CN108379653B - The preparation method of the hydroxyapatite coating layer of surface of carbon/carbon composite - Google Patents
The preparation method of the hydroxyapatite coating layer of surface of carbon/carbon composite Download PDFInfo
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- CN108379653B CN108379653B CN201810498693.XA CN201810498693A CN108379653B CN 108379653 B CN108379653 B CN 108379653B CN 201810498693 A CN201810498693 A CN 201810498693A CN 108379653 B CN108379653 B CN 108379653B
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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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
-
- 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
-
- 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 a kind of preparation methods of the hydroxyapatite coating layer of surface of carbon/carbon composite, deposition liquid is put into generation ultrasonic atomizatio gas in ultrasonic atomizing device, ultrasonic atomizatio gas flows through the surface of carbon/carbon compound material by carrying gas carrying, it is heated outside carbon/carbon compound material by electromagnetic induction method, the surface of carbon/carbon compound material is set to deposit calcium monohydrogen phosphate coating, the carbon/carbon compound material of surface deposition calcium monohydrogen phosphate coating is subjected to hydro-thermal process, obtains hydroxyapatite coating layer.The beneficial effects of the present invention are: hydroxyapatite coating layer preparation method is simple to operation, coating binding force is strong, coating uniform, and hydroxyapatite coating layer has the function of to induce the function of bone tissue regeneration, the growth and the remodeling that regulate and control sclerotin.
Description
Technical field
The present invention relates to a kind of preparation methods of the hydroxyapatite coating layer of surface of carbon/carbon composite.
Background technique
Carbon/carbon compound material overcomes the brittleness of single carbon material, is the NEW TYPE OF COMPOSITE material with carbon fiber reinforced carbon matrix body
Material is suitable with high intensity, high tenacity, corrosion-resistant, high temperature resistant, elasticity modulus and people's bone, compatible with good biomethanics
The advantages that property.
Surface free processing carbon/carbon compound material be it is hydrophobic, belong to bio-inert material, only with bone tissue surface
It is only mechanical bond, chemical bonds cannot be generated with human body, not have and conduct or induce bone tissue regeneration function, implantation is fixed
Period is longer, this is also one of the key factor for influencing carbon/carbon compound material as bone replacement and repair materials.
Therefore the surface of carbon/carbon compound material need to be handled, people pass through the study found that in carbon/carbon compound material
Surface, which prepares bioactive substance-hydroxyapatite (HAP, hydroxyapatite) coating, can solve problem above.Hydroxyl
The molecular formula of apatite is Ca10(PO4)6(OH)2, be a kind of bioactive materials, be vertebrate bone and tooth host inorganic at
Point, with the compatibility of tissue it is good, have no toxic side effect, interfacial activity is better than all kinds of medical stainless steels, titanium alloy, silicon rubber, Chang Ying
For the reparation of biological hard tissue, density 3.16g/cm3, but the strength and toughness of highdensity bulk HAP is insufficient, therefore hydroxyl
The application of base apatite or based on being applied with surface covering.
Chinese patent literature CN102260863A discloses a kind of system of silicon-containing hydroxyapatite coating of carbon/carbon composite material
Preparation Method, by treated carbon/carbon compound material is placed in containing calcium nitrate, ammonium di-hydrogen phosphate flowing aqueous solution in, pass through superelevation
Frequency electromagnetic heating method makes its surface deposit calcium monohydrogen phosphate coating.
Paper (XY Ni, C.C Chu, X.B Xiong, A.J Li, R.C Bai.Preparation of
Hydroxyapatite Coating Using Chemical Liquid Vaporization Deposition on
Carbon/Carbon Composites.RSC Advances, 2014,4 (77), 41129-41134) disclose a kind of liquid phase vapour
Change the method for preparing calcium phosphor coating on the surface C/C.This method is become using the heat of hyperfrequency induction power supply, and to concentrate pyrogenicity to deposit former for skin
Reason, deposits the calcium phosphor coating of high-bond.However, being more than the ion of solution under certain frequency since solution is in flowing
Also it will appear skin effect, cause to deposit binding force decline.
Summary of the invention
The technical problems to be solved by the present invention are: providing a kind of hydroxyapatite coating layer of surface of carbon/carbon composite
Preparation method, improve coating and surface of carbon/carbon composite binding force.
The technical solution adopted by the present invention to solve the technical problems is: a kind of hydroxyl phosphorus of surface of carbon/carbon composite
Deposition liquid is put into generation ultrasonic atomizatio gas in ultrasonic atomizing device by the preparation method of lime stone coating, and ultrasonic atomizatio gas is logical
It crosses and carries the surface that carbon/carbon compound material is flowed through in gas carrying, added outside carbon/carbon compound material by electromagnetic induction method
Heat makes the surface of carbon/carbon compound material deposit calcium monohydrogen phosphate coating, and carbon/carbon of surface deposition calcium monohydrogen phosphate coating is compound
Material carries out hydro-thermal process, obtains hydroxyapatite coating layer.
It further limits, deposition liquid is the calcium nitrate of solvent, the mixed solution of diethyl phosphate to be done with ethyl alcohol, or deposit
Liquid is to do the calcium nitrate of solvent, the mixed solution of triethyl phosphate with ethyl alcohol.
It further limits, carrying gas is nitrogen or argon gas.
It further limits, carbon/carbon compound material carries out hydro-thermal pre-treatment step, hydro-thermal pre-treatment step before being deposited
Are as follows: carbon/carbon compound material is placed in hydrogen peroxide and carries out hydro-thermal process, is cleaned and dried after cooling and completes hydro-thermal pre-treatment.Due to
Surface of carbon/carbon composite after hydro-thermal pre-treatment can produce a large amount of carboxyl, hydroxyl isoreactivity group, these groups
It will form effective chemical bonding with ultrasonic atomizatio gas, be conducive to improve calcium monohydrogen phosphate coating and surface of carbon/carbon composite
Binding force.
It further limits, depositing calcium nitrate in liquid is 0.01mol/L~0.6mol/L, diethyl phosphate or triethyl phosphate
For 0.01mol/L~0.5mol/L.
It further limits, the frequency of oscillation of ultrasonic atomizing device is 1.7MHz~2.4MHz, and the flow velocity of gas is 30ml/
Min~500ml/min.
It further limits, is heated in electromagnetic induction method using high-frequency electromagnetic induction device, electromagnetic induction frequency of oscillation is
300KHz~1MHz, oscillating current are 200A~700A, and sedimentation time is 10min~8h.
It further limiting, the carbon/carbon compound material of surface deposition calcium monohydrogen phosphate coating, which is placed in ammonium hydroxide, carries out hydro-thermal process,
The concentration of ammonium hydroxide is 0.1%~2%, and 85 DEG C~145 DEG C of hydro-thermal process temperature, the processing time is 4h~for 24 hours.
It further limits, carbon/carbon compound material is placed in deposited tube and is deposited, and carries the ultrasound that gas carries deposition liquid
Atomization gas is sent into deposited tube by conveyance conduit from the side of deposited tube, is exported from the other side of deposited tube.
It further limits, the output end side setting flow control valve and absorption plant of deposited tube.
The beneficial effects of the present invention are: hydroxyapatite coating layer preparation method is simple to operation, coating binding force is strong, coating
Uniformly, hydroxyapatite coating layer has the function of to induce the function of bone tissue regeneration, the growth and the remodeling that regulate and control sclerotin.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples；
Fig. 1 is the precipitation equipment of surface of carbon/carbon composite depositing coating.
In figure, 1. induction power supplies, 2. ultrasonic atomizing devices, 3. induction coils, 4. conveyance conduits, 5. carbon/carbon compound materials,
6. deposited tube, 7. carry gas generator, 8. output channels, 9. absorption plants, 10. flow control valves.
Specific embodiment
A kind of preparation method of the hydroxyapatite coating layer of surface of carbon/carbon composite, comprising the following steps:
A. hydro-thermal pre-treatment step: hydrogen peroxide is added in water heating kettle, carbon/carbon compound material 5 is placed in water in water heating kettle
Heat treatment, natural cooling are washed and dried with deionized water.
B. ultrasonic atomizatio deposits: doing solvent configuration with ethyl alcohol and includes the mixed of calcium nitrate, diethyl phosphate or triethyl phosphate
Solution is closed as deposition liquid, deposition liquid is put into ultrasonic atomizing device 2, is generated ultrasonic atomizatio gas, is carried gas nitrogen or argon
Gas carry ultrasonic atomizatio gas by conveyance conduit 4 from the side of the glass tube as deposited tube 6 be sent into glass tube in, gas from
The other side of glass tube exports.
Carbon/carbon compound material 5 after hydro-thermal pre-treatment step is placed in glass tube, heavy on its surface by electromagnetic induction method
Product goes out calcium monohydrogen phosphate coating, is cleaned with deionized water.
Depositing calcium nitrate in liquid is 0.01mol/L~0.6mol/L, and diethyl phosphate or triethyl phosphate are 0.01mol/L
~0.5mol/L, the concentration of ethyl alcohol are 30%~95%.
The frequency of oscillation of ultrasonic atomizing device 2 is 1.7MHz~2.4MHz, carries 0.01~0.2mol/L of concentration of gas,
The flow velocity of gas is 30ml/min~500ml/min.
Heated in electromagnetic induction method using high-frequency electromagnetic induction device, electromagnetic induction frequency of oscillation be 300KHz~
1MHz, oscillating current are 200A~700A, and sedimentation time is 10min~8h.
C. the carbon/carbon compound material 5 of surface deposition calcium monohydrogen phosphate coating hydro-thermal post-processing step: is placed in the water containing ammonium hydroxide
In hot kettle, hydro-thermal process is carried out, natural cooling obtains hydroxyapatite coating layer, and ammonium hydroxide can also be substituted with other alkaline solutions,
Such as potassium hydroxide.
The concentration of ammonium hydroxide is 0.1%~2%, and 85 DEG C~145 DEG C of hydro-thermal process temperature, the processing time is 4h~for 24 hours.
Molecular link in ultrasonic atomizing device 2 between the hydrone of the deposition liquid of liquid is broken up and to generate nature elegant
Water mist is lived since 5 surface of carbon/carbon compound material after hydro-thermal pre-treatment step can produce a large amount of carboxyl, hydroxyl etc.
Property group, these groups and ultrasonic atomizatio gas will form effective chemical bonding, while the Ca in hydroxyapatite2+With carbon/
Stable interaction occurs for the carboxyl on 5 surface of carbon composite, these factors can all improve carbon/carbon compound material 5 and hydroxyl
The binding force of apatite coating.
As shown in Figure 1, used in the preparation method of the hydroxyapatite coating layer on 5 surface of carbon/carbon compound material above
Precipitation equipment includes carrying gas generator 7, ultrasonic atomizing device 2, deposited tube 6 and high-frequency electromagnetic induction device, carries gas hair
Conveyance conduit 4 connects between raw device 7 and ultrasonic atomizing device 2, and the side of ultrasonic atomizing device 2 and deposited tube 6 passes through delivery pipe
Road 4 connects, and high-frequency electromagnetic induction device includes induction power supply 1 and induction coil 3,3 sets of the induction coil outsides in deposited tube 6, sense
It answers power supply 1 to be electrically connected with induction coil 3, carries gas generator 7 and generate carrying gas, deposition liquid is put into ultrasonic atomizing device 2
In, ultrasonic atomizatio gas is generated, gas carrying ultrasonic atomizatio gas is carried and passes through conveyance conduit 4 from the side as deposited tube 6
It is sent into, is exported from the other side of glass tube.Carbon/carbon compound material 5 is placed in deposited tube 6, by induction coil 3 heat carbon/
Carbon composite 5 deposits calcium monohydrogen phosphate coating on its surface.
For the flow velocity of gas in control deposited tube 6, flow control valve 10 is set in the output end side of deposited tube 6.
To protect environment purpose, it is additionally provided with absorption plant 9 in the output end side of deposited tube 6, absorption plant 9 is common to live
Property charcoal composition, for adsorbing the impurity in efferent duct gas, such as nitrate ion, calcium ion energy.
Specifically, as shown in Figure 1, being connected between the output end side and absorption plant 9 of deposited tube 6 by output channel 8,
Flow control valve 10 is arranged on output channel 8.
To be 1.5g/cm in density3Medical carbon/carbon compound material on prepare hydroxyapatite coating layer for, to this hair
It is bright further to be stated:
A. hydro-thermal pre-treatment step: being 1.5g/cm density3Medical carbon/carbon compound material be placed in 50ml test tube, try
Hydrogen peroxide is filled in pipe, after carrying out hydro-thermal process, natural cooling is washed and dried with deionized water, is cleaned simultaneously with deionized water
It is dry.
B. ultrasonic atomizatio deposits: 0.16mol/L calcium nitrate, 0.1mol/L diethyl phosphate with ethyl alcohol being configured to mix molten
Liquid is put into ultrasonic atomizing device 2, generates ultrasonic atomizatio gas.Nitrogen or argon gas are generated by nitrogen or argon gas generator, and it is super
The mixing of sound atomization gas is sent into glass tube by pipeline, deposits calcium monohydrogen phosphate coating on its surface by electromagnetic induction method,
Electromagnetic induction frequency of oscillation is 350KHz, and oscillating current 350A, sedimentation time 10min are cleaned with deionized water.
C. hydro-thermal post-processing step: calcium monohydrogen phosphate painting is placed in the water heating kettle containing 0.1% ammonium hydroxide, is carried out at hydro-thermal
Reason, 85 DEG C of hydro-thermal process temperature, the processing time is 4h, and natural cooling obtains hydroxyapatite coating layer, and the coating binding force is reachable
Critical load 180N, the Vickers hardness of coating are 215.
According to 2 × 104/cm2It is compound that rat osteoblast density is inoculated in medical carbon/carbon with hydroxyapatite coating layer
Material surface carries out scanning electron microscopic observation after cultivating 6d, with PBS cleaning material surface, is fixed with 2.5% glutaraldehyde
2h, then dehydration 20min successively is carried out with 30%, 50%, 70%, 90%, 95% ethyl alcohol, then exchanged with isoamyl acetate
Ethyl alcohol.Hydroxyapatite coating layer can remarkably promote the growth of rat osteoblast.
Claims (10)
1. a kind of preparation method of the hydroxyapatite coating layer of surface of carbon/carbon composite, it is characterized in that: deposition liquid is put into super
Ultrasonic atomizatio gas is generated in sound atomising device, ultrasonic atomizatio gas flows through the table of carbon/carbon compound material by carrying gas carrying
Face is heated outside carbon/carbon compound material by electromagnetic induction method, and the surface of carbon/carbon compound material is made to deposit phosphoric acid
Hydrogen calcium coating,
The carbon/carbon compound material of surface deposition calcium monohydrogen phosphate coating is subjected to hydro-thermal process, obtains hydroxyapatite coating layer,
Carbon/carbon compound material carries out hydro-thermal pre-treatment step before being deposited, the carbon after hydro-thermal pre-treatment/carbon composite wood
Material surface can generate a large amount of carboxyl, hydroxyl.
2. the preparation method of the hydroxyapatite coating layer of surface of carbon/carbon composite according to claim 1, feature
Be: the deposition liquid is the calcium nitrate of solvent, the mixed solution of diethyl phosphate to be done with ethyl alcohol, or deposition liquid is with ethyl alcohol
Do the calcium nitrate of solvent, the mixed solution of triethyl phosphate.
3. the preparation method of the hydroxyapatite coating layer of surface of carbon/carbon composite according to claim 1, feature
Be: the carrying gas is nitrogen or argon gas.
4. the preparation method of the hydroxyapatite coating layer of surface of carbon/carbon composite according to claim 1, feature
It is: hydro-thermal pre-treatment step are as follows: carbon/carbon compound material is placed in hydrogen peroxide and carries out hydro-thermal process, has been cleaned and dried after cooling
At hydro-thermal pre-treatment.
5. the preparation method of the hydroxyapatite coating layer of surface of carbon/carbon composite according to claim 2, feature
Be: calcium nitrate is 0.01mol/L~0.6mol/L in the deposition liquid, and diethyl phosphate or triethyl phosphate are 0.01mol/
L~0.5mol/L.
6. the preparation method of the hydroxyapatite coating layer of surface of carbon/carbon composite according to claim 1, feature
Be: the frequency of oscillation of the ultrasonic atomizing device is 1.7MHz~2.4MHz, and the flow velocity of gas is 30ml/min~500ml/
min。
7. the preparation method of the hydroxyapatite coating layer of surface of carbon/carbon composite according to claim 1, feature
Be: being heated in the electromagnetic induction method using high-frequency electromagnetic induction device, electromagnetic induction frequency of oscillation be 300KHz~
1MHz, oscillating current are 200A~700A, and sedimentation time is 10min~8h.
8. the preparation method of the hydroxyapatite coating layer of surface of carbon/carbon composite according to claim 1, feature
Be: the carbon/carbon compound material of the surface deposition calcium monohydrogen phosphate coating, which is placed in ammonium hydroxide, carries out hydro-thermal process, the concentration of ammonium hydroxide
It is 0.1%~2%, 85 DEG C~145 DEG C of hydro-thermal process temperature, the processing time is 4h~for 24 hours.
9. the preparation method of the hydroxyapatite coating layer of surface of carbon/carbon composite according to claim 1, feature
Be: the carbon/carbon compound material, which is placed in deposited tube, to be deposited, and the ultrasonic atomizatio gas for carrying gas carrying deposition liquid is logical
It crosses conveyance conduit to be sent into deposited tube from the side of deposited tube, be exported from the other side of deposited tube.
10. the preparation method of the hydroxyapatite coating layer of surface of carbon/carbon composite according to claim 9, feature
It is: the output end side setting flow control valve and absorption plant of the deposited tube.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260863A (en) * | 2011-05-05 | 2011-11-30 | 陕西科技大学 | Preparation method of silicon-containing hydroxyapatite coating of carbon/carbon composite material |
| CN103920186A (en) * | 2014-04-17 | 2014-07-16 | 倪昕晔 | Magnesium-containing hydroxyapatite coating on surface of medical material and preparation method of coating |
| WO2014164469A1 (en) * | 2013-03-11 | 2014-10-09 | Kettering University | Wear resistant and biocompatible coatings for medical devices and method of fabrication |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260863A (en) * | 2011-05-05 | 2011-11-30 | 陕西科技大学 | Preparation method of silicon-containing hydroxyapatite coating of carbon/carbon composite material |
| WO2014164469A1 (en) * | 2013-03-11 | 2014-10-09 | Kettering University | Wear resistant and biocompatible coatings for medical devices and method of fabrication |
| CN103920186A (en) * | 2014-04-17 | 2014-07-16 | 倪昕晔 | Magnesium-containing hydroxyapatite coating on surface of medical material and preparation method of coating |
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