CN101991877B - Preparation method of three-phase CaP-glass coating/porous A1203 rack biological composite material - Google Patents

Preparation method of three-phase CaP-glass coating/porous A1203 rack biological composite material Download PDF

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CN101991877B
CN101991877B CN2010105319053A CN201010531905A CN101991877B CN 101991877 B CN101991877 B CN 101991877B CN 2010105319053 A CN2010105319053 A CN 2010105319053A CN 201010531905 A CN201010531905 A CN 201010531905A CN 101991877 B CN101991877 B CN 101991877B
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coating
glass
porous
phase
rack
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CN101991877A (en
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王莉丽
王秀峰
于成龙
江红涛
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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Abstract

The invention provides a preparation method of a three-phase CaP-glass coating/porous A1203 rack biological composite material, which belongs to the technical field of biological medicinal material preparation and comprises the following steps of: coating a composite coating consisting of biological glass using HA (Hydroxylapatite) and phosphate as base bodies on a porous Al2O3 rack to obtain the combination of good biological performance and mechanical performance; mixing HA powder and biological glass powder with different compositions at different proportions to obtain slurry to be coated on the porous Al2O3 rack; carrying out heat treatment for two hours in air at 800 DEG C; and forming the three-phase CaP-glass coating through generating hydroxylapatite (HA), tertiary calcium phosphate (TCP) and calcium hydrophosphate (DCP) principal crystalline phases in the coating phase. The three-phase CaP-glass coating is tightly, uniformly and closely attached on the Al2O3 rack, the highest combining intensity of the three-phase CaP-glass coating can reach 50MPa and is more than two times of that of the pure HA coating, the growth of the osteoblast on the porous Al2O3 rack coated with the three-phase CaP-glass coating is good, and cells can actively pass the coating to be spread into the porous rack.

Description

A kind of three-phase CaP-glass coating/porous Al 2O 3The method for preparing of support Biocomposite material
Technical field
The invention belongs to the bio-medical material preparing technical field, relating to is a kind of three-phase CaP-glass coating/porous Al 2O 3The method for preparing of support Biocomposite material.
Background technology
(hydroxyapatite HA), is the main component (60～70%) of human body natural's bone to hydroxyapatite, has the guided bone of fabulous biological activity and osseous tissue growth.Therefore, caused the great interest of people in the bone alternative aspect.Clinical trial shows that HA has directly and synestotic ability and bone conductibility completely.Yet relatively poor mechanical performance such as intensity and fracture toughness, has limited its application aspect sclerous tissues's replacement.
A kind of coating-substrate system is for example with ZrO 2, Al 2O 3, Ti and alloy thereof are matrix, as coating, can obtain the good combination of mechanical performance and biological property with HA.Research shows, in porous Al 2O 3Apply the HA coating on the support, can obtain the coating of 20～30 μ m thickness, yet the form of coating is a micropore, bond strength is less than 25MPa.If the adhesion between coating and the matrix is very poor, will make the sclerous tissues replacement very difficulty that becomes, and and real people's bone photo ratio, the rate of dissolution of sintering HA and biological activity are all relatively poor.
Summary of the invention
Technical problem to be solved by this invention provides a kind of three-phase CaP-glass coating/porous Al 2O 3The method for preparing of support Biocomposite material, wherein, three-phase CaP-glass coating is closely knit, evenly, closely attached to porous Al 2O 3On the support, the bond strength between coating and the support can reach 50MPa, is more than the twice of pure HA anchoring strength of coating.
For realizing above-mentioned purpose, the present invention also provides a kind of three-phase CaP-glass coating/porous Al 2O 3The method for preparing of support Biocomposite material may further comprise the steps:
Step 1: the preparation of three-phase glass: according to composition formula is xCaO (0.55-x) Na 2O0.45P 2O 5, wherein x gets 0.1～0.5, takes by weighing P 2O 5, NaH 2PO 4And CaCO 3, melt at 1100～1250 ℃ of sintering 1h;
Step 2: the melten glass that step (1) is obtained quenches successively, grinding and sub-sieve, obtains glass powder;
Step 3: glass powder and hydroxyapatite that step (2) is obtained are mixed in the ethanol, and ball milling 24 hours obtains mixed slurry;
Step 4: adopt the immersion process for preparing porous Al 2O 3Support is then in porous Al 2O 3The mixed slurry that applying step on the support (3) obtains, thus make composite coating;
Step 5: after treating the composite coating drying, with porous Al 2O 3Support is heated to 700 ℃ with the speed of 50 ℃/min, and the speed with 5 ℃/min is heated to 800 ℃ again, and insulation 2h is subsequently with the speed cool to room temperature of 1 ℃/min.
Three-phase CaP-glass coating/porous Al of the present invention 2O 3The method for preparing of support Biocomposite material has the following advantages at least: the present invention mixes HA powder body and bio-vitric powder, processes slip, is coated in porous Al then 2O 3On the support, at 800 ℃ of heat treatment 2h in air.Hydroxyapatite (HA), tricalcium phosphate (TCP) and calcium hydrogen phosphate (DCP) principal crystalline phase have appearred in coating mutually, have formed three-phase CaP-glass coating.And this three-phase CaP-glass coating is closely knit, evenly, and closely attached to porous Al 2O 3On the support, the bond strength between coating and the support can reach 50MPa, is more than the twice of pure HA anchoring strength of coating.
Description of drawings
Fig. 1 is 800 ℃ of heat treatments 2 hours, and CaO content is the XRD figure spectrum of the composite coating that makes of the different additions of the glass of 30mol%.
The specific embodiment
Three-phase CaP-glass coating/porous Al of the present invention 2O 3The method for preparing of support Biocomposite material may further comprise the steps:
Embodiment 1
(1) preparation of three-phase glass: according to composition formula is xCaO (0.55-x) Na 2O0.45P 2O 5, wherein x gets 0.1, takes by weighing P 2O 5, NaH 2PO 4And CaCO 3, melt at 1100 ℃ of sintering 1h;
(2) the fused glass that step (1) is obtained quenches successively, grinding and sub-sieve, obtains the glass powder of particle size less than 20 μ m;
(3) (hydroxyapatite HA) is mixed in the ethanol, and ball milling 24 hours obtains mixed slurry, and wherein, glass powder accounts for 5% of glass powder and hydroxyapatite gross mass for glass powder that step (2) is obtained and hydroxyapatite;
(4) adopt the immersion process for preparing porous Al 2O 3Support is then in porous Al 2O 3The mixed slurry that adopts dipping-rotating technics applying step (3) to obtain on the support, thus make composite coating;
(5) treat the composite coating drying after, with porous Al 2O 3Support is heated to 700 ℃ with the speed of 10 ℃/min, and the speed with 5 ℃/min is heated to 800 ℃ again, and insulation 2h is subsequently with the speed cool to room temperature of 1 ℃/min.
Embodiment 2
(1) preparation of three-phase glass: according to composition formula is xCaO (0.55-x) Na 2O0.45P 2O 5, wherein x gets 0.2, takes by weighing P 2O 5, NaH 2PO 4And CaCO 3, melt at 1250 ℃ of sintering 1h;
(2) the fused glass that step (1) is obtained quenches successively, grinding and sub-sieve, obtains the glass powder of particle size less than 20 μ m;
(3) (hydroxyapatite HA) is mixed in the ethanol, and ball milling 24 hours obtains mixed slurry, and wherein, glass powder accounts for 50% of glass powder and hydroxyapatite gross mass for glass powder that step (2) is obtained and hydroxyapatite;
(4) adopt the immersion process for preparing porous Al 2O 3Support is then in porous Al 2O 3The mixed slurry that adopts dipping-rotating technics applying step (3) to obtain on the support, thus make composite coating;
(5) treat the composite coating drying after, with porous Al 2O 3Support is heated to 700 ℃ with the speed of 10 ℃/min, and the speed with 5 ℃/min is heated to 800 ℃ again, and insulation 2h is subsequently with the speed cool to room temperature of 1 ℃/min.
Embodiment 3
(1) preparation of three-phase glass: according to composition formula is xCaO (0.55-x) Na 2O0.45P 2O 5, wherein x gets 0.3, takes by weighing P 2O 5, NaH 2PO 4And CaCO 3, melt at 1150 ℃ of sintering 1h;
(2) the fused glass that step (1) is obtained quenches successively, grinding and sub-sieve, obtains the glass powder of particle size less than 20 μ m;
(3) (hydroxyapatite HA) is mixed in the ethanol, and ball milling 24 hours obtains mixed slurry, and wherein, glass powder accounts for 15% of glass powder and hydroxyapatite gross mass for glass powder that step (2) is obtained and hydroxyapatite;
(4) adopt the immersion process for preparing porous Al 2O 3Support is then in porous Al 2O 3The mixed slurry that adopts dipping-rotating technics applying step (3) to obtain on the support, thus make composite coating;
(5) treat the composite coating drying after, with porous Al 2O 3Support is heated to 700 ℃ with the speed of 10 ℃/min, and the speed with 5 ℃/min is heated to 800 ℃ again, and insulation 2h is subsequently with the speed cool to room temperature of 1 ℃/min.
Embodiment 4
(1) preparation of three-phase glass: according to composition formula is xCaO (0.55-x) Na 2O0.45P 2O 5, wherein x gets 0.5, takes by weighing P 2O 5, NaH 2PO 4And CaCO 3, melt at 1200 ℃ of sintering 1h;
(2) the fused glass that step (1) is obtained quenches successively, grinding and sub-sieve, obtains the glass powder of particle size less than 20 μ m;
(3) (hydroxyapatite HA) is mixed in the ethanol, and ball milling 24 hours obtains mixed slurry, and wherein, glass powder accounts for 35% of glass powder and hydroxyapatite gross mass for glass powder that step (2) is obtained and hydroxyapatite;
(4) adopt the immersion process for preparing porous Al 2O 3Support is then in porous Al 2O 3The mixed slurry that adopts dipping-rotating technics applying step (3) to obtain on the support, thus make composite coating;
(5) treat the composite coating drying after, with porous Al 2O 3Support is heated to 700 ℃ with the speed of 10 ℃/min, and the speed with 5 ℃/min is heated to 800 ℃ again, and insulation 2h is subsequently with the speed cool to room temperature of 1 ℃/min.
The present invention compares with existing procucts and has the following advantages:
1) the three-phase CaP-glass coating and the porous Al that obtain of the present invention 2O 3Combine between the support closely, inaccessible distortion hole does not appear in porous nickel; The glass coating thickness that is coated on the support is about 30 μ m, layering and crackle do not occur, shows to combine perfection between them; And traditional single HA coating, owing to itself be micropore, therefore, and porous Al 2O 3Can't see combining form closely between the support, cause bond strength very low, generally be no more than 25MPa;
2) the glass addition is 35wt%, and CaO content is less than three-phase CaP-glass coating and the porous Al of 30mol% 2O 3The bond strength of support is maximum, has reached 50MPa, almost is the twice (less than 25MPa) of single HA coating.So big adhesion is because the adding of glass, and coating is crypto set more, with matrix combine tightr;
3) see also shown in Figure 1ly, HA occurred in the material phase analysis of the three-phase CaP-glass coating that the present invention obtains, TCP, the DCP principal crystalline phase, their chemical constituent is very similar, makes the more single HA coating biology of three-phase CaP-glass coating activity strengthen greatly;
4) sintering temperature of single HA coating is higher, and generally greater than 1200 ℃, and the three-phase CaP-glass coating fusing point that the present invention obtains is very low, about 800 ℃, has reduced sintering temperature greatly, has improved the form of coating;
5) the present invention has drawn HA, TCP, and the DCP principal crystalline phase promptly increases CaO content in the glass with the Changing Pattern of CaO content in the addition of glass and the glass, and the content of HA phase just increases in the three-phase CaP-glass coating; Increase the addition of glass, the content of HA phase is reducing.So just can control the thing phase content in the three-phase CaP-glass coating;
6) the present invention has drawn three reasons that principal crystalline phase occurs in the three-phase CaP-glass coating, promptly along with the fusing of glass and cooling slowly, crystallization has taken place, and has formed devitrified glass; In fusing-refrigerative process, TCP and DCP have been formed mutually; The difference of the content of these three phases depends on the composition of glass;
7) the single glass coating can produce many other calcium phosphorus phases in the process of burning till, like Ca (PO 3) 2, 4CaO3P 2O 5, NaCaPO 4, DCP and TCP, but there is not the HA phase, biological activity greatly reduces.Yet the three-phase CaP-glass coating that the present invention obtains has only DCP in the process of burning till, TCP, and the HA phase, these phases are biologically active and biocompatibility all;
8) single glass coating is coated in porous Al 2O 3On the support, because serious crackle and layering have appearred in mismatch in coefficient of thermal expansion, however three-phase CaP-glass coating and porous Al that the present invention obtains 2O 3Support combines perfect.
The above is merely one embodiment of the present invention; It or not whole or unique embodiment; The conversion of any equivalence that those of ordinary skills take technical scheme of the present invention through reading description of the present invention is claim of the present invention and contains.

Claims (1)

1. three-phase CaP-glass coating/porous Al 2O 3The method for preparing of support Biocomposite material is characterized in that: may further comprise the steps:
Step 1: the preparation of three-phase glass: according to composition formula is xCaO (0.55-x) Na 2O0.45P 2O 5, wherein x gets 0.1～0.5, takes by weighing P 2O 5, NaH 2PO 4And CaCO 3, melt at 1100～1250 ℃ of sintering 1h;
Step 2: the melten glass that step (1) is obtained quenches successively, grinding and sub-sieve, obtains glass powder;
Step 3: glass powder and hydroxyapatite that step (2) is obtained are mixed in the ethanol, and ball milling 24 hours obtains mixed slurry, and wherein, glass powder accounts for 5～50% of glass powder and hydroxyapatite gross mass;
Step 4: adopt the immersion process for preparing porous Al 2O 3Support is then in porous Al 2O 3The mixed slurry that applying step on the support (3) obtains, thus make composite coating;
Step 5: after treating the composite coating drying, with porous Al 2O 3Support is heated to 700 ℃ with the speed of 50 ℃/min, and the speed with 5 ℃/min is heated to 800 ℃ again, and insulation 2h is subsequently with the speed cool to room temperature of 1 ℃/min.
CN2010105319053A 2010-11-02 2010-11-02 Preparation method of three-phase CaP-glass coating/porous A1203 rack biological composite material Expired - Fee Related CN101991877B (en)

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CN2067157U (en) * 1990-06-01 1990-12-12 中国科学院上海硅酸盐研究所 Surface active alumina biological ceramic implant
CN1080627A (en) * 1992-06-29 1994-01-12 国家建筑材料工业局山东工业陶瓷研究设计院 Biological active incline ceramic material
CN1397518A (en) * 2002-08-28 2003-02-19 中国科学院长春应用化学研究所 Process for preparing nano-class hydroxyphosphorite/alumina bioceramics

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US7740481B2 (en) * 2002-06-21 2010-06-22 Politecnico Di Milano Osteointegrative interface for implantable prostheses and a method for the treatment of the osteointegrative interface
FR2938271B1 (en) * 2008-11-13 2011-09-02 Univ Reims Champagne Ardenne PROCESS FOR THE ELECTRODEPOSITION OF PHOSPHOCALCIUM COATINGS ON METALLIC SUBSTRATES, COATINGS OBTAINED AND IMPLANTABLE MATERIALS COMPRISING SUCH COATINGS

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2067157U (en) * 1990-06-01 1990-12-12 中国科学院上海硅酸盐研究所 Surface active alumina biological ceramic implant
CN1080627A (en) * 1992-06-29 1994-01-12 国家建筑材料工业局山东工业陶瓷研究设计院 Biological active incline ceramic material
CN1397518A (en) * 2002-08-28 2003-02-19 中国科学院长春应用化学研究所 Process for preparing nano-class hydroxyphosphorite/alumina bioceramics

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