CN101838837B - Method for preparing Hap-PAM biological gradient compound coating by impulse hydrothermal electrophoretic polymerization method - Google Patents
Method for preparing Hap-PAM biological gradient compound coating by impulse hydrothermal electrophoretic polymerization method Download PDFInfo
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Abstract
The invention provides a method for preparing a Hap-PAM biological gradient compound coating. The method comprises the following steps of: preparing aqueous solution of acrylamide and suspension of hydroxyapatite isopropyl alcohol respectively from hydroxyapatite, acrylamide monomers, isopropyl alcohol and the like serving as raw materials in a certain concentration ratio, performing DC electrodeposition processing on a carbon/carbon matrix in the aqueous solution of acrylamide for some time, and placing the carbon/carbon matrix in the suspension of hydroxyapatite for hydrothermal electrophoretic polymerization; and preparing the Hap-PAM gradient compound coating which has the advantages of uniform and compact surface, complete crystal orientation and close bonding of the coating and the matrix at different deposition temperatures and voltages. Due to the advantages, particularly higher bonding force, the Hap-PAM biological gradient compound coating has a quite good development prospect in clinical application.
Description
Technical field
The present invention relates to a kind of preparation method of high strength HAp-PAM biological composite coating, be particularly related to the preparation method that a kind of pulsed hydrothermal electrophoresis polymerization prepares the HAp-PAM biological gradient compound coating, can prepare the surface evenly by present method, Stability Analysis of Structures, the biological composite coating high with substrate combinating strength.
Background technology
Bone reparation in recent years and bone alternate material become the focus of biomaterial circle research gradually.As bone reparation and equivalent material, not only to satisfy biocompatibility and biological activity, also to satisfy the mechanical property of human body bone.Given this, mainly aspect biological coating, body material has satisfied the requirement of biomaterial mechanical property to the research emphasis that development in recent years is got up, and coated material then has good biological activity.
Hydroxyapatite (is called for short HA or HAp, its molecular formula Ca
10(PO4)
6(OH)
2) be the main component of inanimate matter in the body bone tissue, it has excellent biological compatibility, biological activity and bone connection (Chen Xiaoming, Li Shipu, Han Qingrong, Deng. silicate journal, 2001,29 (6): 565), the damaged reparation of body bone tissue with rebuild, be considered to a kind of human body planting body material of tool potentiality.Because its fragility is big, load little (Jiang Geng, WangBing Hua, Changjiang University's journal, 2008,5 (3): 20), therefore mainly be used as coated material.And body material mainly contains: the C/C matrix material that medical titanium alloy, magnesium alloy, organic polymer, traditional ceramics material and development in recent years are got up.In these body materials, titanium alloy, its mechanical strength of magnesium alloy are far longer than the mechanical strength of human body bone, behind the implant into body, lost efficacy and often occurred in the junction, interface of alloy and human body bone, alloy is in vivo after for some time in addition, the particle that discharges makes host cell poisoning etc., thereby has been subjected to certain restriction clinically; Be degraded to deleterious organic monomer behind the organic polymer implant into body under the body fluid environment easily, the fragility of traditional ceramics is big, and fatigue performance difference etc. make these materials all can not be applied to clinical as the ideal body material.
Carbon/carbon (C/C) matrix material is a kind of type material that international field of new is given priority to, and has function and structural performance concurrently, excellent combination property, and as bone reparation and bone substitution material, the chemistry of carbon material, physiological property are stablized superior biocompatibility.Carbon/carbon (C/C) composite material toughness is good, can overcome the fragility of single carbon material, and intensity height, fatigue characteristic are superior, particularly its Young's modulus and people's bone photo are worked as, therefore be a kind of biomaterial that has potentiality, has application prospect (Gao Lin, Lin Jiarui.Histological observation of carbonaceous materials containing hydroxyapatite[C] .The International Conference on Carbon 2002,2002, Beijing, China.).
But so far, the main method of preparation hydroxyl apatite biological painting has plasma spraying, laser to cover to melt on carbon/carbon base body, powder slurry coating adds sintering, isobaric compression, electrophoresis, hydro-thermal are synthetic, biomimetic method, electrochemical deposition method, hydro-thermal electrophoretic method etc.
Huang Jianfeng, people such as Zhu Guangyan (Zhu Guangyan, Huang Jianfeng, Wu Jianpeng, Cao Liyun, He Haiyan, Rare Metals Materials and engineering, 2007,2 (36): 749-753) utilize the hydrothermal electrodeposition method to prepare nano level hydroxyapatite coating layer at the C/C matrix surface, when overcoming traditional plasma spraying, electrochemical deposition method causes the non-linear of the thermolysis of HAp and spraying process because of high temperature, and can pass through control current, voltage, the thickness of the accurate control coating of experiment parameter such as temperature, surface tissue and porosity etc., but the coating of this method preparation and the bonding force deficiency of bonding force between the matrix and coating self restrict it and further develop.
People such as Cao Liyun, Li Yinghua (Li Yinghua, Cao Liyun, Huang Jianfeng, once mediate banyan, China's Tissue Engineering Study and clinical rehabilitation, 2008,41 (12): 8143-8146) adopt the hydro-thermal electrophoretic method to prepare C/C base chitosan/HAp composite biological coating, the good mechanical property of C/C matrix material is combined with the good biological of HAp, chitosan is active, and the bone of preparing a new generation substitutes and repair materials.But, still exist between coating and the matrix, the not high problem of bonding force between coating and the coating.
At present, prepare the research of hydroxyapatite coating layer bonding force mainly in depositing operation and the modification of C/C matrix surface to improving the C/C composite material surface both at home and abroad.These methods have improved coating and high base strength to a certain extent, but do not have to solve its not enough problem of bonding force clinically at all.
Summary of the invention
The object of the present invention is to provide a kind of preparation technology simple, the preparation method of the HAp-PAM biological gradient compound coating that cost is low.
For achieving the above object, the technical solution used in the present invention is: step 1: get that the analytically pure acrylamide monomer of 3.5～6.0g is soluble in water makes the acrylamide solution that concentration is 35～60g/L, and then with the analytically pure S-WAT of 0.035～0.060g and the analytically pure ammonium persulfate initiator of 0.035～0.060g add respectively in the acrylamide solution seal after the fully dissolving unglazed place preserve A solution;
Step 2: the hydroxyapatite of getting 2.0～3.0g median size and be 10～50nm is scattered in the Virahol of 150ml, and then adds the iodine of 0.6～1.0g/L, ultra-sonic dispersion 5～12h, and ageing 8～20h gets B solution;
Step 3: the negative electrode that carbon/carbon compound material is fixed on electric deposition device, and be placed in the A solution to adopt under the direct current deposition method room temperature and behind 60V～100V deposition 2～5s, take out, be fixed in the negative electrode of hydrothermal reaction kettle again, B solution is poured in the hydrothermal reaction kettle, compactedness is controlled at 60～70%, the sealing hydrothermal reaction kettle, adopt the pulse electrodeposition polymerization process, control voltage is at 60V～100V, temperature is 120～150 ℃, powered-down behind pulse electrodeposition polymerization 10～60s stops deposition; Treat to take out substrate behind the hydrothermal reaction kettle naturally cooling, oven dry promptly gets hydroxyapatite-polyacrylamide biological gradient compound coating in 50 ℃～80 ℃ baking ovens.
It is 1.8g/cm that carbon/carbon compound material of the present invention adopts density
3The 3D carbon/carbon compound material, be cut to 10mm * 10mm * 2mm thin slice, behind the sanding and polishing with UV-irradiation 20～40min, place distilled water to clean after again with obtaining behind the dehydrated alcohol ultrasonic cleaning hot blast drying.
The gradient cladding that preparation method of the present invention makes has been realized being reduced gradually to hydroxyapatite (HAp) content to coating and matrix bond prescription by the surface, and the graded that polyacrylamide (PAM) content increases gradually.The performance that this coating makes full use of PAM has improved the bonding force of coating and matrix, also utilizes the performance of HAp to guarantee biological compatibility of coating and biological activity, and therefore being expected to it obtains certain effect clinically.
Its advantage applies exists: the amount of controlling AM on carbon/carbon base body by control dc electrodeposition time and voltage, and the surface and the cross-section morphology that wait control coating by control hydrothermal temperature, hydro-thermal deposition voltage, make prepared compound coating evenly fine and close, the coating crystalline phase is stable, and bonding strength is higher.Can reach about 110～150MPa.
Description of drawings
Fig. 1 is the profile scanning Electronic Speculum figure of the HAp-PAM gradient composite coating of the embodiment of the invention 1 preparation.
Embodiment
Below in conjunction with the drawings and the specific embodiments the present invention is described in further detail.
Embodiment 1:
Step 1: get that the analytically pure acrylamide monomer of 3.5g is soluble in water makes the acrylamide solution that concentration is 35g/L, the more analytically pure S-WAT of 0.035g and 0.035g ammonium persulfate initiator are added respectively in the acrylamide solution seal after the fully dissolving unglazed place preserve A solution;
Step 2: the hydroxyapatite of getting the 3.0g median size and be 10～50nm is scattered in the Virahol of 150ml, and then adds the iodine of 0.6g/L, ultra-sonic dispersion 12h, and ageing 8h gets B solution;
Step 3: employing density is 1.8g/cm
33D C/C matrix material, be cut to 10mm * 10mm * 2mm thin slice, use UV-irradiation 20min behind the sanding and polishing, after placing distilled water to clean again with the negative electrode that is fixed on electric deposition device behind the dehydrated alcohol ultrasonic cleaning hot blast drying, and be placed in the A solution to adopt under the direct current deposition method room temperature and behind 80V deposition 5s, take out, be fixed in the negative electrode of hydrothermal reaction kettle again, B solution is poured in the hydrothermal reaction kettle, compactedness is controlled at 65%, and the sealing hydrothermal reaction kettle adopts the pulse electrodeposition polymerization process, control voltage is at 80V, temperature is 120 ℃, and powered-down behind the electrophoretic deposition polyase 13 5s stops deposition; Treat to take out substrate behind the hydrothermal reaction kettle naturally cooling, oven dry promptly gets the HAp-PAM biological gradient compound coating in 80 ℃ of baking ovens.Fig. 1 prepares the profile scanning Electronic Speculum picture of HAp-PAM gradient composite coating for embodiment.As we can see from the figure, prepared compound coating thickness and combines closely between coating and the matrix probably between 25～30 μ m, does not have generation of defects such as crackle, hole.Its bonding strength can reach 150MPa.
Embodiment 2:
Step 1: get that the analytically pure acrylamide monomer of 5g is soluble in water makes the acrylamide solution that concentration is 50g/L, the more analytically pure S-WAT of 0.050g and 0.050g ammonium persulfate initiator are added respectively in the acrylamide solution seal after the fully dissolving unglazed place preserve A solution;
Step 2: the hydroxyapatite of getting the 2.5g median size and be 10～50nm is scattered in the Virahol of 150ml, and then adds the iodine of 1.0g/L, ultra-sonic dispersion 8h, and ageing 15h gets B solution;
Step 3: employing density is 1.8g/cm
33D C/C matrix material, be cut to 10mm * 10mm * 2mm thin slice, use UV-irradiation 30min behind the sanding and polishing, after placing distilled water to clean again with the negative electrode that is fixed on electric deposition device behind the dehydrated alcohol ultrasonic cleaning hot blast drying, and be placed in the A solution to adopt under the direct current deposition method room temperature and behind 100V deposition 3s, take out, be fixed in the negative electrode of hydrothermal reaction kettle again, B solution is poured in the hydrothermal reaction kettle, compactedness is controlled at 70%, and the sealing hydrothermal reaction kettle adopts the pulse electrodeposition polymerization process, control voltage is at 100V, temperature is 150 ℃, and powered-down behind the electrophoretic deposition polymerization 10s stops deposition; Treat to take out substrate behind the hydrothermal reaction kettle naturally cooling, oven dry promptly gets the HAp-PAM biological gradient compound coating in 50 ℃ of baking ovens.
Embodiment 3:
Step 1: get that the analytically pure acrylamide monomer of 6g is soluble in water makes the acrylamide solution that concentration is 60g/L, the more analytically pure S-WAT of 0.060g and 0.060g ammonium persulfate initiator are added respectively in the acrylamide solution seal after the fully dissolving unglazed place preserve A solution;
Step 2: the hydroxyapatite of getting the 2.0g median size and be 10～50nm is scattered in the Virahol of 150ml, and then adds the iodine of 0.8g/L, ultra-sonic dispersion 5h, and ageing 20h gets B solution;
Step 3: employing density is 1.8g/cm
33D C/C matrix material, be cut to 10mm * 10mm * 2mm thin slice, use UV-irradiation 40min behind the sanding and polishing, after placing distilled water to clean again with the negative electrode that is fixed on electric deposition device behind the dehydrated alcohol ultrasonic cleaning hot blast drying, and be placed in the A solution to adopt under the direct current deposition method room temperature and behind 60V deposition 3s, take out, be fixed in the negative electrode of hydrothermal reaction kettle again, B solution is poured in the hydrothermal reaction kettle, compactedness is controlled at 60%, and the sealing hydrothermal reaction kettle adopts the pulse electrodeposition polymerization process, control voltage is at 60V, temperature is 135 ℃, and powered-down behind the electrophoretic deposition polymerization 60s stops deposition; Treat to take out substrate behind the hydrothermal reaction kettle naturally cooling, oven dry promptly gets the HAp-PAM biological gradient compound coating in 80 ℃ of baking ovens.
Embodiment 4:
Step 1: get that the analytically pure acrylamide monomer of 4g is soluble in water makes the acrylamide solution that concentration is 40g/L, the more analytically pure S-WAT of 0.040g and 0.040g ammonium persulfate initiator are added respectively in the acrylamide solution seal after the fully dissolving unglazed place preserve A solution;
Step 2: the hydroxyapatite of getting the 2.8g median size and be 10～50nm is scattered in the Virahol of 150ml, and then adds the iodine of 0.7g/L, ultra-sonic dispersion 10h, and ageing 10h gets B solution;
Step 3: employing density is 1.8g/cm
33D C/C matrix material, be cut to 10mm * 10mm * 2mm thin slice, use UV-irradiation 25min behind the sanding and polishing, after placing distilled water to clean again with the negative electrode that is fixed on electric deposition device behind the dehydrated alcohol ultrasonic cleaning hot blast drying, and be placed in the A solution to adopt under the direct current deposition method room temperature and behind 90V deposition 4s, take out, be fixed in the negative electrode of hydrothermal reaction kettle again, B solution is poured in the hydrothermal reaction kettle, compactedness is controlled at 68%, and the sealing hydrothermal reaction kettle adopts the pulse electrodeposition polymerization process, control voltage is at 90V, temperature is 125 ℃, and powered-down behind the electrophoretic deposition polymerization 25s stops deposition; Treat to take out substrate behind the hydrothermal reaction kettle naturally cooling, oven dry promptly gets the HAp-PAM biological gradient compound coating in 60 ℃ of baking ovens.
Embodiment 5:
Step 1: get that the analytically pure acrylamide monomer of 5.5g is soluble in water makes the acrylamide solution that concentration is 55g/L, the more analytically pure S-WAT of 0.045g and 0.045g ammonium persulfate initiator are added respectively in the acrylamide solution seal after the fully dissolving unglazed place preserve A solution;
Step 2: the hydroxyapatite of getting the 2.3g median size and be 10～50nm is scattered in the Virahol of 150ml, and then adds the iodine of 0.9g/L, ultra-sonic dispersion 6h, and ageing 18h gets B solution;
Step 3: employing density is 1.8g/cm
33D C/C matrix material, be cut to 10mm * 10mm * 2mm thin slice, use UV-irradiation 35min behind the sanding and polishing, after placing distilled water to clean again with the negative electrode that is fixed on electric deposition device behind the dehydrated alcohol ultrasonic cleaning hot blast drying, and be placed in the A solution to adopt under the direct current deposition method room temperature and behind 70V deposition 5s, take out, be fixed in the negative electrode of hydrothermal reaction kettle again, B solution is poured in the hydrothermal reaction kettle, compactedness is controlled at 62%, and the sealing hydrothermal reaction kettle adopts the pulse electrodeposition polymerization process, control voltage is at 70V, temperature is 140 ℃, and powered-down behind the electrophoretic deposition polymerization 50s stops deposition; Treat to take out substrate behind the hydrothermal reaction kettle naturally cooling, oven dry promptly gets the HAp-PAM biological gradient compound coating in 70 ℃ of baking ovens.
Claims (2)
1. the preparation method of hydroxyapatite-polyacrylamide biological gradient compound coating is characterized in that may further comprise the steps:
Step 1: get that the analytically pure acrylamide monomer of 3.5～6.0g is soluble in water makes the acrylamide solution that concentration is 35～60g/L, and then with the analytically pure S-WAT of 0.035～0.060g and 0.035～0.060g ammonium persulfate initiator add respectively in the acrylamide solution seal after the fully dissolving unglazed place preserve A solution;
Step 2: the hydroxyapatite of getting 2.0～3.0g median size and be 10～50nm is scattered in the Virahol of 150ml, and then adds the iodine of 0.6～1.0g/L, ultra-sonic dispersion 5～12h, and ageing 8～20h gets B solution;
Step 3: the negative electrode that carbon/carbon compound material is fixed on electric deposition device, and be placed in the A solution to adopt under the direct current deposition method room temperature and behind 60V～100V deposition 2～5s, take out, be fixed in the negative electrode of hydrothermal reaction kettle again, B solution is poured in the hydrothermal reaction kettle, compactedness is controlled at 60～70%, the sealing hydrothermal reaction kettle, adopt pulse electrophoresis deposition polymerization method, control voltage is at 60V～100V, temperature is 120～150 ℃, powered-down behind pulse electrophoresis deposition polymerization 10～60s stops deposition; Treat to take out substrate behind the hydrothermal reaction kettle naturally cooling, oven dry promptly gets hydroxyapatite-polyacrylamide biological gradient compound coating in 50 ℃～80 ℃ baking ovens.
2. the preparation method of hydroxyapatite according to claim 1-polyacrylamide biological gradient compound coating is characterized in that: it is 1.8g/cm that said carbon/carbon compound material adopts density
3The 3D carbon/carbon compound material, be cut to 10mm * 10mm * 2mm thin slice, behind the sanding and polishing with UV-irradiation 20～40min, place distilled water to clean after again with obtaining behind the dehydrated alcohol ultrasonic cleaning hot blast drying.
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| CN108546156A (en) * | 2018-04-09 | 2018-09-18 | 西北工业大学 | The carbon/carbon compound material and preparation method that silicon carbide is modified with hydroxylapatite gradient coating |
| CN109796941B (en) * | 2019-01-14 | 2020-12-29 | 西南石油大学 | Expansion plugging agent and preparation method thereof, microcapsule type plugging agent, water-based drilling fluid and application thereof |
| CN113106519A (en) * | 2021-04-02 | 2021-07-13 | 福建师范大学 | Zone electrophoresis and electrophoretic deposition method for preparing HA gradient composite coating material |
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| CN1243130C (en) * | 2003-02-24 | 2006-02-22 | 福建师范大学 | Composite hydrothermal and electrodepositing process to prepare hydroxyapatite/TiO2 coating |
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