CN116971050A - Polyurea reinforced epoxy resin anti-corrosion wear-resistant coating for high-speed train - Google Patents
Polyurea reinforced epoxy resin anti-corrosion wear-resistant coating for high-speed train Download PDFInfo
- Publication number
- CN116971050A CN116971050A CN202310862145.1A CN202310862145A CN116971050A CN 116971050 A CN116971050 A CN 116971050A CN 202310862145 A CN202310862145 A CN 202310862145A CN 116971050 A CN116971050 A CN 116971050A
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- CN
- China
- Prior art keywords
- polyurea
- epoxy resin
- nanofiber
- diisocyanate
- epoxy
- 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.)
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Links
- 238000000576 coating method Methods 0.000 title claims abstract description 122
- 229920002396 Polyurea Polymers 0.000 title claims abstract description 117
- 239000011248 coating agent Substances 0.000 title claims abstract description 115
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 78
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 78
- 238000005260 corrosion Methods 0.000 title abstract description 32
- 239000002121 nanofiber Substances 0.000 claims abstract description 85
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 31
- 150000004985 diamines Chemical class 0.000 claims abstract description 28
- 238000012644 addition polymerization Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims description 55
- 239000011159 matrix material Substances 0.000 claims description 33
- 239000004593 Epoxy Substances 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- -1 alkylene glycidyl ether Chemical compound 0.000 claims description 3
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 claims description 3
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 36
- 239000000243 solution Substances 0.000 description 28
- 239000000945 filler Substances 0.000 description 19
- 239000011780 sodium chloride Substances 0.000 description 18
- 229910000838 Al alloy Inorganic materials 0.000 description 15
- 238000003860 storage Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000835 fiber Substances 0.000 description 13
- 238000005299 abrasion Methods 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 230000007547 defect Effects 0.000 description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000002076 thermal analysis method Methods 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920006334 epoxy coating Polymers 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000012765 fibrous filler Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003190 viscoelastic substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- HSHXDCVZWHOWCS-UHFFFAOYSA-N N'-hexadecylthiophene-2-carbohydrazide Chemical compound CCCCCCCCCCCCCCCCNNC(=O)c1cccs1 HSHXDCVZWHOWCS-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010571 fourier transform-infrared absorption spectrum Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009439 industrial construction Methods 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/72—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyureas
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to an anti-corrosion and wear-resistant coating, in particular to a polyurea reinforced epoxy resin anti-corrosion and wear-resistant coating for a high-speed train. The epoxy resin anticorrosive wear-resistant coating contains polyurea nano-fibers, which are prepared by taking diisocyanate and diamine as raw materials and performing addition polymerization. The polyurea nanofiber has a continuous reinforced interface and high dispersibility, and can obviously enhance the corrosion resistance and wear resistance of the traditional epoxy resin within a certain mass ratio range.
Description
Technical Field
The invention relates to an anti-corrosion and wear-resistant coating, in particular to a polyurea reinforced epoxy resin anti-corrosion and wear-resistant coating for a high-speed train.
Background
Because of its light weight and high strength, aluminum alloys can find various applications in a variety of engineering and non-engineering fields, such as automobiles, aerospace, and ships. However, as the application breadth and depth are further widened, the service conditions of the equipment are poorer and worse. On this basis, the wear and corrosion behavior of the aluminum alloy during use is further exacerbated. Under various severe conditions, the aluminum alloy is easy to have physical defects such as air holes, cracks, melting and the like in the use process. For such application problems, the most cost effective approach is to select an appropriate coating as the protective layer for the metal. However, conventional surface coatings have little effect on the long-term protection of aluminum alloy substrates. For example, conventional coatings of high speed trains are severely affected by sand or other hard particles during the running of the trains at high speeds, so that abrasion and corrosion occur, and aluminum alloy bodies may have surface defects in a short time after losing protection, which jeopardizes equipment safety. Therefore, development of a high-performance anti-corrosion and wear-resistant coating is very important.
Disclosure of Invention
The invention provides synthesis and application of a composite coating based on polyurea nanofiber reinforced epoxy resin, and the high-dispersion nanofiber with a continuous reinforced interface can obviously enhance the corrosion resistance and wear resistance of the traditional epoxy resin within a certain mass ratio range. The invention relates to the research of corrosion resistance and wear resistance of a coating, is suitable for being applied to the abrasion and corrosion scenes of aluminum alloy materials, and has good application prospects for corrosion resistance and wear resistance of the outer surface of a high-speed train moving at a high speed.
A polyurea nanofiber is prepared from diisocyanate and diamine through addition polymerization.
The preparation method of the polyurea nanofiber comprises the following steps: providing a diamine solution, wherein the solvent is absolute ethyl alcohol; providing diisocyanate, wherein the solvent is ethyl acetate; firstly, carrying out heat preservation reaction on diamine solution and diisocyanate for 1-2 hours at 40-60 ℃; then reacting for 80-100 minutes at 70-80 ℃ under the condition of stirring; after the reaction is completed, washing with water to remove excessive diisocyanate; drying to obtain polyurea nanofiber.
The application of the polyurea nanofiber in preparing a polyurea epoxy resin composite coating is provided. Optionally, the content of the polyurea nanofiber in the polyurea epoxy composite coating is 0.1wt% to 0.5wt%.
A polyurea epoxy composite coating comprising the polyurea nanofibers and an epoxy matrix; wherein the weight ratio of the polyurea nanofiber to the epoxy resin matrix is (0.1-0.5) (80-120).
The preparation method of the polyurea epoxy resin composite coating comprises the steps of mixing the polyurea nanofiber with an epoxy resin matrix; stirred, then coated on the substrate and cured.
The good dispersibility of the polyurea nanofiber can effectively repair microdefects, and achieves the best barrier property, so that the corrosion diffusion path of electrolyte is prolonged or even inhibited. The contact angle between the polyurea nanofiber prepared by the method and the epoxy resin coating is small, and the coating has good wettability, so that a proper amount of the polyurea nanofiber can be uniformly distributed in the epoxy resin in the coating preparation process. The abrasion resistance of the composite coating is derived from the entangled polyurea nanofibers which can transfer the forces and interfacial resistance of the contact surface, thereby preventing displacement of the coating.
Drawings
FIG. 1 is a Fourier transform infrared absorption spectrum of a synthetic polyurea nanofiber according to example 1 of the present invention.
FIG. 2 is the contact angle of the compacted polyurea nanofiber sheet of example 1 of the present invention with epoxy resin (upper) and 3.5wt% sodium chloride solution (lower), respectively.
FIG. 3 is a Nyquist plot for example 2 of the present invention containing 0.25wt% polyurea fiber composite coatings immersed in a 3.5wt% sodium chloride solution for 28 days.
FIG. 4 is a Bode plot of a composite coating of example 2 of the present invention containing 0.25wt% polyurea fiber immersed in a 3.5wt% sodium chloride solution for 28 days.
FIG. 5 is a dynamic mechanical thermal analysis plot of the storage modulus of a composite coating of the invention example 2 containing 0.25wt% polyurea fiber.
FIG. 6 is a graph showing the two-dimensional morphology of the indentation of the epoxy resin composite coating (PU-0.25%) prepared in example 2 of the present invention.
FIG. 7 is a Nyquist plot for example 3 of the present invention containing 0.1wt% polyurea fiber composite coatings immersed in a 3.5wt% sodium chloride solution for 28 days.
FIG. 8 is a Bode plot of example 3 of the present invention containing 0.1wt% polyurea fiber composite coatings immersed in a 3.5wt% sodium chloride solution for 28 days.
FIG. 9 is a dynamic mechanical thermal analysis plot of the storage modulus of a composite coating of example 3 of the present invention containing 0.1wt% polyurea fiber.
FIG. 10 is a Nyquist plot of comparative example 2 of the present invention containing 0.6wt% polyurea fiber composite coating immersed in a 3.5wt% sodium chloride solution for 28 days.
FIG. 11 is a Bode plot of a composite coating of comparative example 2 of the present invention containing 0.6wt% polyurea fiber immersed in a 3.5wt% sodium chloride solution for 28 days.
FIG. 12 is a dynamic mechanical thermal analysis plot of the storage modulus of a composite coating of comparative example 2 containing 0.6wt% polyurea fiber according to the present invention.
Detailed Description
The epoxy coating and the composite material have the advantages of strong adhesive force to a base material, good chemical resistance, simple process, economy, environmental protection and the like, and are widely applied to municipal engineering, traffic and national defense industrial construction. However, defects such as micro cracks, blisters, micro pores, etc. often occur during the curing process. Such phenomena can occur to reduce the physical protection of the substrate by the coating, and the ingress of external corrosive media can cause serious corrosion damage to the substrate. Thus, internal defects can cause the coating to lose its protective properties under extreme external conditions (abrasion, high salt, uv radiation, etc.). In response to this phenomenon, various researchers have applied a number of approaches to enhance the protective properties of the coating and extend its useful life, including but not limited to the addition of pigments, reinforcing agents and corrosion inhibitors of different morphologies. A series of researches show that the protective performance of the paint can be greatly improved by adding proper filler. Therefore, it is necessary to find a suitable filler to compensate for this disadvantage of the conventional epoxy resins.
Among the various filler choices, selecting the appropriate filler and balancing the affinity between the fibrous filler and the resin remains a hotspot problem. Although researchers have applied various fibrous fillers to impart better properties to coatings and more applications, there are still two problems with the use of fibrous fillers. Firstly, the self-dispersibility of the non-nanofiber filler in the resin is poor, and agglomeration is easy to form in the stirring process; second, the network distribution of fibrous fillers does not greatly improve coating performance.
At least to solve one of the technical problems, the invention introduces polyurea nanofibers as a filler, and explores and confirms the strengthening effect of the polyurea nanofibers on the coating.
Although fibrous polyureas have been widely studied in terms of mechanical properties, hydrolytic stability, chemical resistance, etc., the addition of fillers to epoxy coatings has been rarely studied. The polyurea nanofiber is prepared by adopting addition polymerization reaction of diamine and diisocyanate. The prepared polyurea powder presents a near two-dimensional ultrafine fiber morphology. As a filler, nanofibers with outstanding dispersibility can be uniformly distributed in the coating and cross-linked with each other, greatly reducing the porosity of the coating and enhancing the barrier properties of the coating. The result shows that the prepared polyurea nanofiber has good solubility, dispersibility and hydrophobicity in common organic solvents, so that the composite coating has excellent long-term corrosion resistance.
The invention firstly provides a polyurea nanofiber which is prepared by taking diisocyanate and diamine as raw materials and performing addition polymerization. The polyurea nanofiber has good dispersibility and continuous reinforced interface, and can enhance the corrosion resistance and wear resistance of the traditional epoxy resin.
In some embodiments, the diisocyanate is in excess relative to the diamine to allow the diamine to fully react.
In some embodiments, the mass ratio of diisocyanate to diamine is (3.0-5.0): 3.5-4.0. In order to ensure maximum synthesis of urea groups and to achieve a compatible molecular chain length of the polyurea fibers, the amount of diisocyanate is slightly greater than the amount of diamine, but too high or too low a mass ratio results in excessively severe reactions or a substantial increase in the time. In general, when the mass ratio of diisocyanate to diamine is greater than 3:2, the rapid formation of urea groups may lead to the formation of long molecular chains in the monomer rather than in the monomer, which may reduce the success rate of the synthesis of polyurea fibers, and conversely, may reduce the reaction time efficiency and the polyurea synthesis efficiency.
In some embodiments, the method of preparing the polyurea nanofiber comprises:
providing a diamine solution, wherein the solvent is absolute ethyl alcohol;
providing diisocyanate, wherein the solvent is ethyl acetate;
firstly, carrying out heat preservation reaction on diamine solution and diisocyanate for 1-2 hours at 40-60 ℃; then reacting for 80-100 minutes at 70-80 ℃ under the condition of stirring;
after the reaction is completed, washing with water (deionized water) to remove excessive diisocyanate; drying to obtain polyurea nanofiber.
In some embodiments, the method of preparing the polyurea nanofiber comprises:
1) Dissolving a proper amount of diamine in absolute ethyl alcohol (the dosage of diamine and absolute ethyl alcohol is 1:10 by mass ratio) and carrying out ultrasonic treatment; preparing or preparing diamine solution;
2) After diisocyanate is dissolved in ethyl acetate (the dosage of the diisocyanate and the ethyl acetate is 1:10 by mass ratio), the diisocyanate and the ethyl acetate are added into diamine solution;
in some cases, the diisocyanate is in excess relative to the diamine to fully react the diamine;
in some cases, the mass ratio of diisocyanate to diamine is (3.0-5.0): 3.5-4.0;
3) The flask is kept in an oil bath at 40-60 ℃ for 1-2 hours; then, heating the oil bath to 70-80 ℃ and stirring at 300-600rpm for 80-100 minutes;
4) 10-50mL of deionized water was then added to the flask and stirred for 10-30 minutes to remove excess diisocyanate. Finally, the reaction product is dried in vacuo at a temperature of 50-60 ℃ for 20-30 hours and ground into a powder for use.
In some embodiments, the diisocyanate may be selected from one of diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), toluene Diisocyanate (TDI), hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI).
In some embodiments, the diamine may be selected from one of hexamethylenediamine, ethylenediamine, diaminodiphenylmethane, o-phenylenediamine, diethanolamine.
The invention also provides application of the polyurea nanofiber in preparation of a polyurea epoxy resin composite coating.
In some embodiments, the polyurea nanofibers are present in the polyurea epoxy composite coating in an amount of 0.1wt% to 0.5wt%, preferably 0.25wt%. If the content of the polyurea nanofiber is too high, the porosity of the coating is affected, and the corrosion resistance is reduced; too low does not show performance. The illustration is compared with 0.25%, and the best effect is achieved.
The invention also provides a polyurea epoxy resin composite coating, which comprises the polyurea nanofiber and an epoxy resin matrix; wherein the weight ratio of the polyurea nanofiber to the epoxy resin matrix is (0.1-0.5) (80-120).
In some embodiments, the polyurea nanofibers and the epoxy matrix are present in a mass ratio of (0.1-0.5): 100.
The research shows that the mass ratio of the polyurea nanofiber to the epoxy resin matrix can be freely distributed in the range, and the wear-resistant and corrosion-resistant coating with similar properties can be basically obtained; if the content is less than 0.1:100, the polyurea fibers in the epoxy resin matrix are too loosely dispersed to provide sufficient abrasion and corrosion resistance properties to the resin matrix; if the content is higher than 0.5:100, the dispersibility of the fibers cannot be ensured, and excessive nanofibers can obstruct the crosslinking and film forming of epoxy resin molecules, so that the coating is difficult to cure and form, and the coating is unfavorable to use as the coating.
In some specific examples, the epoxy resin matrix is prepared from uncured epoxy resin, curing agent, diluent, catalyst and dispersing agent according to the mass ratio of (4-6): (8-12): (5-10): (1-5): (1-1.5).
In some embodiments, the method of preparing the epoxy resin matrix includes: the epoxy resin matrix is mainly prepared by mixing uncured epoxy resin, a curing agent, a diluent, a catalyst and a dispersing agent according to a proportion, and stirring (for example, stirring at a speed of 2000-5000rpm for 10-30 minutes) to obtain the epoxy resin matrix.
The polyurea epoxy resin composite coating can be applied to various aluminum alloy material abrasion and corrosion scenes, such as the outer surface of a high-speed moving motor car.
The invention also provides a preparation method of the polyurea epoxy resin composite coating, which comprises the steps of mixing the polyurea nanofiber and an epoxy resin matrix; stirred, then coated on the substrate and cured.
In some embodiments, the stirring is at a speed of 3000 to 4000rpm.
In some embodiments, the substrate is an aluminum alloy, particularly a high speed train body aluminum alloy.
In some embodiments, the substrate (aluminum alloy) is polished (sandpaper) and cleaned (acetone ultrasonic cleaning) prior to coating.
In some embodiments, the curing is performed at room temperature under vacuum for 20-30 hours.
In some embodiments, the uncured epoxy resin may be selected from one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, epoxy cyanuric acid resin, and cycloaliphatic epoxy resin.
In some specific examples, the curing agent may be one or more of tetramethyl ethylenediamine, diethylenetriamine, dibenzylamine ether, benzoyl peroxide, dicyandiamide.
In some embodiments, the diluent may be selected from one or more of alkylene glycidyl ether, n-butanol, benzyl alcohol, xylene, acetone, dimethylformamide.
In some embodiments, the catalyst may be one or more of dibutyl tin, tetrabutyl tin, dibutyl tin dilaurate, tributyl tin chloride.
In some specific examples, the dispersing agent can be one or more of dodecyl dimethyl benzyl ammonium bromide, sodium dodecyl benzene sulfonate, polyvinyl alcohol and hydroxypropyl methyl cellulose.
For pure epoxy coatings, evaporation of the diluent during curing leaves many micropores in the coating. In a severe external corrosive environment, the defects provide a diffusion path for the corrosive medium. The dense oxide film on the surface of the aluminum alloy is damaged by chloride ions in the corrosive medium. At the same time, oxygen dissolved in the salt solution causes depolarization of the metal surface, thereby accelerating the dissolution of the anodic metal.
The composite coating containing the polyurea nanofiber reinforcement mainly improves the corrosion resistance in three aspects: (a) The polyurea nanofibers are staggered, so that an excellent barrier effect is achieved on corrosive solution, the diffusion path of the corrosive solution is zigzag, and the physical barrier effect of the filler is fully applied to the coating; (b) The reduction of coating defects results in reduced penetration of corrosive media; (c) The polyurea nanofibers can uniformly share internal stress caused by expansion of corrosion products, and foaming of the coating is reduced.
The wear-resistant characteristic of the polyurea nanofiber reinforced composite coating is mainly achieved through blending reinforcement caused by the dispersion of the polyurea nanofiber in the coating, so that the storage modulus of the composite coating is greatly improved, and the coating is effectively prevented from deforming under the action of external force.
Example 1
The embodiment provides a polyurea nanofiber-based reinforced epoxy resin composite coating which is synthesized by hexamethylenediamine, diphenylmethane diisocyanate and bisphenol A type epoxy resin matrix.
The method comprises the following steps:
1) Preparation of polyurea nanofibers:
1.2g of hexamethylenediamine was dissolved in 12g of absolute ethanol (about 15 mL) and dispersed by sonication. 1.6g of diphenylmethane diisocyanate was weighed out, dissolved in 16g (about 18 mL) of ethyl acetate, mixed, and added to the hexamethylenediamine solution.
The mixed solution flask was oil-bathed at 50℃and after 1.5 hours of incubation, the oil-bath was heated to 80℃and added to a magnetic rotor and stirred well at 600rpm for 90 minutes.
25mL of deionized water was added to the flask and stirred for 10 minutes to remove excess diisocyanate. Finally, the reaction product was dried in vacuo at a temperature of 60 ℃ for 30 hours and ground into a powder for use. 2.4g of polyurea nanofibers were produced in this example.
2) Preparation of epoxy resin matrix:
20g of bisphenol A type epoxy resin, 10g of dibutyltin and 5g of dodecyldimethylbenzyl ammonium bromide were weighed and placed in a flask with a magnet. Then, 40g of tetramethyl ethylenediamine and 30g of xylene were added to the flask, and stirred at 4000rpm for 30 minutes at normal temperature to obtain an epoxy resin matrix.
3) Preparation of an epoxy resin composite coating:
fixed size aluminum alloy blocks (15 mm. Times.15 mm. Times.5 mm) were polished with sandpaper and then ultrasonically cleaned 3 times with acetone to remove surface contaminants. The polyurea nanofibers and the epoxy resin matrix were mixed at a mass ratio of 0.5:100 and stirred at 3000rpm for 20 minutes. The mixed slurry was sprayed uniformly on the aluminum alloy block and then cured at room temperature under vacuum for 30 hours.
The epoxy resin composite coating prepared in the embodiment is marked as PU-0.5%.
The polyurea reinforced epoxy resin coating prepared by the method can reduce the wear rate by 3/4, and the wear resistance of the coating is obviously improved.
Fourier infrared spectrum analysis is performed on the polyurea nanofiber synthesized in the embodiment, and the result is shown in fig. 1. Wherein the peak of the stretching vibration of the N-H bond appears at 3325cm -1 The asymmetric and symmetric stretching vibration of the C-H bond is 2855cm -1 At 2922cm -1 Respectively embodied. The characteristic peak of the c=o function in the ureido group appears at 1635cm -1 ，1561cm -1 The peak at this point is due to bending vibration of the n—h single bond in the amide bond. From the results of Fourier infrared spectroscopy analysis, it was inferred that the isocyanate group (-NCO) of diphenylmethane diisocyanate and the amino group (-NH) in diamine 2 ) The formation of urea groups (N-CO-N) demonstrates the successful preparation of polyureas based on addition polymerization schemes.
The polyurea nanofibers of this example were compacted into tablets by a powder tablet press and the contact angle of the same volume of epoxy and 3.5wt% sodium chloride solution on the powder tablet was photographed using a high speed camera, the results are shown in fig. 2. The results show a contact angle of 45 ° with the epoxy resin and 90 ° with 3.5wt% sodium chloride solution. The smaller the contact angle, the lower the interfacial tension at the interface between the polyurea nanofibers and the epoxy. After mechanical stirring, the filler and the coating are fully emulsified, so that a proper amount of polyurea nanofibers can be uniformly distributed in the epoxy resin in the coating preparation process. In contrast, the relatively large contact angle with 3.5wt% sodium chloride solution indirectly indicates that the polyurea nanofibers have excellent barrier properties inside the coating during penetration of the corrosive medium into the coating.
Example 2
The embodiment provides a polyurea nanofiber-based reinforced epoxy resin composite coating which is synthesized by diethanolamine, isophthalone diisocyanate and a bisphenol A type epoxy resin matrix.
The method comprises the following steps:
1) Preparation of polyurea nanofibers:
0.8g of diethanolamine was dissolved in 8g of absolute ethanol (about 10 mL) and dispersed by sonication. 1.0g of isoparaffin diisocyanate was weighed out, dissolved in 10g (about 11 mL) of ethyl acetate, mixed, and added to the diethanolamine solution.
The mixed solution flask was oil-bathed at 60℃and after 2 hours of incubation, the oil-bath was heated to 70℃and added to a magnetic rotor and stirred well at 600rpm for 90 minutes.
20mL of deionized water was added to the flask and stirred for 10 minutes to remove excess diisocyanate. Finally, the reaction product was dried in vacuo at a temperature of 50 ℃ for 25 hours and ground into a powder for use. 1.6g of polyurea nanofibers were produced in this example.
2) Preparation of epoxy resin matrix:
16g of bisphenol A type epoxy resin, 16g of dibutyltin dilaurate and 4g of polyvinyl alcohol were weighed into a flask with a magnet. Then, 40g of diethylenetriamine and 20g of alkylene glycidyl ether were added to the flask, and stirred at a speed of 3000rpm for 20 minutes at ordinary temperature to obtain an epoxy resin matrix.
3) Preparation of an epoxy resin composite coating:
fixed size aluminum alloy blocks (15 mm. Times.15 mm. Times.5 mm) were polished with sandpaper and then ultrasonically cleaned 3 times with acetone to remove surface contaminants. The polyurea and epoxy matrix were mixed in a mass ratio of 0.25:100 and stirred at 3500rpm for 15 minutes. The mixed slurry was sprayed uniformly on the aluminum alloy block and then cured at room temperature under vacuum for 20 hours.
The epoxy resin composite coating prepared in the embodiment is marked as PU-0.25%.
The nyquist plot of the epoxy composite coating after soaking in 3.5wt% sodium chloride solution for 28 days is shown in fig. 3. In fig. 3, the capacitance arc diameter of the epoxy composite coating containing 0.25% polyurea nanofibers was significantly increased after 28 days of immersion compared to PU-0% (i.e., comparative example 1). The change in resistance is due to the polyurea nanofibers within the coating forming a physical barrier network.
The Bode pattern of the epoxy composite coating after soaking in 3.5wt% sodium chloride solution for 28 days is shown in FIG. 4. As can be intuitively observed in FIG. 4, the impedance value (|Z|) of PU-0.25% at low frequencies f＝0.01Hz ) Is very high and remains stable over a range of frequencies and then drops rapidly with increasing frequency, indicating that the coating changes from resistive to capacitive properties over the entire frequency range. The coating exhibits resistive properties at low frequencies, |Z| | f＝0.01Hz The larger the electron transfer in the electrolyte, the more difficult and therefore the more corrosion resistant the coating. As corrosive medium permeates, the coating capacitance increases, the resistance decreases, the Bode curve platform is prolonged, and the coating capacitance characteristic is weakened.
The dynamic mechanical thermal analysis curve of the storage modulus of the epoxy resin composite coating is shown in fig. 5. The storage modulus in fig. 5 refers to the energy stored by elastic deformation of a viscoelastic material. It is the contribution of the elastic portion of the viscoelastic material that reflects the resistance of the material to deformation. The storage modulus of the sample shows a tendency to decrease with increasing temperature, since an increase in temperature results in a sufficient movement of bonds in the polymer. As the molecular chain motion becomes active, the coating gradually transitions from a highly elastic state to a viscoelastic state. Based on this, the addition of polyurea nanofibers in both glassy and rubbery states greatly increases the storage modulus. The storage modulus of PU-0.25% is improved by 1170MPa compared with PU-0% (namely comparative example 1 below), indicating that the addition of polyurea nanofibers has excellent reinforcing effect on epoxy coating. The dispersion distribution of the polyurea nanofiber in the PU-0.25% coating has a blending strengthening effect, and can effectively prevent the coating from deforming under the action of external force, so that the PU-0.25% coating has better wear resistance under the applied load. However, the polyurea nanofibers agglomerate with increasing amounts of addition, and the decrease in storage modulus is caused by weak interfacial bonding between the filler and the resin due to filler agglomeration.
In addition, the material rigidity and hardness test is carried out on PU-0.25%, and the indentation two-dimensional morphology is shown in figure 6. As can be seen from fig. 6, under the application of a load, the pits were pressed against the surface of the resin block by a brinell hardness tester. The pit diameter of PU-0% (i.e., comparative example 1 below) was 1.7mm and the depth was 60mm, while the diameter and depth of PU-0.25% were 1.5mm and 35mm, respectively. The difference in pit depth clearly shows that the hardness of the coating is significantly increased due to the addition of polyurea nanofibers.
Example 3
The only difference from example 2 is that: in the preparation of the epoxy resin composite coating, the polyurea nanofibers and the epoxy resin matrix are mixed according to the mass ratio of 0.1:100.
The epoxy resin composite coating prepared in the embodiment is marked as PU-0.1%.
FIGS. 7, 8 and 9 are dynamic mechanical thermal analysis curves of PU-0.1% composite coating soaked in 3.5wt% sodium chloride solution for 28 days, bode plot soaked in 3.5wt% sodium chloride solution for 28 days, and storage modulus, respectively. When the content of the nanofiber filler is 0.1%, the corrosion resistance of the coating is still remarkably improved, however, when the coating is applied practically, the filler is possibly excessively dispersed due to the fact that fewer fillers are used, and the active corrosion resistance is difficult to play. In addition, the storage modulus of the coating is still obviously improved (compared with comparative example 1), and the composite coating with the proportion is ensured to still have a certain abrasion resistance.
Comparative example 1
The epoxy coating differs from example 2 only in that: in the preparation of the epoxy resin coating, polyurea nanofibers are not added.
The epoxy resin coating prepared in this comparative example was marked as PU-0%.
The Nyquist diagram of the epoxy resin coating of the comparative example after being soaked in 3.5wt% sodium chloride solution for 28 days is shown in FIG. 3, the Bode diagram of the epoxy resin composite coating after being soaked in 3.5wt% sodium chloride solution for 28 days is shown in FIG. 4, and the dynamic mechanical thermal analysis curve of the storage modulus of the epoxy resin composite coating is shown in FIG. 5. It is known that epoxy resin coatings without polyurea nanofiber fillers do not have adequate corrosion and wear resistance and require the addition of a certain amount of polyurea nanofibers for conditioning.
Comparative example 2
The only difference from example 2 is that: in the preparation of the epoxy resin composite coating, the polyurea nanofibers and the epoxy resin matrix are mixed according to the mass ratio of 0.6:100.
The epoxy resin composite coating prepared in the comparative example is marked as PU-0.6%.
FIGS. 10, 11, and 12 are dynamic mechanical thermal analysis curves of PU-0.6% composite coating soaked in 3.5wt% sodium chloride solution for 28 days, bode plot soaked in 3.5wt% sodium chloride solution for 28 days, and storage modulus, respectively. Due to the increase of the nanofiber filler, a large number of defect hidden dangers exist in the epoxy resin matrix, so that corrosive media are easy to permeate, and the corrosion resistance is affected. While too much filler can result in slow or insufficient curing of the coating resulting in a substantial decrease in storage modulus, too much filler can have a considerable negative effect on the corrosion and abrasion resistance properties of the coating (in contrast to example 2 and comparative example 1).
The invention prepares the two-dimensional nanofiber material with stable size and excellent performance by a simple addition polymerization method. And introducing the polyurea nanofiber into the epoxy resin coating according to a certain mass ratio. The results indicate that very small amounts of polyurea nanofibers can not only improve the corrosion resistance of the coating, but also help to enhance the wear resistance of the coating. The micro defect of the coating is obviously reduced when the polyurea nanofiber is added in the optimal amount, the polyurea nanofiber can prevent corrosive media from penetrating into a metal substrate, the impedance of the prepared composite coating is improved by nearly four times, and the composite coating can provide durable protection even in a severe environment; the wear resistance of the coating can be greatly improved by reducing the wear rate by 3/4.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. A polyurea nanofiber is characterized in that the polyurea nanofiber is obtained by addition polymerization by taking diisocyanate and diamine as raw materials.
2. The polyurea nanofiber according to claim 1, wherein the mass ratio of diisocyanate to diamine is (3.0-5.0): 3.5-4.0; and/or the number of the groups of groups,
the diisocyanate is selected from one of diphenylmethane diisocyanate, isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate; and/or the number of the groups of groups,
the diamine is selected from one of self diamine, ethylenediamine, diaminodiphenyl methane, o-phenylenediamine and diethanolamine.
3. The method for preparing the polyurea nanofiber according to claim 1 or 2, comprising:
providing a diamine solution, wherein the solvent is absolute ethyl alcohol;
providing diisocyanate, wherein the solvent is ethyl acetate;
firstly, carrying out heat preservation reaction on diamine solution and diisocyanate for 1-2 hours at 40-60 ℃; then reacting for 80-100 minutes at 70-80 ℃ under the condition of stirring;
after the reaction is completed, washing with water to remove excessive diisocyanate; drying to obtain polyurea nanofiber.
4. Use of the polyurea nanofiber according to claim 1 or 2 in the preparation of a polyurea epoxy composite coating; optionally, the content of the polyurea nanofiber in the polyurea epoxy composite coating is 0.1wt% to 0.5wt%, preferably 0.25wt%.
5. A polyurea epoxy composite coating comprising the polyurea nanofiber of claim 1 or 2 and an epoxy matrix; wherein the weight ratio of the polyurea nanofiber to the epoxy resin matrix is (0.1-0.5) (80-120).
6. The polyurea epoxy composite coating of claim 5, wherein the mass ratio of polyurea nanofibers to epoxy matrix is (0.1-0.5): 100.
7. The polyurea epoxy composite coating according to claim 5, wherein the epoxy resin matrix is prepared from uncured epoxy resin, curing agent, diluent, catalyst and dispersing agent according to the mass ratio of (4-6): (8-12): (5-10): (1-5): (1-1.5).
8. The polyurea epoxy composite coating according to claim 7, wherein the uncured epoxy resin is selected from one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, cyanuric acid epoxy resin, and cycloaliphatic epoxy resin; and/or the number of the groups of groups,
the curing agent can be one or more of tetramethyl ethylenediamine, diethylenetriamine, dibenzylamine ether, benzoyl peroxide and dicyandiamide; and/or the number of the groups of groups,
the diluent can be selected from one or more of alkylene glycidyl ether, n-butanol, benzyl alcohol, xylene, acetone and dimethylformamide; and/or the number of the groups of groups,
the catalyst can be one or more of dibutyl tin, tetrabutyl tin, dibutyl tin dilaurate and tributyl tin chloride; and/or the number of the groups of groups,
the dispersing agent can be one or more of dodecyl dimethyl benzyl ammonium bromide, sodium dodecyl benzene sulfonate, polyvinyl alcohol and hydroxypropyl methyl cellulose.
9. The polyurea epoxy composite coating of any one of claims 5-8, wherein the method of preparing the epoxy matrix comprises: the epoxy resin matrix is mainly prepared by mixing uncured epoxy resin, a curing agent, a diluent, a catalyst and a dispersing agent according to a proportion, and stirring the mixture to obtain the epoxy resin matrix.
10. The method of preparing a polyurea epoxy composite coating according to any one of claims 5-9, comprising mixing the polyurea nanofibers with an epoxy matrix; stirred, then coated on the substrate and cured.
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