CN109082692A - In the method for surface of carbon/carbon composite deposition hydroxyapatite coating layer - Google Patents
In the method for surface of carbon/carbon composite deposition hydroxyapatite coating layer Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/08—Carbon ; Graphite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/32—Phosphorus-containing materials, e.g. apatite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
The present invention relates to carbon/carbon compound material technical fields, specifically provide a kind of method in surface of carbon/carbon composite deposition hydroxyapatite coating layer.The method at least includes the following steps: step S01. is using carbon/carbon compound material as cathode, to contain the mixed solution of calcium hydroxide, organic acid, phosphoric acid as electrolyte, hydrothermal electrodeposition reaction is carried out, the surface of carbon/carbon composite is made to be deposited with calcium phosphate dibasic anhydrous coating；The obtained carbon/carbon compound material of step S01 is placed in aqueous slkali and carries out hydro-thermal process by step S02., and calcium phosphate dibasic anhydrous coating original position topology is made to be changed into hydroxyapatite coating layer.The bond strength of HA coating prepared by the present invention and C/C composite material reaches 20N or more, and shear strength, up to 75.8MPa or more, the preparation method simple process is high-efficient, and properties of product are excellent, can satisfy clinical application, are worth of widely use.
Description
Technical field
The invention belongs to carbon/carbon compound material technical fields, more particularly to one kind to deposit hydroxyl in surface of carbon/carbon composite
The method of base apatite coating.
Background technique
The elasticity modulus and bending strength that carbon/carbon (C/C) composite material has and skeleton matches, can be effectively
" stress shielding " effect is avoided, thus is considered as a kind of huge human body hard tissue alternate material of application potential, but due to
Biologically inert is presented in the surface of C/C composite material, not can induce the regeneration of bone tissue.
It is effectively arranging for the biologically inert of improvement C/C composite material in C/C composite material surface coating bioactivity coatings
It applies.Currently used bioactive coating material has dicalcium phosphate dihydrate, fluor-apatite and hydroxyapatite (HA) etc..Wherein,
Hydroxyapatite (HA or HAP) material has good bioactivity and excellent due to identical as human skeleton and dental component
Different chemical stability, and in vitro environment can induction of bone growth, thus become C/C composite material surface bioactivity change
The hot spot coating material of Journal of Sex Research.HA coating can assign its table on the basis of keeping C/C composite material excellent mechanical performance
Face bioactivity, but the bond strength of such bioactivity coatings and C/C matrices of composite material is generally low at present.
Compared to conventional method, there is electrochemical deposition method operation to be easy, simple process, mild condition, coating uniform with
And the advantages that low in cost, but the consistency of the HA coating of electrochemical deposition method preparation is not high, cohesive strength is very low, Bu Nengman
Sufficient et al. Ke requirement, still has gap with the standard of clinical application[1]。
Hydrothermal electrodeposition method combines the advantages of both electrodeposition process and hydro-thermal method, and electrodeposition process is faced in the super of hydro-thermal
It is carried out under boundary's state, the transmission of substance and osmosis greatly enhance under supercriticality, can improve HA painting to a certain extent
The bond strength of layer and C/C matrix.But during Hydrothermal Electrochemical method prepares HA coating, it can be produced in C/C matrix surface
Raw a large amount of hydrogen, it is loose so as to cause coating structure, the HA coating that pattern is fine and close, cohesive strength is high can not be generated[2].Existing water
The bond strength of HA coating and C/C composite material that thermoelectricity sedimentation obtains is unable to satisfy human body hard tissue to life within 10N
The requirement of object anchoring strength of coating.
[1].A.Stoch,A.Brozeka,S.Blazewicz,et al.FTIR Study of
Electrochemically Deposited Hydroxyapatite Coatings on Carbon Materials[J]
.Journal of Molecular Structure,2003 651-653:389–396.
[2] Zhu Guang swallow, influence [J] Wuhan of the such as Huang Jianfeng, the Cao Liyun temperature to C/C composite material surface HAp coating
Polytechnics's journal, 2007,29 (12): 52-54.
Summary of the invention
The purpose of the present invention is to provide it is a kind of surface of carbon/carbon composite deposition hydroxyapatite coating layer method,
Aim to solve the problem that compactness existing for existing surface of carbon/carbon composite hydroxyapatite coating layer is not high, bond strength is low and interior
The problems such as poly- intensity difference.
The present invention is implemented as follows: a kind of method in surface of carbon/carbon composite deposition hydroxyapatite coating layer, institute
The method of stating at least includes the following steps:
Step S01. is made using carbon/carbon compound material as cathode with the mixed solution containing calcium hydroxide, organic acid, phosphoric acid
For electrolyte, hydrothermal electrodeposition reaction is carried out, the surface of carbon/carbon composite is made to be deposited with calcium phosphate dibasic anhydrous coating；
The obtained carbon/carbon compound material of step S01 is placed in aqueous slkali and carries out hydro-thermal process by step S02., makes the nothing
Water calcium monohydrogen phosphate coating original position topology is changed into hydroxyapatite coating layer.
And a kind of carbon/carbon compound material comprising hydroxyapatite coating layer, the hydroxyl of the surface of carbon/carbon composite
Base apatite coating is prepared using method as described above.
The present invention deposits having the beneficial effect that for the method for hydroxyapatite coating layer in surface of carbon/carbon composite:
Compared with the existing technology, the side provided by the invention in surface of carbon/carbon composite deposition hydroxyapatite coating layer
Method deposits calcium phosphate dibasic anhydrous coating, then by anhydrous phosphoric acid by hydro-thermal electrochemical deposition method on cathode C/C matrix
Hydrogen calcium coating hydrothermal treatment be changed into the higher HA coating of C/C substrate combinating strength, prepared HA coating and C/C are compound
The bond strength of material reaches 10N or more, and shear strength is up to 53.6MPa or more, the preparation method simple process, efficiency
Height, and properties of product are excellent, can satisfy clinical application, are worth of widely use.
Carbon/carbon compound material provided by the invention comprising hydroxyapatite coating layer, carries out with the aforedescribed process due to adopting
Preparation, the hydroxyapatite coating layer of acquisition and the bond strength of carbon/carbon compound material are not less than 10N, and shear strength reaches
53.6MPa or more, compactness is good, is very suitable for as human body hard tissue alternate material.
Detailed description of the invention
The technical solution in example is applied in order to illustrate more clearly of the present invention, it below will be to needed in the embodiment attached
Figure is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this field
For those of ordinary skill, without creative efforts, it is also possible to obtain other drawings based on these drawings.
Fig. 1 is that the method in surface of carbon/carbon composite deposition hydroxyapatite coating layer that the embodiment of the present invention 1 provides obtains
The SEM figure of the coating obtained；
Fig. 2 is that the method in surface of carbon/carbon composite deposition hydroxyapatite coating layer that the embodiment of the present invention 1 provides obtains
The critical load curve of the hydroxyapatite coating layer obtained；
Fig. 3 is that the method in surface of carbon/carbon composite deposition hydroxyapatite coating layer that the embodiment of the present invention 2 provides obtains
The SEM figure of the coating obtained；
Fig. 4 is that the method in surface of carbon/carbon composite deposition hydroxyapatite coating layer that the embodiment of the present invention 2 provides obtains
The critical load curve of the hydroxyapatite coating layer obtained；
Fig. 5 is that the method in surface of carbon/carbon composite deposition hydroxyapatite coating layer that the embodiment of the present invention 3 provides obtains
The SEM figure of the coating obtained；
Fig. 6 is that the method in surface of carbon/carbon composite deposition hydroxyapatite coating layer that the embodiment of the present invention 3 provides obtains
The critical load curve of the hydroxyapatite coating layer obtained.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
The present invention provides a kind of method in surface of carbon/carbon composite deposition hydroxyapatite coating layer, and the method is extremely
Less the following steps are included:
Step S01. is made using carbon/carbon compound material as cathode with the mixed solution containing calcium hydroxide, organic acid, phosphoric acid
For electrolyte, hydrothermal electrodeposition reaction is carried out, the surface of carbon/carbon composite is made to be deposited with calcium phosphate dibasic anhydrous coating；
The obtained carbon/carbon compound material of step S01 is placed in aqueous slkali and carries out hydro-thermal process by step S02., makes the nothing
Water calcium monohydrogen phosphate coating original position topology is changed into hydroxyapatite coating layer.
Detailed explanation is done to method of the invention below.
The carbon/carbon compound material of step S01 can pick up from ready-made carbon/carbon compound material, ready-made carbon/carbon composite wood
Material, should be by surface treatment, it is ensured that clean surface.Specifically, it can put it into ammonium persulfate solution, in 160 DEG C
Left and right is heat-treated, and the processing time is 12h or more, and the carbon/carbon compound material through Overheating Treatment, surface impurity can be effective
It is removed, reduces the possibility for causing coating compactness bad because surface is there are impurity in hydroxyapatite coating layer coating procedure
Property.
It, can be using graphite as anode, certainly when carrying out hydrothermal electrodeposition processing, it is not limited to graphite, it can also be with
It is other anode electrodes.
In the present invention, electrolyte can be prepared by following mode:
Organic acid is dissolved in distilled water, the organic acid soln that concentration is 0.65~1.10mol/L, the organic acid are obtained
All calcium hydroxide can not be dissolved if solution concentration is too low, and pH value is too low if excessive concentration, is unfavorable for the progress of reaction.
Anhydrous calcium hydroxide powder is added in above-mentioned organic acid soln, is mixed to clear, acquisition includes organic
First mixed solution of acid, calcium hydroxide.
Phosphoric acid is dissolved in distilled water, certain density phosphoric acid solution is obtained.
Above-mentioned phosphoric acid solution is added in the first mixed solution, stirring, adjusts pH value to 2.0~4.0, obtain electrolyte.
Above-mentioned first calcium hydroxide is dissolved in organic acid soln obtains the first mixed solution phosphoric acid solution is dissolved in described first again
The sequence of mixed solution cannot change, and otherwise can not dissolve the calcium hydroxide of sufficient amount, can not be configured to react required electrolysis
Liquid not can guarantee the proportion of phosphorus and calcium.
Preferably, by atomic ratio, calcium constituent and P elements feed ratio are 1~1.67 in the electrolyte.Under the ratio
More easily generate calcium phosphate dibasic anhydrous.
Preferably, in the electrolyte, the concentration of phosphoric acid is 0.25~0.4mol/L.
Preferably, the concentration of the organic acid is 0.65~1.10mol/L.
Preferably, the mass ratio of the calcium hydroxide and the organic acid soln be 1:50~60, calcium hydroxide with it is organic
The ingredient proportion of acid solution has larger impact to pH, if organic acid soln amount is excessive, pH is overregulated, and is unable to satisfy 2.0
In the range of~4.0.
If aforementioned phosphate concentration, organic acid concentration, calcium hydroxide concentration is excessively high, precipitating can be spontaneously formed, is unfavorable for
The generation of calcium phosphate dibasic anhydrous, concentration is too low, is equally unfavorable for the generation of calcium phosphate dibasic anhydrous.
In electrolytic process, the pH value for controlling the electrolyte is 2.0~4.0, and main purpose is to generate stable nothing
Water calcium monohydrogen phosphate object phase.The pH value of electrolyte can be adjusted by ammonium hydroxide, citric acid, glacial acetic acid, phosphoric acid etc..It is more excellent
Selection of land, the pH of electrolyte is 3 ± 0.5, and within the scope of the pH, the calcium phosphate dibasic anhydrous object phase stability of formation is high, is more advantageous to
Obtain stable hydroxyapatite coating layer.
Preferably, the organic acid is lactic acid.
Preferably, the temperature of the hydrothermal electrodeposition reaction is 70~130 DEG C, and the reaction time is 1~12h, kinetic current
For 1~20mA.Hydrothermal temperature is excessively high to will lead to the unstable direct generation precipitating of electrolyte, and too low will lead to can not generate needs
Calcium phosphate dibasic anhydrous object phase.Similarly, whether the size of electric current is to that can stably generate uniform calcium phosphate dibasic anhydrous and have an impact, therefore
It needs both reaction temperature and electric current is mutually coordinated.
In step S02, the temperature of hydro-thermal process is 100~170 DEG C, and the time of hydro-thermal process is at least for 24 hours.Preferred processing
Temperature be 110~150 DEG C, it is too high or too low for temperature will lead to bond strength decline, as temperature be 155 DEG C when, it is aforementioned its
Under the conditions of him, the hydroxyapatite coating layer of acquisition is 19.21N, and with the rising of hydrothermal temperature, the binding force of coating can be reduced
To 10N or so.
Preferably, the concentration of the aqueous slkali is 0.01~0.1M.Under the concentration, the original of aqueous slkali and calcium monohydrogen phosphate coating
The topological rate uniform in position, is conducive to the compactness for further increasing hydroxyapatite coating layer.
It is further preferred that the aqueous slkali is sodium metasilicate, sodium hydroxide, ammonium hydroxide etc..These types of aqueous slkali topology in situ
It is good to react the hydroxyapatite coating layer compactness generated.
The hydroxyapatite coating layer obtained using the above method, is not less than with the bond strength of the carbon/carbon compound material
10N, shear strength >=53.6Mpa.
Based on the above method, the present invention also provides a kind of carbon/carbon compound materials comprising hydroxyapatite coating layer, this includes
Hydroxyapatite coating layer in the carbon/carbon compound material of hydroxyapatite coating layer is adopted to be prepared with the aforedescribed process.
Under aforementioned preparation condition, the hydroxyapatite coating layer of acquisition and the bond strength of carbon/carbon compound material are not less than
10N, shear strength >=53.6MPa, can satisfy clinical use, be suitble to promote.
It is further preferable that, when pH is 3 ± 0.5, later period hydro-thermal process temperature is 110~150 DEG C under above-mentioned preparation condition
When, the bond strength of the hydroxyapatite coating layer of acquisition and carbon/carbon compound material is not less than 20N, shear strength >=75.8MPa,
Clinically has the effect of superior application.
Technical solution in order to better illustrate the present invention, is illustrated combined with specific embodiments below.
Embodiment 1
A method of hydroxyapatite coating layer is deposited in surface of carbon/carbon composite, comprising the following steps:
(1) surface of carbon/carbon composite is handled: carbon/carbon compound material is put into the ammonium persulfate solution that concentration is 1M,
The hydro-thermal process 12h at 160 DEG C；
(2) preparation of electrolyte: taking 32mL lactic acid, and 600mL distilled water is added and stirs evenly, and compound concentration is 0.68M's
Lactic acid solution；
It is 1:57 according to the mass ratio of calcium hydroxide and lactic acid solution, weighs anhydrous calcium hydroxide powder, it is slowly added
To in above-mentioned lactic acid solution, continuously stirs and uniformly obtain the first mixed solution to clear；
According to 1.67 ± 0.05 calcium phosphorus atoms ratio, phosphoric acid is measured, distilled water is dissolved in, is configured to the phosphoric acid that concentration is 0.3M
Solution；
Above-mentioned prepared phosphoric acid solution is slowly added dropwise into first mixed solution, appropriate glacial acetic acid tune is added
PH value is saved to 2.9, obtains electrolyte；
(3) hydrothermal electrodeposition reacts: above-mentioned steps (2) prepared electrolyte being placed in water heating kettle, is sun with graphite
Pole, step (1) treated carbon/carbon compound material are cathode, are powered after electrolyte heating is reached 90 DEG C, electric current 5mA, into
The reaction of row hydrothermal electrodeposition, deposition 80min obtain calcium phosphate dibasic anhydrous coating；
(4) after end of reaction is cooling, above-mentioned steps (3) resulting sample is cleaned by deionized water, then at 80 DEG C
It is dried in baking oven；
(5) 1.1086g sodium metasilicate is weighed, is added in distilled water and dissolves, obtains the sodium silicate solution that concentration is 0.013M；
(6) sample for being dried above-mentioned steps (4) is put into above-mentioned steps (5) prepared sodium silicate solution,
Hydro-thermal process for 24 hours, obtains final product hydroxyapatite (HA) coating at 140 DEG C, is applied using gained of the deionized water to acquisition
Layer is rinsed, and 80 DEG C of drying can prepare high interfacial bonding strength HA biological active coating in surface of carbon/carbon composite
Layer.
The scanning of Electronic Speculum (SEM) is scanned to the coating of acquisition, as a result as shown in Figure 1.From fig. 1, it can be seen that under low power lens,
Coating is mainly made of the irregular bulk crystals perpendicular to matrix, is tightly combined between crystal, without larger gap；From high power lens
In enlarged photograph can with it is further seen that, HA coating is made of rhabdolith, mutual hinge.
Meanwhile the coating obtained to embodiment 1 is combined the test of intensity and shear strength, the method for test is big carries
The test of lotus scratch, maximum load is 60N when test, and force speed is 10N/min, and scratch length is 5mm.Drill bit scratches coating
Moment obtains critical load, then calculates shear strength.Test results are shown in figure 2, finds the hydroxyl of preparation after tested
The bond strength of base apatite coating and carbon/carbon composite material base body is 22.94N, shear strength 81.2Mpa.
Embodiment 2
A method of hydroxyapatite coating layer is deposited in surface of carbon/carbon composite, comprising the following steps:
(1) surface of carbon/carbon composite is handled: carbon/carbon compound material is placed in the ammonium persulfate solution that concentration is 1M,
The hydro-thermal process 12h at 160 DEG C；
(2) preparation of electrolyte: taking 32mL lactic acid, and 600mL distilled water is added and stirs evenly, and compound concentration is 0.68M's
Lactic acid solution；
It is 1:57 according to the mass ratio of calcium hydroxide and lactic acid solution, weighs anhydrous calcium hydroxide powder, it is slowly added
To in above-mentioned lactic acid solution, continuously stirs uniformly to clear, obtain the first mixed solution；
According to 1.67 ± 0.05 calcium phosphorus atoms ratio, phosphoric acid is measured, distilled water is dissolved in, is configured to the phosphoric acid that concentration is 0.3M
Solution；
Above-mentioned prepared phosphoric acid solution is slowly added dropwise into first mixed solution, appropriate glacial acetic acid tune is added
PH value is saved to 2.9, obtains electrolyte；
(3) hydrothermal electrodeposition reacts: above-mentioned steps (2) prepared electrolyte being placed in water heating kettle, is sun with graphite
Pole, step (1) treated carbon/carbon compound material are cathode, are powered after electrolyte heating is reached 80 DEG C, electric current 5mA, into
The reaction of row hydrothermal electrodeposition, deposition 110min obtain calcium phosphate dibasic anhydrous coating；
(4) after end of reaction is cooling, above-mentioned steps (3) resulting sample is cleaned by deionized water, then at 90 DEG C
It is dried in baking oven；
(5) 1.1086g sodium metasilicate is weighed, is added in distilled water and dissolves, obtains the sodium silicate solution that concentration is 0.013M；
(6) sample for being dried above-mentioned steps (4) is put into above-mentioned steps (5) prepared sodium silicate solution,
Hydro-thermal process for 24 hours, obtains final product hydroxyapatite (HA) coating at 125 DEG C, is applied using gained of the deionized water to acquisition
Layer is rinsed, and 80 DEG C of drying can prepare high interfacial bonding strength HA biological active coating in surface of carbon/carbon composite
Layer.
The scanning of Electronic Speculum (SEM) is scanned to the coating of acquisition, as a result as shown in Figure 3.As can be seen from Figure 3, coating is main
It is made of similar round crystal, it is mutually chimeric between crystal, it almost grows together.From the point of view of the photo that high power lens amplifies.HA coating
It is made of the little particle that sheet links together.Generally speaking, the consistency and uniformity of coating are bright compared with having in document report
Aobvious improvement.
Meanwhile the coating obtained to embodiment 2 is combined the test of intensity and shear strength, the method for test is big carries
The test of lotus scratch, maximum load is 60N when test, and force speed is 10N/min, and scratch length is 5mm.Drill bit scratches coating
Moment obtains critical load, then calculates shear strength.Test results are shown in figure 4, finds the hydroxyl of preparation after tested
The bond strength of base apatite coating and carbon/carbon composite material base body is 31.68N, shear strength 95.42Mpa.
Embodiment 3
A method of hydroxyapatite coating layer is deposited in surface of carbon/carbon composite, comprising the following steps:
(1) surface of carbon/carbon composite is handled: carbon/carbon compound material is placed in the ammonium persulfate solution that concentration is 1M,
The hydro-thermal process 12h at 160 DEG C；
(2) preparation of electrolyte: taking 32mL lactic acid, and 600mL distilled water is added and stirs evenly, and compound concentration is 0.68M's
Lactic acid solution；
It is 1:57 according to the mass ratio of calcium hydroxide and lactic acid solution, weighs anhydrous calcium hydroxide powder, it is slowly added
To in above-mentioned lactic acid solution, continuously stirs uniformly to clear, obtain the first mixed solution；
According to 1.67 ± 0.05 calcium phosphorus atoms ratio, phosphoric acid is measured, distilled water is dissolved in, is configured to the phosphoric acid that concentration is 0.3M
Solution；
Above-mentioned prepared phosphoric acid solution is slowly added dropwise into first mixed solution, appropriate glacial acetic acid tune is added
PH value is saved to 2.9, obtains electrolyte；
(3) hydrothermal electrodeposition reacts: above-mentioned steps (2) prepared electrolyte being placed in water heating kettle, is sun with graphite
Pole, step (1) treated carbon/carbon compound material are cathode, are powered after electrolyte heating is reached 90 DEG C, electric current 5mA, into
The reaction of row hydrothermal electrodeposition, deposition 80min obtain calcium phosphate dibasic anhydrous coating；
(4) after end of reaction is cooling, above-mentioned steps (3) resulting sample is cleaned by deionized water, then at 90 DEG C
It is dried in baking oven；
(5) 1.1086g sodium metasilicate is weighed, is added in distilled water and dissolves, obtains the sodium silicate solution that concentration is 0.013M；
(6) sample for being dried above-mentioned steps (4) is put into above-mentioned steps (5) prepared sodium silicate solution,
Hydro-thermal process for 24 hours, obtains final product hydroxyapatite (HA) coating at 155 DEG C, is applied using gained of the deionized water to acquisition
Layer is rinsed, and 80 DEG C of drying can prepare high interfacial bonding strength HA biological active coating in surface of carbon/carbon composite
Layer.
The scanning of Electronic Speculum (SEM) is scanned to the coating of acquisition, as a result as shown in Figure 5.As can be seen from Figure 5, under low power lens,
Coating is mainly made of the irregular bulk crystals perpendicular to matrix, is tightly combined between crystal, without larger gap；From high power lens
In enlarged photograph can with it is further seen that, HA coating is made of long rhabdolith, more has microlite mutually to combine closely.
Meanwhile the coating obtained to embodiment 3 is combined the test of intensity and shear strength, the method for test is big carries
The test of lotus scratch, maximum load is 60N when test, and force speed is 10N/min, and scratch length is 5mm.Drill bit scratches coating
Moment obtains critical load, then calculates shear strength.Test results are shown in figure 6, finds the hydroxyl of preparation after tested
The bond strength of base apatite coating and carbon/carbon composite material base body is 19.21N, shear strength 74.31Mpa.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of method in surface of carbon/carbon composite deposition hydroxyapatite coating layer, which is characterized in that the method is at least
The following steps are included:
Step S01. using carbon/carbon compound material as cathode, using contain calcium hydroxide, organic acid, phosphoric acid mixed solution as electricity
Liquid is solved, hydrothermal electrodeposition reaction is carried out, the surface of carbon/carbon composite is made to be deposited with calcium phosphate dibasic anhydrous coating；
The obtained carbon/carbon compound material of step S01 is placed in aqueous slkali and carries out hydro-thermal process by step S02., makes the anhydrous phosphorus
Sour hydrogen calcium coating original position topology is changed into hydroxyapatite coating layer.
2. as described in claim 1 in the method for surface of carbon/carbon composite deposition hydroxyapatite coating layer, feature exists
In by atomic ratio, calcium constituent and P elements feed ratio are 1~1.67 in the electrolyte.
3. as claimed in claim 1 or 2 in the method for surface of carbon/carbon composite deposition hydroxyapatite coating layer, feature
It is, the concentration of phosphoric acid is 0.25~0.4mol/L in the electrolyte；
And/or the concentration of the organic acid is 0.65~1.10mol/L；
And/or the mass ratio of the calcium hydroxide and the organic acid soln is 1:50~60.
4. as claimed in claim 1 or 2 in the method for surface of carbon/carbon composite deposition hydroxyapatite coating layer, feature
It is, the pH value of the electrolyte is 2.0~4.0.
5. as described in claim 1 in the method for surface of carbon/carbon composite deposition hydroxyapatite coating layer, feature exists
In in step S02, the temperature of hydro-thermal process is 100~170 DEG C, and the time of hydro-thermal process is at least for 24 hours.
6. as described in claim 1 in the method for surface of carbon/carbon composite deposition hydroxyapatite coating layer, feature exists
In the concentration of the aqueous slkali is 0.01~0.1M.
7. as described in claim 1 in the method for surface of carbon/carbon composite deposition hydroxyapatite coating layer, feature exists
In the organic acid is lactic acid.
8. as described in claim 1 in the method for surface of carbon/carbon composite deposition hydroxyapatite coating layer, feature exists
In the temperature of the hydrothermal electrodeposition reaction is 70~130 DEG C, and the reaction time is 1~12h, and kinetic current is 1~20mA.
9. a kind of carbon/carbon compound material comprising hydroxyapatite coating layer, which is characterized in that the surface of carbon/carbon composite
Hydroxyapatite coating layer using method as described in any one of claims 1 to 8 prepare.
10. as claimed in claim 9 including the carbon/carbon compound material of hydroxyapatite coating layer, which is characterized in that the hydroxyl
The bond strength of apatite coating and the carbon/carbon compound material is not less than 20N, shear strength >=75.8Mpa.
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