CN113563114A - Porous tantalum coating carbon fiber/carbon composite material and preparation method thereof - Google Patents
Porous tantalum coating carbon fiber/carbon composite material and preparation method thereof Download PDFInfo
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- CN113563114A CN113563114A CN202110926429.3A CN202110926429A CN113563114A CN 113563114 A CN113563114 A CN 113563114A CN 202110926429 A CN202110926429 A CN 202110926429A CN 113563114 A CN113563114 A CN 113563114A
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000011248 coating agent Substances 0.000 title claims abstract description 40
- 238000000576 coating method Methods 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 24
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 24
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title claims abstract description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims description 36
- 230000008021 deposition Effects 0.000 claims description 35
- 230000003647 oxidation Effects 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 21
- 238000004140 cleaning Methods 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000006722 reduction reaction Methods 0.000 claims description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims 1
- 210000000988 bone and bone Anatomy 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 6
- 239000012620 biological material Substances 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 206010052428 Wound Diseases 0.000 abstract 1
- 208000027418 Wounds and injury Diseases 0.000 abstract 1
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000000399 orthopedic effect Effects 0.000 description 2
- 230000035755 proliferation Effects 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 210000002449 bone cell Anatomy 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 210000005260 human cell Anatomy 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 230000009818 osteogenic differentiation Effects 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/88—Metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5133—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal with a composition mainly composed of one or more of the refractory metals
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention discloses a porous tantalum coating carbon fiber/carbon composite material and a preparation method thereof. The porous tantalum metal coating material provided by the invention has excellent bone conductivity and bone inductivity of tantalum metal under the condition that the excellent mechanical property of porous carbon fiber/carbon and the elastic modulus and density close to those of human skeleton are reserved; the tantalum metal coating prepared by the process has high purity and compactness, improves the corrosion resistance and wear resistance of the material, effectively solves the problem of performance reduction caused by the falling of carbon particles on the surface of the carbon fiber/carbon composite material, has low cost, and is expected to be used as a novel medical biomaterial for repairing bone wounds and bone defects of multiple parts of a human body.
Description
1.1.1 technical field
The invention relates to the technical field of medical materials, in particular to a porous tantalum coating carbon fiber/carbon composite material and a preparation method thereof.
1.1.2 background Art
Porous carbon fiber/carbon (C)fthe/C) composite material has the characteristics of high strength, high toughness and the like, and also has the elastic modulus and the density similar to those of human bones, and simultaneously Cfthe/C composite material also inherits the biocompatibility of the carbon material and improves the toughness, and the three-dimensional porous structure of the composite material is beneficial to the entry, growth and development of cells, thereby having great application prospect in the aspects of bone repair and bone replacement. Porous CfThe lower density of the/C (1.2681.83g/cm3) is similar to the density of human bones, so that the comfort and the activity function of a patient can be improved; the higher strength (838186MPa) meets the use performance requirement of natural bone (838117 MPa); and the elastic modulus is 18818GPa, so that the stress of the implanted bone combination interface is effectively reduced. However, porous Cfthe/C composite material has poor hydrophobic property and no osteoinductivity, is only mechanically combined with normal bone tissue after being implanted into a human body, and has longer time for bone repair, so that the C composite material has poor hydrophobic property and no osteoinductivity, and the C composite material has longer time for repairing the bonefA layer of bioactive coating is prepared on the surface of the/C composite material, so that C is reservedfthe/C composite material has excellent mechanical property, simultaneously endows the material with biological activity, and can effectively solve the problem of CfThe performance of the/C composite material is reduced due to the shedding of carbon particles on the surface. In recent years, Wangjian et al utilized plasma spray technology at CfThe hydroxyapatite coating is prepared on the surface of the/C composite material, so that the biocompatibility of the material is improved, and bone cell growth is achieved. Zhang et al at CfThe silicon carbide coating is prepared on the surface of the/C composite material, and research shows that C isfThe silicon carbide coating of the/C composite material has excellent biocompatibility and can promote the proliferation of bone tissues.
Tantalum (Ta) has excellent bone conductivity and bone inductivity, is favorable for the adhesion and proliferation of osteogenesis related cells on the surface of the tantalum (Ta) when being implanted into a human body as an orthopedic biomaterial, has a certain promotion effect on the osteogenic differentiation of the adhesion cells, is one of the most widely applied orthopedic biomaterials at present, and also has a plurality of excellent tantalumProperties, such as: excellent mechanical properties, excellent corrosion resistance and the like. However, the density of tantalum is relatively high (16.68 g/cm)3) When pure tantalum is used as a biological material, the density of the tantalum far exceeds the human skeleton density (1.87-1.97 g/cm)3) The burden of the human body is increased, and the activity function of the patient is reduced.
1.1.3 summary of the invention
In view of the above, the present invention aims to provide a method for preparing a porous tantalum-coated carbon fiber/carbon composite material, which can obtain a porous tantalum-coated carbon fiber/carbon composite material with a dense tantalum metal coating, high purity and sufficient thickness.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a preparation method of a porous tantalum coating carbon fiber/carbon composite material comprises the following steps:
(1) cleaning and drying the carbon fiber/carbon composite material, and fixing the carbon fiber/carbon composite material in a deposition chamber; placing metal tantalum powder in an oxidation chamber;
(2) vacuumizing the deposition chamber and the oxidation chamber, and then heating to 88881888 ℃;
(3) introducing ammonia gas into the deposition chamber, and decomposing the ammonia gas into nitrogen and hydrogen; introducing chlorine into the oxidation chamber, and reacting the chlorine in the oxidation chamber with the metal tantalum powder to generate tantalum pentachloride; tantalum pentachloride flows into the deposition chamber from the oxidation chamber to perform a reduction reaction with hydrogen and is deposited on the surface of the carbon fiber/carbon composite material to obtain a tantalum coating;
(4) and cleaning and drying the product after reaction to obtain the porous tantalum coating carbon fiber/carbon composite material.
In the invention, preferably, the cleaning in the step (1) is ultrasonic treatment for 18838min by using alcohol; the drying is carried out for 3 hours in an oven at the temperature of 98 ℃.
In the present invention, it is preferable that the metallic tantalum powder in the step (1) has a purity of 99.99% and a particle size of 488188 μm.
In the present invention, it is preferable that the flow rate of the chlorine gas in the step (3) is 888188ml/min, and the flow rate of the ammonia gas is 888288 ml/min.
In the present invention, the deposition reaction time in step (3) is preferably 68-98 min.
In the present invention, preferably, the cleaning in step (4) is ultrasonic cleaning with a methanol solution, and then cleaning with acetone and distilled water.
In the invention, the method also comprises the step of treating tail gas generated in the experimental process by using a high-concentration sodium hydroxide solution.
In the present invention, it is preferable that the porosity, pore diameter, bending strength and elastic modulus of the carbon fiber/carbon composite material in the step (1) are 38% 847%, 288118 μm, 888182MPa and 11814GPa, respectively.
2. The porous tantalum-coated carbon fiber/carbon composite produced by the method of any one of claims 186.
In the invention, the thickness of the tantalum coating is 38-98 μm, the density of the tantalum coating is 96.7%, the Vickers hardness is 148.6GPa, and the bonding strength is 66 MPa.
The invention has the beneficial effects that:
1. porous C of the inventionfThe density of the/C skeleton was 1.2682.83g/cm3The bending strength is 74888Mpa, which is close to human skeleton, and meets the performance requirement of human skeleton. Porous C prepared by the inventionfThe thickness of the tantalum metal coating deposited on the/C framework reaches 38898 mu m and is uniform, so that the material not only retains the porous CfThe titanium alloy/carbon composite material has excellent performance, excellent bone conductivity and bone inductivity of tantalum metal, and meets the use requirement of biological materials.
2. The porous tantalum coating material prepared by the invention has high porosity, all pores are communicated, and no closed pore exists, so that the porous tantalum coating material is beneficial to the entry of human cells and can promote the repair of bones.
3. Novel porous C of the inventionfthe/C has good processability, can be processed into various complex shapes on the premise of not damaging the pores, and is suitable for repairing long-section bone defects.
4. The invention can control the size and thickness of the tantalum metal coating particles by controlling parameters such as the concentration of reaction gas, the deposition temperature, the reaction time and the like in the chemical vapor deposition process.
8. The invention deposits the metal tantalum coating on the traditional material by utilizing the coating preparation technology, not only utilizes the excellent biological performance of the metal tantalum, but also reduces the cost, and the scheme has very high application prospect in the aspect of cost control.
1.1.4 description of the drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
FIG. 1 is a schematic diagram of an apparatus for depositing tantalum using chemical vapor deposition in accordance with the present invention;
FIG. 2 shows tantalum metal coating and CfSEM topography of/C framework interface;
FIG. 3 is a graph of ammonia gas flow rate variation versus coating deposition rate;
FIG. 4 is a graph of chlorine flow rate variation versus coating deposition rate.
1.1.5 detailed description
The present invention is further described with reference to the following drawings and specific examples so that those skilled in the art can better understand the present invention and can practice the present invention, but the examples are not intended to limit the present invention.
Example 1
In this example, a porous tantalum coating Cfthe/C composite material and the preparation method thereof specifically comprise the following steps:
(1) ultrasonic cleaning with alcohol Cfthe/C skeleton is dried in oven at 98 deg.C for 3 hr, and fixed in deposition chamber, wherein the porous C is arranged in the deposition chamberfThe porosity of the/C skeleton is 48%, the pore diameter is 288118 μm, the bending strength is 88MPa, and the elastic modulus is 12 GPa; metal tantalum powder with a purity of 99.99% and a particle size of 488188 μm was placed in the oxidation chamber. The instrument was checked for tightness, evacuated and set to a deposition temperature of 1888 ℃.
(2) When the temperature rises to 1888 ℃, chlorine (flow rate is 188ml/min) and ammonia (flow rate is 288ml/min) are respectively introduced into the oxidation chamber and the deposition chamber, the ammonia is decomposed into nitrogen and hydrogen in the deposition chamber, the chlorine in the oxidation chamber reacts with the metal tantalum powder to generate tantalum pentachloride, and the tantalum pentachloride flows from the oxidation chamber into the deposition chamber to be reduced with the hydrogenReaction deposited on CfOn the/C skeleton, the reaction time is 98 min. After the furnace is cooled, taking out the sample, polishing and grinding the sample, ultrasonically cleaning the sample by using a methanol solution, cleaning the sample by using acetone and distilled water, and drying the cleaned sample in a 98 ℃ oven for 3 hours to obtain porous Ta-C with the tantalum coating thickness of 98 mu mfAnd C, material. After the reaction is finished, cooling, sampling and cleaning are carried out, high-concentration sodium hydroxide solution is used for treating tail gas generated in the experimental process, and the schematic diagram of the chemical vapor deposition tantalum device is shown in figure 1.
The relevant chemical reaction formula is as follows:
2Ta(s)+8Cl2(g)→2TaCl8(g)
2NH3(g)→N2(g)+3H2(g)
2TaCl8(g)+8H2(g)→2Ta(s)+18HCl(g)
the compactness of the tantalum coating was tested according to the method described in the national standard ISO-21714 and was found to be 96.7%. Tantalum coating and CfThe SEM of the/C interface is shown in FIG. 2, and the results show that the tantalum metal coating has high compactness. And (3) testing the mechanical property of the coating, wherein the hardness of the coating is 148.6GPa, and the bonding strength is 66 MPa.
Example 2
In this example, a porous tantalum coating Cfthe/C composite material and the preparation method thereof specifically comprise the following steps:
(1) ultrasonic cleaning with alcohol Cfthe/C skeleton is dried in oven at 98 deg.C for 3 hr, and fixed in deposition chamber, wherein the porous C is arranged in the deposition chamberfThe porosity of the/C skeleton is 38%, the pore diameter is 188188 μm, the bending strength is 182MPa, and the elastic modulus is 14 GPa; metal tantalum powder with a purity of 99.99% and a particle size of 488188 μm was placed in the oxidation chamber. The instrument was checked for tightness, evacuated and set to a deposition temperature of 1888 ℃.
(2) When the temperature rises to 1888 ℃, chlorine (flow rate is 88ml/min) and ammonia (flow rate is 888288ml/min) are respectively introduced into the oxidation chamber and the deposition chamber, the ammonia in the deposition chamber is decomposed into nitrogen and hydrogen, the chlorine in the oxidation chamber reacts with the metal tantalum powder to generate tantalum pentachloride, and the tantalum pentachloride flows into the deposition chamber from the oxidation chamber and reacts with the hydrogenIs subjected to reduction reaction and is deposited on CfOn the/C framework, the reaction time is 68min, so that the metal tantalum coating is uniformly deposited on the porous CfOn the/C skeleton, the relationship between the ammonia gas flow rate and the deposition rate was obtained, as shown in FIG. 3. After the furnace is cooled, taking out a sample, polishing and grinding the sample, ultrasonically cleaning the sample by using a methanol solution, cleaning the sample by using acetone and distilled water, and drying the cleaned sample in an oven at the temperature of 98 ℃ for 3 hours to obtain Ta-CfAnd C, material. After the reaction is finished, cooling, sampling and cleaning are carried out, and high-concentration calcium hydroxide solution is used for treating tail gas generated in the experimental process. As can be seen from fig. 3, the deposition rate increases with an increase in the flow rate of ammonia gas.
Example 3
(1) Ultrasonic cleaning with alcohol Cfthe/C skeleton is dried in oven at 98 deg.C for 3 hr, and fixed in deposition chamber, wherein the porous C is arranged in the deposition chamberfThe porosity of the/C skeleton was 47%, the pore diameter was 288118 μm, the bending strength was 74MPa, and the elastic modulus was 11 GPa; metal tantalum powder with a purity of 99.99% and a particle size of 488188 μm was placed in the oxidation chamber. The instrument was checked for tightness, evacuated and set to a deposition temperature of 1888 ℃.
(2) When the temperature rises to 1888 ℃, chlorine (with the flow rate of 888188ml/min) and ammonia (with the flow rate of 288ml/min) are respectively introduced into the oxidation chamber and the deposition chamber, the ammonia in the deposition chamber is decomposed into nitrogen and hydrogen, the chlorine in the oxidation chamber reacts with the metal tantalum powder to generate tantalum pentachloride, the tantalum pentachloride flows from the oxidation chamber into the deposition chamber to perform a reduction reaction with the hydrogen to be deposited on the tantalum pentachloride CfOn the/C framework, the reaction time is 68min, so that the metal tantalum coating is uniformly deposited on the porous CfOn the/C skeleton, the relationship between chlorine flow rate and deposition rate was obtained, as shown in FIG. 4. After the furnace is cooled, taking out a sample, polishing and grinding the sample, ultrasonically cleaning the sample by using a methanol solution, cleaning the sample by using acetone and distilled water, and drying the cleaned sample in an oven at the temperature of 98 ℃ for 3 hours to obtain Ta-CfAnd C, material. After the reaction is finished, cooling, sampling and cleaning are carried out, and high-concentration calcium hydroxide solution is used for treating tail gas generated in the experimental process. As can be seen from fig. 4, the deposition rate increases with increasing chlorine flow.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A preparation method of a porous tantalum coating carbon fiber/carbon composite material is characterized by comprising the following steps:
(1) cleaning and drying the carbon fiber/carbon composite material, and fixing the carbon fiber/carbon composite material in a deposition chamber; placing metal tantalum powder in an oxidation chamber;
(2) vacuumizing the deposition chamber and the oxidation chamber, and then heating to 88881888 ℃;
(3) introducing ammonia gas into the deposition chamber, and decomposing the ammonia gas into nitrogen and hydrogen; introducing chlorine into the oxidation chamber, and reacting the chlorine in the oxidation chamber with the metal tantalum powder to generate tantalum pentachloride; tantalum pentachloride flows into the deposition chamber from the oxidation chamber to perform a reduction reaction with hydrogen and is deposited on the surface of the carbon fiber/carbon composite material to obtain a tantalum coating;
(4) and cleaning and drying the product after reaction to obtain the porous tantalum coating carbon fiber/carbon composite material.
2. The method according to claim 1, wherein the cleaning in step (1) is ultrasonic with alcohol for 18838 min; the drying is carried out for 3 hours in an oven at the temperature of 98 ℃.
3. The method of claim 1, wherein said metallic tantalum powder in step (1) has a purity of 99.99% and a particle size of 488188 μm.
4. The method of claim 1, wherein the flow rate of chlorine gas in step (3) is 888188 ml/min; the flow rate of the ammonia gas is 888288 ml/min.
5. The method of claim 1, wherein the deposition reaction time in step (3) is 68-98 min.
6. The method according to claim 1, wherein the cleaning in step (4) is ultrasonic cleaning with a methanol solution, and then cleaning with acetone and distilled water.
7. The method of claim 1, further comprising the step of treating off-gas generated during the experiment with a high concentration sodium hydroxide solution.
8. The method according to claim 1, wherein the porosity, pore diameter, flexural strength and elastic modulus of the carbon fiber/carbon composite in step (1) are 38% 847%, 288118 μm, 888182MPa, 11814GPa, respectively.
9. The porous tantalum-coated carbon fiber/carbon composite produced by the method of any one of claims 186.
10. The porous tantalum-coated carbon fiber/carbon composite material of claim 7, wherein: the thickness of the tantalum coating is 38-98 mu m, the density of the tantalum coating is 96.7%, the Vickers hardness is 148.6GPa, and the bonding strength is 66 MPa.
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