CN111808398A - Preparation method of ZIF-67 lossless modified carbon fiber reinforced composite material - Google Patents
Preparation method of ZIF-67 lossless modified carbon fiber reinforced composite material Download PDFInfo
- Publication number
- CN111808398A CN111808398A CN202010603598.9A CN202010603598A CN111808398A CN 111808398 A CN111808398 A CN 111808398A CN 202010603598 A CN202010603598 A CN 202010603598A CN 111808398 A CN111808398 A CN 111808398A
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- composite material
- zif
- solution
- acetone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000011208 reinforced composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 115
- 239000004917 carbon fiber Substances 0.000 claims abstract description 115
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 106
- 239000002131 composite material Substances 0.000 claims abstract description 89
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000000835 fiber Substances 0.000 claims abstract description 23
- 238000002791 soaking Methods 0.000 claims abstract description 21
- 238000007731 hot pressing Methods 0.000 claims abstract description 20
- 229920006231 aramid fiber Polymers 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 19
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 14
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 238000000967 suction filtration Methods 0.000 claims abstract description 14
- 238000000465 moulding Methods 0.000 claims abstract description 13
- 150000001721 carbon Chemical class 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- 231100000719 pollutant Toxicity 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000004760 aramid Substances 0.000 claims abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 140
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 84
- 239000000243 solution Substances 0.000 claims description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000011259 mixed solution Substances 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000012466 permeate Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 230000001476 alcoholic effect Effects 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000001066 destructive effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 239000000123 paper Substances 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 20
- 238000007605 air drying Methods 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 239000000956 alloy Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 229920001568 phenolic resin Polymers 0.000 description 7
- 239000005011 phenolic resin Substances 0.000 description 7
- 238000004537 pulping Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 239000012456 homogeneous solution Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 isocyanate surface-modified carbon Chemical class 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000003733 fiber-reinforced composite Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 2
- 244000226021 Anacardium occidentale Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 235000020226 cashew nut Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a preparation method of a ZIF-67 lossless modified carbon fiber reinforced composite material, which comprises the following steps: firstly, removing pollutants on the surface of carbon fiber, and immersing the carbon fiber in nitric acid; dissolving cobalt nitrate hexahydrate in an alcohol solution a to form a solution A, dissolving functionalized carbon fibers and 2-methylimidazole in an alcohol solution B to form a solution B, adding the solution A into the solution B to perform hydrothermal reaction, and obtaining ZIF-67 modified carbon fibers; mixing ZIF-67 modified carbon fibers, aramid fibers and paper fibers, and preparing a composite material preform by adopting a suction filtration molding process; and then soaking the composite material in a modified phenolic resin ethanol solution, and performing hot-pressing curing to obtain the ZIF-67 lossless modified carbon fiber reinforced composite material. ZIF-67 is grafted on carbon fibers under a hydrothermal condition to improve the inert smooth environment on the surfaces of the carbon fibers so as to improve the mechanical property of the composite material. The method has simple process and low material preparation cost.
Description
Technical Field
The invention belongs to the technical field of composite material preparation, and particularly relates to a preparation method of a ZIF-67 lossless modified carbon fiber reinforced composite material.
Background
The carbon fiber not only has the intrinsic characteristics of the carbon material, but also has the soft processability of textile fiber, and has a series of excellent performances of high specific strength, high specific modulus, high temperature resistance, chemical corrosion resistance, radiation resistance, fatigue resistance, creep resistance and the like, so that the carbon fiber can be used as a very important structural component. However, the surface of the carbon fiber is of a turbostratic graphite structure, the surface of the carbon fiber hardly contains active functional groups, chemical inertness and lyophobicity are shown, and the bottleneck of the carbon fiber is formed due to poor interface bonding performance of the carbon fiber and a resin matrix. The inherent strength of the carbon fiber can be damaged by adopting a strong oxidation method or a high-energy radiation method, the wettability between the fiber and a matrix is poor due to the grafting of a hydrophobic nano material, and Chinese patent (with the application number of CN201810429653.X) discloses a method for processing the carbon fiber on the surface by electrochemical polymerization modification and a carbon fiber composite material, wherein the carbon fiber is used as an anode, a graphite plate is used as a cathode, and the surface of the carbon fiber is processed under the action of current so as to change the surface state of the carbon fiber, but the inherent strength of the carbon fiber can be damaged by the method; chinese patent (application No. cn201811544172.x) discloses "an isocyanate surface-modified carbon fiber-polypropylene composite material and a preparation method thereof", wherein polyurethane or epoxy resin is used as a sizing chopped carbon fiber, and a long-chain alkyl group is introduced on the surface of the carbon fiber in a surface grafting manner, so as to improve the interface bonding force between the surface of the carbon fiber and a polypropylene matrix, but grafting a macromolecular substance on the surface of the carbon fiber has a great steric hindrance effect, which is not beneficial to the subsequent resin impregnation process. Chinese patent (application No. CN201210544213.1) discloses a "surface treatment method for carbon fibers", in which high-energy plasma emitted at low temperature impacts the surface of carbon fibers to cause a series of physicochemical changes to occur on the surface layer of carbon fibers, so as to obtain a large amount of activated carbon atoms to improve the bonding strength between the carbon fibers and a resin matrix, but this method has high requirements for experimental techniques. Therefore, it is necessary to provide a method for grafting modified carbon fiber without damage to enhance the interfacial strength of the composite material.
Disclosure of Invention
The invention aims to provide a preparation method of a ZIF-67 lossless modified carbon fiber reinforced composite material, which avoids the loss of the existing treatment process to carbon fibers, improves the surface activity of the fibers and does not damage the strength of the fibers.
The invention adopts the technical scheme that the preparation method of the ZIF-67 lossless modified carbon fiber reinforced composite material is implemented according to the following steps:
step 3, dissolving cobalt nitrate hexahydrate in an alcohol solution a to form a uniform solution A, dissolving functionalized carbon fibers and 2-methylimidazole in an alcohol solution B to form a uniform solution B, then quickly adding the solution A into the solution B under the condition of vigorous stirring to perform hydrothermal reaction, after the reaction is finished, sequentially adopting ethanol and methanol to perform centrifugal washing, and drying to obtain the ZIF-67 modified carbon fibers;
and 4, mixing the mass ratio of 25: 8: 8, fully mixing the ZIF-67 modified carbon fibers, the aramid fibers and the paper fibers, and preparing a composite material preform by adopting a suction filtration molding process;
and 5, soaking the composite material preform in the modified phenolic resin ethanol solution to enable the composite material preform to fully and uniformly permeate into the preform, taking out the preform, naturally airing, and carrying out hot-pressing curing to obtain the ZIF-67 nondestructive modified carbon fiber reinforced composite material.
The present invention is also characterized in that,
in the step 1, the method specifically comprises the following steps: under the condition of oil bath, respectively using acetone and mixed solution of acetone and water in a Soxhlet extractor to treat the carbon fibers in a supercritical state;
when acetone is used for treatment, the treatment temperature is 80 ℃, and the treatment time is 2 hours;
when the mixed solution of acetone and water is used for treatment, the treatment temperature is 110 ℃, and the treatment time is 30 min; the volume ratio of acetone to water in the mixed solution of acetone and water is 5: 1.
in the step 2, the treatment temperature is 120 ℃, and the treatment time is 2 h.
In the step 3, the alcohol solution a and the alcohol solution b are respectively mixed by a volume ratio of 1: 1, mixing methanol and ethanol; the mass ratio of the cobalt nitrate hexahydrate to the alcoholic solution a to the functionalized carbon fibers to the 2-methylimidazole to the alcoholic solution b is 1.75-4.37: 32: 0.1: 1.23-1.97: 32.
in the step 3, the hydrothermal reaction temperature is 80-140 ℃, and the reaction time is 24 h; the drying temperature is 60 ℃, and the drying time is 24 h.
In step 5, the hot-pressing curing temperature is 180 ℃, the pressure is 7MPa, and the time is 30 min.
In the step 5, the mass ratio of the composite material preform to the modified phenolic resin is 35-55: 45-65 parts; the modified phenolic resin ethanol solution is prepared from the following components in percentage by mass of 1: 9 and ethanol.
The beneficial effect of the invention is that,
(1) "zeolitic imidazolate framework" (ZIFs) are porous crystalline materials with a tetrahedral framework formed by cross-linking organoimidazolate to transition metals and having a high porosity. On one hand, the ZIF-67 is grafted to the surface of the carbon fiber, so that the roughness of the surface of the carbon fiber can be improved, and the interface bonding strength of the carbon fiber and a resin matrix is improved in a mechanical meshing mode; on the other hand, the large number of pore structures of the ZIF-67 can release the internal stress of the composite material to avoid the generation of stress concentration phenomenon, and meanwhile, the organic ligand of the ZIF-67 can further participate in the curing reaction of resin, so that the mechanical property of the composite material is improved, and the method is a convenient and efficient grafting modification method.
(2) The invention adopts the suction filtration molding process to prepare the composite preform, the process has high molding speed, is favorable for uniformly dispersing the carbon fibers and the filler, and has special effect on the later-stage preparation of the resin-based wet composite material with excellent performance.
(3) The invention improves the inert environment on the surface of the carbon fiber by using ZIF-67, thereby improving the interface strength of the carbon fiber and the resin matrix. The resin-based composite material prepared by taking the modified carbon fiber as the reinforcing fiber has the tensile strength of 47.1MPa, the shear strength of 74.6MPa and excellent mechanical properties.
Drawings
FIG. 1 is a graph showing the comparison of mechanical properties of a modified carbon fiber-reinforced composite material of the present invention and an untreated carbon fiber-reinforced composite material.
Detailed Description
The present invention will be described in detail with reference to the following detailed description and accompanying drawings.
The preparation method of the ZIF-67 lossless modified carbon fiber reinforced composite material is implemented according to the following steps:
the method specifically comprises the following steps: under the condition of oil bath, respectively using acetone and mixed solution of acetone and water in a Soxhlet extractor to treat the carbon fibers in a supercritical state;
when acetone is used for treatment, the treatment temperature is 80 ℃, and the treatment time is 2 hours;
when the mixed solution of acetone and water is used for treatment, the treatment temperature is 110 ℃, and the treatment time is 30 min; the volume ratio of acetone to water in the mixed solution of acetone and water is 5: 1;
the diameter of the carbon fiber is 7-10 μm;
the treatment temperature is 120 ℃, and the treatment time is 2 hours;
step 3, dissolving cobalt nitrate hexahydrate in an alcohol solution a to form a uniform solution A, dissolving functionalized carbon fibers and 2-methylimidazole in an alcohol solution B to form a uniform solution B, then quickly adding the solution A into the solution B under the condition of vigorous stirring to perform hydrothermal reaction, after the reaction is finished, sequentially adopting ethanol and methanol to perform centrifugal washing, and drying to obtain the ZIF-67 modified carbon fibers;
the alcoholic solution a is prepared from 1: 1, mixing methanol and ethanol;
the alcoholic solution b is prepared from 1: 1, mixing methanol and ethanol;
the mass ratio of the cobalt nitrate hexahydrate to the alcoholic solution a to the functionalized carbon fibers to the 2-methylimidazole to the alcoholic solution b is 1.75-4.37: 32: 0.1: 1.23-1.97: 32, a first step of removing the first layer;
the hydrothermal reaction temperature is 80-140 ℃, and the reaction time is 24 h; the drying temperature is 60 ℃, and the drying time is 24 hours;
and 4, mixing the mass ratio of 25: 8: 8, fully mixing the ZIF-67 modified carbon fibers, the aramid fibers and the paper fibers, and preparing a composite material preform by adopting a suction filtration molding process;
the suction filtration forming process comprises the following steps: placing the uniformly mixed liquid of the modified carbon fibers, the aramid fibers and the paper fibers in a suction filtration device, and removing moisture by using a mechanical pump device to obtain a composite material preform;
the diameter of the aramid fiber is 8-15 mu m;
the diameter of the paper fiber is 10-20 μm;
and 5, soaking the composite material preform in the modified phenolic resin ethanol solution to enable the composite material preform to fully and uniformly permeate into the preform, taking out the preform, naturally airing, and carrying out hot-pressing curing to obtain the ZIF-67 nondestructive modified carbon fiber reinforced composite material.
Hot-pressing curing temperature is 180 ℃, pressure is 7MPa, and time is 30 min;
the mass ratio of the composite material preform to the modified phenolic resin is 35-55: 45-65 parts;
the dipping time is 5min, and the dipping temperature is room temperature;
the modified phenolic resin ethanol solution is prepared from the following components in percentage by mass of 1: 9, mixing the modified phenolic resin powder with ethanol;
the modified phenolic resin is butyronitrile modified phenolic resin or cashew nut shell modified phenolic resin;
according to the invention, ZIF-67 is grafted on the carbon fiber under hydrothermal conditions by utilizing the interface bonding strength between the ZIF-67 lossless modified carbon fiber and resin, so that the inert smooth environment on the surface of the carbon fiber is improved, and the mechanical property of the composite material is improved. The method has simple process and lower material preparation cost, thereby having wide application prospect in the field of carbon fiber modified composite materials. The ZIF-67 lossless modified carbon fiber reinforced composite material prepared by the method has the tensile strength of 38.2-47.1MPa and the shear strength of 67.4-74.6 MPa.
Example 1
The preparation method of the ZIF-67 lossless modified carbon fiber reinforced composite material is implemented according to the following steps:
the method specifically comprises the following steps: under the condition of oil bath, respectively using acetone and mixed solution of acetone and water in a Soxhlet extractor to treat the carbon fibers in a supercritical state;
when acetone is used for treatment, the treatment temperature is 80 ℃, and the treatment time is 2 hours;
when the mixed solution of acetone and water is used for treatment, the treatment temperature is 110 ℃, and the treatment time is 30 min; the volume ratio of acetone to water in the mixed solution of acetone and water is 5: 1;
the diameter of the carbon fiber is 7-10 μm;
the treatment temperature is 120 ℃, and the treatment time is 2 hours;
step 3, 0.006mol of cobalt nitrate hexahydrate is dissolved in 20mL of methanol and 20mL of ethanol to form a homogeneous solution A, and 0.1g of carbon fiber is similarly added to a mixed solution B of 0.024mol of 2-methylimidazole in 20mL of methanol and 20mL of ethanol. Then, under the condition of vigorous stirring, quickly adding the solution A into the solution B, carrying out hydrothermal reaction for 24 hours at 120 ℃, respectively cleaning for 3 times by using ethanol and methanol after the reaction is finished, and drying for 24 hours in an oven at 60 ℃ to obtain ZIF-67 modified carbon fibers;
step 4, uniformly mixing 0.75g of ZIF-67 modified carbon fibers, 0.24g of aramid fibers and 0.24g of paper fibers by wet pulping, and performing suction filtration molding to obtain a composite material preform; weighing, airing and recording the mass as W1;
step 5, soaking the composite material preform in the ethanol solution of the modified phenolic resin to enable the composite material preform to fully and uniformly permeate into the preform, taking out the preform and naturally airing the preform to obtain raw paper of the composite material containing the phenolic resin, and weighing the mass of the raw paper of the composite material containing the modified phenolic resin, wherein the mass is marked as W2; the difference Δ W (Δ W ═ W2-W1) between the mass of the modified phenolic resin-containing composite base paper and the mass of the composite preform after air-drying was calculated, and the modified phenolic resin in which 1.28g (i.e., Δ W ═ 1.28g) of the composite preform after air-drying was impregnated was obtained. And then, hot-pressing the base paper of the composite material containing the modified phenolic resin for 30min under the conditions of the hot-pressing temperature of 180 ℃ and the pressure of 7MPa to obtain the ZIF-67 lossless modified carbon fiber reinforced composite material. The tensile strength and the shear strength of the alloy are 47.1MPa and 74.6MPa respectively.
The modified phenolic resin ethanol solution is prepared from the following components in percentage by mass of 1: 9 and ethanol.
Example 2
The preparation method of the ZIF-67 lossless modified carbon fiber reinforced composite material is implemented according to the following steps:
the method specifically comprises the following steps: under the condition of oil bath, respectively using acetone and mixed solution of acetone and water in a Soxhlet extractor to treat the carbon fibers in a supercritical state;
when acetone is used for treatment, the treatment temperature is 80 ℃, and the treatment time is 2 hours;
when the mixed solution of acetone and water is used for treatment, the treatment temperature is 110 ℃, and the treatment time is 30 min; the volume ratio of acetone to water in the mixed solution of acetone and water is 5: 1;
the diameter of the carbon fiber is 7-10 μm;
the treatment temperature is 120 ℃, and the treatment time is 2 hours;
step 3, 0.0075mol of cobalt nitrate hexahydrate is dissolved in 20mL of methanol and 20mL of ethanol to form a uniform solution A, and 0.1g of carbon fiber is added into a mixed solution B formed by dissolving 0.0225mol of 2-methylimidazole in 20mL of methanol and 20mL of ethanol. And then, under the condition of violent stirring, quickly adding the solution A into the solution B, carrying out hydrothermal reaction for 24 hours at the temperature of 120 ℃, respectively washing for 3 times by using ethanol and methanol after the reaction is finished, and drying for 24 hours in an oven at the temperature of 60 ℃ to obtain the ZIF-67 modified carbon fiber.
And 4, respectively weighing 0.75g of modified carbon fiber, 0.24g of aramid fiber and 0.24g of paper fiber, uniformly mixing the carbon fiber, the aramid fiber and the paper fiber by adopting wet pulping, and performing suction filtration molding to obtain a composite material preform. Weighing, airing and recording the mass as W1;
step 5, soaking the composite material preform in a modified phenolic resin ethanol solution with the mass concentration of 10% for 5min, so that the resin can fully and uniformly permeate into the preform, naturally airing to obtain raw paper of the composite material containing the phenolic resin, and weighing the raw paper of the composite material containing the modified phenolic resin, wherein the weight of the raw paper is marked as W2; the difference Δ W (Δ W ═ W2-W1) between the mass of the modified phenolic resin-containing composite base paper and the mass of the composite preform after air-drying was calculated, and the modified phenolic resin in which 1.26g (i.e., Δ W ═ 1.26g) of the composite preform after air-drying was impregnated was obtained. And then, hot-pressing the base paper of the composite material containing the modified phenolic resin for 30min under the conditions of the hot-pressing temperature of 180 ℃ and the pressure of 7MPa to obtain the ZIF-67 lossless modified carbon fiber reinforced composite material. The tensile strength and the shear strength of the alloy are respectively 44.7MPa and 71.8 MPa.
Example 3
The preparation method of the ZIF-67 lossless modified carbon fiber reinforced composite material is implemented according to the following steps:
the method specifically comprises the following steps: under the condition of oil bath, respectively using acetone and mixed solution of acetone and water in a Soxhlet extractor to treat the carbon fibers in a supercritical state;
when acetone is used for treatment, the treatment temperature is 80 ℃, and the treatment time is 2 hours;
when the mixed solution of acetone and water is used for treatment, the treatment temperature is 110 ℃, and the treatment time is 30 min; the volume ratio of acetone to water in the mixed solution of acetone and water is 5: 1;
the diameter of the carbon fiber is 7-10 μm;
step 3, 0.01mol of cobalt nitrate hexahydrate is dissolved in 20mL of methanol and 20mL of ethanol to form a uniform solution A, and 0.1g of carbon fiber is also added to a mixed solution B formed by dissolving 0.02mol of 2-methylimidazole in 20mL of methanol and 20mL of ethanol. And then, under the condition of violent stirring, quickly adding the solution A into the solution B, carrying out hydrothermal reaction for 24 hours at the temperature of 120 ℃, respectively washing for 3 times by using ethanol and methanol after the reaction is finished, and drying for 24 hours in an oven at the temperature of 60 ℃ to obtain the ZIF-67 modified carbon fiber.
And 4, respectively weighing 0.75g of modified carbon fiber, 0.24g of aramid fiber and 0.24g of paper fiber, uniformly mixing the carbon fiber, the aramid fiber and the paper fiber by adopting wet pulping, and performing suction filtration molding to obtain a composite material preform. Weighing, airing and recording the mass as W1;
step 5, soaking the composite material preform in a modified phenolic resin ethanol solution with the mass concentration of 10% for 5min, so that the resin can fully and uniformly permeate into the preform, naturally airing to obtain raw paper of the composite material containing the phenolic resin, and weighing the raw paper of the composite material containing the modified phenolic resin, wherein the weight of the raw paper is marked as W2; the difference Δ W (Δ W ═ W2-W1) between the mass of the modified phenolic resin-containing composite base paper and the mass of the composite preform after air-drying was calculated, and the modified phenolic resin in which 1.31g (i.e., Δ W ═ 1.31g) of the composite preform after air-drying was impregnated was obtained. And then, hot-pressing the base paper of the composite material containing the modified phenolic resin for 30min under the conditions of the hot-pressing temperature of 180 ℃ and the pressure of 7MPa to obtain the ZIF-67 lossless modified carbon fiber reinforced composite material. The tensile strength and the shear strength of the alloy are 42.2MPa and 71.3MPa respectively.
Example 4
The preparation method of the ZIF-67 lossless modified carbon fiber reinforced composite material is implemented according to the following steps:
the method specifically comprises the following steps: under the condition of oil bath, respectively using acetone and mixed solution of acetone and water in a Soxhlet extractor to treat the carbon fibers in a supercritical state;
when acetone is used for treatment, the treatment temperature is 80 ℃, and the treatment time is 2 hours;
when the mixed solution of acetone and water is used for treatment, the treatment temperature is 110 ℃, and the treatment time is 30 min; the volume ratio of acetone to water in the mixed solution of acetone and water is 5: 1;
step 3, 0.015mol of cobalt nitrate hexahydrate is dissolved in 20mL of methanol and 20mL of ethanol to form a uniform solution A, and 0.1g of carbon fiber is also added to a mixed solution B formed by dissolving 0.015mol of 2-methylimidazole in 20mL of methanol and 20mL of ethanol. And then, under the condition of violent stirring, quickly adding the solution A into the solution B, carrying out hydrothermal reaction for 24 hours at the temperature of 120 ℃, respectively washing for 3 times by using ethanol and methanol after the reaction is finished, and drying for 24 hours in an oven at the temperature of 60 ℃ to obtain the ZIF-67 modified carbon fiber.
And 4, weighing 0.75g of modified carbon fiber, 0.24g of aramid fiber and 0.24g of paper fiber, uniformly mixing the carbon fiber, the aramid fiber and the paper fiber by adopting wet pulping, and performing suction filtration molding to obtain a composite material preform. Weighing, airing and recording the mass as W1;
step 5, soaking the composite material preform in a modified phenolic resin ethanol solution with the mass concentration of 10% for 5min, so that the resin can fully and uniformly permeate into the preform, naturally airing to obtain raw paper of the composite material containing the phenolic resin, and weighing the raw paper of the composite material containing the modified phenolic resin, wherein the weight of the raw paper is marked as W2; the difference Δ W (Δ W ═ W2-W1) between the mass of the modified phenolic resin-containing composite base paper and the mass of the composite preform after air-drying was calculated, and the modified phenolic resin in which 1.18g (i.e., Δ W ═ 1.18g) of the composite preform after air-drying was impregnated was obtained. And then, carrying out hot pressing on the composite base paper containing the modified phenolic resin for 30min under the conditions of hot pressing temperature of 180 ℃ and pressure of 7MPa to obtain the ZIF-67 lossless modified carbon fiber reinforced composite. The tensile strength and the shear strength of the alloy are respectively 40.6MPa and 68.3 MPa.
Example 5
The preparation method of the ZIF-67 lossless modified carbon fiber reinforced composite material is implemented according to the following steps:
the method specifically comprises the following steps: under the condition of oil bath, respectively using acetone and mixed solution of acetone and water in a Soxhlet extractor to treat the carbon fibers in a supercritical state;
when acetone is used for treatment, the treatment temperature is 80 ℃, and the treatment time is 2 hours;
when the mixed solution of acetone and water is used for treatment, the treatment temperature is 110 ℃, and the treatment time is 30 min; the volume ratio of acetone to water in the mixed solution of acetone and water is 5: 1;
the diameter of the carbon fiber is 7-10 μm;
the treatment temperature is 120 ℃, and the treatment time is 2 hours;
step 3, 0.006mol of cobalt nitrate hexahydrate is dissolved in 20mL of methanol and 20mL of ethanol to form a homogeneous solution A, and 0.1g of carbon fiber is similarly added to a mixed solution B of 0.024mol of 2-methylimidazole in 20mL of methanol and 20mL of ethanol. And then, under the condition of violent stirring, quickly adding the solution A into the solution B, carrying out hydrothermal reaction for 24 hours at the temperature of 80 ℃, respectively washing for 3 times by using ethanol and methanol after the reaction is finished, and drying for 24 hours in an oven at the temperature of 60 ℃ to obtain the ZIF-67 modified carbon fiber.
And 4, respectively weighing 0.75g of modified carbon fiber, 0.24g of aramid fiber and 0.24g of paper fiber, uniformly mixing the carbon fiber, the aramid fiber and the paper fiber by adopting wet pulping, and performing suction filtration molding to obtain a composite material preform. Weighing, airing and recording the mass as W1;
step 5, soaking the composite material preform in a modified phenolic resin ethanol solution with the mass concentration of 10% for 5min, so that the resin can fully and uniformly permeate into the preform, naturally airing to obtain raw paper of the composite material containing the phenolic resin, and weighing the raw paper of the composite material containing the modified phenolic resin, wherein the weight of the raw paper is marked as W2; the difference Δ W (Δ W ═ W2-W1) between the mass of the modified phenolic resin-containing composite base paper and the mass of the composite preform after air-drying was calculated, and the modified phenolic resin in which 1.14g (i.e., Δ W ═ 1.14g) of the composite preform after air-drying was impregnated was obtained. And then, carrying out hot pressing on the composite base paper containing the modified phenolic resin for 30min under the conditions of hot pressing temperature of 180 ℃ and pressure of 7MPa to obtain the ZIF-67 lossless modified carbon fiber reinforced composite. The tensile strength and the shear strength of the alloy are respectively 38.2MPa and 67.4 MPa.
Example 6
The preparation method of the ZIF-67 lossless modified carbon fiber reinforced composite material is implemented according to the following steps:
the method specifically comprises the following steps: under the condition of oil bath, respectively using acetone and mixed solution of acetone and water in a Soxhlet extractor to treat the carbon fibers in a supercritical state;
when acetone is used for treatment, the treatment temperature is 80 ℃, and the treatment time is 2 hours;
when the mixed solution of acetone and water is used for treatment, the treatment temperature is 110 ℃, and the treatment time is 30 min; the volume ratio of acetone to water in the mixed solution of acetone and water is 5: 1;
the diameter of the carbon fiber is 7-10 μm;
the treatment temperature is 120 ℃, and the treatment time is 2 hours;
step 3, 0.006mol of cobalt nitrate hexahydrate is dissolved in 20mL of methanol and 20mL of ethanol to form a homogeneous solution A, and 0.1g of carbon fiber is similarly added to a mixed solution B of 0.024mol of 2-methylimidazole in 20mL of methanol and 20mL of ethanol. And then, under the condition of violent stirring, quickly adding the solution A into the solution B, carrying out hydrothermal reaction for 24 hours at the temperature of 100 ℃, respectively washing for 3 times by using ethanol and methanol after the reaction is finished, and drying for 24 hours in an oven at the temperature of 60 ℃ to obtain the ZIF-67 modified carbon fiber.
And 4, respectively weighing 0.75g of modified carbon fiber, 0.24g of aramid fiber and 0.24g of paper fiber, uniformly mixing the carbon fiber, the aramid fiber and the paper fiber by adopting wet pulping, and performing suction filtration molding to obtain a composite material preform. Weighing, airing and recording the mass as W1;
step 5, soaking the composite material preform in a modified phenolic resin ethanol solution with the mass concentration of 10% for 5min, so that the resin can fully and uniformly permeate into the preform, naturally airing to obtain raw paper of the composite material containing the phenolic resin, and weighing the raw paper of the composite material containing the modified phenolic resin, wherein the weight of the raw paper is marked as W2; the difference Δ W (Δ W ═ W2-W1) between the mass of the modified phenolic resin-containing composite base paper and the mass of the composite preform after air-drying was calculated, and the modified phenolic resin in which 1.36g (i.e., Δ W ═ 1.36g) of the composite preform after air-drying was impregnated was obtained. And then, carrying out hot pressing on the composite base paper containing the modified phenolic resin for 30min under the conditions of hot pressing temperature of 180 ℃ and pressure of 7MPa to obtain the ZIF-67 lossless modified carbon fiber reinforced composite. The tensile strength and the shear strength of the alloy are 39.4MPa and 69.1MPa respectively.
Example 7
The preparation method of the ZIF-67 lossless modified carbon fiber reinforced composite material is implemented according to the following steps:
the method specifically comprises the following steps: under the condition of oil bath, respectively using acetone and mixed solution of acetone and water in a Soxhlet extractor to treat the carbon fibers in a supercritical state;
when acetone is used for treatment, the treatment temperature is 80 ℃, and the treatment time is 2 hours;
when the mixed solution of acetone and water is used for treatment, the treatment temperature is 110 ℃, and the treatment time is 30 min; the volume ratio of acetone to water in the mixed solution of acetone and water is 5: 1;
the diameter of the carbon fiber is 7-10 μm;
the treatment temperature is 120 ℃, and the treatment time is 2 hours;
step 3, 0.006mol of cobalt nitrate hexahydrate is dissolved in 20mL of methanol and 20mL of ethanol to form a homogeneous solution A, and 0.1g of carbon fiber is similarly added to a mixed solution B of 0.024mol of 2-methylimidazole in 20mL of methanol and 20mL of ethanol. And then, under the condition of violent stirring, quickly adding the solution A into the solution B, carrying out hydrothermal reaction for 24 hours at the temperature of 140 ℃, respectively washing for 3 times by using ethanol and methanol after the reaction is finished, and drying for 24 hours in an oven at the temperature of 60 ℃ to obtain the ZIF-67 modified carbon fiber.
And 4, respectively weighing 0.75g of modified carbon fiber, 0.24g of aramid fiber and 0.24g of paper fiber, uniformly mixing the carbon fiber, the aramid fiber and the paper fiber by adopting wet pulping, and performing suction filtration molding to obtain a composite material preform. Weighing, airing and recording the mass as W1;
step 5, soaking the composite material preform in a modified phenolic resin ethanol solution with the mass concentration of 10% for 5min, so that the resin can fully and uniformly permeate into the preform, naturally airing to obtain raw paper of the composite material containing the phenolic resin, and weighing the raw paper of the composite material containing the modified phenolic resin, wherein the weight of the raw paper is marked as W2; the difference Δ W (Δ W ═ W2-W1) between the mass of the modified phenolic resin-containing composite base paper and the mass of the composite preform after air-drying was calculated, and the modified phenolic resin in which 1.41g (i.e., Δ W ═ 1.41g) of the composite preform after air-drying was impregnated was obtained. And then, carrying out hot pressing on the composite base paper containing the modified phenolic resin for 30min under the conditions of hot pressing temperature of 180 ℃ and pressure of 7MPa to obtain the ZIF-67 lossless modified carbon fiber reinforced composite. The tensile strength and the shear strength of the alloy are 42.9MPa and 73.8MPa respectively.
The mechanical properties of the composite material are characterized by tensile strength and three-point bending strength, and the result is shown in figure 1, wherein CFRP-1 is an untreated carbon fiber reinforced composite material, the tensile strength of a sample is 19.7MPa, the bending strength of the sample is 46.8MPa, and CFRP-2 is a modified carbon fiber reinforced composite material prepared by the method, and the tensile and bending strengths of the sample are 38.2MPa and 74.6 MPa. Through comparison of mechanical properties of samples before and after the ZIF-67 grafting, the tensile strength and the bending strength of the ZIF-67/carbon fiber reinforced composite material after the solvent thermal growth are respectively improved by 93.9% and 59.4% compared with those of the original sample. The result shows that the organic-inorganic hybrid and pore structure of the ZIF-67 can obviously improve the mechanical property of the composite material.
Claims (7)
- The preparation method of the ZIF-67 lossless modified carbon fiber reinforced composite material is characterized by comprising the following steps of:step 1, removing pollutants on the surface of carbon fiber by using acetone;step 2, soaking the carbon fiber obtained in the step 1 in nitric acid for treatment to obtain functionalized carbon fiber;step 3, dissolving cobalt nitrate hexahydrate in an alcohol solution a to form a uniform solution A, dissolving functionalized carbon fibers and 2-methylimidazole in an alcohol solution B to form a uniform solution B, then quickly adding the solution A into the solution B under the condition of vigorous stirring to perform hydrothermal reaction, after the reaction is finished, sequentially adopting ethanol and methanol to perform centrifugal washing, and drying to obtain the ZIF-67 modified carbon fibers;and 4, mixing the mass ratio of 25: 8: 8, fully mixing the ZIF-67 modified carbon fibers, the aramid fibers and the paper fibers, and preparing a composite material preform by adopting a suction filtration molding process;and 5, soaking the composite material preform in the modified phenolic resin ethanol solution to enable the composite material preform to fully and uniformly permeate into the preform, taking out the preform, naturally airing, and carrying out hot-pressing curing to obtain the ZIF-67 nondestructive modified carbon fiber reinforced composite material.
- 2. The method for preparing the ZIF-67 lossless modified carbon fiber reinforced composite material as claimed in claim 1, wherein in the step 1, the specific steps are: under the condition of oil bath, respectively using acetone and mixed solution of acetone and water in a Soxhlet extractor to treat the carbon fibers in a supercritical state;when acetone is used for treatment, the treatment temperature is 80 ℃, and the treatment time is 2 hours;when the mixed solution of acetone and water is used for treatment, the treatment temperature is 110 ℃, and the treatment time is 30 min; the volume ratio of acetone to water in the mixed solution of acetone and water is 5: 1.
- 3. the method of manufacturing ZIF-67 non-destructive modified carbon fiber reinforced composite material according to claim 1, wherein the treatment temperature in step 2 is 120 ℃ and the treatment time is 2 hours.
- 4. The method for preparing the ZIF-67 nondestructively modified carbon fiber reinforced composite material as set forth in claim 1, wherein in the step 3, the alcohol solution a and the alcohol solution b are both mixed in a volume ratio of 1: 1, mixing methanol and ethanol; the mass ratio of the cobalt nitrate hexahydrate to the alcoholic solution a to the functionalized carbon fibers to the 2-methylimidazole to the alcoholic solution b is 1.75-4.37: 32: 0.1: 1.23-1.97: 32.
- 5. the preparation method of the ZIF-67 lossless modified carbon fiber reinforced composite material as claimed in claim 1, wherein in the step 3, the hydrothermal reaction temperature is 80 to 140 ℃ and the reaction time is 24 hours; the drying temperature is 60 ℃, and the drying time is 24 h.
- 6. The method for preparing the ZIF-67 nondestructive modified carbon fiber reinforced composite material as described in claim 1, wherein in the step 5, the hot press curing temperature is 180 ℃, the pressure is 7MPa, and the time is 30 min.
- 7. The preparation method of the ZIF-67 nondestructive modified carbon fiber reinforced composite material of claim 1, wherein in the step 5, the mass ratio of the composite material preform to the modified phenolic resin is 35-55: 45-65 parts; the modified phenolic resin ethanol solution is prepared from the following components in percentage by mass of 1: 9 and ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010603598.9A CN111808398A (en) | 2020-06-29 | 2020-06-29 | Preparation method of ZIF-67 lossless modified carbon fiber reinforced composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010603598.9A CN111808398A (en) | 2020-06-29 | 2020-06-29 | Preparation method of ZIF-67 lossless modified carbon fiber reinforced composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111808398A true CN111808398A (en) | 2020-10-23 |
Family
ID=72855620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010603598.9A Pending CN111808398A (en) | 2020-06-29 | 2020-06-29 | Preparation method of ZIF-67 lossless modified carbon fiber reinforced composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111808398A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106555358A (en) * | 2016-11-23 | 2017-04-05 | 陕西科技大学 | A kind of lossless modified carbon fiber of para-amino benzoic acid strengthens the preparation method of paper substrate Wet-type friction material |
| WO2017123162A1 (en) * | 2016-01-14 | 2017-07-20 | Agency For Science, Technology And Research | Free-standing mof-derived hybrid porous carbon nanofiber mats |
| CN109216045A (en) * | 2018-09-13 | 2019-01-15 | 辽宁大学 | CC@ZIF-67/8-PPY composite material and preparation method and application based on carbon cloth growth in situ |
| CN109608822A (en) * | 2018-12-03 | 2019-04-12 | 陕西科技大学 | A kind of lossless modified carbon fiber reinforced resin base Wet-type friction material of MOF-5 and preparation method thereof |
| CN110578254A (en) * | 2019-10-31 | 2019-12-17 | 中原工学院 | PAN/ZIF-67 composite material with adjustable load form and preparation method thereof |
| CN110938407A (en) * | 2019-12-21 | 2020-03-31 | 哈尔滨工业大学 | Hierarchical-structure hollow CNTs/Co/C fiber wave-absorbing material and preparation method thereof |
-
2020
- 2020-06-29 CN CN202010603598.9A patent/CN111808398A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017123162A1 (en) * | 2016-01-14 | 2017-07-20 | Agency For Science, Technology And Research | Free-standing mof-derived hybrid porous carbon nanofiber mats |
| CN106555358A (en) * | 2016-11-23 | 2017-04-05 | 陕西科技大学 | A kind of lossless modified carbon fiber of para-amino benzoic acid strengthens the preparation method of paper substrate Wet-type friction material |
| CN109216045A (en) * | 2018-09-13 | 2019-01-15 | 辽宁大学 | CC@ZIF-67/8-PPY composite material and preparation method and application based on carbon cloth growth in situ |
| CN109608822A (en) * | 2018-12-03 | 2019-04-12 | 陕西科技大学 | A kind of lossless modified carbon fiber reinforced resin base Wet-type friction material of MOF-5 and preparation method thereof |
| CN110578254A (en) * | 2019-10-31 | 2019-12-17 | 中原工学院 | PAN/ZIF-67 composite material with adjustable load form and preparation method thereof |
| CN110938407A (en) * | 2019-12-21 | 2020-03-31 | 哈尔滨工业大学 | Hierarchical-structure hollow CNTs/Co/C fiber wave-absorbing material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110078515B (en) | Preparation method of graphene oxide modified carbon fiber reinforced silicon carbide ceramic matrix composite | |
| CN109608822B (en) | MOF-5 nondestructive modified carbon fiber reinforced resin-based wet friction material and preparation method thereof | |
| CN109987948B (en) | Preparation method of pyrolytic carbon interface layer of carbon fiber reinforced ceramic matrix composite | |
| Sarikanat | The influence of oligomeric siloxane concentration on the mechanical behaviors of alkalized jute/modified epoxy composites | |
| CN106555358B (en) | A kind of preparation method of the lossless modified carbon fiber enhancing paper substrate Wet-type friction material of p-aminobenzoic acid | |
| CN107761375B (en) | Method for grafting branched molecular tannic acid on surface of carbon fiber | |
| CN107313259B (en) | A kind of method of carbon fiber surface grafting Hyperbranched Aromatic Polyamides | |
| CN107266712B (en) | A kind of method of carbon fiber surface grafting dissaving polymer | |
| CN103850124A (en) | Interface modified carbon fiber/resin matrix composite material and preparation method thereof | |
| CN114197205A (en) | Modified carbon fiber and preparation method and application thereof | |
| WO2021108576A1 (en) | Bamboo structures, and methods for fabrication and use thereof | |
| CN111170752B (en) | Preparation method of silicon carbide ceramic matrix composite and silicon carbide ceramic matrix composite | |
| CN114164709A (en) | Carbon fiber paper with carbon black reinforced conductive network and preparation method thereof | |
| CN111979766A (en) | Method for enhancing interfacial bonding performance of aramid fiber and epoxy resin | |
| KR20200032536A (en) | Manufacturing method of basalt fiber-reinforced epoxy composites with natural graphite flakes intrduced | |
| CN110863341A (en) | Preparation method of PA66 grafted carbon fiber | |
| CN111808398A (en) | Preparation method of ZIF-67 lossless modified carbon fiber reinforced composite material | |
| CN109679279B (en) | Preparation method of silanized carbon fiber/nano manganese dioxide reinforced resin matrix composite material | |
| CN106436448A (en) | Preparation method of paper-base wet friction material with reinforced carbon fibers subjected to damage-free modification of acrylic acid | |
| JPH02275760A (en) | Production of fiber-reinforced b4c composite | |
| Zhang et al. | A novel eco-friendly strategy on the interfacial modification of a carbon-fiber-reinforced polymer composite via chitosan encapsulation | |
| CN111533930A (en) | Preparation method of microfibrillated fiber reinforced composite material | |
| CN115538170B (en) | Modified carbon fiber, preparation method and application thereof, and modified carbon fiber epoxy resin composite material | |
| JP5276378B2 (en) | Method for producing carbon fiber reinforced carbon material | |
| CN114031795B (en) | Method for enhancing interfacial properties of carbon fiber resin matrix composite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201023 |
|
| RJ01 | Rejection of invention patent application after publication |