CN111572130B - Impact-resistant composite material, preparation method and application thereof - Google Patents
Impact-resistant composite material, preparation method and application thereof Download PDFInfo
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- CN111572130B CN111572130B CN202010464636.7A CN202010464636A CN111572130B CN 111572130 B CN111572130 B CN 111572130B CN 202010464636 A CN202010464636 A CN 202010464636A CN 111572130 B CN111572130 B CN 111572130B
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 17
- 239000000835 fiber Substances 0.000 claims abstract description 140
- 239000004744 fabric Substances 0.000 claims abstract description 120
- 239000000463 material Substances 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 238000011049 filling Methods 0.000 claims abstract description 13
- 229920003225 polyurethane elastomer Polymers 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 52
- 239000003795 chemical substances by application Substances 0.000 claims description 48
- 239000012745 toughening agent Substances 0.000 claims description 41
- 150000001412 amines Chemical class 0.000 claims description 38
- 229920005862 polyol Polymers 0.000 claims description 37
- 150000003077 polyols Chemical class 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 35
- 238000005507 spraying Methods 0.000 claims description 34
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000000306 component Substances 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 238000009987 spinning Methods 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 19
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 16
- 230000003712 anti-aging effect Effects 0.000 claims description 16
- 238000003490 calendering Methods 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000002518 antifoaming agent Substances 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000004917 carbon fiber Substances 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 230000002745 absorbent Effects 0.000 claims description 8
- 239000002250 absorbent Substances 0.000 claims description 8
- 239000000498 cooling water Substances 0.000 claims description 8
- 239000008358 core component Substances 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 8
- 239000012895 dilution Substances 0.000 claims description 8
- 238000010041 electrostatic spinning Methods 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 230000010355 oscillation Effects 0.000 claims description 7
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 7
- 229920002748 Basalt fiber Polymers 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 229920006231 aramid fiber Polymers 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- -1 methylene diphenyl Chemical group 0.000 claims description 6
- 239000004005 microsphere Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 239000013530 defoamer Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 4
- HGXVKAPCSIXGAK-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine;4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N.CCC1=CC(C)=C(N)C(CC)=C1N HGXVKAPCSIXGAK-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000008204 material by function Substances 0.000 claims description 4
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 3
- OKHQYCPETODROI-UHFFFAOYSA-N butyl acetate;1,2-xylene Chemical compound CCCCOC(C)=O.CC1=CC=CC=C1C OKHQYCPETODROI-UHFFFAOYSA-N 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- PHEDXBVPIONUQT-UHFFFAOYSA-N Cocarcinogen A1 Natural products CCCCCCCCCCCCCC(=O)OC1C(C)C2(O)C3C=C(C)C(=O)C3(O)CC(CO)=CC2C2C1(OC(C)=O)C2(C)C PHEDXBVPIONUQT-UHFFFAOYSA-N 0.000 claims description 2
- GOKPRTONAXWLTB-KQYNXXCUSA-N [[(2r,3s,4r,5r)-5-(2-amino-6-oxo-3h-purin-9-yl)-3,4-dihydroxyoxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-n-[hydroxy(methylamino)phosphoryl]phosphonamidic acid Chemical compound O[C@@H]1[C@H](O)[C@@H](COP(O)(=O)OP(O)(=O)NP(O)(=O)NC)O[C@H]1N1C(NC(N)=NC2=O)=C2N=C1 GOKPRTONAXWLTB-KQYNXXCUSA-N 0.000 claims description 2
- PHEDXBVPIONUQT-RGYGYFBISA-N phorbol 13-acetate 12-myristate Chemical compound C([C@]1(O)C(=O)C(C)=C[C@H]1[C@@]1(O)[C@H](C)[C@H]2OC(=O)CCCCCCCCCCCCC)C(CO)=C[C@H]1[C@H]1[C@]2(OC(C)=O)C1(C)C PHEDXBVPIONUQT-RGYGYFBISA-N 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 238000009718 spray deposition Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000010382 chemical cross-linking Methods 0.000 abstract description 2
- 230000004927 fusion Effects 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 abstract 1
- 239000000806 elastomer Substances 0.000 abstract 1
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 42
- 239000006185 dispersion Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- JVVXZOOGOGPDRZ-SLFFLAALSA-N [(1R,4aS,10aR)-1,4a-dimethyl-7-propan-2-yl-2,3,4,9,10,10a-hexahydrophenanthren-1-yl]methanamine Chemical compound NC[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 JVVXZOOGOGPDRZ-SLFFLAALSA-N 0.000 description 4
- 239000002121 nanofiber Substances 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 2
- CFXCGWWYIDZIMU-UHFFFAOYSA-N Octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate Chemical compound CCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 CFXCGWWYIDZIMU-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- 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
-
- 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
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- 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
- 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
- B32B5/22—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
-
- 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
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0261—Polyamide fibres
- B32B2262/0269—Aromatic polyamide fibres
-
- 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
-
- 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
- B32B2262/101—Glass fibres
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses an impact-resistant composite material, which comprises continuous phase multilayer fiber cloth and a polyurethane elastomer which does not appear in a filling phase containing a multi-ureido and multi-ureido macromolecule, wherein the multilayer fiber cloth is a plain fiber cloth and a twill fiber cloth which are arranged at intervals, and the total layer number is 3-15. The continuous phase of the impact-resistant composite material adopts plain fiber cloth and twill fiber cloth which are arranged at intervals, the continuous phase adopts a polymer elastomer containing multi-ureido and containing nano functional material short fibers, and the continuous phase and the filling phase are simultaneously subjected to physical fusion and chemical crosslinking, so that the composite material has high uniformity, high strength, high elongation and high impact resistance.
Description
Technical Field
The invention relates to the field of composite materials, in particular to an impact-resistant composite material, a preparation method and application thereof.
Background
The composite material is a novel material formed by combining different materials such as organic polymers, inorganic non-metals or metals through a composite process. The material not only maintains the important characteristics of the original composition material, but also obtains the performance which the original composition does not have through a composite effect. The properties of the components can be complemented and related to each other by material design, resulting in more excellent properties, which are essentially different from simple mixing of general materials.
The fiber composite material takes a fiber skeleton as a continuous phase and takes a mixture of chopped fibers and polymers as filling, and the chopped fibers and the skeleton fibers are mutually entangled, so that the fiber composite material has the advantages of high specific strength, large specific modulus, good corrosion resistance and durability, low thermal expansion coefficient and the like, and can be applied to the fields of corrosion resistance, engineering support, surface protection and the like.
Disclosure of Invention
The invention provides an impact-resistant composite material, which adopts multi-layer fiber cloth as a continuous phase and a mixture of nano functional materials and polymers as a filling phase.
The multi-layer fiber cloth is plain fiber cloth and twill fiber cloth which are arranged at intervals, the thickness of the single-layer fiber cloth is between 0.05 and 0.35mm, and the total layer number is 3 to 15. The 1-3 layers between two adjacent layers of the whole fiber cloth are formed by splicing small fiber cloths, and the same four small fiber cloths are uniformly tiled, so that the generation of waste materials is reduced, the gaps among the small fiber cloths are favorable for infiltration of filling phases, and the generation of cavities in the composite material is reduced. In order to increase the binding force between the small fiber cloths, two small fiber cloths made of the same material can be used for pressing and covering two small fiber cloths in the transverse direction or the longitudinal direction.
From the component, the plain weave fiber cloth of the invention is specifically plain weave glass fiber cloth, plain weave basalt fiber cloth, plain weave carbon fiber cloth or plain weave aramid fiber cloth, and the twill fiber cloth is specifically twill glass fiber cloth, twill basalt fiber cloth, twill carbon fiber cloth or twill aramid fiber cloth. The composition of each layer of fiber cloth can be the same as or different from the composition of other layers of fiber cloth of the same type.
The filling phase polymer is polyurethane elastomer, and the existing polyurethane elastomer can be added with a certain content of functional materials to be intertwined with fiber cloth, so that the interaction between a continuous phase and a filling phase is increased.
Based on the mechanism, the invention adopts polyurethane elastomer with the following weight fraction as filling phase: 49-67% of amine mixture, 32-50% of polyurethane prepolymer and 1-2% of nano functional material.
The amine mixture comprises the following substances in parts by weight: 20-50 parts of glycol polyether amine D400, D2000 or D800, 2-10 parts of one or more of ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or polyethylene polyamine, 3-15 parts of one or more of m-phenylenediamine PDA, m-xylylenediamine MDA, diaminodiphenylmethane HT972, diethyltoluenediamine DETDA or diphenylDBTDA, 2-10 parts of isophoronediamine IPDA or isophoronediamine and polyhydric alcohol polymer, 590 or 593-20 parts of curing agent, T31 or T531-40 parts of curing agent, T6001 or 6200-15 parts of polyisocyanate curing agent, 1-2 parts of one or more of ultraviolet absorber UV531, UV944, UV326, UV327 or UV-p, 0.5-1 part of one or more of dispersing agent BYK5040, BYK1100 or BYK116, 1010, 1076, 1068, 1135, 1157 one or more of 0.5-2 DF, 0.1581 part of defoaming agent, 0.1585-136 part of defoaming agent, and 1-136 part of toughening agent.
The polyurethane prepolymer comprises the following substances in parts by weight: 2-20 parts of MDI, 5-30 parts of a prepolymer of MDI and polyalcohol PG1000-2000, 2-30 parts of a prepolymer of MDI and polyalcohol PT1000-2000,
2-15 parts of hydrogenated HMDI, 2-20 parts of one or more of HDI trimer, HT100, HT600 or N3390, 2-15 parts of polyol prepolymer with HDI and molecular weight of 1000-2000, 1-12 parts of polyol prepolymer with TDI or TDI and molecular weight of 1000-2000, 2-15 parts of isophorone diisocyanate IPDI and polyol polymer with molecular weight of 800-3000, 2-5 parts of toughening agent TP184, 1-3 parts of anti-aging agent 4010 and 10-30 parts of solvent dimethylbenzene butyl acetate, ethyl acetate, PMA, DBE or DBG.
The nano functional material is selected from one of carbon nano tube, graphene, multi-layer graphite microchip, graphite microsphere, nano fumed silica or carbon fiber.
The method for preparing the impact-resistant composite material by combining the polyurethane elastomer with the multi-layer fiber cloth comprises the following steps:
(1) Pretreatment of nano-functional materials
Grinding the nano functional material for standby;
(2) Preparation of the spray liquid
1) Preparation of amine mixtures: adding ultraviolet absorbent and amine components in parts by weight into a container, introducing nitrogen for protection, heating to 50 ℃ by adopting a water bath kettle, stirring for 30-180min at a low rotation speed of 600-800rpm at the temperature until the liquid is clear and transparent, adding a toughening agent, heating to 80-120 ℃, stirring for 60-120min at a high speed of 800-1400rpm at the temperature until the liquid is transparent to form viscous liquid, cooling the flask to 30-40 ℃ by adopting cooling water, adding a dispersing agent, an antioxidant, a defoaming agent and a toughening agent, and stirring for 30-60min at 600-800rpm to obtain stable liquid;
3) Preparation of polyurethane prepolymer: weighing polyurethane prepolymer components according to parts by weight, mixing core components, stirring for 2-5 hours at 50-80 ℃ under the protection of nitrogen, adding a toughening agent and an anti-aging agent, stirring for 1-2 hours at 600-800rpm, and adding a solvent for dilution for later use;
(3) Spray forming
Sequentially arranging plain fiber cloth and twill fiber cloth at intervals to prepare multi-layer fiber cloth, uniformly mixing the substances obtained in the step 2 according to a proportion, adding a curing agent in an amine mixture, dispersing by ultrasonic oscillation of 20000Hz and 900W for 10-30min, stirring and mixing for 30-60min at 600-800rpm to finish blending, adopting high-pressure airless SPU spraying, wherein the spraying distance is 2-50cm, the spraying pressure is 5-16MPa, placing the multi-layer fiber cloth on a pressing plate after the spraying is finished, controlling the calendaring temperature to be 40-70 ℃, and calendaring and curing for 4-12h to obtain the fabric.
The nano functional material in the composite material prepared by the method is sheet-shaped or linear, can be randomly entangled with the fibers of the multi-layer fiber cloth, enhances the binding force between polyurethane and the fiber cloth, and ensures that the composite material has high strength and shock resistance. The impact-resistant composite material can be prepared into a sheet material firstly and then processed according to the use place, and is bonded and fixed by adopting an adhesive, and the multi-layer fiber cloth frame can be directly sprayed, cured and formed on the treated surface.
Further, the invention can improve the nano functional material as follows: immersing the ground nano functional material into mixed acid of nitric acid and sulfuric acid, immersing at 0 ℃ for 1-2h, cooling to-15 ℃, adding hydrogen peroxide, potassium permanganate and hypochlorous acid with the molar ratio of 1 (0.25-0.5) (0.25-1), reacting for 0.5-24h at-10-60 ℃, centrifugally separating, washing a filter cake with deionized water until the pH value of the washing solution is 6-7, placing in a vacuum drying box, drying at 60-70 ℃ for 4-6h, immersing the dried powder in a solution containing NaBH4 and CaCl2 for 8-10h, filtering, washing the filter cake with deionized water, drying at 60 ℃ for 6h in the drying box, dissolving in a solvent, preparing a spinning stock solution, carrying out electrostatic spinning on the obtained spinning stock solution, arranging a high-voltage ionization coil under the spinning nozzle, and cutting nano functional material fibers obtained on a receiving device into short fibers.
According to the technical scheme, the mixed oxidant of hydrogen peroxide, potassium permanganate and hypochlorous acid is adopted to oxidize and partially reduce active groups on the surface of the nano functional material, so that the surface of the nano functional material is provided with hydroxyl and carboxyl, the modified nano functional material can be stably dissolved in a solvent, electrostatic spinning can be carried out, nano fibers can be prepared, the nano fibers can be prepared into chopped fibers which can be used in spraying liquid, the hydroxyl and isocyanate groups on the surface of the chopped fibers react in the forming process after spraying, the hydroxyl and isocyanate groups are combined on a chemical layer, and after the chopped fibers are entangled with fiber cloth, the combination between a continuous phase and a filling phase is tighter, and the strength and the shock resistance of the composite material are further improved.
The technical scheme is further improved in that the spinning hole of the electrostatic spinning is wedge-shaped, after a stable fiber tow is formed, irregular flow of spinning stock solution is more obvious when continuously passing through the wedge-shaped spinning hole, uneven stress occurs, the spinning stock solution passes through the middle high-voltage electric wire to form a nano rod/tube fiber with defects on the surface, the nano rod/tube fiber is provided with electrostatic charge, the nano material generates stress, the large-caliber nano material generates stress orientation in one-dimensional direction to form self-curling nano fiber with large length-diameter ratio, the nano fiber has high elasticity, the curl state can be recovered after external force disappears, and the extensibility of the impact-resistant composite material is improved.
The continuous phase of the impact-resistant composite material adopts plain fiber cloth and twill fiber cloth which are arranged at intervals, the continuous phase adopts polyurethane elastomer containing nano functional material short fibers, physical fusion and chemical crosslinking exist between the continuous phase and the filling phase at the same time, and the composite material has high uniformity, high strength, high elongation and high impact resistance. The impact-resistant composite material can be coated on the surface of conventional I-steel, can be applied to expressway guardrails, ship suspension or container tower crane anti-collision beams and the like, can increase the energy absorption and damping performance of components, and can also be coated on the anti-collision surface of a ship steel platform to increase the impact resistance of the ship steel platform.
Drawings
Fig. 1 is a schematic structural diagram of an impact-resistant composite material according to the present invention, fig. 2 is a partially enlarged view of a portion a in fig. 1, and each portion is as follows: 1. continuous phase, 2, filling phase, 3, plain fiber cloth, 4, twill fiber cloth, 5, nano functional material;
FIG. 3 is a schematic view of a type B0 fiber cloth;
FIG. 4 is a schematic view of a type B1 fiber cloth;
FIG. 5 is a schematic view of a type B2 fiber cloth;
FIG. 6 is an electron microscope image of the nano-functional material fiber obtained in example 4;
fig. 7 and 8 are both electron microscopic views of sections of the impact resistant composite material obtained in example 4.
Detailed Description
The invention is described below in connection with examples which are given solely for the purpose of illustration and are not intended to limit the scope of the invention.
The continuous phase of the impact-resistant composite material in the embodiment 1-6 is multi-layer fiber cloth, the filling phase is polyurethane elastomer, the multi-layer fiber cloth is plain fiber cloth and twill fiber cloth which are arranged at intervals, the thickness of the plain fiber cloth and the twill fiber cloth is 0.05-0.35mm, each layer of plain fiber cloth is independently selected from one of plain glass fiber cloth, plain basalt fiber cloth, plain carbon fiber cloth or plain aramid fiber cloth, and each layer of twill fiber cloth is independently selected from one of twill glass fiber cloth, twill basalt fiber cloth, twill carbon fiber cloth or twill aramid fiber cloth; the whole fiber cloth is A-type fiber cloth, two adjacent layers of A-type fiber cloth are formed by splicing 1-3 layers of four small fiber cloths, the four small fiber cloths are evenly paved into B0-type fiber cloth (figure 3), two transverse small fiber cloths in the four small fiber cloths are pressed and covered into B1-type fiber cloth (figure 4) by the same small fiber cloth, and two vertical small fiber cloths in the four small fiber cloths are pressed and covered into B2-type fiber cloth (figure 5) by the same small fiber cloth. Specific information is shown in table 1.
TABLE 1 specific information on the continuous phases of examples 1-6
Example 1 the filler phase consisted of the following components in weight fraction: 49% of an amine mixture, 50% of a polyurethane prepolymer and 1% of nano fumed silica, wherein the amine mixture comprises the following substances in parts by weight: 50 parts of glycol polyether amine D400, 10 parts of ethylenediamine, 3 parts of m-phenylenediamine PDA, 2 parts of isophorone diamine IPDA, 590 parts of curing agent, T31 parts of curing agent T31, T6001 15 parts of polyisocyanate curing agent T531, 1 part of ultraviolet absorber UV531, 5040 parts of dispersant BYK5040, 1010 2 parts of antioxidant, 0.1 part of defoamer DF116 and 136 parts of toughening agent TP 136; the polyurethane prepolymer comprises the following substances in parts by weight: 20 parts of MDI, 5 parts of a prepolymer of MDI and polyol PG1000, 30 parts of a prepolymer of MDI and polyol PT1000, 15 parts of hydrogenated HMDI, 20 parts of an HDI trimer, 2 parts of a prepolymer of HDI and polyol with a molecular weight of 1000, 12 parts of a prepolymer of TDI and polyol with a molecular weight of 1000, 2 parts of isophorone diisocyanate IPDI and a polymer of polyol with a molecular weight of 3000, 5 parts of a toughening agent TP184, 0 part of an anti-aging agent 4011 part, and 30 parts of solvent dimethylbenzene butyl acetate.
The preparation method of the impact-resistant composite material comprises the following steps: grinding the nano fumed silica for standby; adding ultraviolet absorbent and amine components in parts by weight into a container, introducing nitrogen for protection, heating to 50 ℃ by adopting a water bath kettle, stirring for 180min at a low rotation speed of 600rpm at the temperature until the liquid is clear and transparent, adding a toughening agent, heating to 120 ℃, stirring for 60min at a high rotation speed of 1400rpm at the temperature until the liquid is transparent to form viscous liquid, cooling the flask to 40 ℃ by adopting cooling water, adding a dispersing agent, an antioxidant, a defoaming agent and the toughening agent, and stirring for 30min at 800rpm to obtain stable liquid; weighing the components of the polyurethane prepolymer according to parts by weight, mixing the core components, stirring for 5 hours at 50 ℃ under the protection of nitrogen, adding the toughening agent and the anti-aging agent, stirring for 1 hour at 800rpm, and adding the solvent for dilution for later use; sequentially arranging plain fiber cloth and twill fiber cloth at intervals to prepare multi-layer fiber cloth, uniformly mixing the three prepared components according to a proportion, adding a curing agent in an amine mixture, performing ultrasonic vibration dispersion at 20000Hz and 900W for 30min, stirring and mixing at 600rpm for 30min to finish blending, spraying by adopting a high-pressure airless SPU (SPU) at a spraying distance of 2cm and a spraying pressure of 5MPa, placing the multi-layer fiber cloth on a pressing plate after spraying, controlling the calendering temperature to be 70 ℃, and calendering and curing for 4h to obtain the multi-layer fiber cloth.
Example 2 the filler phase consisted of the following components in weight fraction: 50% of amine mixture, 48% of polyurethane prepolymer and 2% of carbon nano tube, wherein the amine mixture comprises the following substances in parts by weight: the polyurethane foam comprises, by weight, 2000 25 parts of glycol polyether amine D, 4 parts of propylene diamine, 5 parts of m-xylylenediamine MDA, 3 parts of isophorone diamine and a polyol polymer, 593 parts of a curing agent 598 parts of a curing agent T531, 15 parts of a polyisocyanate curing agent T60015 parts of an ultraviolet absorber UV944 1.3 parts of a dispersing agent BYK 1100.6 parts of an antioxidant 1076.7 parts of an antifoaming agent DF831 0.11 parts of a toughening agent TP1587 parts of a toughening agent TP 1582 parts of a polyurethane foam; the polyurethane prepolymer comprises the following substances in parts by weight: 5 parts of MDI, 8 parts of a polyol PG2000 prepolymer, 5 parts of a polyol PT1000 prepolymer, 7 parts of hydrogenated HMDI, 1005 parts of HT, 4 parts of a polyol prepolymer of HDI and molecular weight 15, 3 parts of a polyol prepolymer of TDI and molecular weight 1000, 4 parts of a polyol polymer of isophorone diisocyanate IPDI and molecular weight 1000, 2.2 parts of a toughening agent TP184, 1.2 parts of an anti-aging agent 4010, and 12 parts of solvent ethyl acetate.
The preparation method of the impact-resistant composite material comprises the following steps: grinding the carbon nano tube for standby; adding ultraviolet absorbent and amine components in parts by weight into a container, introducing nitrogen for protection, heating to 50 ℃ by adopting a water bath kettle, stirring at a low rotation speed of 650rpm for 150min until the liquid is clear and transparent, adding a toughening agent, heating to 100 ℃, stirring at a high speed of 1200rpm for 90min until the liquid is transparent to form viscous liquid, cooling the flask to 35 ℃ by adopting cooling water, adding a dispersing agent, an antioxidant, a defoaming agent and the toughening agent, and stirring at 700rpm for 35min to obtain stable liquid; weighing the components of the polyurethane prepolymer according to parts by weight, mixing the core components, stirring for 2-5 hours at 50-80 ℃ under the protection of nitrogen, adding the toughening agent and the anti-aging agent, stirring for 1.5 hours at 700rpm, and adding the solvent for dilution for later use; sequentially arranging plain fiber cloth and twill fiber cloth at intervals to prepare multi-layer fiber cloth, uniformly mixing the three prepared components according to a proportion, adding a curing agent in an amine mixture, performing ultrasonic vibration dispersion at 20000Hz and 900W for 10-30min, stirring and mixing at 700rpm for 40min to complete the preparation, spraying by adopting a high-pressure airless SPU (SPU) at a spraying distance of 15cm and a spraying pressure of 7MPa, placing the multi-layer fiber cloth on a pressing plate after the spraying is completed, controlling the calendering temperature to be 50 ℃, and calendering and curing for 5h to obtain the multi-layer fiber cloth.
Example 3 the filler phase consisted of the following components in weight fraction: 65% of an amine mixture, 32% of a polyurethane prepolymer and 3% of graphene, wherein the amine mixture comprises the following substances in parts by weight: 35 parts of glycol polyether amine D800, 6 parts of diethylenetriamine, 6 parts of diaminodiphenylmethane HT972, 6 parts of isophorone diamine IPDA, 590.5 parts of a curing agent 590, T31 parts of a curing agent T25 parts of a curing agent 6200, 1.5 parts of UV326, 0.75 part of a dispersing agent BYK116, 1.25 parts of an antioxidant 1135, 0.15 part of a defoaming agent DF831 and 1587 parts of a toughening agent TP 1583; the polyurethane prepolymer comprises the following substances in parts by weight: 11 parts of MDI, 17.5 parts of a pre-polymer of MDI and polyol PG2000, 16 parts of a pre-polymer of MDI and polyol PT2000, 8.5 parts of hydrogenated HMDI, 600 parts of HT, 8.5 parts of a pre-polymer of HDI and polyol with a molecular weight of 1000, 6.5 parts of TDI, 8.5 parts of a polymer of isophorone diisocyanate IPDI and polyol with a molecular weight of 2000, 3.5 parts of a toughening agent TP184, 4010.2 parts of an anti-aging agent and 20 parts of a solvent PMA.
The preparation method of the impact-resistant composite material comprises the following steps: placing graphene into a container, slowly dropwise adding 98% sulfuric acid and 70% nitric acid, dispersing by ultrasonic oscillation for 30min, magnetically stirring at 80 ℃ and then carrying out suction filtration, drying a filter cake at 75 ℃ for 5h, crushing, adding the filter cake into a silane coupling agent KH570, soaking for 12h at normal temperature, carrying out vacuum filtration, drying at 60 ℃ for 6h and crushing to obtain graphene containing hydroxyl and carboxyl, dissolving the graphene into a solvent to obtain spinning stock solution, carrying out electrostatic spinning on the obtained spinning stock solution, arranging a high-voltage ionization coil under a spinneret, collecting fibers on a receiving device, and cutting the fibers into short fibers for later use; adding ultraviolet absorbent and amine components in parts by weight into a container, introducing nitrogen for protection, heating to 50 ℃ by adopting a water bath kettle, stirring at a low rotation speed of 750rpm for 60min until the liquid is clear and transparent, adding a toughening agent, heating to 90 ℃, stirring at a high speed of 1000rpm for 80min until the liquid is transparent to form viscous liquid, cooling the flask to 40 ℃ by adopting cooling water, adding a dispersing agent, an antioxidant, a defoaming agent and the toughening agent, and stirring at 800rpm for 40min to obtain stable liquid; weighing the components of the polyurethane prepolymer according to parts by weight, mixing the core components, stirring for 2.5 hours at 55 ℃ under the protection of nitrogen, adding the toughening agent and the anti-aging agent, stirring for 1 hour at 800rpm, and adding a solvent for dilution for later use; sequentially arranging plain fiber cloth and twill fiber cloth at intervals to prepare multi-layer fiber cloth, uniformly mixing the three prepared components according to a proportion, adding a curing agent in an amine mixture, performing ultrasonic vibration dispersion at 20000Hz and 900W for 15min, stirring and mixing at 800rpm for 55min to finish blending, spraying by adopting a high-pressure airless SPU (SPU) at a spraying distance of 20cm and a spraying pressure of 8MPa, placing the multi-layer fiber cloth on a pressing plate after the spraying is finished, controlling the calendering temperature to be 40-70 ℃, and calendering and curing for 6h to obtain the multi-layer fiber cloth.
Example 4 the filler phase consisted of the following components in weight fraction: 48% of an amine mixture, 48% of a polyurethane prepolymer and 4% of graphite microspheres, wherein the amine mixture comprises the following substances in parts by weight: the anti-foaming agent comprises, by weight, 2000 45 parts of glycol polyether amine D, 3 parts of polyethylene polyamine, 6 parts of diphenyl DBTDA, 7 parts of isophorone diamine IPDA, 590 parts of a curing agent 590, 531 17 parts of a curing agent T531, 6200 8 parts of a curing agent, 327 2 parts of an ultraviolet absorber UV, 0.6 part of a dispersing agent BYK5040, 1157.8 parts of an antioxidant 1157, 0.13 part of an antifoaming agent DF116 and 1364 parts of a toughening agent TP; the polyurethane prepolymer comprises the following substances in parts by weight: 20 parts of MDI, 5 parts of a pre-polymer of MDI and polyol PG2000, 25 parts of a pre-polymer of MDI and polyol PT2000, 9 parts of hydrogenated HMDI, N3390 16 parts of a pre-polymer of HDI and polyol with a molecular weight of 1000, 11 parts of a pre-polymer of polyol with a TDI with a molecular weight of 1000, 7 parts of a polymer of isophorone diisocyanate IPDI and polyol with a molecular weight of 2500, 2.6 parts of a toughening agent TP184, 2.8 parts of an anti-aging agent 4010 and 19 parts of a solvent DBG.
The preparation method of the impact-resistant composite material comprises the following steps: placing graphite microspheres into a container, slowly dripping 98% sulfuric acid and 70% nitric acid, dispersing by ultrasonic oscillation for 30min, magnetically stirring at 80 ℃ and then carrying out suction filtration, drying a filter cake at 60-80 ℃ for 5h, crushing and then adding the filter cake into a silane coupling agent KH570, soaking for 12h at normal temperature, carrying out vacuum filtration, drying at 60 ℃ for 6h and then crushing to obtain graphite microspheres containing hydroxyl and carboxyl, dissolving the graphite microspheres in a solvent to obtain a spinning solution, carrying out electrostatic spinning on the obtained spinning solution, arranging a high-voltage ionization coil under a spinning nozzle, collecting fibers on a receiving device, and cutting the fibers into short fibers for later use; adding ultraviolet absorbent and amine components in parts by weight into a container, introducing nitrogen for protection, heating to 50 ℃ by adopting a water bath kettle, stirring for 120min at a low rotation speed of 600-800rpm until the liquid is clear and transparent, adding a toughening agent, heating to 95 ℃, stirring for 100min at a high rotation speed of 1100rpm until the liquid is transparent to form viscous liquid, cooling the flask to 30 ℃ by adopting cooling water, adding a dispersing agent, an antioxidant, a defoaming agent and the toughening agent, and stirring for 60min at 600rpm to obtain stable liquid; weighing the components of the polyurethane prepolymer according to parts by weight, mixing the core components, stirring for 4 hours at 75 ℃ under the protection of nitrogen, adding the toughening agent and the anti-aging agent, stirring for 1.5 hours at 700rpm, and adding the solvent for dilution for later use; sequentially arranging plain fiber cloth and twill fiber cloth at intervals to prepare multi-layer fiber cloth, uniformly mixing the three prepared components according to a proportion, adding a curing agent in an amine mixture, performing ultrasonic vibration dispersion at 20000Hz and 900W for 25min, stirring and mixing at 800rpm for 45min to complete the preparation, spraying by adopting a high-pressure airless SPU (SPU) at a spraying distance of 45cm and a spraying pressure of 12MPa, placing the multi-layer fiber cloth on a pressing plate after the spraying is completed, controlling the calendering temperature to be 50 ℃, and calendering and curing for 12h to obtain the multi-layer fiber cloth.
Example 5 the filler phase consisted of the following components in weight fraction: 63% of an amine mixture, 32% of a polyurethane prepolymer and 5% of chopped carbon fibers, wherein the amine mixture comprises the following substances in parts by weight: 45 parts of glycol polyether amine D, 4 parts of ethylenediamine, 1 part of propylenediamine, 2 parts of polyethylene polyamine, 2 parts of diaminodiphenylmethane HT972 parts of diethyltoluenediamine DETDA 6 parts of isophorone diamine IPDA 8 parts of curing agent 593 parts of curing agent T531, 35 parts of curing agent T6200 13 parts of ultraviolet absorber UV 531.7 parts of UV-p0.8 parts of dispersing agent BYK 5040.3 parts of BYK11000.3 parts of BYK 116.2 parts of antioxidant 1010.3 parts of 1135.6 parts of antioxidant 1157.6 parts of defoamer DF 116.17 parts of toughening agent TP136 parts of plasticizer 136; the polyurethane prepolymer comprises the following substances in parts by weight: 18 parts of MDI, 27 parts of a prepolymer of MDI and polyol PG1000, 27 parts of a prepolymer of MDI and polyol PT1000, 14 parts of hydrogenated HMDI, 600 parts of HT, 9 parts of N3390, 13 parts of a prepolymer of HDI and polyol with molecular weight of 2000, 10 parts of TDI, 12 parts of isophorone diisocyanate IPDI and a polymer of polyol with molecular weight of 3000, 4.5 parts of a toughening agent TP184, 2.4 parts of an anti-aging agent 4010 and 26 parts of a solvent DBG.
The preparation method of the impact-resistant composite material comprises the following steps: putting chopped carbon fibers into a container, slowly dripping 98% sulfuric acid and 70% nitric acid, dispersing for 30min by ultrasonic oscillation, performing magnetic stirring at 80 ℃ and then performing suction filtration, drying a filter cake at 80 ℃ for 5h, crushing, adding the filter cake into a silane coupling agent KH570, soaking for 12h at normal temperature, performing vacuum filtration, drying at 60 ℃ for 6h, crushing to obtain chopped carbon fibers containing hydroxyl and carboxyl, dissolving the chopped carbon fibers into a solvent to obtain a spinning solution, performing electrostatic spinning on the obtained spinning solution, arranging a high-voltage ionization coil under a spinneret, collecting the fibers on a receiving device, and cutting the fibers into short fibers for later use; adding ultraviolet absorbent and amine components in parts by weight into a container, introducing nitrogen for protection, heating to 50 ℃ by adopting a water bath kettle, stirring for 30min at a low rotation speed of 800rpm at the temperature until the liquid is clear and transparent, adding a toughening agent, heating to 80 ℃, stirring for 120min at a high rotation speed of 800rpm at the temperature until the liquid is transparent to form viscous liquid, cooling the flask to 30 ℃ by adopting cooling water, adding a dispersing agent, an antioxidant, a defoaming agent and the toughening agent, and stirring for 60min at 600rpm to obtain stable liquid; weighing the components of the polyurethane prepolymer according to parts by weight, mixing the core components, stirring for 2 hours at 50 ℃ under the protection of nitrogen, adding the toughening agent and the anti-aging agent, stirring for 2 hours at 600rpm, and adding the solvent for dilution for later use; sequentially arranging plain fiber cloth and twill fiber cloth at intervals to prepare multi-layer fiber cloth, uniformly mixing the three prepared components according to a proportion, adding a curing agent in an amine mixture, performing ultrasonic vibration dispersion for 10min at 20000Hz and 900W, stirring and mixing for 60min at 800rpm to finish blending, spraying by adopting a high-pressure airless SPU (SPU) at a spraying distance of 50cm and a spraying pressure of 16MPa, placing the multi-layer fiber cloth on a pressing plate after the spraying is finished, controlling the calendering temperature to be 40-70 ℃, and calendering and curing for 12h to obtain the multi-layer fiber cloth.
Example 6 the filler phase consisted of the following components in weight fraction: 62% of an amine mixture, 32% of a polyurethane prepolymer and 6% of a multi-layer graphite microchip, wherein the amine mixture comprises the following substances in parts by weight: 800 parts of glycol polyether amine D, 2 parts of polyethylene polyamine, 15 parts of diethyl toluene diamine DETDA, 10 parts of isophorone diamine and polyol polymer, 593 parts of curing agent, T31 parts of curing agent, 6200 15 parts of curing agent, uv-p 2 parts of ultraviolet absorber, 0.5 part of dispersant BYK116, 0.5 part of antioxidant 1135, 0.2 part of defoamer DF116 and 136 parts of toughening agent TP 136; the polyurethane prepolymer comprises the following substances in parts by weight: 2 parts of MDI, 30 parts of a polyol PG1000 prepolymer, 2 parts of an MDI and polyol PT2000 prepolymer, 2 parts of hydrogenated HMDI, 2 parts of HT600, 15 parts of an HDI and polyol prepolymer with a molecular weight of 2000, 1 part of TDI, 15 parts of isophorone diisocyanate IPDI and a polyol polymer with a molecular weight of 1500, 2 parts of a toughening agent TP184, 0 part of an anti-aging agent 4013 and 10 parts of a solvent PMA.
The preparation method of the impact-resistant composite material comprises the following steps: placing the multi-layer graphite microchip into a container, slowly dripping 98% sulfuric acid and 70% nitric acid, dispersing by ultrasonic oscillation for 30min, magnetically stirring at 80 ℃ and then carrying out suction filtration, drying a filter cake at 60-80 ℃ for 5h, crushing and then adding the filter cake into a silane coupling agent KH570, soaking for 12h at normal temperature, carrying out vacuum filtration, drying at 60 ℃ for 6h and then crushing to obtain the multi-layer graphite microchip containing hydroxyl and carboxyl, dissolving the multi-layer graphite microchip into a solvent to obtain a spinning solution, carrying out electrostatic spinning on the obtained spinning solution, arranging a high-voltage ionization coil under the spinning nozzle, collecting fibers on a receiving device and cutting the fibers into short fibers for later use; adding ultraviolet absorbent and amine components in parts by weight into a container, introducing nitrogen for protection, heating to 50 ℃ by adopting a water bath kettle, stirring at a low rotation speed of 750rpm for 130min until the liquid is clear and transparent, adding a toughening agent, heating to 95 ℃, stirring at a high speed of 1300rpm for 105min until the liquid is transparent to form viscous liquid, cooling the flask to 37 ℃ by adopting cooling water, adding a dispersing agent, an antioxidant, a defoaming agent and the toughening agent, and stirring at 650rpm for 48min to obtain stable liquid; weighing the components of the polyurethane prepolymer according to parts by weight, mixing the core components, stirring for 3.5 hours at 65 ℃ under the protection of nitrogen, adding the toughening agent and the anti-aging agent, stirring for 2 hours at 800rpm, and adding a solvent for dilution for later use; sequentially arranging plain fiber cloth and twill fiber cloth at intervals to prepare multi-layer fiber cloth, uniformly mixing the three prepared components according to a proportion, adding a curing agent in an amine mixture, performing ultrasonic vibration dispersion at 20000Hz and 900W for 30min, stirring and mixing at 800rpm for 60min to finish blending, spraying by adopting a high-pressure airless SPU (SPU) at a spraying distance of 30cm and a spraying pressure of 8MPa, placing the multi-layer fiber cloth on a pressing plate after spraying, controlling the calendaring temperature to be 40-70 ℃, and calendaring and curing for 12h to obtain the multi-layer fiber cloth.
The impact-resistant composite sheets obtained in examples 1 to 6 were subjected to detection of the correlation index, and the results are shown in tables 2 to 6.
TABLE 2 tensile Properties (GB/T528-2009)
Table 3 compression Property (GB/T7757-2009)
TABLE 4 bending Property (ASTM-626M)
TABLE 5 impact resistance (GB/T1450.2-2005)
Note that: speed 3.5m/s, pre-elevation angle 150 degrees.
TABLE 6 shear Property (GB/T1450.2-2005)
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (8)
1. An impact-resistant composite material comprises continuous phase multilayer fiber cloth and a filling phase polyurethane elastomer, and is characterized in that the multilayer fiber cloth is plain fiber cloth and twill fiber cloth which are arranged at intervals, and the total layer number is 3-15;
the polyurethane elastomer consists of the following components in parts by weight: 49% -67% of amine mixture, 32% -50% of polyurethane prepolymer and 1% -6% of nano functional material;
the amine mixture comprises the following substances in parts by weight: 20-50 parts of glycol polyether amine D400, D2000 or D800, 2-10 parts of one or more of ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or polyethylenepolyamine, 3-15 parts of one or more of m-phenylenediamine, m-xylylenediamine MDA or diethyltoluenediamine DETDA, 2-10 parts of isophoronediamine IPDA or isophoronediamine and polyalcohol polymer, 590 or 593-20 parts of curing agent, 10-40 parts of curing agent T31, 6200-15 parts of curing agent, 1-2 parts of one or more of ultraviolet absorber UV531, UV944, UV326, UV327 or UV-p, 0.5-1 part of one or more of dispersing agent BYK5040 or BYK116, 0.5-2 parts of defoamer DF 831.1-0.2 parts of antioxidant 1010, 1076, 1068, 1135 parts of defoamer and 1587-5 parts of toughening agent TP;
the polyurethane prepolymer comprises the following substances in parts by weight: 2-20 parts of MDI (methylene diphenyl oxide), 5-30 parts of a prepolymer of MDI and polyol PG1000-2000, 2-30 parts of a prepolymer of MDI and polyol PT1000-2000, 2-15 parts of HMDI (high-molecular-weight-modified polyethylene), 2-20 parts of one or more of HT100, HT600 or N3390, 2-15 parts of a prepolymer of HDI and polyol with the molecular weight of 1000-2000, 1-12 parts of a prepolymer of TDI or TDI and polyol with the molecular weight of 1000-2000, 2-15 parts of isophorone diisocyanate IPDI and polyol polymer with the molecular weight of 800-3000, 2-5 parts of a toughening agent TP184, 1-3 parts of an anti-aging agent 4010, and 10-30 parts of solvent dimethylbenzene butyl acetate, ethyl acetate, PMA, DBE or DBG;
the nano functional material is selected from one of graphene, a multi-layer graphite microchip, a graphite microsphere or a carbon fiber;
the pretreatment of the nano functional material is as follows: placing nano functional material into a container, slowly dripping 98% sulfuric acid and 70% nitric acid, dispersing by ultrasonic oscillation for 30min, magnetically stirring at 80 ℃ and then carrying out suction filtration, drying a filter cake at 60-80 ℃ for 5h, crushing and then adding the filter cake into a silane coupling agent KH570, soaking for 12h at normal temperature, carrying out vacuum filtration, drying at 60 ℃ for 6h and then crushing to obtain nano functional material containing hydroxyl and carboxyl, dissolving the nano functional material into a solvent to obtain spinning solution, carrying out electrostatic spinning on the obtained spinning solution, arranging a high-voltage ionization coil under a spinneret, and cutting fibers collected on a receiving device into short fibers.
2. The impact resistant composite material of claim 1, wherein the plain weave fiber cloth and the twill weave fiber cloth each have a thickness of 0.05 to 0.35mm; the 1-3 layers between two adjacent layers of the whole fiber cloth are formed by splicing small fiber cloths.
3. The impact resistant composite of claim 2, wherein the small pieces of fiber cloth are uniformly tiled for the same four pieces.
4. An impact resistant composite material according to claim 3, wherein two of said four small fiber cloths in the transverse or vertical direction are laminated by the same small fiber cloth.
5. The impact resistant composite material according to any one of claims 1 to 4, wherein each layer of the plain weave fiber cloth is independently selected from one of plain weave glass fiber cloth, plain weave basalt fiber cloth, plain weave carbon fiber cloth, or plain weave aramid fiber cloth; each layer of the twill fiber cloth is independently selected from one of twill glass fiber cloth, twill basalt fiber cloth, twill carbon fiber cloth or twill aramid fiber cloth.
6. A method of making an impact resistant composite material as defined in claim 5, comprising the steps of:
(1) Pretreatment of nano-functional materials
(2) Preparation of the spray liquid
1) Preparation of amine mixtures: adding ultraviolet absorbent and amine components in parts by weight into a container, introducing nitrogen for protection, heating to 50 ℃ by adopting a water bath kettle, stirring for 30-180min at a low rotation speed of 600-800rpm at the temperature until the liquid is clear and transparent, adding a toughening agent, heating to 80-120 ℃, stirring for 60-120min at a high speed of 800-1400rpm at the temperature until the liquid is transparent to form viscous liquid, cooling the flask to 30-40 ℃ by adopting cooling water, adding a dispersing agent, an antioxidant, a defoaming agent and a toughening agent, and stirring for 30-60min at 600-800rpm to obtain stable liquid;
3) Preparation of polyurethane prepolymer: weighing polyurethane prepolymer components according to parts by weight, mixing core components, stirring for 2-5 hours at 50-80 ℃ under the protection of nitrogen, adding a toughening agent and an anti-aging agent, stirring for 1-2 hours at 600-800rpm, and adding a solvent for dilution for later use;
(3) Spray forming
Sequentially arranging plain fiber cloth and twill fiber cloth at intervals to prepare multi-layer fiber cloth, uniformly mixing the substances obtained in the step 2 according to a proportion, adding a curing agent in an amine mixture, dispersing by ultrasonic oscillation of 20000Hz and 900W for 10-30min, stirring and mixing for 30-60min at 600-800rpm to finish blending, adopting high-pressure airless SPU spraying, wherein the spraying distance is 2-50cm, the spraying pressure is 5-16MPa, placing the multi-layer fiber cloth on a pressing plate after the spraying is finished, controlling the calendaring temperature to be 40-70 ℃, and calendaring and curing for 4-12h to obtain the fabric.
7. An I-steel applied to highway guardrails, ship suspension or container crane anti-collision beams, which is characterized in that the surface of the I-steel is provided with the anti-collision composite material prepared by the method of claim 6.
8. Use of an impact resistant composite material according to any one of claims 1 to 5 for protection of marine steel platform impact surfaces.
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