CN114110413B - Carbon fiber composite material thick-wall gas cylinder and preparation method thereof - Google Patents
Carbon fiber composite material thick-wall gas cylinder and preparation method thereof Download PDFInfo
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- CN114110413B CN114110413B CN202111326434.7A CN202111326434A CN114110413B CN 114110413 B CN114110413 B CN 114110413B CN 202111326434 A CN202111326434 A CN 202111326434A CN 114110413 B CN114110413 B CN 114110413B
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
- F17C1/02—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge involving reinforcing arrangements
- F17C1/04—Protecting sheathings
- F17C1/06—Protecting sheathings built-up from wound-on bands or filamentary material, e.g. wires
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2201/00—Vessel construction, in particular geometry, arrangement or size
- F17C2201/01—Shape
- F17C2201/0104—Shape cylindrical
- F17C2201/0109—Shape cylindrical with exteriorly curved end-piece
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2201/00—Vessel construction, in particular geometry, arrangement or size
- F17C2201/03—Orientation
- F17C2201/035—Orientation with substantially horizontal main axis
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2203/00—Vessel construction, in particular walls or details thereof
- F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
- F17C2203/0634—Materials for walls or layers thereof
- F17C2203/0658—Synthetics
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2203/00—Vessel construction, in particular walls or details thereof
- F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
- F17C2203/0634—Materials for walls or layers thereof
- F17C2203/0658—Synthetics
- F17C2203/0663—Synthetics in form of fibers or filaments
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2203/00—Vessel construction, in particular walls or details thereof
- F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
- F17C2203/0634—Materials for walls or layers thereof
- F17C2203/0658—Synthetics
- F17C2203/0663—Synthetics in form of fibers or filaments
- F17C2203/067—Synthetics in form of fibers or filaments helically wound
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Filling Or Discharging Of Gas Storage Vessels (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
The invention discloses a preparation method of a carbon fiber composite material thick-wall gas cylinder, which comprises the steps of firstly preparing a low-viscosity high-toughness winding resin, then enabling carbon fibers to be soaked in the low-viscosity high-toughness winding resin, winding the carbon fibers on the outer surface of a lining in a specific winding and arranging mode, and curing the carbon fibers by a specific curing system to obtain the carbon fiber composite material thick-wall gas cylinder. The low-viscosity high-toughness winding resin and the carbon fiber prepared by the invention have good interface matching performance, particularly domestic T800 carbon fiber, and the winding and arrangement modes of the carbon fiber comprise a multi-level step-by-step reaming layering structure, a proper tension decreasing system and the like, so that the good exertion of the strength of the carbon fiber can be ensured; the domestic T800 carbon fiber composite material thick-wall gas cylinder prepared by the method has burst pressure of more than 230MPa and volume of 70L, the weight of the composite material gas cylinder is not more than 80kg, the product quality is excellent, and the method is suitable for application scenes such as storing high-pressure hydrogen for vehicles in a new energy vehicle-mounted hydrogen storage system.
Description
Technical Field
The invention belongs to the field of new energy vehicle-mounted hydrogen storage systems, and relates to a carbon fiber composite material thick-wall gas cylinder and a preparation method thereof.
Background
The carbon fiber composite material has the excellent characteristics of light weight, high strength, fatigue resistance and the like, and is widely applied to the fields of aerospace, civil products and the like. Along with the increasing importance of energy conservation and emission reduction in various countries in the world, concepts such as carbon neutralization are provided, and research and application of new energy automobiles are widely developed. Fuel cell automobiles have received a great deal of attention as one of new energy automobiles. The vehicle-mounted hydrogen storage bottle is used as a key component of a power system and plays an important role in storing high-pressure hydrogen. In recent years, intensive researches on high-pressure storage gas cylinders are carried out by taking research units such as Zhejiang university, style, kotek and the like as representatives, and the national standard of high-pressure 70MPa composite hydrogen storage gas cylinders of aluminum alloy inner containers, the standard of nonmetallic lining high-pressure 70MPa composite groups and the like are formed at present.
However, the carbon fiber used in the prior high-pressure composite material hydrogen storage cylinder is mainly imported fiber such as Japanese east T700S, T S, and the application of domestic carbon fiber to form the high-pressure 70MPa composite material hydrogen storage cylinder is rare. With the increasing investment of the development of the domestic carbon fiber in recent years, the performance of the domestic carbon fiber is obviously improved, for example, the domestic T800 carbon fiber basically reaches or exceeds the performance of the imported equivalent fiber, and the preparation of the composite material hydrogen storage cylinder by adopting the domestic T800 carbon fiber is beneficial to promoting the application of the domestic carbon fiber. Compared with T700 fiber, the T800 carbon fiber has obviously improved tensile property, and the composite material gas cylinder prepared by adopting the T800 carbon fiber has good weight reduction effect. Because the bursting pressure of the 70MPa composite material hydrogen storage cylinder is more than 2.5 times of the working pressure of the hydrogen storage cylinder, taking the outer diameter of a conventional 300mm liner as an example, the thickness of a composite material layer is about 30mm, and the composite material hydrogen storage cylinder is a typical thick-wall composite material cylinder, how to exert the performance of the domestic T800 carbon fiber is a key problem for promoting the domestic carbon fiber to be applied to the field of high-pressure hydrogen storage cylinders.
Disclosure of Invention
The invention aims to overcome the defects and provide a preparation method of a carbon fiber composite material thick-wall gas cylinder, which comprises the steps of firstly preparing low-viscosity high-toughness winding resin, then soaking carbon fibers in the low-viscosity high-toughness winding resin, winding the carbon fibers on the outer surface of a lining in a specific winding and arranging mode, and curing the carbon fibers by a specific curing system to obtain the carbon fiber composite material thick-wall gas cylinder. The low-viscosity high-toughness winding resin and the carbon fiber prepared by the invention have good interface matching performance, particularly domestic T800 carbon fiber, and the winding and arrangement modes of the carbon fiber comprise a multi-level step-by-step reaming layering structure, a proper tension decreasing system and the like, so that the strength of the carbon fiber can be well exerted; the domestic T800 carbon fiber composite material thick-wall gas cylinder prepared by the method has burst pressure of more than 230MPa and volume of 70L, the weight of the composite material gas cylinder is not more than 80kg, the product quality is excellent, and the method is suitable for application scenes such as storing high-pressure hydrogen for vehicles in a new energy vehicle-mounted hydrogen storage system.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a preparation method of a carbon fiber composite thick-wall gas cylinder comprises the following steps:
(1) Preparing resin A by using the following raw materials in parts by weight:
(2) Preparing a curing agent B by using the following raw materials in parts by weight:
20 parts of diethyl toluenediamine;
5-6 parts of diaminodiphenyl methane;
0.5 to 0.8 portion of 2-ethyl-4-methylimidazole;
(3) Uniformly mixing the resin A and the curing agent B to obtain winding resin; the mass part ratio of the resin A to the curing agent B is 100:23-27;
(4) Manufacturing a lining of the carbon fiber composite thick-wall gas cylinder, coating the winding resin obtained in the step (3) on the outer surface of the lining to form a winding resin layer, winding the electrochemical corrosion-resistant glass fiber composite material on the surface of the winding resin layer to form an electrochemical corrosion-resistant glass fiber composite material layer;
(5) Soaking carbon fibers in the winding resin prepared in the step (3) according to a preset threading sequence, and winding the surface of the electrochemical corrosion-resistant glass fiber composite material layer formed in the step (4) to form a carbon fiber composite material layer;
(6) And (3) solidifying the product obtained in the step (5) to obtain the carbon fiber composite thick-wall gas cylinder.
Further, the carbon fiber used in the step (5) is domestic T800 carbon fiber.
Further, in the step (1), the raw materials are mixed and then preheated to 30-40 ℃, and the mixture is stirred uniformly to obtain resin A;
in the step (2), the raw materials are mixed and heated to 80-100 ℃, and the mixture is stirred to a transparent state to obtain a curing agent B;
in the step (3), the curing agent B is cooled to 40-60 ℃ and is uniformly mixed with the resin A to obtain the winding resin.
Further, in the step (4), the nozzles at the two ends of the metal lining are connected with winding support rods, the winding support rods are arranged on a winding machine, and the surface of the winding resin layer is wound with the electrochemical corrosion-resistant glass fiber composite material by the winding machine;
in the step (4), a lining of the carbon fiber composite material thick-wall gas cylinder is manufactured, the outer surface of the lining is cleaned, and winding resin obtained in the step (3) is coated on the outer surface of the lining to form a winding resin layer.
Further, in the step (5), at the temperature of 30-40 ℃, the carbon fibers are soaked in the winding resin obtained in the step (3) according to the preset threading sequence, and the surface of the electrochemical corrosion resistant glass fiber composite material layer formed in the step (4) is wound in a winding mode of combining spiral winding and circumferential winding; a tension decreasing system is adopted during winding;
the spiral winding adopts a step-by-step reaming scheme for 5 times.
Further, in the step (6), the specific curing step is that the heat is preserved for 8 hours at 70+/-3 ℃ in sequence, the heat is preserved for 4 hours at 120+/-3 ℃ and the temperature is reduced to 40 ℃ after the heat is preserved for 5 hours at 150+/-3 ℃; the curing temperature rising rate is 20-30 ℃/h; and (3) maintaining the rotation of the product obtained in the step (5) in the curing process, wherein the rotation speed is 1-3 rpm.
Further, in the step (3), the mass part ratio of the resin A to the curing agent B is 100:25.
Further, in the step (4), the glass fibers in the electrochemical corrosion-resistant glass fiber composite material are S4C-660JA glass fibers;
in the step (5), the number of winding yarn groups when the carbon fiber winds the surface of the electrochemical corrosion-resistant glass fiber composite material layer formed in the step (4) is 3-5 groups of yarns, and the carbon fiber used in the step (5) is TG800-24K carbon fiber.
Further, in the step (5), the winding line type sequence when the carbon fiber winds the surface of the electrochemical corrosion resistant glass fiber composite material layer formed in the step (4) is as follows: 3 layers of circumferential winding/14 ° spiral winding/19 ° spiral winding/25 ° spiral winding/3 layers of circumferential winding/30 ° spiral winding/36 ° spiral winding/42 ° spiral winding/3 layers of circumferential winding/75 ° spiral winding/14 ° spiral winding/19 ° spiral winding/25 ° spiral winding/3 layers of circumferential winding/30 ° spiral winding/36 ° spiral winding/42 ° spiral winding/4 layers of circumferential winding/14 ° spiral winding/19 ° spiral winding/25 ° spiral winding/3 layers of circumferential winding/30 ° spiral winding/36 ° spiral winding/42 ° spiral winding/3 layers of circumferential winding/75 ° spiral winding; winding/10 DEG spiral winding/14 DEG spiral winding/19 DEG spiral winding/3-layer circumferential winding/25 DEG spiral winding/30 DEG spiral winding/36 DEG spiral winding/3-layer circumferential winding/75 DEG spiral winding/10 DEG spiral winding/14 DEG spiral winding/3-layer circumferential winding/19 DEG spiral winding/25 DEG spiral winding/30 DEG spiral winding/2-layer 75 DEG spiral winding/1-layer circumferential winding/75 DEG spiral winding/10 DEG spiral winding/14 DEG spiral winding/3-layer circumferential winding/19 DEG spiral winding/25 DEG spiral winding/4-layer circumferential winding, each layer represents a cyclically wound layer.
Further, in the step (5), the initial tension of the wound fiber is 60 to 80N/bundle, and after each winding cycle, the tension of the next winding cycle becomes 99% of the previous cycle.
The carbon fiber composite material thick-wall gas cylinder is obtained by the preparation method of the carbon fiber composite material thick-wall gas cylinder, the inner liner in the carbon fiber composite material thick-wall gas cylinder is made of metal, the outer diameter of the inner liner is more than 300mm, the wall thickness of the inner liner barrel section is more than or equal to 7mm, and the volume is more than or equal to 70L.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the preparation method of the carbon fiber composite material thick-wall gas cylinder, a winding resin system with low viscosity and high toughness is designed, so that carbon fibers are well soaked in the winding process, the phenomenon of dry yarn is avoided, the interface combination between the high-toughness resin system and the carbon fibers is good, no resin cracks are generated in the fatigue process of the gas cylinder, and the quality of the gas cylinder is improved; the winding resin system designed by the invention is particularly suitable for infiltration of domestic T800 carbon fibers;
(2) According to the preparation method of the carbon fiber composite material thick-wall gas cylinder, the glass fiber winding layer is used as the electrochemical corrosion prevention layer, so that potential difference between the carbon fiber composite material layer and the metal lining is prevented, and electrochemical corrosion to the lining is avoided;
(3) According to the preparation method of the carbon fiber composite material thick-wall gas cylinder, a winding scheme of the carbon fiber is designed to be that spiral winding and circumferential winding alternate with each other, and 5 times of gradual uniform reaming are carried out; the optimal range of the number of the winding yarn groups is designed to be 3-5 groups of yarns, so that the winding forming efficiency is improved; in addition, the initial tension of the winding fiber is 60-80 per bundle, after each winding cycle, the tension of the next winding cycle is changed into 99% of the previous cycle, the outer and inner loose of the carbon fiber composite material layer are avoided, and the problem that the playing strength of the fiber is low due to overlarge tension decrease is avoided; when the volume of the composite material gas cylinder prepared by the method is equal to 70L, the weight of the gas cylinder is not more than 80kg, and the bursting strength is not less than 230MPa;
(4) According to the preparation method of the carbon fiber composite material thick-wall gas cylinder, provided by the invention, the air and small molecules in the carbon fiber composite material winding layer can escape conveniently through a specific curing system, so that conditions are provided for uniform curing of resin, non-uniform curing of the carbon fiber composite material layer is prevented, and the defects of no air hole inclusion and the like in nondestructive inspection of the gas cylinder are ensured.
Drawings
Fig. 1 is a schematic sectional view of a thick-wall gas cylinder made of carbon fiber composite material.
Detailed Description
The features and advantages of the present invention will become more apparent and clear from the following detailed description of the invention.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. Although various aspects of the embodiments are illustrated in the accompanying drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
The invention discloses a preparation method of a carbon fiber composite material thick-wall gas cylinder, which adopts a high-toughness impact-resistant wet winding resin system suitable for winding and forming of a wet spinning carbon fiber composite material, and simultaneously provides a fiber winding and layering arrangement mode, and the fiber playing strength is obviously improved. The preparation method of the invention comprises the following steps:
step 1: low viscosity (room temperature viscosity <1000 mpa.s) high toughness (room temperature elongation at break > 5%) winding resin system configuration:
firstly, respectively preparing a resin A component and a curing agent B component according to the proportion of each component;
the resin A component is prepared from the following raw materials in parts by weight: bisphenol a epoxy resin: ethylene glycol diglycidyl ether: tetrahydrophthalic acid diglycidyl ester: polyurethane modified epoxy resin=70:20-24:10-12:10-12; the raw materials are mixed and preheated to 30-40 ℃ and stirred uniformly during the preparation;
the curing agent B is prepared from the following raw materials in parts by weight: diethyl toluene diamine: diaminodiphenylmethane: 2-ethyl-4-methylimidazole=20:5-6:0.5-0.8, and the raw materials are mixed and preheated to 80-100 ℃ and stirred to a transparent state when the raw materials are prepared;
and finally, cooling the component B of the curing agent to 40-60 ℃, and according to the component A of the resin: mixing and stirring the resin A component and the curing agent B component uniformly in a weight part ratio of the curing agent B component=100:23-27 to obtain winding resin;
step 2: winding an electrochemical corrosion prevention layer: connecting nozzles at two ends of a metal lining with winding support rods, mounting the winding support rods on a winding machine, cleaning dust, greasy dirt and the like on the outer surface of the lining by using acetone or other sol, brushing a layer of low-viscosity high-toughness winding resin prepared in the step 1, and winding a layer of electrochemical corrosion-resistant glass fiber composite material on the outer surface of the winding resin;
step 3: winding: soaking continuous carbon fibers in the winding resin obtained in the step 1 at 30-40 ℃ according to the yarn penetrating sequence, and winding an electrochemical corrosion-resistant glass fiber composite material layer on the outer surface of the lining, wherein the winding mode adopts a mode of combining spiral direction and annular direction, and the spiral direction winding adopts a 5-time step-by-step reaming scheme (step reaming means that the polar hole diameter of each later layer of spiral winding layer is larger than that of the polar hole of the last layer of spiral winding layer); a tension decreasing system is adopted during winding;
step 4: curing system: and (3) adopting 70+/-3 ℃/8 h+120+/-3 ℃/4h+150+/-3 ℃/5h, and cooling to 40 ℃ along with an oven after curing, wherein the composite material gas cylinder is kept rotating at a low speed during curing, and the rotating speed is 1-3 rpm.
Further, in the step 3, the carbon fiber is domestic T800 carbon fiber;
in the step 1, the low-viscosity high-toughness winding resin system is prepared from the following raw materials in parts by weight: curing agent B component = 100:25.
In the step 2, the glass fiber adopted in the electrochemical corrosion-resistant glass fiber composite material is S4C-660JA, and the matrix is the winding resin prepared in the step 1.
Further, in the step 3, the number of carbon fiber winding yarn groups is 4 groups of yarns; the carbon fiber is TG800-24K carbon fiber.
Further, in step 3, the winding order of the carbon fibers is as follows: 3 layers of circumferential windings/14 ° spiral windings/19 ° spiral windings/25 ° spiral windings/3 layers of circumferential windings/30 ° spiral windings/36 ° spiral windings/42 ° spiral windings/3 layers of circumferential windings/75 ° spiral windings/14 ° spiral windings/19 ° spiral windings/3 layers of circumferential windings/30 ° spiral windings/36 ° spiral windings/42 ° spiral windings/4 layers of circumferential windings/14 ° spiral windings/19 ° spiral windings/25 ° spiral windings/3 layers of circumferential windings/30 ° spiral windings/36 ° spiral windings/42 ° spiral windings/3 layers of circumferential windings/75 ° spiral windings/10 ° spiral windings/14 ° spiral windings/19 ° spiral windings/3 layers of circumferential windings/25 ° spiral windings/30 ° spiral windings/36 ° spiral windings/3 layers of circumferential windings/75 ° spiral windings/10 ° spiral windings/14 ° spiral windings/19 ° spiral windings/25 ° spiral windings/30 ° spiral windings/2 layers/75 ° spiral windings/1 ° circumferential windings/10 ° spiral windings/10 ° circumferential windings/3 ° spiral windings/3 layers/75 ° spiral windings/10 ° circumferential windings/10 ° spiral windings/10 ° circumferential windings/3 ° spiral windings/3/1 ° circumferential windings/10 ° circumferential windings/3 ° spiral windings/3/10 ° circumferential windings/3/10 ° spiral windings/10 ° circumferential windings/3/10 ° spiral windings/10 ° circumferential windings/represented by one/4/3/14 ° circumferential windings/3/one/14 ° circumferential windings/3/roll windings/each.
Further, in step 3, the initial tension of the wound fiber is 60 to 80N/bundle, and after each winding cycle, the tension of the next winding cycle becomes 99% of the previous cycle.
The thick-wall gas cylinder made of the carbon fiber composite material is obtained based on the preparation method, as shown in figure 1, the outer diameter of a metal lining 1 is more than 300mm, the wall thickness of a lining cylinder section 4 is more than or equal to 7mm, the volume is more than or equal to 70L, an electrochemical corrosion-resistant glass fiber composite material layer 2 and a carbon fiber composite material layer 3 are wound on the outer surface of the lining, in addition, in figure 1, 5 represents a seal head section, and 6 represents the R angle position of the seal head.
Example 1:
the preparation method of the carbon fiber composite material thick-wall gas cylinder in the embodiment comprises the following steps:
step 1: low viscosity high toughness winding resin system configuration:
respectively preparing a resin component A and a curing agent component B according to the proportion of the components;
the resin A component is prepared from the following raw materials in parts by weight: ethylene glycol diglycidyl ether: tetrahydrophthalic acid diglycidyl ester: polyurethane modified epoxy resin=70:20:10:10, and the mixture of the raw materials is preheated and uniformly stirred during configuration;
the curing agent B is prepared from the following raw materials in parts by weight: diaminodiphenylmethane: 2-ethyl-4-methylimidazole=20:5:0.5, and when the preparation is carried out, the mixture of the raw materials is preheated to 80-100 ℃ and stirred to a transparent state;
cooling the component B of the curing agent to 40-60 ℃, and the component A of the resin according to the weight part ratio: curing agent B component = 100:25, mixing and stirring the resin a component and curing agent B component until uniform;
step 2: winding an electrochemical corrosion prevention layer: connecting nozzles at two ends of a metal lining with winding support rods, mounting the metal lining on a winding machine, cleaning the outer surface of the lining, brushing a layer of low-viscosity high-toughness winding resin prepared in the step 1, wherein the outer diameter of the metal lining is 348mm, the wall thickness of a barrel body section is 7mm, and the volume is 70L, and winding a layer of electrochemical corrosion-resistant glass fiber S4C-660JA composite material layer on the outer surface of the metal lining;
step 3: winding: soaking continuous 4 groups of domestic TG800-24K carbon fibers in the winding resin obtained in the step 1 at 30-40 ℃ according to the threading sequence, winding the outer surface of the liner in a mode of combining spiral direction and annular direction, wherein the spiral direction winding adopts a 5-time step-by-step reaming scheme; the winding line type sequence of the carbon fiber is as follows: 3 layers of circumferential winding/14 ° spiral winding/19 ° spiral winding/25 ° spiral winding/3 layers of circumferential winding/30 ° spiral winding/36 ° spiral winding/42 ° spiral winding/3 layers of circumferential winding/75 ° spiral winding/14 ° spiral winding/19 ° spiral winding/25 ° spiral winding/3 layers of circumferential winding/30 ° spiral winding/36 ° spiral winding/42 ° spiral winding/4 layers of circumferential winding/14 ° spiral winding/19 ° spiral winding/25 ° spiral winding/3 layers of circumferential winding/30 ° spiral winding/36 ° spiral winding/42 ° spiral winding/3 layers of circumferential winding/75 ° spiral winding; winding/10 DEG spiral winding/14 DEG spiral winding/19 DEG spiral winding/3-layer circumferential winding/25 DEG spiral winding/30 DEG spiral winding/36 DEG spiral winding/3-layer circumferential winding/75 DEG spiral winding/10 DEG spiral winding/14 DEG spiral winding/3-layer circumferential winding/19 DEG spiral winding/25 DEG spiral winding/30 DEG spiral winding/2-layer 75 DEG spiral winding/1-layer circumferential winding/75 DEG spiral winding/10 DEG spiral winding/14 DEG spiral winding/3-layer circumferential winding/19 DEG spiral winding/25 DEG spiral winding/4-layer circumferential winding, each layer represents a cyclically wound layer, wound with an initial fiber tension of 70N/bundle, after each winding cycle, the tension of the next winding cycle becomes 99% of the previous cycle.
Step 4: curing system: and (3) adopting 70 ℃/8 hours+120 ℃/4hours+150 ℃/5 hours, wherein the curing heating rate is 20-30 ℃/h, cooling to 40 ℃ along with an oven after curing is finished, and discharging the composite material gas cylinder out of the oven, wherein the composite material gas cylinder is kept to rotate at a low speed during curing, and the rotation rate is 1-3 rpm.
The domestic T800 carbon fiber composite material thick-wall gas cylinder produced by the preparation method has the volume of 70L, the weight of the gas cylinder is not more than 80kg, and the bursting strength is not less than 230MPa; the gas cylinder has no defects of air hole inclusion and the like in nondestructive inspection after solidification.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
What is not described in detail in the present specification is a well known technology to those skilled in the art.
Claims (8)
1. The preparation method of the carbon fiber composite material thick-wall gas cylinder is characterized by comprising the following steps of:
(1) Preparing resin A by using the following raw materials in parts by weight:
(2) Preparing a curing agent B by using the following raw materials in parts by weight:
20 parts of diethyl toluenediamine;
5-6 parts of diaminodiphenyl methane;
0.5 to 0.8 portion of 2-ethyl-4-methylimidazole;
(3) Uniformly mixing the resin A and the curing agent B to obtain winding resin; the mass part ratio of the resin A to the curing agent B is 100:25;
(4) Manufacturing a lining of the carbon fiber composite thick-wall gas cylinder, coating the winding resin obtained in the step (3) on the outer surface of the lining to form a winding resin layer, winding the electrochemical corrosion-resistant glass fiber composite material on the surface of the winding resin layer to form an electrochemical corrosion-resistant glass fiber composite material layer;
(5) Soaking carbon fibers in the winding resin prepared in the step (3) according to a preset threading sequence, and winding the surface of the electrochemical corrosion-resistant glass fiber composite material layer formed in the step (4) to form a carbon fiber composite material layer;
(6) Solidifying the product obtained in the step (5) to obtain a carbon fiber composite thick-wall gas cylinder;
the inner liner in the carbon fiber composite material thick-wall gas cylinder is made of metal, the outer diameter of the inner liner is more than 300mm, the wall thickness of the inner liner cylinder section is more than or equal to 7mm, and the volume is more than or equal to 70L;
the carbon fiber used in the step (5) is domestic T800 carbon fiber;
in the step (1), the raw materials are mixed and preheated to 30-40 ℃ and stirred uniformly to obtain resin A;
in the step (2), the raw materials are mixed and heated to 80-100 ℃, and the mixture is stirred to a transparent state to obtain a curing agent B;
in the step (3), the curing agent B is cooled to 40-60 ℃ and is uniformly mixed with the resin A to obtain the winding resin.
2. The method for manufacturing a thick-wall gas cylinder made of carbon fiber composite material according to claim 1, wherein in the step (4), two ends of the metal lining are connected with winding support rods through nozzles, the winding support rods are installed on a winding machine, and the winding machine is utilized to wind the electrochemical corrosion-resistant glass fiber composite material on the surface of the winding resin layer;
in the step (4), a lining of the carbon fiber composite material thick-wall gas cylinder is manufactured, the outer surface of the lining is cleaned, and winding resin obtained in the step (3) is coated on the outer surface of the lining to form a winding resin layer.
3. The method for preparing a carbon fiber composite material thick-wall gas cylinder according to claim 1, wherein in the step (5), at a temperature of 30-40 ℃, carbon fibers are soaked in winding resin obtained in the step (3) according to a preset threading sequence, and the surface of the electrochemical corrosion resistant glass fiber composite material layer formed in the step (4) is wound in a winding mode of combining spiral winding and circumferential winding; a tension decreasing system is adopted during winding;
the spiral winding adopts a step-by-step reaming scheme for 5 times; step-by-step reaming means that the diameter of each electrode hole of the spiral winding layer of the next layer is larger than that of the electrode hole of the spiral winding layer of the last layer.
4. The method for preparing the carbon fiber composite material thick-wall gas cylinder according to claim 1, wherein in the step (6), the concrete steps of curing are that heat preservation is carried out for 8 hours at 70+/-3 ℃, heat preservation is carried out for 4 hours at 120+/-3 ℃ and heat preservation is carried out for 5 hours at 150+/-3 ℃ and then the temperature is reduced to 40 ℃; the curing temperature rising rate is 20-30 ℃/h; and (3) maintaining the rotation of the product obtained in the step (5) in the curing process, wherein the rotation speed is 1-3 rpm.
5. The method for manufacturing a carbon fiber composite thick-wall gas cylinder according to claim 1, wherein in the step (4), the glass fibers in the electrochemical corrosion-resistant glass fiber composite are S4C-660JA glass fibers;
in the step (5), the number of winding yarn groups when the carbon fiber winds the surface of the electrochemical corrosion-resistant glass fiber composite material layer formed in the step (4) is 3-5 groups of yarns, and the carbon fiber used in the step (5) is TG800-24K carbon fiber.
6. The method for preparing a thick-wall gas cylinder made of carbon fiber composite material according to claim 3, wherein in the step (5), the winding line type sequence when the carbon fiber winds the surface of the glass fiber composite material layer for preventing electrochemical corrosion formed in the step (4) is as follows: 3 layers of circumferential winding/14 ° spiral winding/19 ° spiral winding/25 ° spiral winding/3 layers of circumferential winding/30 ° spiral winding/36 ° spiral winding/42 ° spiral winding/3 layers of circumferential winding/75 ° spiral winding/14 ° spiral winding/19 ° spiral winding/25 ° spiral winding/3 layers of circumferential winding/30 ° spiral winding/36 ° spiral winding/42 ° spiral winding/4 layers of circumferential winding/14 ° spiral winding/19 ° spiral winding/25 ° spiral winding/3 layers of circumferential winding/30 ° spiral winding/36 ° spiral winding/42 ° spiral winding/3 layers of circumferential winding/75 ° spiral winding; winding/10 DEG spiral winding/14 DEG spiral winding/19 DEG spiral winding/3-layer circumferential winding/25 DEG spiral winding/30 DEG spiral winding/36 DEG spiral winding/3-layer circumferential winding/75 DEG spiral winding/10 DEG spiral winding/14 DEG spiral winding/3-layer circumferential winding/19 DEG spiral winding/25 DEG spiral winding/30 DEG spiral winding/2-layer 75 DEG spiral winding/1-layer circumferential winding/75 DEG spiral winding/10 DEG spiral winding/14 DEG spiral winding/3-layer circumferential winding/19 DEG spiral winding/25 DEG spiral winding/4-layer circumferential winding, each layer represents a cyclically wound layer.
7. The method for manufacturing a carbon fiber composite material thick-wall gas cylinder according to claim 6, wherein in the step (5), the initial winding fiber tension is 60 to 80N/bundle, and the tension in the next winding cycle becomes 99% of the previous cycle after each winding cycle.
8. The carbon fiber composite material thick-wall gas cylinder is characterized in that the carbon fiber composite material thick-wall gas cylinder is obtained by adopting the preparation method of the carbon fiber composite material thick-wall gas cylinder according to any one of claims 1-7, wherein a lining in the carbon fiber composite material thick-wall gas cylinder is made of a metal material, the outer diameter of the lining is more than 300mm, the wall thickness of a lining cylinder section is more than or equal to 7mm, and the volume is more than or equal to 70L.
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