CN107326338A - It is a kind of to realize the dispersed method of CNT in Ca P base biological coatings - Google Patents

It is a kind of to realize the dispersed method of CNT in Ca P base biological coatings Download PDF

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CN107326338A
CN107326338A CN201710469681.XA CN201710469681A CN107326338A CN 107326338 A CN107326338 A CN 107326338A CN 201710469681 A CN201710469681 A CN 201710469681A CN 107326338 A CN107326338 A CN 107326338A
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carbon
cnt
deposition
biological coatings
dispersed
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CN107326338B (en
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李贺军
刘守杰
张磊磊
孙佳佳
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Northwestern Polytechnical University
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    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • 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
    • A61L27/303—Carbon
    • 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
    • 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
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • 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
    • C25D5/54—Electroplating of non-metallic surfaces
    • 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
    • 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
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/04—Coatings containing a composite material such as inorganic/organic, i.e. material comprising different phases
    • 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 the dispersed method of CNT is realized in Ca P base biological coatings, by after surface of carbon/carbon composite pulse electrodeposition Ca P base biological coatings, pulse electrodeposition processing is carried out again to it, catalyst iron is set to be dispersed in Ca P base biological coatings, then using dimethylbenzene as carbon source, ethylenediamine is growth regulator, and chemical vapor carbon deposition nanotube finally realizes that CNT is dispersed in Ca P base biological coatings.Beneficial effect：CNT is uniformly applied in Ca P biological coatings, ultimately forms dispersed CNT and the composite coating combined closely by Ca P biological coatings.

Description

It is a kind of that the dispersed method of CNT is realized in Ca-P base biological coatings
Technical field
The invention belongs to technical field of biological material, it is related to one kind and realizes that CNT is dispersed in Ca-P base biological coatings Method.
Background technology
Ca-P base ceramic materials and inorganic matter in skeleton are similar, with excellent bioactivity and bio-compatible Property, it is often compound with metal material, nonmetallic materials and polymeric material, as can load-bearing can induce the life of bone tissue regeneration again Thing alternate material.Mainly first the mixing CNT with Ca-P powder machineries of CNT enhancing Ca-P coatings is prepared at present Afterwards, it is coated with matrix surface.This method not can effectively solve the problem that CNT disperses inequality in Ca-P base biomaterials The problem of, and damage in various degree can be also caused to CNT.
Document 1 " Y.Chen, Y.Q.Zhang, T.H.Zhang, C.H.Gan, C.Y.Zheng, G.Yu.Carbon nanotube reinforced hydroxyapatite composite coatings produced through laser Surface alloying.Carbon 44 (2006) 37-45. " report mechanical mixture CNT and hydroxy apatite powder Afterwards, carbon nano-tube reinforced hydroxylapatite composite coating is prepared in titanium alloy surface using laser surface alloying method.As a result Show that content of carbon nanotubes is more, disperse uneven phenomenon more obvious.
" Y.H.Meng, C.Y.Tang, C.P.Tsui.Fabrication and the characterization of of document 2 needle-like nano-HA and HA/MWCNT composites.Journal of Materials Science: It can be that a kind of CNT that improves divides that Materials in Medicine 19 (2008) 75-81. ", which are reported using soda acid processing, Dissipate a kind of method of property.Still there is the problem of CNT is easily reunited in Ca-P biological coatings.
The content of the invention
The technical problem to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes that one kind realizes carbon nanometer in Ca-P base biological coatings The dispersed method of pipe, solves the problem of CNT is easily reunited in Ca-P biological coatings.
Technical scheme
It is a kind of that the dispersed method of CNT is realized in Ca-P base biological coatings, it is characterised in that step is as follows：
Step 1：Pulse electrodeposition device will be placed in after four water-calcium nitrate solution and ammonium dihydrogen phosphate in equal volume mixing In, using carbon/carbon composite material base body as negative electrode, graphite is deposited as anode, is obtained in surface of carbon/carbon composite Ca-P base biological coatings are named as A；
Deposition process conditions are：Sedimentation time is 1.0-2.0h, and deposition voltage is 5.0-10.0V, and depositing temperature is 60-80 DEG C, pulse switching time ratio is 0.25-1.00；
The concentration of the four water-calcium nitrate solution is 1.67 × 10-2-1.67mol/L；
The concentration of the ammonium dihydrogen phosphate is 1.00 × 10-2-1.00mol/L；
Step 2：A is dried into laggard horizontal pulse electrodeposition process, realizes and catalyst iron is introduced in Ca-P base biological coatings, It is named as B；Pulse electrodeposition processing；
Pulse electrodeposition treatment process condition is：The aqueous ferrous sulfate solution concentration of electrolyte six is 0.02-2.00g/ml, is sunk Product time 0.5-1.5h, deposition voltage be 5.0-10.0V, depositing temperature be 60-80 DEG C, pulse switching time ratio be 0.25- 1.00；
Step 3：By B as chemical vapor deposition tube furnace intracavitary, using double injection method deposition of carbon nanotubes, realize CNT is dispersed in Ca-P base biological coatings；
The technique of deposition of carbon nanotubes is：At 400-600 DEG C after hydrogen reducing catalyst iron, in 750-900 DEG C, argon Under the conditions of gas, hydrogen flowing quantity are respectively 400 and 200sccm, using dimethylbenzene as carbon source, ethylenediamine is growth regulator, injection rate ratio For 5.0-10.0, injection time is 0.5-2h.
Beneficial effect
It is proposed by the present invention it is a kind of the dispersed method of CNT is realized in Ca-P base biological coatings, by After surface of carbon/carbon composite pulse electrodeposition Ca-P base biological coatings, pulse electrodeposition processing is carried out again to it, makes catalyst Iron is dispersed in Ca-P base biological coatings, then using dimethylbenzene as carbon source, and ethylenediamine is growth regulator, chemical vapor carbon deposition Nanotube, finally realizes that CNT is dispersed in Ca-P base biological coatings.Superiority：From figure 1 it appears that this reality Apply example and prepare catalyst iron and be dispersed in porous C a-P biological coatings.Calcium, phosphorus, oxygen and ferro element are distributed in the coating in figure Situation, wherein calcium, phosphorus, oxygen element are Ca-P biological coating components, and ferro element is the catalyst iron obtained after electro-deposition.From In Fig. 2 as can be seen that CNT be uniformly applied in Ca-P biological coatings, ultimately form dispersed CNT with The composite coating combined closely by Ca-P biological coatings.
Brief description of the drawings
Fig. 1 is the energy spectrum diagram of electro-deposition catalyst iron in porous C a-P biological coatings of the inventive method embodiment 4.
Fig. 2 is the scanning electricity in porous C a-P biological coating situ deposition of carbon nanotubes of the inventive method embodiment 4 Mirror picture.
Embodiment
In conjunction with embodiment, accompanying drawing, the invention will be further described：
Embodiment 1：
It is respectively 1.67 × 10 by concentration-2Mol/L four water-calcium nitrate solution and 1.00 × 10-2Mol/L biphosphate Ammonium salt solution is uniformly mixed in equal volume, then using carbon/carbon composite material base body as negative electrode, and graphite is positioned over pulse electricity as anode In precipitation equipment, sedimentation time is 1.5h, and deposition voltage is 5V, and depositing temperature is 70 DEG C, and pulse switching time ratio is 1.00. The Ca-P base biological coatings that will be obtained in surface of carbon/carbon composite, are named as A；
After A is dried, pulse electrodeposition processing is carried out to A, process conditions are：The aqueous ferrous sulfate solution concentration of electrolyte six For 0.2g/ml, sedimentation time 1h, deposition voltage is 5V, and depositing temperature is 70 DEG C, and pulse switching time ratio is 1.00.So as to real Catalyst iron is introduced in present Ca-P base biological coatings, B is named as；
B is placed in chemical vapor deposition tube furnace intracavitary, using double injection method deposition of carbon nanotubes, depositing operation is： At 400 DEG C after hydrogen reducing catalyst iron, at 750 DEG C, under the conditions of argon gas, hydrogen flowing quantity are respectively 400 and 200sccm, with Dimethylbenzene is carbon source, and ethylenediamine is growth regulator, and injection rate ratio is 5.0, and injection time is 0.5h.It is final to realize in the life of Ca-P bases CNT is dispersed in thing coating.
Embodiment 2：
It is respectively 1.67 × 10 by concentration-1Mol/L four water-calcium nitrate solution and 1.00 × 10-1Mol/L biphosphate Ammonium salt solution is uniformly mixed in equal volume, then using carbon/carbon composite material base body as negative electrode, and graphite is positioned over pulse electricity as anode In precipitation equipment, sedimentation time is 1.5h, and deposition voltage is 7.5V, and depositing temperature is 80 DEG C, and pulse switching time ratio is 0.50.The Ca-P base biological coatings that will be obtained in surface of carbon/carbon composite, are named as A；
After A is dried, pulse electrodeposition processing is carried out to A, process conditions are：The aqueous ferrous sulfate solution concentration of electrolyte six For 2g/ml, sedimentation time 0.5h, deposition voltage is 7.5V, and depositing temperature is 80 DEG C, and pulse switching time ratio is 0.50.So as to Realize and catalyst iron is introduced in Ca-P base biological coatings, be named as B；
B is placed in chemical vapor deposition tube furnace intracavitary, using double injection method deposition of carbon nanotubes, depositing operation is： At 450 DEG C after hydrogen reducing catalyst iron, at 800 DEG C, under the conditions of argon gas, hydrogen flowing quantity are respectively 400 and 200sccm, with Dimethylbenzene is carbon source, and ethylenediamine is growth regulator, and injection rate ratio is 10, and injection time is 1h.It is final to realize in Ca-P bases biology CNT is uniformly distributed in coating.
Embodiment 3：
It is respectively 1.67mol/L four water-calcium nitrate solution and the 1.00mol/L body such as ammonium dihydrogen phosphate by concentration The uniform mixing of product, then using carbon/carbon composite material base body as negative electrode, graphite is positioned over pulse electrodeposition device as anode In, sedimentation time is 1h, and deposition voltage is 10V, and depositing temperature is 60 DEG C, and pulse switching time ratio is 0.25.Will be in carbon/carbon The Ca-P base biological coatings that composite material surface is obtained are named as A；
After A is dried, pulse electrodeposition processing is carried out to A, process conditions are：The aqueous ferrous sulfate solution concentration of electrolyte six For 0.02g/ml, sedimentation time 1.5h, deposition voltage is 10V, and depositing temperature is 60 DEG C, and pulse switching time ratio is 0.25.From And realize and catalyst iron is introduced in Ca-P base biological coatings, it is named as B；
B is placed in chemical vapor deposition tube furnace intracavitary, using double injection method deposition of carbon nanotubes, depositing operation is： At 500 DEG C after hydrogen reducing catalyst iron, at 900 DEG C, under the conditions of argon gas, hydrogen flowing quantity are respectively 400 and 200sccm, with Dimethylbenzene is carbon source, and ethylenediamine is growth regulator, and injection rate ratio is 5.0, and injection time is 1.5h.It is final to realize in the life of Ca-P bases CNT is dispersed in thing coating.
Embodiment 4：
It is respectively 1.67 × 10 by concentration-2Mol/L four water-calcium nitrate solution and 1.00 × 10-2Mol/L biphosphate Ammonium salt solution is uniformly mixed in equal volume, then using carbon/carbon composite material base body as negative electrode, and graphite is positioned over pulse electricity as anode In precipitation equipment, sedimentation time is 2h, and deposition voltage is 10V, and depositing temperature is 60 DEG C, and pulse switching time ratio is 0.25.Will The Ca-P base biological coatings obtained in surface of carbon/carbon composite are named as A；
After A is dried, pulse electrodeposition processing is carried out to A.Process conditions are：The aqueous ferrous sulfate solution concentration of electrolyte six For 0.02g/ml, sedimentation time 0.5h, deposition voltage is 10V, and depositing temperature is 60 DEG C, and pulse switching time ratio is 0.25.From And realize and catalyst iron is introduced in Ca-P base biological coatings, it is named as B；
B is placed in chemical vapor deposition tube furnace intracavitary, using double injection method deposition of carbon nanotubes, depositing operation is： At 500 DEG C after hydrogen reducing catalyst iron, at 850 DEG C, under the conditions of argon gas, hydrogen flowing quantity are respectively 400 and 200sccm, with Dimethylbenzene is carbon source, and ethylenediamine is growth regulator, and injection rate ratio is 7.5, and injection time is 1h.It is final to realize in Ca-P bases biology CNT is dispersed in coating.
Embodiment 5：
It is respectively 1.67 × 10 by concentration-1Mol/L four water-calcium nitrate solution and 1.00 × 10-1Mol/L biphosphate Ammonium salt solution is uniformly mixed in equal volume, then using carbon/carbon composite material base body as negative electrode, and graphite is positioned over pulse electricity as anode In precipitation equipment, sedimentation time is 1h, and deposition voltage is 10V, and depositing temperature is 60 DEG C, and pulse switching time ratio is 0.75.Will The Ca-P base biological coatings obtained in surface of carbon/carbon composite are named as A；
After A is dried, pulse electrodeposition processing is carried out to A.Process conditions are：The aqueous ferrous sulfate solution concentration of electrolyte six For 0.2g/ml, sedimentation time 1h, deposition voltage is 7.5V, and depositing temperature is 60 DEG C, and pulse switching time ratio is 0.75.So as to Realize and catalyst iron is introduced in Ca-P base biological coatings, be named as B；
B is placed in chemical vapor deposition tube furnace intracavitary, using double injection method deposition of carbon nanotubes, depositing operation is： At 600 DEG C after hydrogen reducing catalyst iron, at 900 DEG C, under the conditions of argon gas, hydrogen flowing quantity are respectively 400 and 200sccm, with Dimethylbenzene is carbon source, and ethylenediamine is growth regulator, and injection rate ratio is 5, and injection time is 0.5h.It is final to realize in Ca-P bases biology CNT is dispersed in coating.
Embodiment 6：
It is respectively 1.67mol/L four water-calcium nitrate solution and the 1.00mol/L body such as ammonium dihydrogen phosphate by concentration The uniform mixing of product, then using carbon/carbon composite material base body as negative electrode, graphite is positioned over pulse electrodeposition device as anode In, sedimentation time is 2h, and deposition voltage is 7.5V, and depositing temperature is 80 DEG C, and pulse switching time ratio is 1.00.Will be in carbon/carbon The Ca-P base biological coatings that composite material surface is obtained are named as A；
After A is dried, pulse electrodeposition processing is carried out to A.Process conditions are：The aqueous ferrous sulfate solution concentration of electrolyte six For 2g/ml, sedimentation time 1h, deposition voltage is 7.5V, and depositing temperature is 60 DEG C, and pulse switching time ratio is 1.00.So as to real Catalyst iron is introduced in present Ca-P base biological coatings, B is named as；
B is placed in chemical vapor deposition tube furnace intracavitary, using double injection method deposition of carbon nanotubes, depositing operation is： At 550 DEG C after hydrogen reducing catalyst iron, at 900 DEG C, under the conditions of argon gas, hydrogen flowing quantity are respectively 400 and 200sccm, with Dimethylbenzene is carbon source, and ethylenediamine is growth regulator, and injection rate ratio is 10, and injection time is 1.5h.It is final to realize in the life of Ca-P bases CNT is dispersed in thing coating.

Claims (1)

1. a kind of realize the dispersed method of CNT in Ca-P base biological coatings, it is characterised in that step is as follows：
Step 1：It will be placed in after four water-calcium nitrate solution and ammonium dihydrogen phosphate in equal volume mixing in pulse electrodeposition device, with Carbon/carbon composite material base body is deposited as negative electrode, graphite as anode, the Ca-P obtained in surface of carbon/carbon composite Base biological coating is named as A；
Deposition process conditions are：Sedimentation time is 1.0-2.0h, and deposition voltage is 5.0-10.0V, and depositing temperature is 60-80 DEG C, Pulse switching time ratio is 0.25-1.00；
The concentration of the four water-calcium nitrate solution is 1.67 × 10-2-1.67mol/L；
The concentration of the ammonium dihydrogen phosphate is 1.00 × 10-2-1.00mol/L；
Step 2：A is dried into laggard horizontal pulse electrodeposition process, realizes and catalyst iron is introduced in Ca-P base biological coatings, name For B；Pulse electrodeposition processing；
Pulse electrodeposition treatment process condition is：The aqueous ferrous sulfate solution concentration of electrolyte six is 0.02-2.00g/ml, during deposition Between 0.5-1.5h, deposition voltage be 5.0-10.0V, depositing temperature be 60-80 DEG C, pulse switching time ratio be 0.25-1.00；
Step 3：By B as chemical vapor deposition tube furnace intracavitary, using double injection method deposition of carbon nanotubes, realize in Ca-P CNT is dispersed in base biological coating；
The technique of deposition of carbon nanotubes is：At 400-600 DEG C after hydrogen reducing catalyst iron, in 750-900 DEG C, argon gas, hydrogen Under the conditions of throughput is respectively 400 and 200sccm, using dimethylbenzene as carbon source, ethylenediamine is growth regulator, injection rate ratio is 5.0- 10.0, injection time is 0.5-2h.
CN201710469681.XA 2017-06-20 2017-06-20 A method of realizing that carbon nanotube is evenly dispersed in Ca-P base biological coating Active CN107326338B (en)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN109179355A (en) * 2018-09-28 2019-01-11 西北工业大学 A kind of metal oxide/calcium phosphorus bilayer micron tube and preparation method
CN112457000A (en) * 2020-12-21 2021-03-09 西北工业大学 (Si-N) @ C-Ca-P-C biomedical bone replacement composite material and preparation method thereof
CN112939628A (en) * 2021-01-22 2021-06-11 西北工业大学 Honeycomb structure and sandwich structure composite biological coating and preparation method thereof
CN113564559A (en) * 2021-07-28 2021-10-29 福州大学 Rapid in-situ preparation method of CNTs @ TC4 composite powder

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109179355A (en) * 2018-09-28 2019-01-11 西北工业大学 A kind of metal oxide/calcium phosphorus bilayer micron tube and preparation method
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CN112457000B (en) * 2020-12-21 2022-08-05 西北工业大学 (Si-N) @ C-Ca-P-C biomedical bone replacement composite material and preparation method thereof
CN112939628A (en) * 2021-01-22 2021-06-11 西北工业大学 Honeycomb structure and sandwich structure composite biological coating and preparation method thereof
CN113564559A (en) * 2021-07-28 2021-10-29 福州大学 Rapid in-situ preparation method of CNTs @ TC4 composite powder

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