CN111117151B - Thermoplastic composite material low-temperature liquid oxygen storage tank cylinder with gradient resin layer and manufacturing method thereof - Google Patents
Thermoplastic composite material low-temperature liquid oxygen storage tank cylinder with gradient resin layer and manufacturing method thereof Download PDFInfo
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- 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
- C08K7/06—Elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02K—JET-PROPULSION PLANTS
- F02K9/00—Rocket-engine plants, i.e. plants carrying both fuel and oxidant therefor; Control thereof
- F02K9/42—Rocket-engine plants, i.e. plants carrying both fuel and oxidant therefor; Control thereof using liquid or gaseous propellants
- F02K9/60—Constructional parts; Details not otherwise provided for
- F02K9/605—Reservoirs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses a thermoplastic composite material low-temperature liquid oxygen storage tank cylinder with a gradient resin layer and a manufacturing method thereof.
Description
Technical Field
The invention belongs to the field of aerospace transportation, and particularly relates to a structural design of a barrel body of an ultra-low temperature propellant composite material storage box of a carrier rocket
Background
The propellant tank is a key part of a power system and a structural system of the aerospace vehicle, and the light weight level of the propellant tank determines the main performance index of the vehicle. Compared with the existing aluminum alloy storage tank, the composite material of the propellant storage tank can reduce the mass by 20-40%, can meet the requirements of the next generation deep space exploration technology, and can reduce the cost. The composite materials used in propellant tanks not only require structural efficiency, but must also be capable of carrying ultra-low temperature propellants (liquid hydrogen: 40k, liquid oxygen: 90 k). The storage tank in such a working environment has mainly 3 problems of (1) low-temperature loading: the fuel micromolecules permeate the composite material, and the micromolecules leak from a seepage channel formed by microcracks in the composite material; (2) chemical compatibility: the liquid oxygen has strong oxidizability, and the composite material is used as an organic material and has the capability of not being oxidized by the liquid oxygen; (3) low-temperature mechanical properties: the storage tank of the composite material is in an ultralow temperature environment and needs to have excellent low-temperature mechanical properties.
For the research of the storage tank composite material, at present, much attention is paid to fiber reinforced thermosetting resin-based composite materials, but the problems of liquid oxygen compatibility of resin matrix and leakage of fuel micromolecules are not well solved. As the thermoplastic resin has the characteristics of high toughness and good gas barrier property, aiming at the problems, the invention provides a method for constructing a gradient resin layer by using the thermoplastic resin with liquid-oxygen compatibility and excellent mechanical property as a resin matrix of a composite material storage tank and a method for constructing the gradient resin layer by using thermoplastic prepreg tapes with different fiber contents to block the leakage of fuel micromolecules.
Disclosure of Invention
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a rocket low-temperature composite material propellant storage tank, which is made of thermoplastic resin with a flame retardant grade of V0 and carbon fibers, and the content of the thermoplastic resin in the storage tank is gradually reduced from inside to outside.
Further, in the technical scheme, the content of the thermoplastic resin from the inside to the outside is 50-60wt%, 40-50 wt% and 30-40 wt% in sequence.
According to the requirements of liquid oxygen compatibility and structural strength, qualified thermoplastic resins such as polyether ether ketone, polyether sulfone, polyether imide and polytetrafluoroethylene including but not limited to the above resins are selected from thermoplastic engineering plastics with the flame retardant grade of V0 and good toughness, and the selected resins must pass a liquid oxygen compatibility test with the test standard of ASTM G86-17.
The present invention is directed to composite storage bin manufacturing based on an automated tape or filament placement process. The continuous fiber reinforced thermoplastic composite prepreg tape with gradient resin content is prepared by a solution or melt impregnation process, and the gradient concentration change interval and the corresponding length of the resin content of the prepreg tape are set according to the specific size of the composite fuel storage tank.
The preparation method of the storage box selects different preparation methods according to the properties of the adopted materials, and concretely comprises three aspects of determining the manufacturing process of the prepreg tape, forming the prepreg tape with gradient resin content and manufacturing the storage box.
Determining a manufacturing process of the prepreg tape: for thermoplastic resins which are relatively easy to dissolve in a solvent, such as polyether sulfone and polyetherimide, solvents such as dimethyl sulfoxide and N-methyl pyrrolidone can be adopted to dissolve the thermoplastic resin, resin solutions with different concentrations are obtained by controlling the proportion of the resin and the solution, and a thermoplastic prepreg tape is prepared by a solution impregnation process; for thermoplastic resins which are difficult to dissolve in a solvent, such as PFA resin and polyether ether ketone resin, a melt extrusion process can be adopted to prepare a thermoplastic prepreg tape, and polyether sulfone and polyether imide which are easy to dissolve can also be adopted to prepare thermoplasticity by a melt extrusion process.
Forming the resin content gradient prepreg tape: for the prepreg tape solution impregnation process, the prepreg tape with gradually changed resin content is obtained by changing the process parameters such as the concentration of the thermoplastic resin solution, the impregnation speed, the size of the carbon fiber tows and the like; for the melt extrusion process, the manufacturing of the prepreg tape storage box with gradually changed resin content is obtained by changing parameters such as extrusion pressure, impregnation speed and opening size of a die: and (3) paving the thermoplastic prepreg tape by using automatic paving equipment with a laser heating part according to the sequence that the resin content of the storage tank cylinder is gradually reduced from inside to outside and then is kept unchanged, so as to finish the manufacture of the storage tank cylinder with the gradient resin layer structure.
The layering of the cylinder of the composite material storage box obtained by the automatic laying process meets the following requirements:
the innermost layer is a high resin content layer, and the number of 50-60wt% of the high resin content layer is not more than 1/4 of the total number of layers; the middle layer is a medium resin content layer, 40-50 wt% of the medium resin content layer is not higher than 1/3 of the total layers; the remaining layers are layers having a resin content of 30 to 40 wt% and the number of layers is not less than 2/3 of the total number of layers.
The small fuel molecules (such as liquid hydrogen, liquid oxygen and the like) hardly penetrate through the resin matrix, so that the continuous fiber reinforced thermoplastic prepreg tape with the gradient change of the resin content is utilized, the resin content of the inner layer structure of the storage tank at the position close to the propellant in the cylinder body in the winding and forming process of the storage tank is highest, and the resin content is kept unchanged after gradually decreasing along the radial direction of the cylinder body, thereby achieving the purpose of blocking the leakage of the small molecules and meeting the requirement of mechanical property. In the forming process, an automatic tape laying machine which takes hot air, infrared rays, laser and the like as heat sources is utilized, and thermoplastic prepreg tapes are sequentially laid according to the structure that the resin content of the storage tank cylinder is gradually reduced from inside to outside and then is kept unchanged, so that the manufacture of the storage tank cylinder with the gradient resin layer structure is completed. Wherein, the inner layer high resin content layer can obstruct the leakage of small molecules, and the low resin content layer can improve the mechanical property of the material.
The invention has the advantages and characteristics that: the mechanical properties of the thermoplastic composite material are generally better than those of the thermosetting composite material under the condition of low temperature, especially in the aspect of toughness (see figure 1); the tank cylinder structure with the gradient of the resin content (figures 2 and 3) constructed by the continuous fiber reinforced thermoplastic prepreg tape with the gradient of the resin content can effectively reduce the leakage of small fuel molecules.
Description of the drawings:
FIG. 1: before and after liquid oxygen compatibility test of the liquid oxygen compatible thermoplastic resin, comparing graphs, wherein 1, 3 and 5 in the graphs are PEI, PES and PFA corresponding to the shapes of the resin before the test, and 2, 4 and 6 are the shapes after the test;
FIG. 2: the cross section of the cylinder structure of the storage tank with gradually changed resin content gradient is shown as 1-carbon fiber; 2-a resin matrix; a-high resin content ply (resin content 50-60%); b-medium resin content ply (resin content 40-50%); c. d-lower resin content ply (resin content 30-40%);
FIG. 3: the structure of the fuel storage tank cylinder with the gradient resin layer structure is schematically shown;
FIG. 4: a comparison graph of the front (left) and rear (right) appearance of a composite material sample prepared from the prepreg obtained in example 1 in a liquid oxygen compatibility test;
FIG. 5: the composite sample prepared from the gradient prepreg obtained in example 2 was subjected to a liquid oxygen compatibility test for the front (left) and rear (right) morphology.
Detailed description of the preferred embodiments
1. Screening raw materials: engineering thermoplastics rated at V0 are determined according to the American society for testing and materials liquid oxygen compatibility test Standard ASTM D2512-95 and the Chinese aerospace industry Standard QJ 3177-2003. Combining the corresponding mechanical properties and processability, relatively suitable thermoplastic resins are obtained such as: polyethersulfone (PES), Polyetherimide (PEI), soluble Polytetrafluoroethylene (PFA) (fig. 1), Polyetheretherketone (PEEK), and the like.
Example 1
The manufacturing method of the thermoplastic composite material low-temperature liquid oxygen storage tank cylinder with the gradient resin layer comprises the following steps:
1. determining a manufacturing process of the resin gradient prepreg tape by a solution impregnation method: polyethersulfone, polyetherimide and polyetheretherketone resins are soluble in partially polar solvents and therefore can be used to prepare thermoplastic prepreg tapes by solution impregnation. For example, in the case of molding a polyethersulfone resin (PES) prepreg tape, PES resin may be dissolved in a good solvent such as dimethylsulfoxide or N-methylpyrrolidone to obtain resin solutions having different concentrations. In this example, solutions having PES mass fractions of 10 to 60% were each prepared using N-methylpyrrolidone under heating in a 100 ℃ oil bath.
2. Forming the prepreg tape: the prepreg tape with gradually changed resin content is obtained by changing the process parameters such as the concentration of the thermoplastic resin solution, the impregnation speed, the size of the carbon fiber tows and the like. Taking a prepreg tape with the length of 100m, the width of 1m and the thickness of 0.3mm as an example, the resin gradient concentration range and the length area distribution of the prepreg tape are as follows: 0-10m, and 60% of resin; 10-30m, resin content 50%; 30-100m and 40% of resin. The specific manufacturing method comprises the steps of distributing 200 bundles of 24k carbon fibers, passing the distributed carbon fibers through a polyether sulfone solution impregnation tank with the concentration of 40%, wherein the temperature of the impregnation tank is 100 ℃, drawing the carbon fibers at the speed of 0.5 m/h through a drawing device, and the temperature of a rubber roller is 130 ℃, heating the carbon fiber bundles by using a blower, removing a solvent, and rolling; when the carbon fiber tows are wound to a fixed length, the impregnation tank is replaced, the carbon fiber tows are drawn by a drawing device according to 1 m/h through a 30% polyethersulfone solution impregnation tank, the carbon fiber tows are heated by a blower, the solvent is removed, and the carbon fiber tows are wound; similarly, when the carbon fiber tows are wound to a fixed length, the impregnation tank is replaced, the carbon fiber tows are pulled by a traction device at a speed of 2 m/h through a polyether sulfone solution impregnation tank with the concentration of 20%, the carbon fiber tows are heated by a blower, the solvent is removed, and the carbon fiber tows are wound. Obtaining the thermoplastic composite material prepreg tape with continuous fibers and gradually changed resin concentration gradient. The length of the rolling is related to the size of the structural dimension of the storage box.
3. And (3) paving the thermoplastic prepreg tape by using automatic paving equipment with a laser heating part according to the sequence that the resin content of the storage tank cylinder is gradually reduced from inside to outside and then is kept unchanged, so as to finish the manufacture of the storage tank cylinder with the gradient resin layer structure.
4. The innermost layer is a high resin content layer, and the number of the high resin content layers is not more than 1/4 of the total number of layers; the middle layer is a medium resin content layer, and the number of the medium resin content layers is not higher than 1/3 of the total layers; the rest layers are layers with lower resin content, and the number of the layers is not less than 2/3 of the total number of the layers;
5. the prepreg is used for preparing an orthogonal laminated plate by a mould pressing process, and the laminated plate is used for testing the liquid oxygen compatibility of the composite material. Layering mode: 2 layers of prepreg tape with 60% resin content, 2 layers of prepreg tape with 50% resin content and 6 layers of prepreg tape with 40% resin content. Curing process, which comprises heating at 320 deg.C under 1Mpa for 30min, naturally cooling, and demolding. The material was tested for liquid oxygen compatibility according to ASTM G86 standard, material dimensions: thickness 1.4mm, diameter 19 mm.
Example 2
The manufacturing method of the thermoplastic composite material low-temperature liquid oxygen storage tank cylinder with the gradient resin layer comprises the following steps:
1. determining the manufacturing process of the hot-melt resin gradient prepreg tape: almost all thermoplastic resins can be used in the hot melt process to make thermoplastic resin-based prepreg tapes. Taking polyfluoro resin (PFA) as an example, a thermoplastic prepreg tape with gradient thermal resin is prepared.
2. Molding the resin gradient thermoplastic prepreg tape: taking a prepreg tape with the length of 100m, the width of 1m and the thickness of 0.3mm as an example, the resin gradient concentration range and the length area distribution of the prepreg tape are as follows: 0-10m, and 60% of resin; 10-30m, resin content 50%; 30-100m and 40% of resin. The specific manufacturing method comprises the steps of distributing 200 carbon fiber tows, enabling the carbon fiber tows to pass through an extruder neck mold, enabling the temperature of the extruder to be 350-plus-370 ℃, enabling the passing speed to be 1m/min, then shaping the carbon fiber tows through a compression roller, enabling the gap between the compression rollers to be 0.25mm, enabling the temperature of the compression roller to be 200-plus-250 ℃, rolling, adjusting the passing speed of the carbon fiber tows to be 1.5-1.8m/min when the carbon fiber tows are rolled to a fixed length, and enabling other conditions to be unchanged and rolling. When the winding is wound to a fixed length, the winding is carried out at a speed of 2-2.3m/min by a traction device, and other conditions are unchanged. Obtaining the thermoplastic composite material prepreg tape with continuous fibers and gradually changed resin concentration gradient. The length of the rolling is related to the size of the structural dimension of the storage box.
3. And (3) paving the thermoplastic prepreg tape by using automatic paving equipment with a laser heating part according to the sequence that the resin content of the storage tank cylinder is gradually reduced from inside to outside and then is kept unchanged, so as to finish the manufacture of the storage tank cylinder with the gradient resin layer structure.
4. The innermost layer is a high resin content layer, and the number of the high resin content layers is not more than 1/4 of the total number of layers; the middle layer is a medium resin content layer, and the number of the medium resin content layers is not higher than 1/3 of the total layers; the remaining layers are lower resin content layers, the number of layers being not less than 2/3 of the total number of layers.
5. The prepreg is used for preparing an orthogonal laminated plate by a mould pressing process, and the laminated plate is used for testing the liquid oxygen compatibility of the composite material. Layering mode: 2 layers of prepreg tape with 60% resin content, 2 layers of prepreg tape with 50% resin content and 6 layers of prepreg tape with 40% resin content. Curing process, which comprises heating at 380 deg.C for 20min under 1.5Mpa, naturally cooling, and demolding. The material was tested for liquid oxygen compatibility according to ASTM G86 standard, material dimensions: thickness 1.4mm, diameter 19 mm.
Claims (3)
1. A rocket low-temperature composite material propellant storage tank is characterized in that the storage tank material is composed of thermoplastic resin with a flame retardant grade of V0 grade and carbon fiber, and the content of the thermoplastic resin of the storage tank material is gradually reduced from inside to outside;
the content of the thermoplastic resin in the storage box from the inside to the outside is 50-60wt%, 40-50 wt% and 30-40 wt% in sequence;
the thermoplastic resin is selected from polyether ether ketone, polyether sulfone, polyether imide and polyfluoro resin.
2. The method of manufacturing a tank according to claim 1, wherein: the method comprises the steps of determining a prepreg tape manufacturing process, forming the prepreg tape with gradient resin content and gradient, and manufacturing a storage tank;
determining a manufacturing process of the prepreg tape: for thermoplastic resins polyether sulfone and polyether imide which are relatively easy to dissolve in a solvent, a solvent dimethyl sulfoxide or N-methyl pyrrolidone is adopted to dissolve the thermoplastic resins, resin solutions with different concentrations are obtained by controlling the proportion of the resins to the solutions, and a thermoplastic prepreg tape is prepared by a solution impregnation process; or preparing a thermoplastic prepreg tape by adopting a melt extrusion process;
preparing thermoplastic prepreg tapes by adopting a melt extrusion process for thermoplastic resin PFA resin and polyether ether ketone resin which are difficult to dissolve in a solvent;
forming the resin content gradient prepreg tape: for the prepreg tape solution impregnation process, the prepreg tape with gradually changed resin content is obtained by changing the concentration of the thermoplastic resin solution, the impregnation speed and the size process parameters of the carbon fiber tows; for the melt extrusion process, the prepreg tape with gradually changed resin content is obtained by changing the parameters of extrusion pressure, impregnation speed and the size of the opening of the die;
manufacturing of the storage tank: and (3) paving the thermoplastic prepreg tape by using automatic paving equipment with a laser heating part according to the sequence that the resin content of the storage tank cylinder is gradually reduced from inside to outside and then is kept unchanged, so as to finish the manufacture of the storage tank cylinder with the gradient resin layer structure.
3. The method of manufacturing a tank according to claim 2, wherein: the layering of the cylinder of the composite material storage box obtained by the automatic laying process meets the following requirements:
the innermost layer is a high resin content layer, and the number of 50-60wt% of the high resin content layer is not more than 1/4 of the total number of layers; the middle layer is a medium resin content layer, 40-50 wt% of the medium resin content layer is not higher than 1/3 of the total layers; the remaining layers are layers having a resin content of 30 to 40 wt% and the number of layers is not less than 2/3 of the total number of layers.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106586036A (en) * | 2016-12-09 | 2017-04-26 | 大连理工大学 | Launch vehicle composite storage tank with stiffening beams and processing method of storage tank |
| CN107097979A (en) * | 2017-03-30 | 2017-08-29 | 哈尔滨工业大学 | A kind of annular composite material tank structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106586036A (en) * | 2016-12-09 | 2017-04-26 | 大连理工大学 | Launch vehicle composite storage tank with stiffening beams and processing method of storage tank |
| CN107097979A (en) * | 2017-03-30 | 2017-08-29 | 哈尔滨工业大学 | A kind of annular composite material tank structure |
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