CN113320243A - Self-lubricating coating and preparation method and application thereof - Google Patents
Self-lubricating coating and preparation method and application thereof Download PDFInfo
- Publication number
- CN113320243A CN113320243A CN202110600615.8A CN202110600615A CN113320243A CN 113320243 A CN113320243 A CN 113320243A CN 202110600615 A CN202110600615 A CN 202110600615A CN 113320243 A CN113320243 A CN 113320243A
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- fiber cotton
- molybdenum disulfide
- self
- adhesive
- 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
- 238000000576 coating method Methods 0.000 title claims abstract description 53
- 239000011248 coating agent Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 113
- 239000004917 carbon fiber Substances 0.000 claims abstract description 113
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 113
- 229920000742 Cotton Polymers 0.000 claims abstract description 100
- 239000000853 adhesive Substances 0.000 claims abstract description 59
- 230000001070 adhesive effect Effects 0.000 claims abstract description 59
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 56
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 39
- -1 phenolic aldehyde acetal Chemical class 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 230000001680 brushing effect Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000004026 adhesive bonding Methods 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 15
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 230000001050 lubricating effect Effects 0.000 description 19
- 239000000835 fiber Substances 0.000 description 12
- 239000002783 friction material Substances 0.000 description 11
- 239000003292 glue Substances 0.000 description 10
- 238000005238 degreasing Methods 0.000 description 9
- 238000010428 oil painting Methods 0.000 description 9
- 239000003973 paint Substances 0.000 description 9
- 238000007788 roughening Methods 0.000 description 9
- 230000003014 reinforcing effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000032683 aging Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 239000011354 acetal resin Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- 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
- B32B15/00—Layered products comprising a layer of metal
-
- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
-
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
-
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/53—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with hydrogen sulfide or its salts; with polysulfides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/41—Phenol-aldehyde or phenol-ketone resins
-
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0076—Curing, vulcanising, cross-linking
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention belongs to the technical field of self-lubricating coatings, and particularly relates to a self-lubricating coating and a preparation method and application thereof. The coating takes carbon fiber cotton as a material framework, and molybdenum disulfide and phenolic aldehyde acetal adhesive are filled in gaps of the framework; the coating material not only has higher mechanical strength, but also can realize excellent self-lubricating effect, and can be widely applied to brakes, clutches and friction transmission devices of various machine equipment as a braking material.
Description
Technical Field
The invention belongs to the technical field of self-lubricating coatings, and particularly relates to a self-lubricating coating and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The friction material is widely used as the brake material in brakes, clutches and friction transmission devices of various transportation vehicles (such as automobiles, trains, airplanes, ships and the like) and various machine equipment. In the braking device, the friction performance of the friction material is utilized to convert the kinetic energy of the rotation into heat energy and other forms of energy, so that the transmission device is braked.
Based on the increasingly high requirements of modern society on environmental protection and safety, the developed countries of the world automobile industry rapidly develop research and development of non-asbestos friction materials, and non-asbestos semimetal type friction materials, sintered metal type friction materials, substitute fiber reinforced or polymer bonded friction materials, composite fiber friction materials, ceramic fiber friction materials and the like are successively promoted.
The self-lubricating coating technology is a method for lubricating a friction pair interface by coating or plating a solid substance on the friction pair interface as a solid lubricating material or a solid lubricant so as to reduce friction or reduce friction.
Among various friction materials, fiber reinforced friction materials have attracted much attention because the reinforcing fibers in the fiber reinforced friction materials allow the materials to have mechanical effects such as strength, toughness, impact resistance, shear, and tension without mechanical damage such as cracks, fractures, and chipping. The fiber used for material reinforcement mainly comprises carbon fiber, ceramic fiber, glass fiber, aramid fiber and the like. At present, in view of the excellent performance of carbon fiber, the carbon fiber is widely used as a reinforcing phase, molybdenum disulfide, graphite, talcum powder, soft metal and metal oxide are used as a lubricating phase, and a carbon fiber coating with a self-lubricating function is prepared. The reinforcing phase and the lubricating phase are often bonded by adopting an adhesive, the existing adhesive is generally an epoxy resin adhesive, a polyurethane adhesive, a polyvinyl acetate adhesive and the like, however, the inventor finds that the mechanical strength and the self-lubricating effect of the existing self-lubricating carbon fiber coating are relatively limited, and further research is needed to obtain a coating material with high mechanical strength and self-lubricating effect.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a self-lubricating coating, and a preparation method and application thereof, wherein the self-lubricating coating takes carbon fiber cotton as a reinforcing phase, molybdenum disulfide as a lubricating phase and phenolic aldehyde acetal as an adhesive, the coating material not only has higher mechanical strength, but also can realize excellent self-lubricating effect, and can be widely applied to brakes, clutches and friction transmission devices of various machine equipment as a braking material.
In order to achieve the above object, the present invention provides, in a first aspect, a self-lubricating coating, which uses carbon fiber cotton as a material skeleton, and molybdenum disulfide and a phenolic acetal adhesive are filled in the voids of the skeleton.
Wherein the mass ratio of the carbon fiber cotton, the molybdenum disulfide and the phenolic aldehyde acetal adhesive is (50-55): (0.9-1.1): (9-11).
The second aspect of the present invention provides a preparation method of the self-lubricating coating, specifically comprising:
step one, weighing molybdenum disulfide and phenolic aldehyde acetal adhesive according to a certain proportion, and uniformly mixing;
step two, taking a proper amount of carbon fiber cotton, and soaking the carbon fiber cotton in the adhesive mixed with molybdenum disulfide until the carbon fiber cotton is completely soaked;
selecting a board with a proper size and placing the soaked carbon fiber cotton on the board;
and step four, pressurizing and curing the prepared sample.
The third aspect of the invention provides an application of the self-lubricating coating in the fields of aerospace, automobiles, biomedical treatment, petroleum equipment and electronics.
One or more embodiments of the present invention have at least the following advantageous effects:
(1) according to the invention, the carbon fiber cotton is used as a reinforcing phase, so that the surface with low relative friction coefficient and uniform surface friction performance can be compounded with the molybdenum disulfide through the adhesive, and the compact load among the carbon fiber cotton, the carbon fiber cotton and the molybdenum disulfide can be enhanced.
(2) The phenolic acetal has good curing adhesion and high adhesive bonding strength to carbon fiber cotton and molybdenum disulfide, and the phenolic acetal adhesive has the advantages of phenolic aldehyde and polyvinyl acetal resin, and is good in mechanical strength and excellent in flexibility. In addition, the phenolic acetal adhesive has excellent vibration resistance and fatigue resistance, and has excellent water resistance, humidity and heat aging resistance, especially excellent atmospheric aging resistance and excellent medium resistance. According to the invention, phenolic aldehyde acetal is used as an adhesive to assist the compounding of carbon fiber cotton and molybdenum disulfide, so that the finally obtained coating has excellent mechanical strength and self-lubricating effect.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a sectional view of a self-lubricating coating prepared in example 1 of the present invention;
fig. 2 is a surface view of the self-lubricating coating prepared in example 1 of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background art, the mechanical strength and the self-lubricating effect of the existing self-lubricating carbon fiber coating are limited, and further research is needed to obtain a coating material with both high mechanical strength and self-lubricating effect.
In order to solve the technical problems, the invention provides a self-lubricating coating which takes carbon fiber cotton as a material framework, and molybdenum disulfide and phenolic aldehyde acetal adhesive are filled in gaps of the framework.
The carbon fiber is a novel high-strength and high-modulus fiber material, has the properties of 'outer flexibility and inner rigidity', is lighter than metal aluminum in mass, but has higher strength than steel, has corrosion resistance, and is an important material in the aspects of national defense, military industry and civil use. It not only has the intrinsic characteristic of carbon material, but also has the soft workability of fibre, so that it is a new generation of reinforced fibre. The carbon fiber cotton with a special fiber arrangement structure is adopted in the invention, but not other carbon fiber braided fabrics, because the fiber direction arrangement in the carbon fiber cotton is random, and the fiber arrangement in the carbon fiber braided fabrics is ordered, the order can cause the friction force to be enhanced along a certain specific direction, thus on one hand, the surface friction coefficient is enhanced, and on the other hand, the surface friction performance is not uniform. The carbon fiber cotton is used as a reinforcing phase, so that the surface with low relative friction coefficient and uniform surface friction performance and the lubricating phase are compounded through the adhesive, and the compact load among the carbon fiber cotton, the carbon fiber cotton and the lubricating phase is enhanced.
According to the invention, molybdenum disulfide is used as a reinforcing phase, and is not used as other lubricating materials such as graphite, talcum powder and the like, on one hand, because the friction coefficient of molybdenum disulfide is lower (0.03-0.06), and the lubricating property of molybdenum disulfide is not caused by an adsorption film or gas, the lubricating property is inherent in molybdenum disulfide, the molybdenum disulfide is easy to delaminate, and a molybdenum disulfide protective film is formed on the surface of the reinforcing phase, so that the lubricating effect is effectively provided.
The phenolic acetal adhesive is adopted to adhere the reinforcing phase and the lubricating phase, because the phenolic acetal has good curing adhesion and high adhesive strength to the carbon fiber cotton and the molybdenum disulfide, and the phenolic acetal adhesive has the advantages of phenolic aldehyde and polyvinyl acetal resin, and has good mechanical strength and excellent flexibility. In addition, the phenolic acetal adhesive has excellent vibration resistance and fatigue resistance, and has excellent water resistance, humidity and heat aging resistance, especially excellent atmospheric aging resistance and excellent medium resistance. According to the invention, phenolic aldehyde acetal is used as an adhesive to assist the compounding of carbon fiber cotton and molybdenum disulfide, so that the finally obtained coating has excellent mechanical strength and self-lubricating effect.
When the coating is rubbed, the carbon fiber cotton is taken as the skeleton of the material to mainly enhance the strength, modulus and impact resistance of the coating, so that the coating is not damaged by cracks and the like. In addition, when carbon fiber cotton is extruded during coating friction, molybdenum disulfide is extruded to the surface, molybdenum disulfide is a layered compound and is very easy to layer, a molybdenum disulfide protective film is formed on the surface of carbon fiber, the friction coefficient of molybdenum disulfide is low, the friction resistance is small, and lubrication can be effectively provided for the coating. Therefore, the coating material can be applied to traffic, such as brake materials in brakes, clutches and friction transmission devices of various machine equipment.
The reasonable proportion of the carbon fiber cotton, the molybdenum disulfide and the phenolic aldehyde acetal adhesive is the premise of ensuring that the coating material has excellent mechanical strength and self-lubricating effect, the imbalance of the overall strength and the self-lubricating property of the coating material can be caused by the excessive amount of any one component of the carbon fiber cotton or the molybdenum disulfide, the decrease of the proportion of an activity enhancing phase and a lubricating phase can be caused by the excessive amount of the phenolic aldehyde acetal adhesive, the coating material with high strength and self-lubricating property is difficult to obtain, the adhesion effect is difficult to exert by the insufficient amount of the phenolic aldehyde acetal adhesive, and the carbon fiber cotton and the molybdenum disulfide can not be tightly compounded, so that as an optimal implementation mode, the mass ratio of the carbon fiber cotton, the molybdenum disulfide and the phenolic aldehyde acetal is (50-55): (0.9-1.1): (9-11);
further, the mass ratio of the carbon fiber cotton, the molybdenum disulfide and the phenolic aldehyde acetal adhesive is 50: 1: 10;
the second aspect of the present invention provides a preparation method of the self-lubricating coating, specifically comprising:
step one, weighing molybdenum disulfide and phenolic aldehyde acetal adhesive according to a certain proportion, and uniformly mixing;
step two, taking a proper amount of carbon fiber cotton, and soaking the carbon fiber cotton in the adhesive mixed with molybdenum disulfide until the carbon fiber cotton is completely soaked;
selecting a board with a proper size and placing the soaked carbon fiber cotton on the board;
and step four, pressurizing and curing the prepared sample.
Wherein,
in order to obtain the coating material with the specific ratio, the mass ratio of the molybdenum disulfide to the phenolic aldehyde acetal adhesive is 1: 10;
in order to make the carbon fiber cotton present a clean and flat surface and enable the carbon fiber cotton to be tightly compounded with molybdenum disulfide, as a preferred embodiment, the surface of the carbon fiber cotton needs to be flat and roughened, degreased by an organic solvent, decontaminated and then soaked.
In one or more embodiments of the invention, the carbon fiber cotton has a gauge of 2mm thickness, a grammage of 1.5 g/10 cm square, and a sample size of 4cm by 25 cm;
further, the organic solvent includes, but is not limited to, ethanol, acetone.
Furthermore, the plate material is not limited and is an iron plate, an aluminum plate, a titanium plate or other metal alloy plates;
if the plate is an aluminum plate, the surface of the plate needs to be chemically treated, and then the soaked carbon fiber cotton is placed on the plate;
the soaked carbon fiber cotton shows that the phenomenon of unevenness can occur due to the action of liquid tension, so that the surface of the soaked carbon fiber cotton needs to be uniformly coated and brushed for 2-3 times by a gluing tool, and the soaked carbon fiber cotton is aired for 20-30 minutes at intervals every time (when the glue layer is not sticky);
in one or more embodiments of the present invention, the curing pressure is 0.1 to 0.2MPa, the curing temperature is 175-185 ℃, the curing time is 2 to 3 hours, and the material is taken out after the oven temperature is naturally cooled to room temperature.
The third aspect of the invention provides an application of the self-lubricating coating in the fields of aerospace, automobiles, biomedical treatment, petroleum equipment and electronics.
In order to make the technical solution of the present invention more clearly understood by those skilled in the art, the technical solution of the present invention will be described in detail below with reference to specific examples and comparative examples.
Example 1
The embodiment provides a preparation method of a self-lubricating coating, which specifically comprises the following steps:
(1) according to the following steps: weighing molybdenum disulfide and phenolic aldehyde acetal adhesive according to the mass ratio of 10, and uniformly mixing;
(2) taking carbon fiber cotton (specification: thickness 2mm, 1.5 g/10 square centimeter) with the size of 4cm × 25cm, building and flattening the surface of the carbon fiber cotton, roughening, degreasing by ethanol, removing dirt, and soaking in an adhesive mixed with molybdenum disulfide until the carbon fiber cotton is completely soaked;
(3) uniformly brushing the surface of the soaked carbon fiber cotton for 3 times by using an oil painting brush, and airing for 20 minutes at intervals each time until the glue layer is not sticky;
(4) selecting a plate with a proper size and placing the carbon fiber cotton coated with the paint on the plate;
(5) and (3) pressurizing and curing the prepared sample at the temperature of 180 ℃ for 2 hours under the pressure of 0.2MPa, and taking out the sample after the temperature of an oven is naturally cooled to room temperature.
The sectional view and the surface view of the coating material prepared in this example are shown in fig. 1 and fig. 2, respectively.
Example 2
(1) According to the weight ratio of 0.9: weighing molybdenum disulfide and phenolic aldehyde acetal adhesive according to the mass ratio of 10, and uniformly mixing;
(2) taking carbon fiber cotton (specification: thickness 2mm, 1.5 g/10 square centimeter) with the size of 4cm × 25cm, building and flattening the surface of the carbon fiber cotton, roughening, degreasing by acetone, removing dirt, and soaking in an adhesive mixed with molybdenum disulfide until the carbon fiber cotton is completely soaked;
(3) uniformly brushing the surface of the soaked carbon fiber cotton for 3 times by using an oil painting brush, and airing for 20 minutes at intervals each time until the glue layer is not sticky;
(4) selecting a plate with a proper size and placing the carbon fiber cotton coated with the paint on the plate;
(5) and (3) pressurizing and curing the prepared sample at the temperature of 180 ℃ for 3 hours under the pressure of 0.1MPa, and taking out the sample after the temperature of an oven is naturally cooled to room temperature.
Example 3
(1) According to the following steps: 11, weighing molybdenum disulfide and a phenolic aldehyde acetal adhesive according to the mass ratio, and uniformly mixing;
(2) taking carbon fiber cotton (specification: thickness 2mm, 1.5 g/10 square centimeter) with the size of 4cm × 25cm, building and flattening the surface of the carbon fiber cotton, roughening, degreasing by ethanol, removing dirt, and soaking in an adhesive mixed with molybdenum disulfide until the carbon fiber cotton is completely soaked;
(3) uniformly brushing the surface of the soaked carbon fiber cotton for 3 times by using an oil painting brush, and airing for 20 minutes at intervals each time until the glue layer is not sticky;
(4) selecting a plate with a proper size and placing the carbon fiber cotton coated with the paint on the plate;
(5) and (3) pressurizing and curing the prepared sample at the temperature of 175 ℃ for 2 hours under the pressure of 0.2MPa, and taking out the sample after the temperature of an oven is naturally cooled to room temperature.
Example 4
(1) According to the following steps: weighing molybdenum disulfide and phenolic aldehyde acetal adhesive according to the mass ratio of 10, and uniformly mixing;
(2) taking carbon fiber cotton (specification: thickness 2mm, 1.5 g/10 square centimeter) with the size of 4cm × 25cm, building and flattening the surface of the carbon fiber cotton, roughening, degreasing by ethanol, removing dirt, and soaking in an adhesive mixed with molybdenum disulfide until the carbon fiber cotton is completely soaked;
(3) uniformly brushing the surface of the soaked carbon fiber cotton for 3 times by using an oil painting brush, and airing for 20 minutes at intervals each time until the glue layer is not sticky;
(4) selecting a plate with a proper size and placing the carbon fiber cotton coated with the paint on the plate;
(5) and (3) pressurizing and curing the prepared sample at 185 ℃ for 2 hours under 0.1MPa, and taking out the sample after the temperature of an oven is naturally cooled to room temperature.
Comparative example 1
(1) According to the following steps: weighing molybdenum disulfide and a phenolic resin adhesive according to the mass ratio of 10, and uniformly mixing;
(2) taking carbon fiber cotton (specification: thickness 2mm, 1.5 g/10 square centimeter) with the size of 4cm × 25cm, building and flattening the surface of the carbon fiber cotton, roughening, degreasing by ethanol, removing dirt, and soaking in an adhesive mixed with molybdenum disulfide until the carbon fiber cotton is completely soaked;
(3) uniformly brushing the surface of the soaked carbon fiber cotton for 3 times by using an oil painting brush, and airing for 20 minutes at intervals each time until the glue layer is not sticky;
(4) selecting a plate with a proper size and placing the carbon fiber cotton coated with the paint on the plate;
(5) and (3) pressurizing and curing the prepared sample at the temperature of 180 ℃ for 2 hours under the pressure of 0.2MPa, and taking out the sample after the temperature of an oven is naturally cooled to room temperature.
Comparative example 2
(1) According to the following steps: weighing molybdenum disulfide and polyvinyl acetal adhesive according to the mass ratio of 10, and uniformly mixing;
(2) taking carbon fiber cotton (specification: thickness 2mm, 1.5 g/10 square centimeter) with the size of 4cm × 25cm, building and flattening the surface of the carbon fiber cotton, roughening, degreasing by ethanol, removing dirt, and soaking in an adhesive mixed with molybdenum disulfide until the carbon fiber cotton is completely soaked;
(3) uniformly brushing the surface of the soaked carbon fiber cotton for 3 times by using an oil painting brush, and airing for 20 minutes at intervals each time until the glue layer is not sticky;
(4) selecting a plate with a proper size and placing the carbon fiber cotton coated with the paint on the plate;
(5) and (3) pressurizing and curing the prepared sample at the temperature of 180 ℃ for 2 hours under the pressure of 0.2MPa, and taking out the sample after the temperature of an oven is naturally cooled to room temperature.
Comparative example 3
(1) According to the following steps: weighing molybdenum disulfide and a polyvinyl acetate adhesive according to the mass ratio of 10, and uniformly mixing;
(2) taking carbon fiber cotton (specification: thickness 2mm, 1.5 g/10 square centimeter) with the size of 4cm × 25cm, building and flattening the surface of the carbon fiber cotton, roughening, degreasing by ethanol, removing dirt, and soaking in an adhesive mixed with molybdenum disulfide until the carbon fiber cotton is completely soaked;
(3) uniformly brushing the surface of the soaked carbon fiber cotton for 3 times by using an oil painting brush, and airing for 20 minutes at intervals each time until the glue layer is not sticky;
(4) selecting a plate with a proper size and placing the carbon fiber cotton coated with the paint on the plate;
(5) and (3) pressurizing and curing the prepared sample at the temperature of 180 ℃ for 2 hours under the pressure of 0.2MPa, and taking out the sample after the temperature of an oven is naturally cooled to room temperature.
Comparative example 4
(1) According to the following steps: 10, weighing graphite and a phenolic acetal adhesive according to the mass ratio, and uniformly mixing;
(2) selecting carbon fiber cotton (specification: thickness 2mm, 1.5 g/10 cm) with size of 4cm × 25 cm;
the carbon fiber cotton is prepared by leveling and roughening the surface of the carbon fiber cotton, degreasing by ethanol, removing dirt, and soaking in an adhesive mixed with molybdenum disulfide until the carbon fiber cotton is completely soaked;
(3) uniformly brushing the surface of the soaked carbon fiber cotton for 3 times by using an oil painting brush, and airing for 20 minutes at intervals each time until the glue layer is not sticky;
(4) selecting a plate with a proper size and placing the carbon fiber cotton coated with the paint on the plate;
(5) and (3) pressurizing and curing the prepared sample at the temperature of 180 ℃ for 2 hours under the pressure of 0.2MPa, and taking out the sample after the temperature of an oven is naturally cooled to room temperature.
Comparative example 5
(1) According to the following steps: 10, weighing talcum powder and phenolic acetal adhesive according to the mass ratio, and uniformly mixing;
(2) selecting carbon fiber cotton (specification: thickness 2mm, 1.5 g/10 cm) with size of 4cm × 25 cm;
the carbon fiber cotton is prepared by leveling and roughening the surface of the carbon fiber cotton, degreasing by ethanol, removing dirt, and soaking in an adhesive mixed with molybdenum disulfide until the carbon fiber cotton is completely soaked;
(3) uniformly brushing the surface of the soaked carbon fiber cotton for 3 times by using an oil painting brush, and airing for 20 minutes at intervals each time until the glue layer is not sticky;
(4) selecting a plate with a proper size and placing the carbon fiber cotton coated with the paint on the plate;
(5) and (3) pressurizing and curing the prepared sample at the temperature of 180 ℃ for 2 hours under the pressure of 0.2MPa, and taking out the sample after the temperature of an oven is naturally cooled to room temperature.
And (3) performance testing:
TABLE 1 comparison of peel strengths of carbon fiber coatings with different binders
The data in table 1 show that the carbon fiber coating with the phenolic acetal adhesive has the highest stripping strength, the best mechanical property, the lowest uneven coefficient and the good uniformity.
TABLE 2 carbon fiber coating coefficient of friction contrast (pressure 20N) with different binders and lubricating materials
As can be seen from the data in table 2, on one hand, for the same lubricating phase carbon fiber cotton coating, the value of the friction coefficient is also changed along with the change of the adhesive, and when phenolic acetal is used as the adhesive, the friction coefficient is the smallest, which indicates that the coating has the most excellent self-lubricating effect; on the other hand, for the same adhesive, when the lubricating phase is changed, the friction coefficient is also changed, which shows that the selection of the lubricating phase also has an influence on the self-lubricating effect of the coating. Therefore, the high-self-lubricating coating obtained by the invention is derived from the combined action of the lubricating phase and the adhesive, and the friction coefficient of the carbon fiber cotton coating is the lowest under the condition that molybdenum disulfide is used as the lubricating phase and phenolic aldehyde acetal is used as the adhesive, so that the friction resistance generated between friction devices is the lowest.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A self-lubricating coating characterized by: the coating takes carbon fiber cotton as a material framework, and molybdenum disulfide and phenolic aldehyde acetal adhesive are filled in gaps of the framework.
2. Self-lubricating coating according to claim 1, characterized in that: the mass ratio of the carbon fiber cotton to the molybdenum disulfide to the phenolic aldehyde acetal adhesive is (50-55): (0.9-1.1): (9-11);
preferably, the mass ratio of the carbon fiber cotton to the molybdenum disulfide to the phenolic aldehyde acetal adhesive is 50: 1: 10.
3. a method for preparing a self-lubricating coating according to claim 1 or 2, characterized in that:
step one, weighing molybdenum disulfide and phenolic aldehyde acetal adhesive according to a certain proportion, and uniformly mixing;
step two, taking a proper amount of carbon fiber cotton, and soaking the carbon fiber cotton in the adhesive mixed with molybdenum disulfide until the carbon fiber cotton is completely soaked;
selecting a board with a proper size and placing the soaked carbon fiber cotton on the board;
and step four, pressurizing and curing the prepared sample.
4. The method of claim 3, wherein: the mass ratio of the molybdenum disulfide to the phenolic acetal adhesive is 1: 10.
5. The method of claim 3, wherein: the surface of the carbon fiber cotton needs to be smooth and roughened, and is degreased and decontaminated by an organic solvent and then soaked.
6. The method of claim 3, wherein: the plates are iron plates, aluminum plates, titanium plates and metal alloy plates;
if the plate is an aluminum plate, the surface of the plate needs to be chemically treated, and then the soaked carbon fiber cotton is placed on the plate.
7. The method of claim 3, wherein: the specification of the carbon fiber cotton is as follows: thickness 2mm, gram weight 1.5 g/10 square centimeter, sample size 4cm 25 cm;
the organic solvent includes, but is not limited to, ethanol, acetone.
8. The method of claim 3, wherein: and uniformly brushing the surface of the soaked carbon fiber cotton for 2-3 times by using a gluing tool, and airing for 20-30 minutes at intervals each time.
9. The method of claim 3, wherein: the curing temperature is 175-185 ℃, the curing time is 2-3 hours, and the material is taken out after the temperature of the oven is naturally cooled to the room temperature.
10. Use of the self-lubricating coating of claim 1 or 2 in the aerospace, automotive, biomedical, petroleum equipment and electronics fields.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110600615.8A CN113320243A (en) | 2021-05-31 | 2021-05-31 | Self-lubricating coating and preparation method and application thereof |
| PCT/CN2021/098976 WO2022252260A1 (en) | 2021-05-31 | 2021-06-08 | Self-lubricating coating, preparation method therefor, and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110600615.8A CN113320243A (en) | 2021-05-31 | 2021-05-31 | Self-lubricating coating and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113320243A true CN113320243A (en) | 2021-08-31 |
Family
ID=77422606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110600615.8A Pending CN113320243A (en) | 2021-05-31 | 2021-05-31 | Self-lubricating coating and preparation method and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN113320243A (en) |
| WO (1) | WO2022252260A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116285572B (en) * | 2023-02-24 | 2024-03-26 | 上海骋润高分子材料有限公司 | High-lubrication coating and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1260494A (en) * | 1968-05-27 | 1972-01-19 | Dow Corning | Terazzo self-lubricated composite |
| EP0437136A2 (en) * | 1990-01-10 | 1991-07-17 | Matra Defense | Manufacture of impregnated articles, and the use of such articles as rotating bearings |
| CN101319464A (en) * | 2008-05-30 | 2008-12-10 | 广州市晶邦液压密封技术有限公司 | Self-lubricating materials and technique for producing helicoidal surface underlayer of transmission nut by the same |
| US20120294557A1 (en) * | 2011-05-16 | 2012-11-22 | New Hampshire Ball Bearings, Inc. | Novel self-lubricating surface coating composition |
| CN103112931A (en) * | 2013-02-26 | 2013-05-22 | 吴英 | Electric ion replacement processing device for reducing liquid conductivity |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450492B (en) * | 2013-08-28 | 2016-01-20 | 陕西科技大学 | Carbon cloth friction materials of a kind of molybdenumdisulphide modification and preparation method thereof |
| CN104480717A (en) * | 2014-10-31 | 2015-04-01 | 山东腾工轴承有限公司 | Self-lubricating joint bearing polytetrafluoroethylene/kevlar fabric liner modified material and modification method |
| CN106523514A (en) * | 2016-11-10 | 2017-03-22 | 长春安旨科技有限公司 | High-temperature resisting macromolecule self-lubricating bearing and preparing method thereof |
| CN111730947B (en) * | 2020-07-07 | 2021-04-23 | 中国科学院兰州化学物理研究所 | Composite fiber fabric antifriction material and preparation method and application thereof |
| CN112812496B (en) * | 2021-01-04 | 2021-11-12 | 中国科学院兰州化学物理研究所 | Mxene-V2C modified carbon fiber fabric self-lubricating material and preparation method thereof |
-
2021
- 2021-05-31 CN CN202110600615.8A patent/CN113320243A/en active Pending
- 2021-06-08 WO PCT/CN2021/098976 patent/WO2022252260A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1260494A (en) * | 1968-05-27 | 1972-01-19 | Dow Corning | Terazzo self-lubricated composite |
| EP0437136A2 (en) * | 1990-01-10 | 1991-07-17 | Matra Defense | Manufacture of impregnated articles, and the use of such articles as rotating bearings |
| CN101319464A (en) * | 2008-05-30 | 2008-12-10 | 广州市晶邦液压密封技术有限公司 | Self-lubricating materials and technique for producing helicoidal surface underlayer of transmission nut by the same |
| US20120294557A1 (en) * | 2011-05-16 | 2012-11-22 | New Hampshire Ball Bearings, Inc. | Novel self-lubricating surface coating composition |
| CN103112931A (en) * | 2013-02-26 | 2013-05-22 | 吴英 | Electric ion replacement processing device for reducing liquid conductivity |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2022252260A1 (en) | 2022-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3219925B1 (en) | Composite aerofoil | |
| US2650185A (en) | Method of bonding faying surfaces of metallic members | |
| JP4501861B2 (en) | Titanium or titanium alloy, adhesive resin composition, prepreg and composite material | |
| JP6436593B2 (en) | Adhesive gel sheet having adhesive application, method for producing the same, method for fixing a pair of adherends, and composite material | |
| JP2006505655A (en) | Polymer composite structure reinforced with shape memory alloy and manufacturing method thereof | |
| WO2019188020A1 (en) | Internal mold release agent for fiber-reinforced composite material, fiber-reinforced composite material, molding method therefor, and joining method for fiber-reinforced resin molded product | |
| Nasreen et al. | Effect of surface treatment on the performance of composite‐composite and composite‐metal adhesive joints | |
| JP5508434B2 (en) | Composite material surface film | |
| CN113320243A (en) | Self-lubricating coating and preparation method and application thereof | |
| Ocaña et al. | Evaluation of degradation of structural adhesive joints in functional automotive applications | |
| KR100497727B1 (en) | Surface sheet and sandwich structure using the same | |
| JP2006198784A (en) | Fiber reinforced composite material and its manufacturing method | |
| Gao et al. | The preparation and properties of novel structural damping composites reinforced by nitrile rubber coated 3‐D braided carbon fibers | |
| JP2000516879A (en) | Hybrid material and method for producing the same | |
| Hynes et al. | Mechanical and microstructural characterization of hybrid fiber metal laminates obtained through sustainable manufacturing | |
| CN110529531A (en) | Friction plate structure and its manufacturing method | |
| WO2002081189A1 (en) | Bonding material for gel coat applications | |
| Kuteneva et al. | Adhesive and impact strength of hybrid layered metal-polymer composites reinforced by basalt fiber | |
| JP2004338207A (en) | Composite material and its manufacturing method | |
| JP5077731B2 (en) | Energy absorbing member | |
| CN110744886A (en) | Metal protective film and preparation method thereof | |
| KR20170005999A (en) | Manufacturing methods of thermosetting resins for manufacturing fiber composite materials leaf spring of automobile, prepreg and prepreg sheet | |
| GB2378995A (en) | Composite material | |
| JPS6049078A (en) | Adhesive sheet for reinforcing metallic plate | |
| KR102207414B1 (en) | Adhesion Method of Vibration Reduction Structure With Plastic Composite Material and Magnetic Rheological Elastomer |
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: 20210831 |
|
| RJ01 | Rejection of invention patent application after publication |