CN117801474A - Connecting tail top material for winding composite material high-pressure container, and preparation method and application thereof - Google Patents
Connecting tail top material for winding composite material high-pressure container, and preparation method and application thereof Download PDFInfo
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- CN117801474A CN117801474A CN202410019330.9A CN202410019330A CN117801474A CN 117801474 A CN117801474 A CN 117801474A CN 202410019330 A CN202410019330 A CN 202410019330A CN 117801474 A CN117801474 A CN 117801474A
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- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 238000004804 winding Methods 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000835 fiber Substances 0.000 claims abstract description 97
- 239000010453 quartz Substances 0.000 claims abstract description 95
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 95
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052582 BN Inorganic materials 0.000 claims abstract description 41
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002135 nanosheet Substances 0.000 claims abstract description 41
- 239000003822 epoxy resin Substances 0.000 claims abstract description 38
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 38
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 34
- 239000002109 single walled nanotube Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 41
- 238000001816 cooling Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 24
- -1 pyridine dimethyl anhydride Chemical class 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005498 polishing Methods 0.000 claims description 13
- 239000002041 carbon nanotube Substances 0.000 claims description 12
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000012943 hotmelt Substances 0.000 claims description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 4
- TWWAWPHAOPTQEU-UHFFFAOYSA-N 4-methyl-2-benzofuran-1,3-dione Chemical compound CC1=CC=CC2=C1C(=O)OC2=O TWWAWPHAOPTQEU-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- UXBJQNMACGPHEH-UHFFFAOYSA-N SC(C(=O)OC(C(=C)S)=O)=C Chemical compound SC(C(=O)OC(C(=C)S)=O)=C UXBJQNMACGPHEH-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- MCQOWYALZVKMAR-UHFFFAOYSA-N furo[3,4-b]pyridine-5,7-dione Chemical group C1=CC=C2C(=O)OC(=O)C2=N1 MCQOWYALZVKMAR-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 21
- 238000005452 bending Methods 0.000 abstract description 15
- 238000010438 heat treatment Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 4
- 239000011259 mixed solution Substances 0.000 description 44
- 238000004140 cleaning Methods 0.000 description 22
- 239000002904 solvent Substances 0.000 description 22
- 238000003756 stirring Methods 0.000 description 22
- 238000003825 pressing Methods 0.000 description 21
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 20
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 238000010008 shearing Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000227 grinding Methods 0.000 description 11
- 239000012535 impurity Substances 0.000 description 11
- 238000003754 machining Methods 0.000 description 11
- 238000001132 ultrasonic dispersion Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 6
- 239000012611 container material Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000002679 ablation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004283 Sodium sorbate Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 239000011885 synergistic combination Substances 0.000 description 1
- 238000004046 wet winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/329—Phosphorus containing acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
The application relates to a connecting tail top material for winding a composite material high-pressure container, a preparation method and application thereof, and belongs to the technical field of materials for pressure containers. The tail top connecting material comprises the following raw material components in parts by weight: 80-120 parts of epoxy resin; 25-35 parts of quartz chopped fiber; 10-20 parts of boron nitride nano-sheets; 3-10 parts of curing agent; 1-3 parts of single-wall carbon nano tube; 0.2 to 0.5 part of phosphoric acid; 50-70 parts of organic solvent. The connecting tail top material is prepared by a hot press forming process, the whole process is pressurized to be not lower than 3MPa, and the heating treatment is carried out under the specific temperature condition, wherein the single-wall carbon nano tube, the boron nitride nano sheet and the epoxy resin matrix have good compatibility effect, the tensile strength and the bending strength of the connecting tail seat can be obviously improved under the assistance of phosphoric acid, and meanwhile, the connecting tail top material also has good thermal expansion coefficient and low-temperature shrinkage rate.
Description
Technical Field
The application relates to a connecting tail top material for winding a composite material high-pressure container, a preparation method and application thereof, and belongs to the technical field of materials for pressure containers.
Background
At present, a wet winding forming process is mostly adopted in the carbon fiber composite material high-pressure gas cylinder, in the forming process, an inner container material with a connecting seat at the head and a smooth tail is required to be prepared, the inner container material can be an alloy material or a composite material, and the related research of the inner container of the composite material at present is spotlighted, so that the related research of the composite material high-pressure gas cylinder is also gradually increased. In the process of winding and forming the outer side of the inner container by a wet method, the tail of the inner container is smooth due to the limitation of a preparation process, a connecting tail seat is required to be additionally and fixedly arranged for further winding, and the connecting tail seat is matched with a head connecting seat naturally formed in the process of preparing the inner container, so that the winding of the carbon fiber composite material such as presoaked can be realized.
Because most of the inner container materials in the prior art are alloy materials, the connecting tailstock materials matched with the inner container materials are also alloy materials, in order to adapt to the research direction of the composite material inner container, the connecting tailstock materials are necessary to be provided, the connecting tailstock materials in the prior art are prepared based on the composite material inner container materials, however, the connecting tailstock materials play a role in the winding process, the connecting tailstock materials are required to have better tensile property and bending resistance, the connecting tailstock materials are different from the composite material inner container in multiple points concerning hydrogen permeability, shearing strength and other properties, and meanwhile, the requirements are also provided for the deformation of the connecting tailstock under the conditions of high temperature and low temperature due to the working condition of the high-pressure gas cylinder.
Therefore, the technical scheme aims at the problems in the prior art, and particularly provides a connecting tail top material for winding a composite material high-pressure container, so as to meet the requirements of the existing composite material high-pressure gas cylinder on a connecting tail seat, and the connecting tail seat is required to have excellent tensile strength, bending strength performance, thermal expansion coefficient and low-temperature shrinkage rate performance.
Disclosure of Invention
In order to solve the problems, the connecting tail top material for winding the composite material high-pressure container and the preparation method and application thereof are provided, and the connecting tail top for winding the composite material high-pressure container has excellent tensile strength, bending strength performance, thermal expansion coefficient and low-temperature shrinkage rate performance, so that the connecting tail base can be better applied to the preparation process of the high-pressure container, can bear larger pressure and strength as the connecting tail top for winding the outer composite material, and is smaller in deformation under the conditions of high temperature and low temperature, and accords with the use of the high-pressure container under the conditions of low temperature and high temperature.
According to one aspect of the application, a connecting tail top material for winding a composite material high-pressure container is provided, which comprises the following raw material components in parts by weight:
80-120 parts of epoxy resin;
25-35 parts of quartz chopped fiber;
10-20 parts of boron nitride nano-sheets;
3-10 parts of curing agent;
1-3 parts of single-wall carbon nano tube;
0.2 to 0.5 part of phosphoric acid;
50-70 parts of organic solvent.
The epoxy resin used in the present application is not particularly limited, and examples thereof include bisphenol A epoxy resin (E-51, E-54, E-56), aromatic hydrocarbon epoxy resin (E-220, N-770), epoxidized soybean oil resin (815C, 828), isocyanate epoxy resin (E-10, E-30), alicyclic epoxy resin (E-201, E-206) and gel type epoxy resin (MY 720, MY 750) which are commonly used.
Preferably, the epoxy resin is bisphenol a type epoxy resin.
Optionally, the bisphenol A type epoxy resin has a viscosity of 8000-12000 mPa.s at 25 ℃ and a hydroxyl content of 0.15-0.25 mmol/g.
Optionally, the length of the single-walled carbon nanotube is 1-5 μm, and the outer diameter is not more than 2 μm; and/or the number of the groups of groups,
the plane size of the boron nitride nano sheet is 50-200 nm, and the thickness is less than 50nm; and/or the number of the groups of groups,
the length of the chopped fiber is 10-20 mm.
Optionally, the organic solvent is one or more of N-methyl pyrrolidone, N-dimethylacetamide and N-methyl-2-pyrrolidone, and the curing agent is one or more of pyridine dimethyl anhydride, methacrylic anhydride, mercapto acrylic anhydride, diethanolamine, triethanolamine, resorcinol, methylphthalic anhydride, cyclohexaphthalic anhydride, resorcinol and o-cresol.
Optionally, the organic solvent is N-methyl pyrrolidone, and the curing agent is pyridine dimethyl anhydride.
According to another aspect of the present application, there is provided a method for preparing a connection tail top for winding a composite material high-pressure container, using any one of the connection tail top materials for winding a composite material high-pressure container, the method for preparing the connection tail top material comprising the steps of:
s1, dispersing and dissolving boron nitride nano-sheets and carbon nano-tubes in an organic solvent, adding epoxy resin and phosphoric acid, and uniformly mixing;
s2, pre-soaking the quartz chopped fibers by a hot-melt method;
s3, performing hot press molding after drying;
and S4, cooling to 45-55 ℃, demolding, polishing and carrying out subsequent machine tool processing treatment to obtain the connecting tail top.
Optionally, the hot-melt prepreg treatment in the step S2 comprises a step of treating for 5-7 hours at the temperature of 65-75 ℃.
Optionally, the conditions of hot press forming in the step S3 include: pressurizing at least 3MPa in the whole course, treating at 40+ -5deg.C for 30+ -10 min, treating at 55+ -5deg.C for 30+ -10 min, treating at 70+ -5deg.C for 30+ -10 min, treating at 100+ -5deg.C for 90+ -10 min, treating at 130+ -5deg.C for 30+ -10 min, and treating at 160+ -5deg.C for 180+ -10 min.
According to a final aspect of the present application there is provided the use of any of the above described composite high pressure vessel winding connection tail cap materials in the manufacture of pressure vessels.
Benefits of the present application include, but are not limited to:
1. according to the connecting tail top material for winding the composite material high-pressure container, the boron nitride nano sheet and the single-walled carbon nano tube have obvious synergy on tensile property and bending resistance, the boron nitride nano sheet and the single-walled carbon nano tube can be fully combined on the surface of the quartz chopped fiber through the epoxy resin material in the presoaking process, and after hot press forming, the boron nitride nano sheet with larger size is matched with the single-walled carbon nano tube with very small size together, and the connecting tail top material with better bending resistance and tensile property can be obtained by matching with the quartz chopped fiber.
2. According to the connecting tail top material for winding the composite material high-pressure container, the phosphoric acid is added to be matched with the boron nitride nano sheet and the single-wall carbon nano tube, so that the dispersing effect of the boron nitride nano sheet and the single-wall carbon nano tube in an epoxy resin matrix can be obviously improved, the tensile property and the bending resistance are obviously improved, and the thermal expansion coefficient and the cold shrinkage rate are also obviously improved.
3. The connecting tail top material for winding the composite material high-pressure container provided by the application is used for comparing and screening the epoxy resin matrix matched with the connecting tail top material, wherein the compatibility effect of bisphenol A type epoxy resin, the boron nitride nano-sheet and the single-walled carbon nano-tube is optimal, and the best compatibility lifting effect can be achieved with phosphoric acid, the boron nitride nano-sheet and the single-walled carbon nano-tube.
4. The connecting tail top material for winding the composite material high-pressure container develops a complete process for preparing the connecting tail top, explores the presoaking temperature and duration and the hot press forming process parameters, and can obtain better thermal expansion coefficient and cold shrinkage rate performance after continuous exploration and optimization of the process parameters.
5. The connecting tail top material for winding the composite material high-pressure container has excellent tensile strength, bending strength performance, thermal expansion coefficient and low-temperature shrinkage rate performance, so that the connecting tail base can be better applied to the preparation process of the high-pressure container, can bear larger pressure and strength as the connecting tail top of the composite material for winding the outer layer, and accords with the use of the high-pressure container under the conditions of low temperature and high temperature due to smaller deformation under the conditions of high temperature and low temperature.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples, and the raw materials and catalysts in the examples of the present application are commercially available unless otherwise specified.
Example 1
The connecting tail top material for winding the composite material high-pressure container comprises the following raw material components in parts by weight:
100 parts of bisphenol A type epoxy resin;
30 parts of quartz chopped fiber;
15 parts of boron nitride nano-sheets;
5 parts of pyridine dimethyl anhydride;
2 parts of single-walled carbon nanotubes;
0.3 parts of phosphoric acid;
60 parts of N-methylpyrrolidone.
The step of preparing the connecting tail top for winding the composite material high-pressure container by using the connecting tail top material for winding the composite material high-pressure container comprises the following steps of:
s0: weighing the components according to the raw material components for standby;
s1: adding 100mL of N-methylpyrrolidone solvent into a three-necked flask, and adding the weighed carbon nano tube (length of 2-3 mu m, outer diameter of 1-2 mu m) and boron nitride nano sheet (size of 50-100 nm, thickness of 30-40 nm); performing ultrasonic dispersion treatment on the mixed solution for 30min by using an ultrasonic pulverizer (power 600W, frequency 40 kHz); adding pre-weighed bisphenol A epoxy resin and phosphoric acid, and stirring and mixing; transferring the mixed solution into a high-speed shearing stirrer (rotating speed 10000 rpm), and mixing for 10min to obtain uniform mixed solution.
S2: pre-cleaning quartz chopped fibers (15-20 mm) by using an N-methyl pyrrolidone solvent to remove surface impurities, drying the quartz chopped fibers in an oven, suspending the quartz chopped fibers in the prepared S1 mixed solution, manually stirring and impregnating, taking out the impregnated quartz chopped fibers, controlling the impregnating amount to be 30-50%, placing the impregnated quartz chopped fibers in a hot air circulation bellows, performing heat treatment for 6 hours at 70 ℃ for pre-curing, cleaning the pre-cured quartz chopped fibers to remove unreacted resin on the surface, and continuously drying in the oven for 1 hour.
S3: putting the quartz chopped fiber in the step S2 into a cylindrical mould pressing die for hot press forming, and pressurizing at least 3MPa in the whole process, wherein the temperature conditions and the curing time are as follows: pressing and solidifying at 40 ℃ for 30min, 55 ℃ for 30min, 70 ℃ for 30min, 100 ℃ for 90min, 130 ℃ for 30min, 160 ℃ for 180min, cooling to 45 ℃, demolding, and cooling to room temperature.
S4: and polishing the surface of the molded body by using a water grinding wheel to remove burrs, and then carrying out finish machining in a numerical control machining center to obtain the connecting tail top with the designed shape and size.
Example 2
The connecting tail top material for winding the composite material high-pressure container comprises the following raw material components in parts by weight:
80 parts of bisphenol A type epoxy resin;
25 parts of quartz chopped fiber;
10 parts of boron nitride nano-sheet;
3 parts of pyridine dimethyl anhydride;
1 part of single-walled carbon nanotubes;
0.2 parts of phosphoric acid;
50 parts of N-methylpyrrolidone.
The step of preparing the connecting tail top for winding the composite material high-pressure container by using the connecting tail top material for winding the composite material high-pressure container comprises the following steps of:
s0: weighing the components according to the raw material components for standby;
s1: adding 100mL of N-methylpyrrolidone solvent into a three-necked flask, and adding the weighed carbon nano tube (length of 2-3 mu m, outer diameter of 1-2 mu m) and boron nitride nano sheet (size of 50-100 nm, thickness of 30-40 nm); performing ultrasonic dispersion treatment on the mixed solution for 30min by using an ultrasonic pulverizer (power 600W, frequency 40 kHz); adding pre-weighed bisphenol A epoxy resin and phosphoric acid, and stirring and mixing; transferring the mixed solution into a high-speed shearing stirrer (rotating speed 10000 rpm), and mixing for 10min to obtain uniform mixed solution.
S2: pre-cleaning quartz chopped fibers (10-15 mm) by using an N-methyl pyrrolidone solvent to remove surface impurities, drying the quartz chopped fibers in an oven, suspending the quartz chopped fibers in the prepared S1 mixed solution, manually stirring and impregnating, taking out the impregnated quartz chopped fibers, controlling the impregnating amount to be 30-50%, placing the impregnated quartz chopped fibers in a hot air circulation bellows, performing heat treatment for 7h at 65 ℃ for pre-curing, cleaning the pre-cured quartz chopped fibers to remove unreacted resin on the surface, and continuously drying in the oven for 1h.
S3: putting the quartz chopped fiber in the step S2 into a cylindrical mould pressing die for hot press forming, and pressurizing at least 3MPa in the whole process, wherein the temperature conditions and the curing time are as follows: pressing at 45deg.C for 20min, 60 deg.C for 20min, 75 deg.C for 20min, 1005 deg.C for 80min, 135 deg.C for 20min, 165 deg.C for 170min, cooling to 50deg.C, demolding, and cooling to room temperature.
S4: and polishing the surface of the molded body by using a water grinding wheel to remove burrs, and then carrying out finish machining in a numerical control machining center to obtain the connecting tail top with the designed shape and size.
Example 3
The connecting tail top material for winding the composite material high-pressure container comprises the following raw material components in parts by weight:
120 parts of bisphenol A type epoxy resin;
35 parts of quartz chopped fiber;
20 parts of boron nitride nano-sheets;
10 parts of pyridine dimethyl anhydride;
3 parts of single-walled carbon nanotubes;
0.5 parts of phosphoric acid;
70 parts of N-methyl pyrrolidone.
The step of preparing the connecting tail top for winding the composite material high-pressure container by using the connecting tail top material for winding the composite material high-pressure container comprises the following steps of:
s0: weighing the components according to the raw material components for standby;
s1: adding 100mL of N-methylpyrrolidone solvent into a three-necked flask, and adding the weighed carbon nano tube (length of 2-3 mu m, outer diameter of 1-2 mu m) and boron nitride nano sheet (size of 50-100 nm, thickness of 30-40 nm); performing ultrasonic dispersion treatment on the mixed solution for 30min by using an ultrasonic pulverizer (power 600W, frequency 40 kHz); adding pre-weighed bisphenol A epoxy resin and phosphoric acid, and stirring and mixing; transferring the mixed solution into a high-speed shearing stirrer (rotating speed 10000 rpm), and mixing for 10min to obtain uniform mixed solution.
S2: pre-cleaning quartz chopped fibers (15-20 mm) by using an N-methyl pyrrolidone solvent to remove surface impurities, drying the quartz chopped fibers in an oven, suspending the quartz chopped fibers in the prepared S1 mixed solution, manually stirring and impregnating, taking out the impregnated quartz chopped fibers, controlling the impregnating amount to be 30-50%, placing the impregnated quartz chopped fibers in a hot air circulation bellows, performing heat treatment for 5 hours at 75 ℃ for pre-curing, cleaning the pre-cured quartz chopped fibers to remove unreacted resin on the surface, and continuously drying in the oven for 1 hour.
S3: putting the quartz chopped fiber in the step S2 into a cylindrical mould pressing die for hot press forming, and pressurizing at least 3MPa in the whole process, wherein the temperature conditions and the curing time are as follows: pressing and solidifying at 35 ℃ for 40min, 560 ℃ for 40min, 65 ℃ for 40min, 95 ℃ for 80min, 125 ℃ for 40min, 155 ℃ for 170min, cooling to 40 ℃, demolding, and cooling to room temperature.
S4: and polishing the surface of the molded body by using a water grinding wheel to remove burrs, and then carrying out finish machining in a numerical control machining center to obtain the connecting tail top with the designed shape and size.
Example 4
The connecting tail top material for winding the composite material high-pressure container comprises the following raw material components in parts by weight:
100 parts of bisphenol A type epoxy resin;
30 parts of quartz chopped fiber;
15 parts of boron nitride nano-sheets;
5 parts of pyridine dimethyl anhydride;
2 parts of single-walled carbon nanotubes;
0.3 parts of phosphoric acid;
60 parts of N-methylpyrrolidone.
The step of preparing the connecting tail top for winding the composite material high-pressure container by using the connecting tail top material for winding the composite material high-pressure container comprises the following steps of:
s0: weighing the components according to the raw material components for standby;
s1: adding 100mL of N-methylpyrrolidone solvent into a three-necked flask, and adding the weighed carbon nano tube (length of 2-3 mu m, outer diameter of 1-2 mu m) and boron nitride nano sheet (size of 50-100 nm, thickness of 30-40 nm); performing ultrasonic dispersion treatment on the mixed solution for 30min by using an ultrasonic pulverizer (power 600W, frequency 40 kHz); adding pre-weighed bisphenol A epoxy resin and phosphoric acid, and stirring and mixing; transferring the mixed solution into a high-speed shearing stirrer (rotating speed 10000 rpm), and mixing for 10min to obtain uniform mixed solution.
S2: pre-cleaning quartz chopped fibers (15-20 mm) by using an N-methyl pyrrolidone solvent to remove surface impurities, drying the quartz chopped fibers in an oven, suspending the quartz chopped fibers in the prepared S1 mixed solution, manually stirring and impregnating, taking out the impregnated quartz chopped fibers, controlling the impregnating amount to be 30-50%, placing the impregnated quartz chopped fibers in a hot air circulation bellows, performing heat treatment for 6 hours at 70 ℃ for pre-curing, cleaning the pre-cured quartz chopped fibers to remove unreacted resin on the surface, and continuously drying in the oven for 1 hour.
S3: putting the quartz chopped fiber in the step S2 into a cylindrical mould pressing die for hot press forming, and pressurizing at least 3MPa in the whole process, wherein the temperature conditions and the curing time are as follows: pressing and solidifying at 40 ℃ for 30min, 55 ℃ for 30min, 70 ℃ for 30min, 100 ℃ for 90min, 130 ℃ for 240min, cooling to 45 ℃, demolding, and cooling to room temperature.
S4: and polishing the surface of the molded body by using a water grinding wheel to remove burrs, and then carrying out finish machining in a numerical control machining center to obtain the connecting tail top with the designed shape and size.
Example 5
The connecting tail top material for winding the composite material high-pressure container comprises the following raw material components in parts by weight:
100 parts of bisphenol A type epoxy resin;
30 parts of quartz chopped fiber;
15 parts of boron nitride nano-sheets;
5 parts of pyridine dimethyl anhydride;
2 parts of single-walled carbon nanotubes;
0.3 parts of phosphoric acid;
60 parts of N-methylpyrrolidone.
The step of preparing the connecting tail top for winding the composite material high-pressure container by using the connecting tail top material for winding the composite material high-pressure container comprises the following steps of:
s0: weighing the components according to the raw material components for standby;
s1: adding 100mL of N-methylpyrrolidone solvent into a three-necked flask, and adding the weighed carbon nano tube (length of 2-3 mu m, outer diameter of 1-2 mu m) and boron nitride nano sheet (size of 50-100 nm, thickness of 30-40 nm); performing ultrasonic dispersion treatment on the mixed solution for 30min by using an ultrasonic pulverizer (power 600W, frequency 40 kHz); adding pre-weighed bisphenol A epoxy resin and phosphoric acid, and stirring and mixing; transferring the mixed solution into a high-speed shearing stirrer (rotating speed 10000 rpm), and mixing for 10min to obtain uniform mixed solution.
S2: pre-cleaning quartz chopped fibers (15-20 mm) by using an N-methyl pyrrolidone solvent to remove surface impurities, drying the quartz chopped fibers in an oven, suspending the quartz chopped fibers in the prepared S1 mixed solution, manually stirring and impregnating, taking out the impregnated quartz chopped fibers, controlling the impregnating amount to be 30-50%, placing the impregnated quartz chopped fibers in a hot air circulation bellows, performing heat treatment for 6 hours at 70 ℃ for pre-curing, cleaning the pre-cured quartz chopped fibers to remove unreacted resin on the surface, and continuously drying in the oven for 1 hour.
S3: putting the quartz chopped fiber in the step S2 into a cylindrical mould pressing die for hot press forming, and pressurizing at least 3MPa in the whole process, wherein the temperature conditions and the curing time are as follows: solidifying at 40deg.C for 60min, solidifying at 100deg.C for 120min, solidifying at 130deg.C for 30min, solidifying at 160deg.C for 180min, cooling to 45deg.C, demolding, and cooling to room temperature.
S4: and polishing the surface of the molded body by using a water grinding wheel to remove burrs, and then carrying out finish machining in a numerical control machining center to obtain the connecting tail top with the designed shape and size.
Example 6
The connecting tail top material for winding the composite material high-pressure container comprises the following raw material components in parts by weight:
100 parts of bisphenol A type epoxy resin;
30 parts of quartz chopped fiber;
15 parts of boron nitride nano-sheets;
5 parts of pyridine dimethyl anhydride;
2 parts of single-walled carbon nanotubes;
0.3 parts of phosphoric acid;
60 parts of N-methylpyrrolidone.
The step of preparing the connecting tail top for winding the composite material high-pressure container by using the connecting tail top material for winding the composite material high-pressure container comprises the following steps of:
s0: weighing the components according to the raw material components for standby;
s1: adding 100mL of N-methylpyrrolidone solvent into a three-necked flask, and adding the weighed carbon nano tube (length of 2-3 mu m, outer diameter of 1-2 mu m) and boron nitride nano sheet (size of 50-100 nm, thickness of 30-40 nm); performing ultrasonic dispersion treatment on the mixed solution for 30min by using an ultrasonic pulverizer (power 600W, frequency 40 kHz); adding pre-weighed bisphenol A epoxy resin and phosphoric acid, and stirring and mixing; transferring the mixed solution into a high-speed shearing stirrer (rotating speed 10000 rpm), and mixing for 10min to obtain uniform mixed solution.
S2: pre-cleaning quartz chopped fibers (15-20 mm) by using an N-methyl pyrrolidone solvent to remove surface impurities, drying the quartz chopped fibers in an oven, suspending the quartz chopped fibers in the prepared S1 mixed solution, manually stirring and impregnating, taking out the impregnated quartz chopped fibers, controlling the impregnating amount to be 30-50%, placing the impregnated quartz chopped fibers in a hot air circulation bellows, performing heat treatment for 6 hours at 50 ℃ for pre-curing, cleaning the pre-cured quartz chopped fibers to remove unreacted resin on the surface, and continuously drying in the oven for 1 hour.
S3: putting the quartz chopped fiber in the step S2 into a cylindrical mould pressing die for hot press forming, and pressurizing at least 3MPa in the whole process, wherein the temperature conditions and the curing time are as follows: pressing and solidifying at 40 ℃ for 30min, 55 ℃ for 30min, 70 ℃ for 30min, 100 ℃ for 90min, 130 ℃ for 30min, 160 ℃ for 180min, cooling to 45 ℃, demolding, and cooling to room temperature.
S4: and polishing the surface of the molded body by using a water grinding wheel to remove burrs, and then carrying out finish machining in a numerical control machining center to obtain the connecting tail top with the designed shape and size.
Comparative example 1
The connecting tail top material for winding the composite material high-pressure container comprises the following raw material components in parts by weight:
100 parts of bisphenol A type epoxy resin;
30 parts of quartz chopped fiber;
17 parts of boron nitride nano-sheets;
5 parts of pyridine dimethyl anhydride;
0.3 parts of phosphoric acid;
60 parts of N-methylpyrrolidone.
The step of preparing the connecting tail top for winding the composite material high-pressure container by using the connecting tail top material for winding the composite material high-pressure container comprises the following steps of:
s0: weighing the components according to the raw material components for standby;
s1: adding 100mL of N-methyl pyrrolidone solvent into a three-necked flask, and adding the weighed boron nitride nanosheets (the size is 50-100 nm, and the thickness is 30-40 nm); performing ultrasonic dispersion treatment on the mixed solution for 30min by using an ultrasonic pulverizer (power 600W, frequency 40 kHz); adding pre-weighed bisphenol A epoxy resin and phosphoric acid, and stirring and mixing; transferring the mixed solution into a high-speed shearing stirrer (rotating speed 10000 rpm), and mixing for 10min to obtain uniform mixed solution.
S2: pre-cleaning quartz chopped fibers (15-20 mm) by using an N-methyl pyrrolidone solvent to remove surface impurities, drying the quartz chopped fibers in an oven, suspending the quartz chopped fibers in the prepared S1 mixed solution, manually stirring and impregnating, taking out the impregnated quartz chopped fibers, controlling the impregnating amount to be 30-50%, placing the impregnated quartz chopped fibers in a hot air circulation bellows, performing heat treatment for 6 hours at 70 ℃ for pre-curing, cleaning the pre-cured quartz chopped fibers to remove unreacted resin on the surface, and continuously drying in the oven for 1 hour.
S3: putting the quartz chopped fiber in the step S2 into a cylindrical mould pressing die for hot press forming, and pressurizing at least 3MPa in the whole process, wherein the temperature conditions and the curing time are as follows: pressing and solidifying at 40 ℃ for 30min, 55 ℃ for 30min, 70 ℃ for 30min, 100 ℃ for 90min, 130 ℃ for 30min, 160 ℃ for 180min, cooling to 45 ℃, demolding, and cooling to room temperature.
S4: and polishing the surface of the molded body by using a water grinding wheel to remove burrs, and then carrying out finish machining in a numerical control machining center to obtain the connecting tail top with the designed shape and size.
Comparative example 2
The connecting tail top material for winding the composite material high-pressure container comprises the following raw material components in parts by weight:
100 parts of bisphenol A type epoxy resin;
30 parts of quartz chopped fiber;
5 parts of pyridine dimethyl anhydride;
17 parts of single-walled carbon nanotubes;
0.3 parts of phosphoric acid;
60 parts of N-methylpyrrolidone.
The step of preparing the connecting tail top for winding the composite material high-pressure container by using the connecting tail top material for winding the composite material high-pressure container comprises the following steps of:
s0: weighing the components according to the raw material components for standby;
s1: adding 100mL of N-methylpyrrolidone solvent into a three-necked flask, and adding the weighed carbon nano tube (the length is 2-3 mu m, and the outer diameter is 1-2 mu m); performing ultrasonic dispersion treatment on the mixed solution for 30min by using an ultrasonic pulverizer (power 600W, frequency 40 kHz); adding pre-weighed bisphenol A epoxy resin and phosphoric acid, and stirring and mixing; transferring the mixed solution into a high-speed shearing stirrer (rotating speed 10000 rpm), and mixing for 10min to obtain uniform mixed solution.
S2: pre-cleaning quartz chopped fibers (15-20 mm) by using an N-methyl pyrrolidone solvent to remove surface impurities, drying the quartz chopped fibers in an oven, suspending the quartz chopped fibers in the prepared S1 mixed solution, manually stirring and impregnating, taking out the impregnated quartz chopped fibers, controlling the impregnating amount to be 30-50%, placing the impregnated quartz chopped fibers in a hot air circulation bellows, performing heat treatment for 6 hours at 70 ℃ for pre-curing, cleaning the pre-cured quartz chopped fibers to remove unreacted resin on the surface, and continuously drying in the oven for 1 hour.
S3: putting the quartz chopped fiber in the step S2 into a cylindrical mould pressing die for hot press forming, and pressurizing at least 3MPa in the whole process, wherein the temperature conditions and the curing time are as follows: pressing and solidifying at 40 ℃ for 30min, 55 ℃ for 30min, 70 ℃ for 30min, 100 ℃ for 90min, 130 ℃ for 30min, 160 ℃ for 180min, cooling to 45 ℃, demolding, and cooling to room temperature.
S4: and polishing the surface of the molded body by using a water grinding wheel to remove burrs, and then carrying out finish machining in a numerical control machining center to obtain the connecting tail top with the designed shape and size.
Comparative example 3
The connecting tail top material for winding the composite material high-pressure container comprises the following raw material components in parts by weight:
100 parts of aromatic hydrocarbon epoxy resin;
30 parts of quartz chopped fiber;
15 parts of boron nitride nano-sheets;
5 parts of pyridine dimethyl anhydride;
2 parts of single-walled carbon nanotubes;
0.3 parts of phosphoric acid;
60 parts of N-methylpyrrolidone.
The step of preparing the connecting tail top for winding the composite material high-pressure container by using the connecting tail top material for winding the composite material high-pressure container comprises the following steps of:
s0: weighing the components according to the raw material components for standby;
s1: adding 100mL of N-methylpyrrolidone solvent into a three-necked flask, and adding the weighed carbon nano tube (length of 2-3 mu m, outer diameter of 1-2 mu m) and boron nitride nano sheet (size of 50-100 nm, thickness of 30-40 nm); performing ultrasonic dispersion treatment on the mixed solution for 30min by using an ultrasonic pulverizer (power 600W, frequency 40 kHz); adding pre-weighed aromatic hydrocarbon epoxy resin and phosphoric acid, and stirring and mixing; transferring the mixed solution into a high-speed shearing stirrer (rotating speed 10000 rpm), and mixing for 10min to obtain uniform mixed solution.
S2: pre-cleaning quartz chopped fibers (15-20 mm) by using an N-methyl pyrrolidone solvent to remove surface impurities, drying the quartz chopped fibers in an oven, suspending the quartz chopped fibers in the prepared S1 mixed solution, manually stirring and impregnating, taking out the impregnated quartz chopped fibers, controlling the impregnating amount to be 30-50%, placing the impregnated quartz chopped fibers in a hot air circulation bellows, performing heat treatment for 6 hours at 70 ℃ for pre-curing, cleaning the pre-cured quartz chopped fibers to remove unreacted resin on the surface, and continuously drying in the oven for 1 hour.
S3: putting the quartz chopped fiber in the step S2 into a cylindrical mould pressing die for hot press forming, and pressurizing at least 3MPa in the whole process, wherein the temperature conditions and the curing time are as follows: pressing and solidifying at 40 ℃ for 30min, 55 ℃ for 30min, 70 ℃ for 30min, 100 ℃ for 90min, 130 ℃ for 30min, 160 ℃ for 180min, cooling to 45 ℃, demolding, and cooling to room temperature.
S4: and polishing the surface of the molded body by using a water grinding wheel to remove burrs, and then carrying out finish machining in a numerical control machining center to obtain the connecting tail top with the designed shape and size.
Comparative example 4
The connecting tail top material for winding the composite material high-pressure container comprises the following raw material components in parts by weight:
100 parts of isocyanate epoxy resin;
30 parts of quartz chopped fiber;
15 parts of boron nitride nano-sheets;
5 parts of pyridine dimethyl anhydride;
2 parts of single-walled carbon nanotubes;
0.3 parts of phosphoric acid;
60 parts of N-methylpyrrolidone.
The step of preparing the connecting tail top for winding the composite material high-pressure container by using the connecting tail top material for winding the composite material high-pressure container comprises the following steps of:
s0: weighing the components according to the raw material components for standby;
s1: adding 100mL of N-methylpyrrolidone solvent into a three-necked flask, and adding the weighed carbon nano tube (length of 2-3 mu m, outer diameter of 1-2 mu m) and boron nitride nano sheet (size of 50-100 nm, thickness of 30-40 nm); performing ultrasonic dispersion treatment on the mixed solution for 30min by using an ultrasonic pulverizer (power 600W, frequency 40 kHz); adding pre-weighed isocyanate epoxy resin and phosphoric acid, and stirring and mixing; transferring the mixed solution into a high-speed shearing stirrer (rotating speed 10000 rpm), and mixing for 10min to obtain uniform mixed solution.
S2: pre-cleaning quartz chopped fibers (15-20 mm) by using an N-methyl pyrrolidone solvent to remove surface impurities, drying the quartz chopped fibers in an oven, suspending the quartz chopped fibers in the prepared S1 mixed solution, manually stirring and impregnating, taking out the impregnated quartz chopped fibers, controlling the impregnating amount to be 30-50%, placing the impregnated quartz chopped fibers in a hot air circulation bellows, performing heat treatment for 6 hours at 70 ℃ for pre-curing, cleaning the pre-cured quartz chopped fibers to remove unreacted resin on the surface, and continuously drying in the oven for 1 hour.
S3: putting the quartz chopped fiber in the step S2 into a cylindrical mould pressing die for hot press forming, and pressurizing at least 3MPa in the whole process, wherein the temperature conditions and the curing time are as follows: pressing and solidifying at 40 ℃ for 30min, 55 ℃ for 30min, 70 ℃ for 30min, 100 ℃ for 90min, 130 ℃ for 30min, 160 ℃ for 180min, cooling to 45 ℃, demolding, and cooling to room temperature.
S4: and polishing the surface of the molded body by using a water grinding wheel to remove burrs, and then carrying out finish machining in a numerical control machining center to obtain the connecting tail top with the designed shape and size.
Comparative example 5
The connecting tail top material for winding the composite material high-pressure container comprises the following raw material components in parts by weight:
100 parts of gel type epoxy resin;
30 parts of quartz chopped fiber;
15 parts of boron nitride nano-sheets;
5 parts of pyridine dimethyl anhydride;
2 parts of single-walled carbon nanotubes;
0.3 parts of phosphoric acid;
60 parts of N-methylpyrrolidone.
The step of preparing the connecting tail top for winding the composite material high-pressure container by using the connecting tail top material for winding the composite material high-pressure container comprises the following steps of:
s0: weighing the components according to the raw material components for standby;
s1: adding 100mL of N-methylpyrrolidone solvent into a three-necked flask, and adding the weighed carbon nano tube (length of 2-3 mu m, outer diameter of 1-2 mu m) and boron nitride nano sheet (size of 50-100 nm, thickness of 30-40 nm); performing ultrasonic dispersion treatment on the mixed solution for 30min by using an ultrasonic pulverizer (power 600W, frequency 40 kHz); adding pre-weighed gel-type epoxy resin and phosphoric acid, and stirring and mixing; transferring the mixed solution into a high-speed shearing stirrer (rotating speed 10000 rpm), and mixing for 10min to obtain uniform mixed solution.
S2: pre-cleaning quartz chopped fibers (15-20 mm) by using an N-methyl pyrrolidone solvent to remove surface impurities, drying the quartz chopped fibers in an oven, suspending the quartz chopped fibers in the prepared S1 mixed solution, manually stirring and impregnating, taking out the impregnated quartz chopped fibers, controlling the impregnating amount to be 30-50%, placing the impregnated quartz chopped fibers in a hot air circulation bellows, performing heat treatment for 6 hours at 70 ℃ for pre-curing, cleaning the pre-cured quartz chopped fibers to remove unreacted resin on the surface, and continuously drying in the oven for 1 hour.
S3: putting the quartz chopped fiber in the step S2 into a cylindrical mould pressing die for hot press forming, and pressurizing at least 3MPa in the whole process, wherein the temperature conditions and the curing time are as follows: pressing and solidifying at 40 ℃ for 30min, 55 ℃ for 30min, 70 ℃ for 30min, 100 ℃ for 90min, 130 ℃ for 30min, 160 ℃ for 180min, cooling to 45 ℃, demolding, and cooling to room temperature.
S4: and polishing the surface of the molded body by using a water grinding wheel to remove burrs, and then carrying out finish machining in a numerical control machining center to obtain the connecting tail top with the designed shape and size.
Comparative example 6
This comparative example was essentially the same as example 1 except that the connecting tail top material for high pressure vessel winding of the composite material contained no phosphoric acid, and therefore, the phosphoric acid was not added correspondingly in the preparation step.
Test example 1
In the test example, performance tests are carried out on the connecting tail jacks prepared in the example and the comparative example, wherein the test performances comprise thermal expansion coefficient, low-temperature shrinkage, tensile strength, bending strength and ablation resistance, in the performance tests of the low-temperature shrinkage and the thermal expansion coefficient, the deformation degree of the resin matrix composite material under the conditions of low temperature and high temperature can be tested, and the test is carried out by a thermal engine analyzer (TMA) at the temperature range of-100 ℃ to 200 ℃ and the heating rate of 10 ℃/min and according to the ASTM E831 standard; the tensile strength and the bending strength are tested by a universal material tester, and the testing standard is respectively carried out according to ASTM D3039 (tensile strength) and ASTM D7264 (bending resistance), and the testing speed is 2mm/min; the ablation performance test uses an oxygen/propane ablation device, and the heat flow is set to 116KW/m according to ASTM E285 standard 2 The oxypropane volume ratio was 1.0, and the material mass loss rate was recorded. The results of the performance tests are shown in Table 1 below.
TABLE 1 Performance test results
As can be seen from the results of Table 1, examples 1 to 3 in this scheme have a good thermal expansion coefficient (15.5×10 -6 /℃～16.2*10 -6 Per deg.c), low temperature shrinkage and tensile strength (34.1 x 10 -6 /℃～34.8*10 -6 Per DEG C), flexural strength (1.47 x 10 3 MPa～1.54*10 3 MPa) and ablation resistance (1.2-1.3%), wherein compared with example 1 according to comparative examples 1 and 2, the addition of the boron nitride nanosheets and the single wall carbon nanotubes in the scheme of the application can improve the bending resistance and tensile strength, and the synergistic combination of the two can play a further synergistic effect, so that the bending resistance and the tensile strength are greatly improved, and the obvious synergistic effect is achieved. As can be seen from comparative examples 3, 4 and 5, compared with example 1, the selection of the epoxy resin has a larger influence on bending resistance and tensile property, wherein the synergistic effect of the bisphenol a epoxy resin and the boron nitride nano-sheet and the single-walled carbon nano-tube is most obvious, and as can be seen from comparative example 6, the further addition of phosphoric acid and the boron nitride nano-sheet and the single-walled carbon nano-tube are used in a matched manner, so that the bending resistance and the tensile property are obviously improved, the thermal expansion coefficient and the cold shrinkage property are also obviously improved, and experimental staff find that the addition of phosphoric acid can obviously improve the bonding property of the boron nitride nano-sheet, the single-walled carbon nano-tube and the epoxy resin, thereby being beneficial to the dispersion of the boron nitride nano-sheet and the single-walled carbon nano-tube and the interface bonding effect of the boron nitride nano-sheet and the single-walled carbon nano-tube and the epoxy resin.
The foregoing is merely exemplary of the present application, and the scope of the present application is not limited to the specific embodiments, but is defined by the claims of the present application. Various modifications and changes may be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical ideas and principles of the present application should be included in the protection scope of the present application.
Claims (10)
1. The connecting tail top material for winding the composite material high-pressure container is characterized by comprising the following raw material components in parts by weight:
80-120 parts of epoxy resin;
25-35 parts of quartz chopped fiber;
10-20 parts of boron nitride nano-sheets;
3-10 parts of curing agent;
1-3 parts of single-wall carbon nano tube;
0.2 to 0.5 part of phosphoric acid;
50-70 parts of organic solvent.
2. The composite high pressure vessel winding connection tail cap material of claim 2, wherein the epoxy resin is bisphenol a type epoxy resin.
3. The connecting tail top material for winding composite material high-pressure containers according to claim 2, characterized in that the bisphenol a type epoxy resin has a viscosity of 8000-12000 mPa-s at 25 ℃ and a hydroxyl group content of 0.15-0.25 mmol/g.
4. The connecting tail cap material for winding composite material high pressure vessels according to claim 1 wherein the single wall carbon nanotubes have a length of 1 to 5 μm and an outer diameter of no more than 2 μm; and/or the number of the groups of groups,
the plane size of the boron nitride nano sheet is 50-200 nm, and the thickness is less than 50nm; and/or the number of the groups of groups,
the length of the chopped fiber is 10-20 mm.
5. The connecting tail top material for winding a composite high-pressure container according to claim 1, wherein the organic solvent is one or more of N-methyl pyrrolidone, N-dimethylacetamide and N-methyl-2-pyrrolidone, and the curing agent is one or more of pyridine dimethyl anhydride, methacrylic anhydride, mercapto acrylic anhydride, diethanolamine, triethanolamine, resorcinol, methylphthalic anhydride, cyclohexanephthalic anhydride, resorcinol and o-cresol.
6. The connecting tail top material for winding composite high-pressure containers according to claim 5, wherein the organic solvent is N-methyl pyrrolidone and the curing agent is pyridine dicarboxylic acid anhydride.
7. A method for preparing a connecting tail top for winding a composite material high-pressure container, which is characterized in that the connecting tail top material for winding the composite material high-pressure container is adopted, and the method for preparing the connecting tail top material comprises the following steps:
s1, dispersing and dissolving boron nitride nano-sheets and carbon nano-tubes in an organic solvent, adding epoxy resin and phosphoric acid, and uniformly mixing;
s2, pre-soaking the quartz chopped fibers by a hot-melt method;
s3, performing hot press molding after drying;
and S4, cooling to 45-55 ℃, demolding, polishing and carrying out subsequent machine tool processing treatment to obtain the connecting tail top.
8. The method for producing a connecting tail cap for high-pressure container winding of composite material according to claim 7, wherein the hot-melt prepreg in step S2 comprises a step of treating at 65 to 75 ℃ for 5 to 7 hours.
9. The method for producing a connecting tail cap for high-pressure container winding of composite material according to claim 7, wherein the conditions for hot press forming in step S3 include: pressurizing at least 3MPa in the whole course, treating at 40+ -5deg.C for 30+ -10 min, treating at 55+ -5deg.C for 30+ -10 min, treating at 70+ -5deg.C for 30+ -10 min, treating at 100+ -5deg.C for 90+ -10 min, treating at 130+ -5deg.C for 30+ -10 min, and treating at 160+ -5deg.C for 180+ -10 min.
10. Use of a connecting tail cap material for the winding of a composite high pressure vessel according to any one of claims 1 to 6 in the manufacture of a pressure vessel.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101568144B1 (en) * | 2014-05-27 | 2015-11-11 | 경상대학교산학협력단 | Nanocomposite containing carbon nanotubes and manufacturing method of the same |
| WO2016086587A1 (en) * | 2014-12-04 | 2016-06-09 | 中国科学院过程工程研究所 | Thermally conductive and insulating epoxy resin composition and preparation method therefor and use thereof |
| KR20200086123A (en) * | 2019-01-08 | 2020-07-16 | 인하대학교 산학협력단 | Basalt fiber reinforced epoxy composites reinforced with ozone treated single-walled carbon nanotubes and method for manufacturing the same |
| WO2020258621A1 (en) * | 2019-06-26 | 2020-12-30 | 苏州太湖电工新材料股份有限公司 | High thermal conductivity modified epoxy resin and preparation method therefor |
| CN112778703A (en) * | 2021-01-06 | 2021-05-11 | 沈阳航空航天大学 | High-toughness and heat-conducting epoxy resin composite material and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101568144B1 (en) * | 2014-05-27 | 2015-11-11 | 경상대학교산학협력단 | Nanocomposite containing carbon nanotubes and manufacturing method of the same |
| WO2016086587A1 (en) * | 2014-12-04 | 2016-06-09 | 中国科学院过程工程研究所 | Thermally conductive and insulating epoxy resin composition and preparation method therefor and use thereof |
| KR20200086123A (en) * | 2019-01-08 | 2020-07-16 | 인하대학교 산학협력단 | Basalt fiber reinforced epoxy composites reinforced with ozone treated single-walled carbon nanotubes and method for manufacturing the same |
| WO2020258621A1 (en) * | 2019-06-26 | 2020-12-30 | 苏州太湖电工新材料股份有限公司 | High thermal conductivity modified epoxy resin and preparation method therefor |
| CN112778703A (en) * | 2021-01-06 | 2021-05-11 | 沈阳航空航天大学 | High-toughness and heat-conducting epoxy resin composite material and preparation method thereof |
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