CN102304746A - Polypyrrole calcium phosphate/magnesium oxide bioceramic coating and preparation method thereof - Google Patents

Polypyrrole calcium phosphate/magnesium oxide bioceramic coating and preparation method thereof Download PDF

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CN102304746A
CN102304746A CN201110288767A CN201110288767A CN102304746A CN 102304746 A CN102304746 A CN 102304746A CN 201110288767 A CN201110288767 A CN 201110288767A CN 201110288767 A CN201110288767 A CN 201110288767A CN 102304746 A CN102304746 A CN 102304746A
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polypyrrole
calcium phosphate
electrolytic solution
arc oxidation
differential arc
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曲立杰
李慕勤
马臣
王晶彦
庄明辉
王晶
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Jiamusi University
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Jiamusi University
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Abstract

The invention relates to a polypyrrole calcium phosphate/magnesium oxide bioceramic coating and a preparation method thereof, and relates to a magnesium alloy surface ceramic coating and a preparation method thereof. The invention aims to solve the technical problem that the degradation rate of the surface-treated magnesium and magnesium alloy used as a bone fixation material is too high in the later stage of bone healing. The coating is prepared through the following steps: sanding the Mg-Zn-Zr-Ca alloy by use of abrasive paper and performing microarc oxidation and electrochemical deposition. The method comprises the following steps: 1) treating the surface of a base material; 2) preparing a microarc oxidation electrolyte; 3) performing microarc oxidation treatment; and 4) performing electrochemical deposition to obtain the polypyrrole calcium phosphate/magnesium oxide bioceramic coating. The polypyrrole calcium phosphate/magnesium oxide bioceramic coating can be used for developing bone fixation materials such as magnesium-based bone plates, bone screws and the like.

Description

Polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coating and preparation method thereof
Technical field
The present invention relates to Mg alloy surface ceramic coating and preparation method thereof.
Background technology
Present clinical application bone immobilizing material; As the bio-medical material that is widely used in hone lamella, nail mainly is titanium or titanium alloy, stainless steel etc.; But be not complementary owing to its relatively poor biodegradability causes its mechanical property and people's osseous tissue, can produce stress-shielding effect and need carry out second operation and take out undegradable planting body.Magnesium and magnesium alloy density and Young's modulus and human body bone are approaching, have good mechanical performance and biological degradability.But, because it has the clinical application that very high erosion rate has limited magnesium and magnesium alloy thereof.In recent years, the appearance of technology such as kinds of surface treatment technology such as alkali thermal treatment, coating switch technology, oxide covering technology, differential arc oxidation and galvanic deposit, feasible magnesium and magnesium alloy as bone immobilizing material obtained extensive studies.In the biological coating preparation process, the following two large problems of main existence:
1) high temperature deposition biological activity element, be prone to cause hydroxyapatite (HA) decompose, decrystallized, be prone to dissolving, bonding strength is low, crackle appears in coating, the coating internal stress is crossed problems such as height.
2) it is lower to exist interface bond strength during low temperature depositing; Thick coating is spent problems such as thin.
Therefore need the new biomaterial surface treatment technology of development; Differential arc oxidization technique belongs to the characteristics of environmental type process for modifying surface because of it; The most important thing is to form bottom compact surfaces porous biological coating in base metal surface through its discharge breakdown effect and in the effect of non-ferrous metal surface in situ high temperature sintering.Feasible magnesium and the magnesium alloy as bone immobilizing material of the appearance of this technology has slower erosion rate in initial planting, can the favorable mechanical performance be provided for osseous tissue.But in the later stage of knitting, the degradation rate of surface-treated magnesium and magnesium alloy thereof is too fast.
Summary of the invention
The present invention will solve as the surface treatment magnesium of bone immobilizing material and magnesium alloy in the too fast technical problem of the later stage degradation speed of knitting, and polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coating and preparation method thereof is provided.
Polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coating is that the Mg-Zn-Zr-Ca alloy is processed through sand papering, differential arc oxidation and electro-chemical deposition process successively, and it is CaH that differential arc oxidation is handled used differential arc oxidation electrolytic solution 2PO 4With NaOH according to the configuration of 1: 1~4 mol ratio, CaH in the differential arc oxidation electrolytic solution 2PO 4Concentration 0.05~0.08mol/L, the solvent of differential arc oxidation electrolytic solution is a distilled water; The used electrolytic solution of electro-chemical deposition process is by Ca (NO 3) 2, NH 4H 2PO 4, pyrroles and distilled water forms Ca (NO in the electrolytic solution 3) 2Concentration be 0.042~0.21mol/L, NH 4H 2PO 4Concentration be 0.025~0.125mol/L, pyrroles's concentration is 0.01~0.05mol/L.
The preparation method of polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coating is undertaken by following step:
Step 1, be base material, use 500 orders, 800 orders, 1000 orders and 1200 order sand paperings successively, clean under ultrasonic environment with acetone, dehydrated alcohol and distilled water successively then with the Mg-Zn-Zr-Ca alloy;
Step 2, with CaH 2PO 4With NaOH according to 1: 1~4 mol ratio configuration differential arc oxidation electrolytic solution, CaH in the differential arc oxidation electrolytic solution 2PO 4Concentration 0.05~0.08mol/L, the solvent of differential arc oxidation electrolytic solution is a distilled water;
Step 3, the base material that step 1 is handled are put into the differential arc oxidation electrolytic solution of step 2 preparation, are 10%~30% in dutycycle then, interelectrode distance is that 40mm, voltage are to carry out differential arc oxidation under 200V~450V and 20~40 ℃ of conditions of electrolyte temperature to handle 2min~10min;
Step 4, will put in the electrolytic solution through the base material that step 3 is handled, be 10~40mA/cm at pulse current density then 2, dutycycle is 50%~80%, interelectrode distance is that 10mm and electrolyte temperature are to carry out electrochemical deposition 10~60min under 40 ℃ of conditions; Promptly obtain polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coating; The said electrolytic solution of step 4 is by Ca (NO 3) 2, NH 4H 2PO 4, pyrroles and distilled water forms Ca (NO in the electrolytic solution 3) 2Concentration be 0.042~0.21mol/L, NH 4H 2PO 4Concentration be 0.025~0.125mol/L, pyrroles's concentration is 0.01~0.05mol/L.
The inventive method step 3 can also be carried out the differential arc oxidation processing under ultrasonic wave is auxiliary, hyperacoustic operating frequency is 40KHz, and hyperacoustic power is 400~800W.
Polypyrrole calcium phosphate of the present invention/Natural manganese dioxide bio-ceramic coating is that ultrasonic technique is incorporated in the differential arc oxidation treating processes, utilizes ultrasonication to realize the micropore size that differential arc oxidation is obtained, the regulation and control of structure.Utilize electrochemical deposition technique, realize the sealing of hole effect, still can make material have very high biological activity simultaneously.The superpolymer polypyrrole (PPy) that will have biology performance is incorporated in the electrodeposit liquid; Use the electroconductibility and the cell compatibility of polypyrrole; Improve the deposition of ion on oxidation film layer of biologically active; To improve the biological activity of magnesium and alloy oxidation layer thereof; Guarantee that magnesium and alloy thereof have degradation rate suitable under the physiological environment; But galvanic deposit polypyrrole composite biological coatings is the healing of accelerated bone tissue simultaneously, and shortens the healing stage between bone immobilizing material and the human body bone.
Polypyrrole calcium phosphate of the present invention/Natural manganese dioxide bio-ceramic coating can be used for developing bone immobilizing materials such as magnesium base hone lamella, nail.
Description of drawings
Fig. 1 is that the Natural manganese dioxide bio-ceramic coating magnification of test one preparation is 1000 stereoscan photograph; Fig. 2 is that the polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coating magnification of test one preparation is 300 stereoscan photograph.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coating is that the Mg-Zn-Zr-Ca alloy is processed through sand papering, differential arc oxidation and electro-chemical deposition process successively in this embodiment, and it is CaH that differential arc oxidation is handled used differential arc oxidation electrolytic solution 2PO 4With NaOH according to the configuration of 1: 1~4 mol ratio, CaH in the differential arc oxidation electrolytic solution 2PO 4Concentration 0.05~0.08mol/L, the solvent of differential arc oxidation electrolytic solution is a distilled water; The used electrolytic solution of electro-chemical deposition process is by Ca (NO 3) 2, NH 4H 2PO 4, pyrroles and distilled water forms Ca (NO in the electrolytic solution 3) 2Concentration be 0.042~0.21mol/L, NH 4H 2PO 4Concentration be 0.025~0.125mol/L, the concentration of polypyrrole is 0.01~0.05mol/L.
Embodiment two: the preparation method of polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coating is undertaken by following step in this embodiment:
Step 1, be base material, use 500 orders, 800 orders, 1000 orders and 1200 order sand paperings successively, clean under ultrasonic environment with acetone, dehydrated alcohol and distilled water successively then with the Mg-Zn-Zr-Ca alloy;
Step 2, with CaH 2PO 4With NaOH according to 1: 1~4 mol ratio configuration differential arc oxidation electrolytic solution, CaH in the differential arc oxidation electrolytic solution 2PO 4Concentration 0.05~0.08mol/L, the solvent of differential arc oxidation electrolytic solution is a distilled water;
Step 3, the base material that step 1 is handled are put into the differential arc oxidation electrolytic solution of step 2 preparation, are 10%~30% in dutycycle then, interelectrode distance is that 40mm, voltage are to carry out differential arc oxidation under 200V~450V and 20~40 ℃ of conditions of electrolyte temperature to handle 2min~10min;
Step 4, will put in the electrolytic solution through the base material that step 3 is handled, be 10~40mA/cm at pulse current density then 2, dutycycle is 50%~80%, interelectrode distance is that 10mm and electrolyte temperature are to carry out electrochemical deposition 10~60min under 40 ℃ of conditions; Promptly obtain polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coating; The said electrolytic solution of step 4 is by Ca (NO 3) 2, NH 4H 2PO 4, pyrroles and distilled water forms Ca (NO in the electrolytic solution 3) 2Concentration be 0.042~0.21mol/L, NH 4H 2PO 4Concentration be 0.025~0.125mol/L, the concentration of polypyrrole is 0.01~0.05mol/L.
Embodiment three: the preparation method of polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coating is undertaken by following step in this embodiment:
Step 1, be base material, use 500 orders, 800 orders, 1000 orders and 1200 order sand paperings successively, clean under ultrasonic environment with acetone, dehydrated alcohol and distilled water successively then with the Mg-Zn-Zr-Ca alloy;
Step 2, with CaH 2PO 4With NaOH according to 1: 1~4 mol ratio configuration differential arc oxidation electrolytic solution, CaH in the differential arc oxidation electrolytic solution 2PO 4Concentration 0.05~0.08mol/L, the solvent of differential arc oxidation electrolytic solution is a distilled water;
Step 3, the base material that step 1 is handled are put into the differential arc oxidation electrolytic solution of step 2 preparation, are 10%~30% in dutycycle then, interelectrode distance is that 40mm, voltage are under 200V~450V and 20~40 ℃ of conditions of electrolyte temperature and at the auxiliary differential arc oxidation processing 2min~10min that carries out down of ultrasonic wave;
Step 4, will put in the electrolytic solution through the base material that step 3 is handled, be 10~40mA/cm at pulse current density then 2, dutycycle is 50%~80%, interelectrode distance is that 10mm and electrolyte temperature are to carry out electrochemical deposition 10~60min under 40 ℃ of conditions; Promptly obtain polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coating; The said electrolytic solution of step 4 is by Ca (NO 3) 2, NH 4H 2PO 4, pyrroles and distilled water forms Ca (NO in the electrolytic solution 3) 2Concentration be 0.042~0.21mol/L, NH 4H 2PO 4Concentration be 0.025~0.125mol/L, the concentration of polypyrrole is 0.01~0.05mol/L.
Hyperacoustic operating frequency is 40KHz in this embodiment, and hyperacoustic power is 400~800W.
Embodiment four: what this embodiment was different with embodiment two or three is: it is 250V~400V that the step 3 differential arc oxidation is handled applied voltage.Other step is identical with embodiment two or three with parameter.
Embodiment five: what this embodiment was different with one of embodiment two to four is: the step 3 differential arc oxidation is handled 3min~7min.Other step is identical with one of embodiment two to four with parameter.
Embodiment six: what this embodiment was different with one of embodiment two to four is: the step 3 differential arc oxidation is handled 5min.Other step is identical with one of embodiment two to four with parameter.
Embodiment seven: what this embodiment was different with one of embodiment two to six is: the said pyrroles's of step 4 concentration is 0.01~0.03mol/L.Other step is identical with one of embodiment two to six with parameter.
Embodiment eight: what this embodiment was different with one of embodiment two to six is: the said pyrroles's of step 4 concentration is 0.02mol/L.Other step is identical with one of embodiment two to six with parameter.
Embodiment nine: what this embodiment was different with one of embodiment two to eight is: the step 4 electrochemical deposition time is 20~40min.Other step is identical with one of embodiment two to eight with parameter.
Embodiment ten: what this embodiment was different with one of embodiment two to eight is: the step 4 electrochemical deposition time is 30min.Other step is identical with one of embodiment two to eight with parameter.
Adopt following verification experimental verification invention effect:
Test one: the preparation method of polypyrrole calcium phosphate/Natural manganese dioxide compound coating carries out according to following steps: one, matrix is prepared; Mg-5%Zn-(0.3%-0.6%) Zr-0.2%Ca is a body material; It is prepared into is of a size of Φ 15mm * 1.5mm; Use 500 orders, 800 orders, 1000 orders, 1200 order sand paperings successively, utilize acetone, dehydrated alcohol, distilled water under ultrasonic environment, to clean 10 minutes then successively; Two, with CaH 2PO 4With NaOH be 1: 4 proportional arrangement differential arc oxidation electrolytic solution according to mol ratio, CaH in the differential arc oxidation electrolytic solution 2PO 4Concentration 0.079mol/L, the solvent of differential arc oxidation electrolytic solution is a distilled water; Three, the body material in the step 1 being carried out differential arc oxidation in the electrolytic solution of step 2 configuration handles; Dutycycle is 10%; Interelectrode distance is 40mm; Voltage is 300V; Oxidization time is 5min, and electrolyte temperature is 30 ℃, simultaneously auxiliary ultrasonic processing; Ultrasonic power is 60% (operating frequency is 40KHz, and power is 1000W); The magnesium base oxidation film layer that obtains in the step 3 put in the electrolytic solution that electrolytic solution is 0.21mol/L and 0.125mol/L carry out electrochemical deposition, the deposition pulse current density is 20mA/cm 2, dutycycle is 60%, and interelectrode distance is 10mm, and electrolyte temperature is 40 ℃, and electrodeposition time is 25min, pyrroles's concentration is 0.01mol/L.
Test one polypyrrole calcium phosphate/Natural manganese dioxide compound coating stereoscan photograph such as Fig. 1 that obtains, shown in 2, Fig. 1 is that differential arc oxidation is handled the surface topography that obtains, the dendritic of Fig. 2 mesexine is the polypyrrole calcium phosphate coating that obtains under the electrodeposition condition.As can be seen from the figure, the differential arc oxidation coating micropore is sealed by deposition layer, accomplishes the end in view.
The corrosion resisting property of the test one polypyrrole calcium phosphate/Natural manganese dioxide compound coating that obtains detects carries out according to following method: difference selective corrosion liquid NaCl (0.9%), NaCl (0.9%)+5%BSA (bovine serum albumin).Research contains the polypyrrole calcium phosphate/degradation behavior of Natural manganese dioxide compound coating in above-mentioned solution, promptly measures Mg in the erosion rate of material in above-mentioned corrosive fluid, the corrosive fluid 2+Concentration, corrosion before and after surface topography and phase composite, the sedimental composition of corrosion specimen surface and corrosion pit place of sample; The result obtains polypyrrole calcium phosphate/Natural manganese dioxide compound coating in above-mentioned corrosive liquid behind the week age; Corrosion product is not seen on the surface, and single magnesium oxide layer is corroded and dissolves.
Test two: the preparation method of polypyrrole calcium phosphate/Natural manganese dioxide compound coating carries out according to following steps: one, matrix is prepared; Mg-5%Zn-(0.3%-0.6%) Zr-0.2%Ca is a body material; It is prepared into is of a size of Φ 15mm * 1.5mm; Use 500 orders, 800 orders, 1000 orders, 1200 order sand paperings successively, utilize acetone, dehydrated alcohol, distilled water under ultrasonic environment, to clean 10 minutes then successively; Two, with CaH 2PO 4With NaOH be 1: 4 proportional arrangement differential arc oxidation electrolytic solution according to mol ratio, CaH in the differential arc oxidation electrolytic solution 2PO 4Concentration 0.079mol/L, the solvent of differential arc oxidation electrolytic solution is a distilled water; Three, the body material in the step 1 being carried out differential arc oxidation in the electrolytic solution of step 2 configuration handles; Dutycycle is 10%; Interelectrode distance is 40mm; Voltage is 300V; Oxidization time is 5min, and electrolyte temperature is 25 ℃, simultaneously auxiliary ultrasonic processing; Ultrasonic power is 60% (operating frequency is 40KHz, and power is 1000W); The magnesium base oxidation film layer that obtains in the step 3 put in the electrolytic solution that electrolytic solution is 0.21mol/L and 0.125mol/L carry out electrochemical deposition, the deposition pulse current density is 20mA/cm 2, dutycycle is 60%, and interelectrode distance is 10mm, and electrolyte temperature is 40 ℃, and electrodeposition time is 25min, the concentration of polypyrrole is 0.01mol/L.
The corrosion resisting property of the test two polypyrrole calcium phosphate/Natural manganese dioxide compound coatings that obtain detects carries out according to following method: difference selective corrosion liquid SBF (simulated body fluid), SBF+5%BSA, PBS (phosphate buffer soln), PBS+5%BSA.Research contains the polypyrrole calcium phosphate/degradation behavior of Natural manganese dioxide compound coating in above-mentioned solution, promptly measures Mg in the erosion rate of material in above-mentioned corrosive fluid, the corrosive fluid 2+Concentration, corrosion before and after surface topography and phase composite, the sedimental composition of corrosion specimen surface and corrosion pit place of sample; The result obtains polypyrrole calcium phosphate/Natural manganese dioxide compound coating in above-mentioned corrosive liquid behind the week age; Corrosion product is not seen on the surface yet, and single magnesium oxide layer is corroded and dissolves.
Test three: the preparation method of polypyrrole calcium phosphate/Natural manganese dioxide compound coating carries out according to following steps: one, matrix is prepared; Mg-5%Zn-(0.3%-0.6%) Zr-0.2%Ca is a body material; It is prepared into is of a size of Φ 15mm * 1.5mm; Use 500 orders, 800 orders, 1000 orders, 1200 order sand paperings successively, utilize acetone, dehydrated alcohol, distilled water under ultrasonic environment, to clean 10 minutes then successively; Two, with CaH 2PO 4With NaOH be 1: 4 proportional arrangement differential arc oxidation electrolytic solution according to mol ratio, CaH in the differential arc oxidation electrolytic solution 2PO 4Concentration 0.079mol/L, the solvent of differential arc oxidation electrolytic solution is a distilled water; Three, the body material in the step 1 is carried out differential arc oxidation in the electrolytic solution of step 2 configuration and handle, dutycycle is 10%, and interelectrode distance is 40mm, and voltage is 300V, and oxidization time is 5min, and electrolyte temperature is 30 ℃; The magnesium base oxidation film layer that obtains in the step 3 put in the electrolytic solution that electrolytic solution is 0.21mol/L and 0.125mol/L carry out electrochemical deposition, the deposition pulse current density is 20mA/cm 2, dutycycle is 60%, and interelectrode distance is 10mm, and electrolyte temperature is 40 ℃, and electrodeposition time is 25min, pyrroles's concentration is 0.01mol/L.
The corrosion resisting property of the test three polypyrrole calcium phosphate/Natural manganese dioxide compound coatings that obtain detects carries out according to following method: difference selective corrosion liquid NaCl (0.9%), NaCl (0.9%)+5%BSA (bovine serum albumin).Research contains the polypyrrole calcium phosphate/degradation behavior of Natural manganese dioxide compound coating in above-mentioned solution, promptly measures Mg in the erosion rate of material in above-mentioned corrosive fluid, the corrosive fluid 2+Concentration, corrosion before and after surface topography and phase composite, the sedimental composition of corrosion specimen surface and corrosion pit place of sample; The result obtains polypyrrole calcium phosphate/Natural manganese dioxide compound coating in above-mentioned corrosive liquid behind the week age; Corrosion product is not seen on the surface, and single magnesium oxide layer is corroded and dissolves.

Claims (10)

1. polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coating; It is characterized in that polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coating is that the Mg-Zn-Zr-Ca alloy is processed through sand papering, differential arc oxidation and electro-chemical deposition process successively, it is CaH that differential arc oxidation is handled used differential arc oxidation electrolytic solution 2PO 4With NaOH according to the configuration of 1: 1~4 mol ratio, CaH in the differential arc oxidation electrolytic solution 2PO 4Concentration 0.05~0.08mol/L, the solvent of differential arc oxidation electrolytic solution is a distilled water; The used electrolytic solution of electro-chemical deposition process is by Ca (NO 3) 2, NH 4H 2PO 4, pyrroles and distilled water forms Ca (NO in the electrolytic solution 3) 2Concentration be 0.042~0.21mol/L, NH 4H 2PO 4Concentration be 0.025~0.125mol/L, pyrroles's concentration is 0.01~0.05mol/L.
2. the preparation method of polypyrrole calcium phosphate as claimed in claim 1/Natural manganese dioxide bio-ceramic coating is characterized in that the preparation method of polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coating is undertaken by following step:
Step 1, be base material, use 500 orders, 800 orders, 1000 orders and 1200 order sand paperings successively, clean under ultrasonic environment with acetone, dehydrated alcohol and distilled water successively then with the Mg-Zn-Zr-Ca alloy;
Step 2, with CaH 2PO 4With NaOH according to 1: 1~4 mol ratio configuration differential arc oxidation electrolytic solution, CaH in the differential arc oxidation electrolytic solution 2PO 4Concentration 0.05~0.08mol/L, the solvent of differential arc oxidation electrolytic solution is a distilled water;
Step 3, the base material that step 1 is handled are put into the differential arc oxidation electrolytic solution of step 2 preparation, are that 10%-30%, interelectrode distance are that 40mm, voltage are to carry out differential arc oxidation under 200V~450V and 20~40 ℃ of conditions of electrolyte temperature to handle 2min~10min in dutycycle then;
Step 4, will put in the electrolytic solution through the base material that step 3 is handled, be 10~40mA/cm at pulse current density then 2, dutycycle is 50%~80%, interelectrode distance is that 10mm and electrolyte temperature are to carry out electrochemical deposition 10~60min under 40 ℃ of conditions; Promptly obtain polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coating; The said electrolytic solution of step 4 is by Ca (NO 3) 2, NH 4H 2PO 4, pyrroles and distilled water forms Ca (NO in the electrolytic solution 3) 2Concentration be 0.042~0.21mol/L, NH 4H 2PO 4Concentration be 0.025~0.125mol/L, pyrroles's concentration is 0.01~0.05mol/L.
3. the preparation method of polypyrrole calcium phosphate according to claim 2/Natural manganese dioxide bio-ceramic coating; It is characterized in that step 3 is under ultrasonic wave is auxiliary, to carry out differential arc oxidation to handle; Hyperacoustic operating frequency is 40KHz, and hyperacoustic power is 400~800W.
4. according to the preparation method of claim 2 or 3 described polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coatings, it is characterized in that it is 250V~400V that the step 3 differential arc oxidation is handled applied voltage.
5. according to the preparation method of claim 2 or 3 described polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coatings, it is characterized in that step 3 differential arc oxidation processing 3min~7min.
6. according to the preparation method of claim 2 or 3 described polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coatings, it is characterized in that step 3 differential arc oxidation processing 5min.
7. according to the preparation method of claim 2 or 3 described polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coatings, the concentration that it is characterized in that the said polypyrrole of step 4 is 0.01~0.03mol/L.
8. according to the preparation method of claim 2 or 3 described polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coatings, the concentration that it is characterized in that the said polypyrrole of step 4 is 0.02mol/L.
9. according to the preparation method of claim 2 or 3 described polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coatings, it is characterized in that the step 4 electrochemical deposition time is 20~40min.
10. according to the preparation method of claim 2 or 3 described polypyrrole calcium phosphate/Natural manganese dioxide bio-ceramic coatings, it is characterized in that the step 4 electrochemical deposition time is 30min.
CN201110288767A 2011-09-26 2011-09-26 Polypyrrole calcium phosphate/magnesium oxide bioceramic coating and preparation method thereof Pending CN102304746A (en)

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CN106702459A (en) * 2016-11-28 2017-05-24 燕山大学 Method for preparing anti-abrasion porous zirconium oxide ceramic layer at surface of zirconium alloy
CN109023363A (en) * 2018-07-16 2018-12-18 北京科技大学 A kind of ferroaluminium adhesive layer/compound hydrogen resistance coating of zirconium oxide layer and preparation method thereof
CN109432514A (en) * 2018-12-12 2019-03-08 西南大学 Have degradable magnesium alloy bone nail and preparation method that squamous imitates bone nano-structured coating
CN109680319A (en) * 2019-03-07 2019-04-26 东北大学 The preparation method of the corrosion-resistant coatings of Mg alloy surface based on calcium salt
CN109680319B (en) * 2019-03-07 2020-04-07 东北大学 Preparation method of calcium salt-based magnesium alloy surface corrosion-resistant self-repairing coating
WO2020177223A1 (en) * 2019-03-07 2020-09-10 东北大学 Preparation method for calcium salt-based magnesium alloy surface corrosion-resistant self-repairing coating
CN110241453A (en) * 2019-04-25 2019-09-17 西南大学 A kind of release fluoride and the degradable kirsite bone nail of cerium and preparation method thereof

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