8mol/L NaOH solution, at 80 DEG C of insulation 8h.To dry up with deionized water washings again after cooling.
3) 1 is got) obtained nano HA powder body, commercial goods nano ZnO powder and Mg (NO
3)
26H
2o powder body, adds in analytical pure isopropyl alcohol by 1:1:1 mass percent, makes the total concentration of electrophoretic deposition suspension be 12g/L, supersonic oscillations 30min(power 200W), then magnetic agitation 5h, rear ageing 3h, obtained nano HA/ZnO electrophoretic deposition suspension.
4) poured in hydro-thermal electrophoresis reactor by above-mentioned obtained electrophoretic deposition suspension, compactedness controls 70%, the pure titanio sheet after surface preparation is fixed on the negative electrode of hydro-thermal electrophoresis reactor, and is dipped in suspension; Employing Pt is anode; Sealed reactor, is incubated 60min after being heated to 80 DEG C; Switch on power, regulation voltage between 15V, and keeps constant, cuts off the electricity supply after electro-deposition 120s, stops deposition; After natural cooling, take out substrate, be placed in electric drying oven with forced convection dry 10min at 60 DEG C, obtain HA/ZnO composite coating.
Embodiment 2
1) commercially available analytically pure Ca (NO is selected
3)
24H
2o, (NH
2)
2hPO
4, CO (NH2) 2 is raw material, adopts the hydroxy apatite powder of chemical precipitation method synthesis of nano size.Concrete technology is as follows: first according to the mol ratio of Ca/P=2.0 by analytical pure Ca (NO
3)
24H
2o and (NH
2)
2hPO
4mixing, adds distilled water and dissolves, ensure the Ca in solution
2+ion concentration is 0.4mol/L; Ca (NO in mass ratio
3)
24H
2o and (NH
2)
2hPO
4gross mass/carbamide=1:10 adds carbamide powder body, adds dispersant Polyethylene Glycol simultaneously, and Polyethylene Glycol addition is 3% of gross mass, and then rapid stirring makes abundant reaction, and reaction temperature remains on 60 DEG C; Note sealed container, prevent Ammonia valatilization; Water-bath is put into, 50 DEG C of ageing 12h after abundant stirring 2h; Suspension filtered is washed, first cleans 3 times with distilled water, then use washes of absolute alcohol 3 times, the soluble impurity (PO that removing is residual
3 4-and Ca
2+ion etc.), filtered on buchner funnel is placed on dry 12h in the freezer dryer of 60 DEG C, namely obtains the nano HA powder body that mean diameter is 80nm.
2) select commercial pure titanium TA1 as base material, sample size is 10mm × 20mm × 3mm, adopts the cleaning of water, acetone, EtOH Sonicate with sand paper machinery sanding and polishing.And then immerse in 12mol/L KOH solution, at 100 DEG C of insulation 5h.To dry up with deionized water washings again after cooling.
3) 1 is got) obtained nano HA powder body, commercial goods nano ZnO powder and Mg (NO
3)
26H
2o powder body, adds in analytical pure isopropyl alcohol by 5:1:2 mass percent, makes the total concentration of electrophoretic deposition suspension be 6g/L, supersonic oscillations 60min(power 200W), then magnetic agitation 2h, rear ageing 1h, obtained nano HA/ZnO electrophoretic deposition suspension.
4) poured in hydro-thermal electrophoresis reactor by above-mentioned obtained electrophoretic deposition suspension, compactedness controls 80%, the pure titanio sheet after surface preparation is fixed on the negative electrode of hydro-thermal electrophoresis reactor, and is dipped in suspension; Employing Pt is anode; Sealed reactor, is incubated 40min after being heated to 100 DEG C; Switch on power, regulation voltage between 40V, and keeps constant, cuts off the electricity supply after electro-deposition 30s, stops deposition; After natural cooling, take out substrate, be placed in electric drying oven with forced convection dry 20min at 40 DEG C, obtain HA/ZnO composite coating.
Embodiment 3
1) commercially available analytically pure Ca (NO is selected
3)
24H
2o, (NH
2)
2hPO
4, CO (NH2) 2 is raw material, adopts the hydroxy apatite powder of chemical precipitation method synthesis of nano size.Concrete technology is as follows: first according to the mol ratio of Ca/P=1.4 by analytical pure Ca (NO
3)
24H
2o and (NH
2)
2hPO
4mixing, adds distilled water and dissolves, ensure the Ca in solution
2+ion concentration is 0.03mol/L; Ca (NO in mass ratio
3)
24H
2o and (NH
2)
2hPO
4gross mass/carbamide=1:8 adds carbamide powder body, adds dispersant Polyethylene Glycol simultaneously, and Polyethylene Glycol addition is 5% of gross mass, and then rapid stirring makes abundant reaction, and reaction temperature remains on 40 DEG C; Note sealed container, prevent Ammonia valatilization; Water-bath is put into, 50 DEG C of ageing 18h after abundant stirring 3h; Suspension filtered is washed, first cleans 3 times with distilled water, then use washes of absolute alcohol 3 times, the soluble impurity (PO that removing is residual
3 4-and Ca
2+ion etc.), filtered on buchner funnel is placed on dry 24h in the freezer dryer of 40 DEG C, namely obtains the nano HA powder body that mean diameter is 10nm.
2) select commercial pure titanium TA1 as base material, sample size is 10mm × 20mm × 3mm, adopts the cleaning of water, acetone, EtOH Sonicate with sand paper machinery sanding and polishing.And then immerse in 6mol/L NaOH solution, at 60 DEG C of insulation 8h.To dry up with deionized water washings again after cooling.
3) 1 is got) obtained nano HA powder body, commercial goods nano ZnO powder and Mg (NO
3)
26H
2o powder body, adds in analytical pure isopropyl alcohol by 10:1:1 mass percent, makes the total concentration of electrophoretic deposition suspension be 10g/L, supersonic oscillations 30min(power 200W), then magnetic agitation 4h, rear ageing 2h, obtained nano HA/ZnO electrophoretic deposition suspension.
4) poured in hydro-thermal electrophoresis reactor by above-mentioned obtained electrophoretic deposition suspension, compactedness controls 60%, the pure titanio sheet after surface preparation is fixed on the negative electrode of hydro-thermal electrophoresis reactor, and is dipped in suspension; Employing Pt is anode; Sealed reactor, is incubated 40min after being heated to 80 DEG C; Switch on power, regulation voltage between 50V, and keeps constant, cuts off the electricity supply after electro-deposition 120s, stops deposition; After natural cooling, take out substrate, be placed in electric drying oven with forced convection dry 20min at 60 DEG C, obtain HA/ZnO composite coating.
Embodiment 4
1) commercially available analytically pure Ca (NO is selected
3)
24H
2o, (NH
2)
2hPO
4, CO (NH2) 2 is raw material, adopts the hydroxy apatite powder of chemical precipitation method synthesis of nano size.Concrete technology is as follows: first according to the mol ratio of Ca/P=2.0 by analytical pure Ca (NO
3)
24H
2o and (NH
2)
2hPO
4mixing, adds distilled water and dissolves, ensure the Ca in solution
2+ion concentration is 0.4mol/L; Ca (NO in mass ratio
3)
24H
2o and (NH
2)
2hPO
4gross mass/carbamide=1:10 adds carbamide powder body, adds dispersant Polyethylene Glycol simultaneously, and Polyethylene Glycol addition is 5% of gross mass, and then rapid stirring makes abundant reaction, and reaction temperature remains on 60 DEG C; Note sealed container, prevent Ammonia valatilization; Water-bath is put into, 60 DEG C of ageing 18h after abundant stirring 3h; Suspension filtered is washed, first cleans 3 times with distilled water, then use washes of absolute alcohol 3 times, the soluble impurity (PO that removing is residual
3 4-and Ca
2+ion etc.), filtered on buchner funnel is placed on dry 24h in the freezer dryer of 40 DEG C, namely obtains the nano HA powder body that mean diameter is 67nm.
2) select commercial pure titanium TA1 as base material, sample size is 10mm × 20mm × 3mm, adopts the cleaning of water, acetone, EtOH Sonicate with sand paper machinery sanding and polishing.And then immerse in 6mol/L NaOH solution, at 60 DEG C of insulation 8h.To dry up with deionized water washings again after cooling.
3) 1 is got) obtained nano HA powder body, commercial goods nano ZnO powder and Mg (NO
3)
26H
2o powder body, adds in analytical pure isopropyl alcohol by 2:1:1 mass percent, makes the total concentration of electrophoretic deposition suspension be 6g/L, supersonic oscillations 30min(power 200W), then magnetic agitation 2h, rear ageing 1h, obtained nano HA/ZnO electrophoretic deposition suspension.
4) poured in hydro-thermal electrophoresis reactor by above-mentioned obtained electrophoretic deposition suspension, compactedness controls 80%, the pure titanio sheet after surface preparation is fixed on the negative electrode of hydro-thermal electrophoresis reactor, and is dipped in suspension; Employing Pt is anode; Sealed reactor, is incubated 40min after being heated to 100 DEG C; Switch on power, regulation voltage between 50V, and keeps constant, cuts off the electricity supply after electro-deposition 30s, stops deposition; After natural cooling, take out substrate, be placed in electric drying oven with forced convection dry 20min at 40 DEG C, obtain HA/ZnO composite coating.
Embodiment 5
1) commercially available analytically pure Ca (NO is selected
3)
24H
2o, (NH
2)
2hPO
4, CO (NH2) 2 is raw material, adopts the hydroxy apatite powder of chemical precipitation method synthesis of nano size.Concrete technology is as follows: first according to the mol ratio of Ca/P=1.4 by analytical pure Ca (NO
3)
24H
2o and (NH
2)
2hPO
4mixing, adds distilled water and dissolves, ensure the Ca in solution
2+ion concentration is 0.03mol/L; Ca (NO in mass ratio
3)
24H
2o and (NH
2)
2hPO
4gross mass/carbamide=1:8 adds carbamide powder body, adds dispersant Polyethylene Glycol simultaneously, and Polyethylene Glycol addition is 5% of gross mass, and then rapid stirring makes abundant reaction, and reaction temperature remains on 60 DEG C; Note sealed container, prevent Ammonia valatilization; Water-bath is put into, 60 DEG C of ageing 12h after abundant stirring 2h; Suspension filtered is washed, first cleans 3 times with distilled water, then use washes of absolute alcohol 3 times, the soluble impurity (PO that removing is residual
3 4-and Ca
2+ion etc.), filtered on buchner funnel is placed on dry 24h in the freezer dryer of 40 DEG C, namely obtains the nano HA powder body that mean diameter is 20nm.
2) select commercial pure titanium TA1 as base material, sample size is 10mm × 20mm × 3mm, adopts the cleaning of water, acetone, EtOH Sonicate with sand paper machinery sanding and polishing.And then immerse in 6mol/L NaOH solution, at 100 DEG C of insulation 8h.To dry up with deionized water washings again after cooling.
3) 1 is got) obtained nano HA powder body, commercial goods nano ZnO powder and Mg (NO
3)
26H
2o powder body, adds in analytical pure isopropyl alcohol by 1:1:1 mass percent, makes the total concentration of electrophoretic deposition suspension be 10g/L, supersonic oscillations 30min(power 200W), then magnetic agitation 5h, rear ageing 3h, obtained nano HA/ZnO electrophoretic deposition suspension.
4) poured in hydro-thermal electrophoresis reactor by above-mentioned obtained electrophoretic deposition suspension, compactedness controls 60%, the pure titanio sheet after surface preparation is fixed on the negative electrode of hydro-thermal electrophoresis reactor, and is dipped in suspension; Employing Pt is anode; Sealed reactor, is incubated 40min after being heated to 80 DEG C; Switch on power, regulation voltage between 50V, and keeps constant, cuts off the electricity supply after electro-deposition 120s, stops deposition; After natural cooling, take out substrate, be placed in electric drying oven with forced convection dry 20min at 60 DEG C, obtain HA/ZnO composite coating.
Comparative example 1
According to China Patent Publication No. CN1772969A example 3, the hard tissue substituting material of obtained hydroxylapatite/carbon nanotube composite coating.
Comparative example 2
According to China Patent Publication No. CN101385873A example 4, the hard tissue substituting material of obtained HA/ chitosan composite coating.
Method of testing and result
1, the thickness of composite coating
With reference to GB/T 11374-2012, adopt lossless detection method to measure composite coating thickness, the results are shown in Table 1.
2, bond strength
With reference to ASTM-C633-2001 and GB/T 8642-2002, adopt bonding sample pulling method, the bond strength of HA/ZnO coating is tested, the results are shown in Table 1.
Table 1
| Classification | Average coating thickness (μm) | Bond strength (MPa) |
| Embodiment 1 | 60 | 45 |
| Embodiment 2 | 40 | 40 |
| Embodiment 3 | 120 | 35 |
| Embodiment 4 | 30 | 40 |
| Embodiment 5 | 150 | 37 |
| Comparative example 1 | 68 | 34.5 |
| Comparative example 2 | 85 | 20.5 |
As can be seen from Table 1, the interface bond strength of hard tissue substituting material of the present invention is greater than 35MPa, and comparative example 1 is 34.5MPa, and comparative example 2 is 20.5MPa.Illustrate that the interface bond strength of hard tissue substituting material of the present invention is better.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (12)
1. a hard tissue substituting material, is characterized in that, described material comprises matrix and composite coating, and described composite coating is hydroxyapatite/zinc oxide composite coating, and in described composite coating, the weight ratio of hydroxyapatite and zinc oxide is 1-10:1.
2. hard tissue substituting material according to claim 1, is characterized in that, the mean diameter of described hydroxyapatite is 10-80nm.
3. hard tissue substituting material according to claim 1 and 2, is characterized in that, the thickness of described composite coating is 30-150 μm.
4. hard tissue substituting material according to claim 3, is characterized in that, described matrix is medical titanium or titanium alloy.
5. a preparation method for hard tissue substituting material, is characterized in that, the method comprises the following steps:
Prepared by S1, nano hydroxyapatite powder;
S2, substrate pretreated;
S3, electrophoretic deposition suspension configure: first by hydroxy apatite powder, ZnO powder body and Mg (NO
3)
26H
2o powder body joins in isopropyl alcohol by the mass percent of (1-10): 1:1-2, makes the total concentration of electrophoretic deposition suspension be 6-12g/L; Then obtained nano HA/ZnO electrophoretic deposition suspension after supersonic oscillations, magnetic agitation and ageing;
S4, electrophoretic deposition process, poured in hydro-thermal electrophoresis reactor by nano HA/ZnO electrophoretic deposition suspension, compactedness controls at 60-80%; Then pretreated for step S2 matrix is fixed on the negative electrode of hydro-thermal electrophoresis reactor, platinum or rustless steel are anode, and are dipped in suspension by negative electrode and anode; Sealed reactor, carries out electro-deposition, and after electro-deposition, namely cool drying obtains the substitution material with HA/ZnO composite coating.
6. the preparation method of hard tissue substituting material according to claim 5, is characterized in that, in step S4, before electro-deposition, after nano HA/ZnO electrophoretic deposition suspension is heated to 80-100 DEG C, is incubated 40-60min.
7. the preparation method of hard tissue substituting material according to claim 6, is characterized in that, in step S4, the voltage of described electro-deposition is 15-50V, and keeps constant, and the time of electro-deposition is 30-120s.
8. the preparation method of hard tissue substituting material according to claim 5, is characterized in that, described step S1 nano hydroxyapatite powder preparation method is: first according to the mol ratio of Ca/P=1.4-2.0 by analytical pure Ca (NO
3)
24H
2o and (NH
2)
2hPO
4mixing, adds distilled water and dissolves, ensure the Ca in solution
2+ion concentration is 0.03-0.4mol/L; Ca (NO in mass ratio
3)
24H
2o and (NH
2)
2hPO
4gross mass/carbamide=1:5-10 adds carbamide powder body, adds dispersant Polyethylene Glycol simultaneously, and Polyethylene Glycol addition is the 3-5% of gross mass, then stirs and makes it fully react, carry out water-bath ageing after reaction; Finally by the suspension filtered after ageing, wash, be drying to obtain nano hydroxyapatite powder.
9. the preparation method of hard tissue substituting material according to claim 8, is characterized in that, the temperature of described reaction is 40-60 DEG C, and the time is 2-3h.
10. the preparation method of hard tissue substituting material according to claim 8, is characterized in that, the temperature of described water-bath is 50-60 DEG C, and digestion time is 12-18h.
The preparation method of 11. hard tissue substituting materials according to claim 8, is characterized in that, the method for described washing, for first to clean 3 times with distilled water, then uses washes of absolute alcohol 3 times; Described hothouse is dry 12-24h in the freezer dryer of 40-60 DEG C.
The preparation method of 12. hard tissue substituting materials according to claim 5, is characterized in that, the method for described substrate pretreated is: after matrix is carried out surperficial mechanical sanding and polishing, uses at least one ultrasonic cleaning in water, acetone, ethanol successively; Then soaked by matrix in 6-12mol/L alkali liquor, at 60-100 DEG C, insulation 5-8h, dries up with deionized water washings after cooling again.
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Cited By (2)
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| CN106191835A (en) * | 2016-08-03 | 2016-12-07 | 北方工业大学 | Preparation method of novel magnesium alloy hydroxyapatite composite membrane |
| JP2020200529A (en) * | 2019-06-13 | 2020-12-17 | 国立研究開発法人物質・材料研究機構 | Production method of laminate, and laminate |
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| CN101385873A (en) * | 2008-10-29 | 2009-03-18 | 陕西科技大学 | Preparation method of nano-hydroxyapatite biocomposite coating |
| CN102793948A (en) * | 2012-08-22 | 2012-11-28 | 浙江大学 | Biomedical calcium phosphate/zinc oxide nano-rod array composite coating on surface of medical metal and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106191835A (en) * | 2016-08-03 | 2016-12-07 | 北方工业大学 | Preparation method of novel magnesium alloy hydroxyapatite composite membrane |
| CN106191835B (en) * | 2016-08-03 | 2018-10-23 | 北方工业大学 | A kind of preparation method of magnesium alloy hydroxyapatite composite film |
| JP2020200529A (en) * | 2019-06-13 | 2020-12-17 | 国立研究開発法人物質・材料研究機構 | Production method of laminate, and laminate |
| JP7340798B2 (en) | 2019-06-13 | 2023-09-08 | 国立研究開発法人物質・材料研究機構 | Method for manufacturing a laminate, and laminate |
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