CN112066240A - High-pressure low-temperature composite material gas cylinder used in liquid oxygen environment and manufacturing method - Google Patents
High-pressure low-temperature composite material gas cylinder used in liquid oxygen environment and manufacturing method Download PDFInfo
- Publication number
- CN112066240A CN112066240A CN202010773031.6A CN202010773031A CN112066240A CN 112066240 A CN112066240 A CN 112066240A CN 202010773031 A CN202010773031 A CN 202010773031A CN 112066240 A CN112066240 A CN 112066240A
- Authority
- CN
- China
- Prior art keywords
- liquid oxygen
- gas cylinder
- composite material
- aluminum alloy
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 239000002131 composite material Substances 0.000 title claims abstract description 88
- 239000007789 gas Substances 0.000 title claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 101
- 229920005989 resin Polymers 0.000 claims abstract description 101
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 56
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 39
- 239000004917 carbon fiber Substances 0.000 claims abstract description 39
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000000835 fiber Substances 0.000 claims abstract description 10
- 238000012360 testing method Methods 0.000 claims description 59
- 238000004804 winding Methods 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- 239000003292 glue Substances 0.000 claims description 16
- 238000009863 impact test Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000009661 fatigue test Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- 238000004880 explosion Methods 0.000 claims description 6
- 238000005238 degreasing Methods 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 230000009172 bursting Effects 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000003754 machining Methods 0.000 claims description 4
- 238000009987 spinning Methods 0.000 claims description 4
- 238000012935 Averaging Methods 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- WPZJSWWEEJJSIZ-UHFFFAOYSA-N tetrabromobisphenol-F Natural products C1=C(Br)C(O)=C(Br)C=C1CC1=CC(Br)=C(O)C(Br)=C1 WPZJSWWEEJJSIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007769 metal material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000013585 weight reducing agent Substances 0.000 abstract description 3
- 239000001307 helium Substances 0.000 description 10
- 229910052734 helium Inorganic materials 0.000 description 10
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 10
- 238000003860 storage Methods 0.000 description 8
- 239000003380 propellant Substances 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 238000005422 blasting Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
- B29C70/681—Component parts, details or accessories; Auxiliary operations
-
- 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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
- B29C70/681—Component parts, details or accessories; Auxiliary operations
- B29C70/683—Pretreatment of the preformed part, e.g. insert
-
- 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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
- B29C70/78—Moulding material on one side only of the preformed part
-
- 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
- F17C1/16—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge constructed of plastics materials
-
- 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
- F17C2203/0602—Wall structures; Special features thereof
- F17C2203/0612—Wall structures
- F17C2203/0614—Single wall
- F17C2203/0619—Single wall with two layers
-
- 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
- F17C2270/00—Applications
- F17C2270/01—Applications for fluid transport or storage
- F17C2270/0186—Applications for fluid transport or storage in the air or in space
Abstract
The invention provides a high-pressure low-temperature composite material gas cylinder used in a liquid oxygen environment and a manufacturing method thereof, wherein the manufacturing method comprises the following steps: the aluminum alloy liner, the liquid oxygen compatible resin system, the carbon fiber composite layer and the aluminum alloy tailstock; the liquid oxygen compatible resin system and the carbon fiber composite layer cover the outer surface of the aluminum alloy lining, and the aluminum alloy tailstock is connected with the aluminum alloy lining and is positioned at the tail part of the aluminum alloy lining to form a high-pressure low-temperature conforming material gas cylinder used in a liquid oxygen environment. The invention adopts a liquid oxygen compatible resin system, and the resin system is compatible with liquid oxygen and can be used in a liquid oxygen environment. The fibre adopts the carbon fiber, compares in the gas cylinder of the metal material of general use, has advantages such as intensity height, light in weight. Therefore, the weight reduction effect is achieved for the high-pressure low-temperature gas cylinder.
Description
Technical Field
The invention relates to manufacturing of aerospace vehicle equipment, in particular to a high-pressure low-temperature composite material gas cylinder used in a liquid oxygen environment and a manufacturing method thereof, and more particularly relates to a high-pressure low-temperature composite material gas cylinder used in a liquid oxygen environment and used in a carrier rocket cold helium pressurizing conveying system taking liquid oxygen/kerosene as propellant components and a manufacturing method thereof.
Background
The cold helium pressurization is one of the advanced technical schemes of pressurization of the current carrier rocket propellant, and means that cold helium gas after being subjected to ground cooling is filled into a gas cylinder arranged in a low-temperature propellant of a storage box, and the gas storage capacity of one cold helium gas cylinder is about 5.6 times of that of a normal-temperature gas cylinder under the same pressure and the same volume by utilizing the characteristic of high helium gas density under high pressure and low temperature, so that the weight of a pressurization system can be reduced, and the carrying capacity of the rocket is improved. In addition, in the pressurizing mode, the gas cylinder is arranged in the propellant storage box, so that the installation space of the whole pressurizing system is saved, and the structural mass of the whole rocket is favorably reduced.
In a new generation of carrier rocket taking liquid oxygen/kerosene as propellant, in order to meet the requirement of high-pressure storage of low-temperature helium gas, a cold helium composite material gas cylinder needs to be placed in a liquid oxygen storage box to improve the storage density of the helium gas, so that the cold helium composite material gas cylinder compatible with the liquid oxygen needs to be developed.
Because the composite material is applied less in the low-temperature field, particularly the application research under the cryogenic condition of the liquid oxygen temperature is less and less. In view of the above problems, intensive studies in these directions are required. Starting from the exploration of liquid oxygen compatibility, a matrix resin system is selected by combining with testing means such as a liquid oxygen compatibility test, a low-temperature mechanical property test and the like, so that a basis is provided for developing a low-temperature composite material with stable and reliable performance; and then the carbon fiber low-temperature composite material pressure container meeting the service performance requirement is prepared. The method has important significance for keeping the current status of the aerospace big country and further reducing the gap with the world advanced aerospace technology, and can meet the requirements of other national defense fields and civil fields on liquid oxygen and low-temperature containers.
Patent document CN109366106A (application number: 201811436408.8) discloses a large-volume titanium alloy gas cylinder suitable for liquid oxygen environment, a manufacturing method and an application thereof, wherein the large-volume titanium alloy gas cylinder comprises a gas cylinder body, a pipe joint and a sealing structure; threads are processed at the connecting part of the gas cylinder body and the pipe joint, and the sealing structure is connected and pressed through the threads; the gas cylinder is made of a metal material compatible with a liquid oxygen environment, and the pipe joint is made of austenitic stainless steel or high-temperature alloy; the compatibility is that the gas cylinder material does not generate physical and chemical reaction when contacting with the internal and external media.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a high-pressure low-temperature composite material gas cylinder used in a liquid oxygen environment and a manufacturing method thereof.
The invention provides a high-pressure low-temperature composite material gas cylinder used in a liquid oxygen environment, which comprises: the composite material comprises an aluminum alloy lining 1, a liquid oxygen compatible resin system, a carbon fiber composite layer 2 and an aluminum alloy tailstock 3;
the liquid oxygen compatible resin system and the carbon fiber composite layer 2 cover the outer surface of the aluminum alloy lining 1, and the aluminum alloy tailstock 3 is connected with the aluminum alloy lining 1 and is positioned at the tail part of the aluminum alloy lining to form a high-pressure low-temperature conforming material gas cylinder used in a liquid oxygen environment.
Preferably, the liquid oxygen compatible resin system and the carbon fiber composite layer 2 are coated on the outer surface of the aluminum alloy lining 1 in a mode of winding in a hoop direction and a spiral direction alternately.
Preferably, the liquid oxygen compatible resin system and the carbon fiber composite layer 2 comprise liquid oxygen compatible resin, a curing agent and carbon fibers;
the liquid oxygen compatible resin includes: bisphenol A epoxy resin, tetrabromobisphenol F resin, a catalyst, an antioxidant and an auxiliary agent;
the curing agent comprises an epoxy resin curing agent;
the liquid oxygen compatible resin system is formed by uniformly dissolving and stirring liquid oxygen compatible resin and a curing agent according to a preset proportion.
The invention provides a method for manufacturing a high-pressure low-temperature composite material gas cylinder used in a liquid oxygen environment, which comprises the following steps:
step M1: designing the overall dimension of the lining according to the containing volume, the using conditions and the using times of the composite material gas cylinder, and manufacturing the aluminum alloy lining by the processes of deep drawing, spinning, closing and machining;
step M2: connecting the aluminum alloy lining with an aluminum alloy tailstock;
step M3: the liquid oxygen compatible resin and the curing agent are proportioned according to a preset proportion and then cured into a liquid oxygen compatible resin system meeting preset conditions;
step M4: the liquid oxygen compatible resin system is subjected to liquid oxygen impact test and mechanical property test to verify that the liquid oxygen compatible resin is not incompatible with liquid oxygen when used in a liquid oxygen environment;
step M5: designing the number of layers and the wall thickness of the winding layer according to the strength of the winding layer made of the composite material;
step M6: before winding, carrying out oil removal treatment on tooling equipment used in the winding process;
step M7: clamping an aluminum alloy lining on a winding machine, removing oil on the outer surface of the lining, proportioning carbon fiber, liquid oxygen compatible resin and a curing agent according to a preset proportion, heating, stirring and dissolving in a high-temperature water bath environment, pouring prepared glue solution into a glue dipping tank, and winding the fiber bundle on the aluminum alloy lining in a winding mode combining the circumferential direction and the spiral direction by soaking the fiber bundle in the resin;
step M8: placing the wound composite material gas cylinder in a heating furnace for curing;
step M9: carrying out a hydraulic strength test, an air tightness test, a hydraulic fatigue test, a hydraulic bursting test, a hydraulic strength test, an air tightness test and a hydraulic fatigue test on the cured composite material gas cylinder, wherein the test result meets the use requirement of the low-temperature composite material gas cylinder used in a liquid oxygen environment;
step M10: and (4) carrying out oil removal and degreasing treatment on the high-pressure low-temperature composite material gas cylinder which is processed and tested.
Preferably, the step M2 includes: the liquid oxygen compatible resin and the curing agent are dissolved and stirred by a method of heating and stirring to form a liquid oxygen compatible resin system.
Preferably, the liquid oxygen impact test in step M3 includes: the liquid oxygen compatible resin and the curing agent are proportioned according to a preset proportion and then cured into a wafer with a preset diameter and thickness under preset conditions, and the liquid oxygen compatibility is tested according to a preset standard; if the impact test has no sensitive reaction for the preset times, the liquid oxygen compatible resin is compatible with the liquid oxygen;
the sensitive reaction comprises the following steps: scorching, flashing, explosion and/or burning phenomena.
Preferably, the mechanical property test in the step M3 includes: testing the tensile strength and the shear strength of the combined sample of the resin and the carbon fiber at normal temperature and liquid nitrogen temperature according to a preset standard; and (3) testing the mechanical properties of the sample at normal temperature and liquid nitrogen temperature in a universal mechanical testing machine, stretching preset group data of the sample, shearing the preset group data of the sample, and averaging after testing to judge whether the use requirements are met.
Preferably, the step M6 includes: and winding by adopting a method of continuously preparing a small amount of glue for multiple times in a winding process.
Compared with the prior art, the invention has the following beneficial effects:
1. in the method, the materials selected for the high-pressure low-temperature composite material gas cylinder used in the liquid oxygen environment are all liquid oxygen compatible materials, and the lining, the composite layer and the tailstock are all light materials, so that the weight is lighter than that of the gas cylinder made of all-metal materials under the condition of meeting the strength, the weight reduction effect is achieved, and the gas storage density per unit mass is improved.
2. The resin system selected in the method is a liquid oxygen compatible resin system, and the resin system can not generate scorching, flashing, explosion and burning phenomena under the impact energy with the magnitude of 98J; meanwhile, the normal-temperature and low-temperature mechanical property tests of the sample wound by the resin system and the carbon fibers meet the requirements, and the resin system can be used for producing and processing a high-pressure low-temperature composite material gas cylinder used in a liquid oxygen environment;
3. in the method, high-temperature dissolution and stirring are adopted for dissolving the high-viscosity resin and the curing agent, the viscosity of the high-viscosity resin is reduced to some extent at a certain temperature, and the epoxy resin curing agent can be changed from a solid state to a liquid state, so that the dissolution and stirring speed is increased, the operation difficulty is reduced, and the working efficiency is improved;
4. in the method, a small amount of glue is prepared for multiple times during winding, the method has great advantages aiming at the resin system with limited service time, and the problem that the resin system cannot be completely used and cured due to large glue preparation amount is avoided, and meanwhile, the viscosity of the resin system is increased along with the lengthening of time, so that the feasibility of the process is influenced. A small amount of glue is prepared for multiple times, so that the material loss of a resin system in the using process is avoided, and meanwhile, the manufacturability is optimized, so that the viscosity of the resin system is maintained in a certain range.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a high pressure low temperature composite gas cylinder used in liquid oxygen environment;
1-an aluminum alloy lining; 2-liquid oxygen compatible resin system and carbon fiber composite layer; 3-aluminum alloy tailstock.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
The invention aims to develop and produce a high-pressure low-temperature composite material gas cylinder used in a liquid oxygen environment. Meanwhile, the technical defect that the existing high-viscosity resin is wound on the gas cylinder is overcome. The high-pressure low-temperature composite material gas cylinder which is light in weight, reliable in process and applicable to a liquid oxygen environment and the preparation method thereof are provided.
Example 1
According to the present invention, as shown in fig. 1, a high-pressure low-temperature composite gas cylinder used in a liquid oxygen environment includes: the composite material comprises an aluminum alloy lining 1, a liquid oxygen compatible resin system, a carbon fiber composite layer 2 and an aluminum alloy tailstock 3;
the liquid oxygen compatible resin system and the carbon fiber composite layer 2 cover the outer surface of the aluminum alloy lining 1, and the aluminum alloy tailstock 3 is connected with the aluminum alloy lining 1 and is positioned at the tail part of the aluminum alloy lining to form a high-pressure low-temperature conforming material gas cylinder used in a liquid oxygen environment.
Specifically, the liquid oxygen compatible resin system and the carbon fiber composite layer 2 are covered on the outer surface of the aluminum alloy lining 1 in a mode of winding in an annular direction and a spiral direction alternately, and meanwhile, the width, the thickness, the arrangement mode and the like of yarn sheets are designed according to process requirements; the yarn sheet is a carbon fiber yarn bundle, the width of the carbon fiber yarn bundle, the thickness of the carbon fiber yarn bundle and the winding angle of the carbon fiber yarn bundle.
Specifically, the liquid oxygen compatible resin system and the carbon fiber composite layer 2 comprise liquid oxygen compatible resin, a curing agent and carbon fibers;
the liquid oxygen compatible resin includes: bisphenol A epoxy resin, tetrabromobisphenol F resin, a catalyst, an antioxidant and an auxiliary agent;
the curing agent comprises an epoxy resin curing agent;
the liquid oxygen compatible resin system is formed by uniformly dissolving and stirring liquid oxygen compatible resin and a curing agent according to a preset proportion.
The invention provides a method for manufacturing a high-pressure low-temperature composite material gas cylinder used in a liquid oxygen environment, which comprises the following steps:
step M1: designing the overall dimension of the lining according to the containing volume, the using conditions and the using times of the composite material gas cylinder, and manufacturing the aluminum alloy lining by the processes of deep drawing, spinning, closing and machining;
step M2: connecting the aluminum alloy lining with an aluminum alloy tailstock;
step M3: the liquid oxygen compatible resin and the curing agent are proportioned according to a preset proportion and then cured into a liquid oxygen compatible resin system meeting preset conditions;
step M4: the liquid oxygen compatible resin system is subjected to liquid oxygen impact test and mechanical property test to verify that the liquid oxygen compatible resin is not incompatible with liquid oxygen when used in a liquid oxygen environment;
step M5: designing the number of layers and the wall thickness of the winding layer according to the strength of the winding layer made of the composite material;
step M6: before winding, carrying out oil removal treatment on tooling equipment used in the winding process;
step M7: clamping an aluminum alloy lining on a winding machine, removing oil on the outer surface of the lining, proportioning carbon fiber, liquid oxygen compatible resin and a curing agent according to a preset proportion, heating, stirring and dissolving in a high-temperature water bath environment, pouring prepared glue solution into a glue dipping tank, and winding the fiber bundle on the aluminum alloy lining in a winding mode combining the circumferential direction and the spiral direction by soaking the fiber bundle in the resin;
step M8: placing the wound composite material gas cylinder in a heating furnace for curing;
step M9: carrying out a hydraulic strength test, an air tightness test, a hydraulic fatigue test, a hydraulic bursting test, a hydraulic strength test, an air tightness test and a hydraulic fatigue test on the cured composite material gas cylinder, wherein the test result meets the use requirement of the low-temperature composite material gas cylinder used in a liquid oxygen environment;
step M10: and (4) carrying out oil removal and degreasing treatment on the high-pressure low-temperature composite material gas cylinder which is processed and tested.
Specifically, the step M2 includes: the liquid oxygen compatible resin and the curing agent are dissolved and stirred by a method of heating and stirring to form a liquid oxygen compatible resin system.
Specifically, the liquid oxygen impact test in the step M3 includes: the liquid oxygen compatible resin and the curing agent are proportioned according to a preset proportion and then cured into a wafer with a preset diameter and thickness under preset conditions, and the liquid oxygen compatibility is tested according to a preset standard; if the impact test has no sensitive reaction for the preset times, the liquid oxygen compatible resin is compatible with the liquid oxygen;
the sensitive reaction comprises the following steps: scorching, flashing, explosion and/or burning phenomena.
Specifically, the mechanical property test in the step M3 includes: testing the tensile strength and the shear strength of the combined sample of the resin and the carbon fiber at normal temperature and liquid nitrogen temperature according to a preset standard; and (3) testing the mechanical properties of the sample at normal temperature and liquid nitrogen temperature in a universal mechanical testing machine, stretching preset group data of the sample, shearing the preset group data of the sample, and averaging after testing to judge whether the use requirements are met.
Specifically, the step M6 includes: and winding by adopting a method of continuously preparing a small amount of glue for multiple times in a winding process.
Example 2
Example 2 is a modification of example 1
The technical solution of the invention is as follows: the high-pressure low-temperature composite material gas cylinder used in the liquid oxygen environment comprises an aluminum alloy lining, a liquid oxygen compatible resin system, a carbon fiber composite layer and an aluminum alloy tailstock, wherein the outer surface of the aluminum alloy lining is covered with the composite material layer formed by the liquid oxygen compatible resin system and the carbon fibers in an annular and spiral alternately winding mode. Forming the high-pressure low-temperature composite material gas cylinder used in the liquid oxygen environment.
The lining material is aluminum alloy 6061. The fiber material is carbon fiber, and the resin system is a liquid oxygen compatible resin system. The tailstock is an aluminum alloy tailstock, and the materials are all liquid oxygen compatible metal materials. Meanwhile, under the condition that the aluminum alloy and the carbon fiber material meet the strength requirement, the weight reduction effect is achieved compared with a metal material;
the winding process of the composite material winding layer is designed according to the design requirement of the composite material gas cylinder, the composite layer is processed in a mode of combining annular winding and spiral winding, and the annular and spiral equal-strength design is considered in the design. The hoop strength is slightly higher than the spiral strength, and the difference is not higher than 2%. Thus obtaining the circumferential winding layer number and thickness and the spiral winding layer number and thickness;
the resin system adopted by the composite material winding layer is a liquid oxygen compatible resin system, and the liquid oxygen impact test sample and the mechanical property sample are prepared by adopting the resin system. The liquid oxygen impact test sample is subjected to 20 groups of liquid oxygen impact tests with the magnitude of 98J according to the standard QJ3177, and the liquid oxygen compatibility of the material is considered when phenomena such as scorching, flashing, explosion, burning and the like do not occur in the impact tests.
The epoxy value of the epoxy resin of which the resin system is a liquid oxygen compatible resin system adopted by the composite material winding layer is 0.14-0.45 eq/100g, and the bromine content is 5-25%.
The mechanical property test sample prepared by adopting the liquid oxygen compatible resin system and the carbon fiber is subjected to mechanical property tests at normal temperature and liquid nitrogen temperature, and the tensile strength under the normal temperature environment is more than or equal to 2100 MPa; the shear strength is more than or equal to 50 MPa; the tensile strength under the low-temperature environment is more than or equal to 1400 MPa; the shear strength is more than or equal to 50 MPa; the test result meets the use requirement of a liquid oxygen environment, and the resin is proved to be applicable to the winding of a high-pressure low-temperature composite material gas cylinder;
the liquid oxygen compatible resin system adopted by the composite material winding layer is high-viscosity resin, and the curing agent is a solid curing agent. Proportionally mixing the high-viscosity resin and the curing agent, and heating and stirring in a high-temperature water bath;
the liquid oxygen compatible resin system has higher viscosity and is easy to solidify in the winding process, so that glue is prepared by adopting a method of continuously preparing a small amount of glue for many times in the winding process;
the high-pressure low-temperature composite material gas cylinder used in the liquid oxygen environment avoids any combustible and impurities from being wound into the gas cylinder in the production and processing process. And after winding is finished, carrying out oil removal and degreasing treatment on the surface and the inner wall of the gas cylinder.
A manufacturing method of a high-pressure low-temperature composite material gas cylinder used in a liquid oxygen environment comprises the following specific implementation method:
(1) the invention provides a high-pressure low-temperature composite material gas cylinder for a liquid oxygen environment, which is a light pressure container and is used for storing helium under the cryogenic condition of liquid oxygen temperature;
(2) the high-pressure low-temperature composite material gas cylinder used in the liquid oxygen environment comprises an aluminum alloy lining (1), a composite material winding layer (2) and an aluminum alloy tailstock (3);
(3) the aluminum alloy lining is used for containing a storage medium, is manufactured by the processes of deep drawing, spinning, closing, machining and the like, and the overall dimension of the lining is designed according to the containing volume, the using conditions and the using times of the composite material gas cylinder, so that the aluminum alloy lining meeting the requirements is obtained;
(4) liquid oxygen impact test: the resin and the curing agent are mixed according to the ratio of 100: 15-100: 30 and then cured into 20 wafers with the diameter of 20-25 mm and the thickness of 3-4 mm, and the liquid oxygen compatibility is tested according to the QJ3177 standard. If no sensitive reaction (phenomena of scorching, flashing, explosion, burning and the like) exists in 20 times of impact tests, the resin is compatible with liquid oxygen;
(5) mechanical property test: the tensile strength and shear strength of the resin and carbon fiber combined sample at normal temperature and liquid nitrogen temperature are tested according to the standard GB/T1458. The mechanical property test is carried out on the alloy at normal temperature and liquid nitrogen temperature by a universal mechanical testing machine. Set of 5 tensile specimens and set of 9 shear specimens. After testing, taking an average value to judge whether the use requirement is met;
(6) and designing the number of layers and the wall thickness of the winding layer according to the strength of the winding layer made of the composite material. According to 2 times of safety coefficient and design of annular and spiral equal strength, the fiber adopts carbon fiber, and the resin adopts a liquid oxygen compatible resin system;
(7) before winding, the tooling equipment used in the winding process is subjected to oil removal treatment, so that the phenomenon that liquid oxygen is incompatible due to the fact that grease and impurities are wound into a composite layer is avoided;
(8) and clamping the aluminum alloy lining on a winding machine, and performing oil removal treatment on the outer surface of the lining. Taking 4 bundles of carbon fibers, proportioning liquid oxygen compatible resin and a curing agent according to the proportion of 100: 15-100: 30, heating, stirring and dissolving in a high-temperature water bath environment, pouring prepared glue solution into a glue dipping tank, and winding the fiber bundles on an aluminum alloy inner container in a winding mode of combining the circumferential direction and the spiral direction by soaking the fiber bundles in the resin;
(9) and (3) placing the wound composite material gas cylinder in a heating furnace for curing, wherein the curing temperature is 80-140 ℃, and the curing time is 10 hours. After the solidification is finished, obtaining a high-pressure low-temperature composite material gas cylinder used in a liquid oxygen environment;
(10) and carrying out a hydraulic strength test, an air tightness test, a hydraulic fatigue test and a hydraulic bursting test on the solidified gas cylinder, wherein the hydraulic strength test, the air tightness test and the hydraulic fatigue test all meet the requirements of the standards GB/T9251, GB/T12137 and GB/T9252. The hydraulic blasting test meets the requirements of the standard GB/T15385, and the blasting value is more than or equal to 2 times of the safety coefficient;
(11) after the normal-temperature hydraulic strength test and the air-tight test are carried out on the gas cylinder, a liquid oxygen environment soaking test (including inflation soaking, non-inflation soaking and the like), a liquid oxygen environment inflation and deflation test and a liquid nitrogen temperature zone blasting test are carried out. The test result meets the use requirement of the low-temperature composite material gas cylinder used in the liquid oxygen environment;
(12) and (4) carrying out oil removal and degreasing treatment on the high-pressure low-temperature composite material gas cylinder which is processed and tested. Finally, the whole production process of the product is finished.
In the description of the present application, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience in describing the present application and simplifying the description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present application.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (8)
1. A high-pressure low-temperature composite gas cylinder used in a liquid oxygen environment is characterized by comprising: the composite material comprises an aluminum alloy lining (1), a liquid oxygen compatible resin system, a carbon fiber composite layer (2) and an aluminum alloy tailstock (3);
the liquid oxygen compatible resin system and the carbon fiber composite layer (2) cover the outer surface of the aluminum alloy lining (1), and the aluminum alloy tailstock (3) is connected with the aluminum alloy lining (1) and is positioned at the tail part of the aluminum alloy lining (1) to form a high-pressure low-temperature conforming material gas cylinder used in a liquid oxygen environment.
2. The gas cylinder made of high-pressure low-temperature composite material used in liquid oxygen environment according to claim 1, wherein the liquid oxygen compatible resin system and the carbon fiber composite layer (2) are coated on the outer surface of the aluminum alloy lining (1) in a mode of winding in a circumferential direction and a spiral direction alternately.
3. The high-pressure low-temperature composite material gas cylinder used in the liquid oxygen environment according to claim 1, wherein the liquid oxygen compatible resin system and carbon fiber composite layer (2) comprises liquid oxygen compatible resin, a curing agent and carbon fibers;
the liquid oxygen compatible resin includes: bisphenol A epoxy resin, tetrabromobisphenol F resin, a catalyst, an antioxidant and an auxiliary agent;
the curing agent comprises an epoxy resin curing agent;
the liquid oxygen compatible resin system is formed by uniformly dissolving and stirring liquid oxygen compatible resin and a curing agent according to a preset proportion.
4. A manufacturing method of a high-pressure low-temperature composite material gas cylinder used in a liquid oxygen environment is characterized by comprising the following steps:
step M1: designing the overall dimension of the lining according to the containing volume, the using conditions and the using times of the composite material gas cylinder, and manufacturing the aluminum alloy lining by the processes of deep drawing, spinning, closing and machining;
step M2: connecting the aluminum alloy lining with an aluminum alloy tailstock;
step M3: the liquid oxygen compatible resin and the curing agent are proportioned according to a preset proportion and then cured into a liquid oxygen compatible resin system meeting preset conditions;
step M4: the liquid oxygen compatible resin system is subjected to liquid oxygen impact test and mechanical property test to verify that the liquid oxygen compatible resin is not incompatible with liquid oxygen when used in a liquid oxygen environment;
step M5: designing the number of layers and the wall thickness of the winding layer according to the strength of the winding layer made of the composite material;
step M6: before winding, carrying out oil removal treatment on tooling equipment used in the winding process;
step M7: clamping an aluminum alloy lining on a winding machine, removing oil on the outer surface of the lining, proportioning carbon fiber, liquid oxygen compatible resin and a curing agent according to a preset proportion, heating, stirring and dissolving in a high-temperature water bath environment, pouring prepared glue solution into a glue dipping tank, and winding the fiber bundle on the aluminum alloy lining in a winding mode combining the circumferential direction and the spiral direction by soaking the fiber bundle in the resin;
step M8: placing the wound composite material gas cylinder in a heating furnace for curing;
step M9: carrying out a hydraulic strength test, an air tightness test, a hydraulic fatigue test, a hydraulic bursting test, a hydraulic strength test, an air tightness test and a hydraulic fatigue test on the cured composite material gas cylinder, wherein the test result meets the use requirement of the low-temperature composite material gas cylinder used in a liquid oxygen environment;
step M10: and (4) carrying out oil removal and degreasing treatment on the high-pressure low-temperature composite material gas cylinder which is processed and tested.
5. The method for manufacturing a high-pressure low-temperature composite material gas cylinder used in a liquid oxygen environment according to claim 4, wherein the step M2 comprises: the liquid oxygen compatible resin and the curing agent are dissolved and stirred by a method of heating and stirring to form a liquid oxygen compatible resin system.
6. The method for manufacturing the high-pressure low-temperature composite material gas cylinder used in the liquid oxygen environment according to claim 4, wherein the liquid oxygen impact test in the step M3 comprises: the liquid oxygen compatible resin and the curing agent are proportioned according to a preset proportion and then cured into a wafer with a preset diameter and thickness under preset conditions, and the liquid oxygen compatibility is tested according to a preset standard; if the impact test has no sensitive reaction for the preset times, the liquid oxygen compatible resin is compatible with the liquid oxygen;
the sensitive reaction comprises the following steps: scorching, flashing, explosion and/or burning phenomena.
7. The method for manufacturing the high-pressure low-temperature composite material gas cylinder used in the liquid oxygen environment according to claim 4, wherein the mechanical property test in the step M3 comprises the following steps: testing the tensile strength and the shear strength of the combined sample of the resin and the carbon fiber at normal temperature and liquid nitrogen temperature according to a preset standard; and (3) testing the mechanical properties of the sample at normal temperature and liquid nitrogen temperature in a universal mechanical testing machine, stretching preset group data of the sample, shearing the preset group data of the sample, and averaging after testing to judge whether the use requirements are met.
8. The method for manufacturing a high-pressure low-temperature composite material gas cylinder used in a liquid oxygen environment according to claim 4, wherein the step M6 comprises: and winding by adopting a method of continuously preparing a small amount of glue for multiple times in a winding process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010773031.6A CN112066240A (en) | 2020-08-04 | 2020-08-04 | High-pressure low-temperature composite material gas cylinder used in liquid oxygen environment and manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010773031.6A CN112066240A (en) | 2020-08-04 | 2020-08-04 | High-pressure low-temperature composite material gas cylinder used in liquid oxygen environment and manufacturing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112066240A true CN112066240A (en) | 2020-12-11 |
Family
ID=73656908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010773031.6A Pending CN112066240A (en) | 2020-08-04 | 2020-08-04 | High-pressure low-temperature composite material gas cylinder used in liquid oxygen environment and manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112066240A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113500797A (en) * | 2021-07-06 | 2021-10-15 | 南通曙光机电工程有限公司 | Preparation method of stainless steel pressure vessel wound carbon fiber |
| CN115076591A (en) * | 2022-06-06 | 2022-09-20 | 光年探索(江苏)空间技术有限公司 | Stainless steel II-type gas cylinder and manufacturing method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011933A (en) * | 2010-09-29 | 2011-04-13 | 沈阳斯林达安科新技术有限公司 | Hydrogen aluminum alloy inner container carbon fiber fully-winding gas cylinder for vehicle and production process thereof |
| CN102211405A (en) * | 2010-04-09 | 2011-10-12 | 航天材料及工艺研究所 | Process for forming light-weight and high-pressure gas bottle made of composite material |
| CN108342081A (en) * | 2018-02-09 | 2018-07-31 | 中国人民解放军陆军军医大学 | A kind of carbon fibre resin liquid-oxygen container and preparation method thereof |
| CN109366106A (en) * | 2018-11-28 | 2019-02-22 | 北京宇航系统工程研究所 | A kind of big volume titanium alloy cylinder, manufacturing method and its application suitable for liquid oxygen environment |
| CN109838682A (en) * | 2019-03-04 | 2019-06-04 | 西华大学 | A kind of 35MPa aluminium alloy inner container winds the compressed natural gas bottle of basalt fibre entirely |
| CN110467795A (en) * | 2019-08-09 | 2019-11-19 | 大连理工大学 | A kind of low viscosity liquid oxygen compatible epoxy system and preparation method thereof for wet laid fiber winding |
| CN111040379A (en) * | 2019-11-25 | 2020-04-21 | 北京宇航系统工程研究所 | Low-temperature resin system used in liquid oxygen environment and preparation method and application thereof |
-
2020
- 2020-08-04 CN CN202010773031.6A patent/CN112066240A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211405A (en) * | 2010-04-09 | 2011-10-12 | 航天材料及工艺研究所 | Process for forming light-weight and high-pressure gas bottle made of composite material |
| CN102011933A (en) * | 2010-09-29 | 2011-04-13 | 沈阳斯林达安科新技术有限公司 | Hydrogen aluminum alloy inner container carbon fiber fully-winding gas cylinder for vehicle and production process thereof |
| CN108342081A (en) * | 2018-02-09 | 2018-07-31 | 中国人民解放军陆军军医大学 | A kind of carbon fibre resin liquid-oxygen container and preparation method thereof |
| CN109366106A (en) * | 2018-11-28 | 2019-02-22 | 北京宇航系统工程研究所 | A kind of big volume titanium alloy cylinder, manufacturing method and its application suitable for liquid oxygen environment |
| CN109838682A (en) * | 2019-03-04 | 2019-06-04 | 西华大学 | A kind of 35MPa aluminium alloy inner container winds the compressed natural gas bottle of basalt fibre entirely |
| CN110467795A (en) * | 2019-08-09 | 2019-11-19 | 大连理工大学 | A kind of low viscosity liquid oxygen compatible epoxy system and preparation method thereof for wet laid fiber winding |
| CN111040379A (en) * | 2019-11-25 | 2020-04-21 | 北京宇航系统工程研究所 | Low-temperature resin system used in liquid oxygen environment and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 章基凯: "《有机硅材料》", 31 October 1999 * |
| 郭玉明: "《第十四届全国复合材料学术会议论文集》", 30 September 2006 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113500797A (en) * | 2021-07-06 | 2021-10-15 | 南通曙光机电工程有限公司 | Preparation method of stainless steel pressure vessel wound carbon fiber |
| CN115076591A (en) * | 2022-06-06 | 2022-09-20 | 光年探索(江苏)空间技术有限公司 | Stainless steel II-type gas cylinder and manufacturing method thereof |
| CN115076591B (en) * | 2022-06-06 | 2024-01-26 | 光年探索(江苏)空间技术有限公司 | Stainless steel II-type gas cylinder and manufacturing method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Azeem et al. | Application of filament winding technology in composite pressure vessels and challenges: a review | |
| Shen | A filament-wound structure technology overview | |
| CN112066240A (en) | High-pressure low-temperature composite material gas cylinder used in liquid oxygen environment and manufacturing method | |
| JP2007002256A (en) | Method for production of prepreg tow and/or prepreg | |
| CN103994319B (en) | Thin-wall metal liner fiber is wound around winding and the solidification method of lightweight gas cylinder entirely | |
| JP2019070130A (en) | Low-viscosity liquid epoxy resin composition and pressure container manufactured from the same | |
| Cho et al. | Effect of dome curvature on failure mode of type4 composite pressure vessel | |
| Lark | Recent advances in lightweight, filament-wound composite pressure vessel technology | |
| Yan et al. | Review on linerless type V cryo-compressed hydrogen storage vessels: Resin toughening and hydrogen-barrier properties control | |
| Ballinger et al. | Review and history of PSI elastomeric diaphragm tanks | |
| CN113432030A (en) | Method for manufacturing bottle type container with stainless steel liner and carbon fiber wound completely | |
| CN113446510A (en) | Large-diameter seamless steel inner container circumferential winding gas cylinder and manufacturing method thereof | |
| Achary et al. | Composite development and applications for cryogenic tankage | |
| Shivamurthy et al. | Design, fabrication, and testing of epoxy/glass-reinforced pressure vessel for high-pressure gas storage | |
| RU2175088C1 (en) | Pressure vessel and method of its manufacture (versions) | |
| Chashchilov et al. | Development of a polymer composite material with an epoxy binder for producing a high-pressure cylinder | |
| Lark | Filament-wound composite vessels material technology | |
| Faddoul | Structural considerations in design of lightweight glass-fiber composite pressure vessels | |
| CN114105660B (en) | Material composition for hydrogen storage structure, material for hydrogen storage structure, and hydrogen storage single tube | |
| MORRIS et al. | Lighter weight fiber/metal pressure vessels using carbon overwrap | |
| Mallick et al. | Microcrack resistant polymers enabling lightweight composite hydrogen storage vessels | |
| MURRAY et al. | Development of composite pressure vessels with nonmetallic liners | |
| Meyer et al. | Linerless composite cryogenic technology | |
| Erturan et al. | Development of Carbon Composite/Aluminum Liner Hybrid Rocket Motor Case | |
| COŞKUN et al. | Effects Of Stacking Sequence on the Structural Performance of Composite Overwrapped Pressure Vessels |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201211 |
|
| RJ01 | Rejection of invention patent application after publication |