CN115087630A - 陶瓷复合材料 - Google Patents
陶瓷复合材料 Download PDFInfo
- Publication number
- CN115087630A CN115087630A CN202080096052.7A CN202080096052A CN115087630A CN 115087630 A CN115087630 A CN 115087630A CN 202080096052 A CN202080096052 A CN 202080096052A CN 115087630 A CN115087630 A CN 115087630A
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- CN
- China
- Prior art keywords
- wax
- polymer
- ceramic
- composition
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 239000000919 ceramic Substances 0.000 title claims description 190
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 117
- 229920000642 polymer Polymers 0.000 claims abstract description 117
- 239000000758 substrate Substances 0.000 claims abstract description 111
- 239000011347 resin Substances 0.000 claims abstract description 98
- 229920005989 resin Polymers 0.000 claims abstract description 98
- 239000011148 porous material Substances 0.000 claims abstract description 95
- 239000000463 material Substances 0.000 claims description 131
- 229910052782 aluminium Inorganic materials 0.000 claims description 105
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 103
- 239000001993 wax Substances 0.000 claims description 103
- 239000000203 mixture Substances 0.000 claims description 90
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 63
- 239000002184 metal Substances 0.000 claims description 43
- 229910052751 metal Inorganic materials 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 230000007797 corrosion Effects 0.000 claims description 35
- 238000005260 corrosion Methods 0.000 claims description 35
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 32
- 239000011787 zinc oxide Substances 0.000 claims description 32
- -1 polyethylene Polymers 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 22
- 238000012360 testing method Methods 0.000 claims description 22
- 239000012188 paraffin wax Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- 229910052725 zinc Inorganic materials 0.000 claims description 17
- 239000011701 zinc Substances 0.000 claims description 17
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 16
- 238000004132 cross linking Methods 0.000 claims description 16
- 229910052749 magnesium Inorganic materials 0.000 claims description 16
- 239000011777 magnesium Substances 0.000 claims description 16
- 238000012986 modification Methods 0.000 claims description 16
- 230000004048 modification Effects 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 239000002383 tung oil Substances 0.000 claims description 14
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 13
- 229910052684 Cerium Inorganic materials 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229920002635 polyurethane Polymers 0.000 claims description 12
- 239000004814 polyurethane Substances 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052753 mercury Inorganic materials 0.000 claims description 10
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 9
- 238000002459 porosimetry Methods 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- 239000011135 tin Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 235000019198 oils Nutrition 0.000 claims description 8
- 230000003287 optical effect Effects 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 230000015556 catabolic process Effects 0.000 claims description 7
- 230000007547 defect Effects 0.000 claims description 7
- 238000006731 degradation reaction Methods 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 6
- 229920001709 polysilazane Polymers 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 230000009257 reactivity Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 229910000838 Al alloy Inorganic materials 0.000 claims description 4
- 229920002101 Chitin Polymers 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 241000196324 Embryophyta Species 0.000 claims description 4
- 244000043261 Hevea brasiliensis Species 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229920001800 Shellac Polymers 0.000 claims description 4
- 239000004203 carnauba wax Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 150000004676 glycans Chemical class 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- 229920003052 natural elastomer Polymers 0.000 claims description 4
- 229920001194 natural rubber Polymers 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 239000004208 shellac Substances 0.000 claims description 4
- 235000013874 shellac Nutrition 0.000 claims description 4
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 claims description 4
- 229940113147 shellac Drugs 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 239000004166 Lanolin Substances 0.000 claims description 3
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 239000004111 Potassium silicate Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 3
- 235000019498 Walnut oil Nutrition 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 235000013871 bee wax Nutrition 0.000 claims description 3
- 239000012166 beeswax Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 235000013869 carnauba wax Nutrition 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 235000019388 lanolin Nutrition 0.000 claims description 3
- 229940039717 lanolin Drugs 0.000 claims description 3
- 239000000944 linseed oil Substances 0.000 claims description 3
- 235000021388 linseed oil Nutrition 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 239000012170 montan wax Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 3
- 239000011118 polyvinyl acetate Substances 0.000 claims description 3
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 3
- 239000002516 radical scavenger Substances 0.000 claims description 3
- 230000008439 repair process Effects 0.000 claims description 3
- 230000000979 retarding effect Effects 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 239000008170 walnut oil Substances 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012963 UV stabilizer Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229940092738 beeswax Drugs 0.000 claims description 2
- 235000019809 paraffin wax Nutrition 0.000 claims description 2
- 235000019271 petrolatum Nutrition 0.000 claims description 2
- 239000012169 petroleum derived wax Substances 0.000 claims description 2
- 235000019381 petroleum wax Nutrition 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 claims description 2
- 230000002940 repellent Effects 0.000 claims description 2
- 239000005871 repellent Substances 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012180 soy wax Substances 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003431 cross linking reagent Substances 0.000 claims 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims 1
- 159000000000 sodium salts Chemical class 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 44
- 239000000523 sample Substances 0.000 description 42
- 238000000034 method Methods 0.000 description 38
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 24
- 230000006870 function Effects 0.000 description 22
- 230000010287 polarization Effects 0.000 description 21
- 239000000565 sealant Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 18
- 235000012245 magnesium oxide Nutrition 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 17
- 239000000395 magnesium oxide Substances 0.000 description 17
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 17
- 229910000000 metal hydroxide Inorganic materials 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 150000004692 metal hydroxides Chemical class 0.000 description 15
- 239000000049 pigment Substances 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 14
- 150000004679 hydroxides Chemical class 0.000 description 14
- 229910044991 metal oxide Inorganic materials 0.000 description 14
- 239000003973 paint Substances 0.000 description 13
- 150000004706 metal oxides Chemical class 0.000 description 12
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
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- 238000005259 measurement Methods 0.000 description 8
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- 239000007787 solid Substances 0.000 description 8
- 229910052688 Gadolinium Inorganic materials 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 description 7
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 230000000813 microbial effect Effects 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 6
- 239000004584 polyacrylic acid Substances 0.000 description 6
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- 238000004381 surface treatment Methods 0.000 description 6
- 230000002195 synergetic effect Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000011133 lead Substances 0.000 description 5
- 230000000670 limiting effect Effects 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000011343 solid material Substances 0.000 description 5
- 239000011800 void material Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000000443 aerosol Substances 0.000 description 4
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 4
- 229910001334 3003 aluminium alloy Inorganic materials 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
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Abstract
公开了复合陶瓷材料,其中基材上的陶瓷材料的互连网络包含具有可及孔隙体积的孔隙,所述可及孔隙体积至少部分填充有聚合物、树脂和/或蜡。
Description
相关申请的交叉引用
本申请要求2019年12月12日提交的PCT申请号PCT/US2019/065978的优先权,并要求2020年3月13日提交的美国临时申请号62/989,092、2020年3月13日提交的美国临时申请号62/989,150、2020年6月12日提交的美国临时申请号63/038,642、2020年6月12日提交的美国临时申请号63/038,693以及2020年6月16日提交的美国临时申请号63/039,965的权益,所有专利文献全文以引用方式并入本文中。
技术领域
本发明涉及陶瓷复合材料,特别是多孔陶瓷材料的复合材料,其中陶瓷的互连网络含有至少部分填充有聚合物、树脂和/或蜡的可及孔隙体积。
背景技术
复合材料可以通过并入来自构成复合材料的每种材料的特性而提供协同益处。金属基材,特别是铝基材,可能遭受附加层的不良粘附,并且还可能在损害天然氧化物的情况下遭受腐蚀。聚合物、树脂和蜡材料通常用于为下层基材提供保护或者改变基材与环境相互作用的方式。将这些材料直接施加到光滑的金属基材可导致较差的粘附性或美学挑战,诸如滴落、流痕和斑点,或与施加的材料量相关的其他问题。具有更好的粘附性、均匀性和/或美学特性的材料将是理想的。
发明内容
提供了复合材料和包含该复合材料的组合物。还提供了使用该复合材料的应用。
在一个方面,提供一种组合物,其包括:(i)复合材料,所述复合材料包括浸渍到多孔陶瓷材料中的聚合物、蜡和/或树脂,其中所述多孔陶瓷材料包括具有可及孔隙体积的互连孔隙网络,所述可及孔隙体积至少部分地填充有所述聚合物、蜡和/或树脂;以及(ii)基材,其中所述复合材料与所述基材接触。在一些实施方案中,复合材料的至少一部分或基本上全部与基材直接接触。在一些实施方案中,至少约20质量%、30质量%、40质量%、50质量%、60质量%、70质量%、80质量%或90质量%的陶瓷材料是互连的。
在一些实施方案中,基材和陶瓷材料各自包含原生金属,并且陶瓷材料中的原生金属不同于基材中的原生金属。在其他实施方案中,基材和陶瓷材料各自包含原生金属,并且陶瓷材料中的原生金属与基材中的原生金属相同。
在一些实施方案中,复合材料具有约1微米至约100微米的厚度。
陶瓷材料可包括稀土元素、过渡金属元素、碱土金属元素或铝。陶瓷材料可包括氧化物、氢氧化物和/或层状双氢氧化物。在一些实施方案中,氧化物、氢氧化物和/或层状双氢氧化物包括铁、铝、镁、铈、锌、锰、钛、铬、镍、钴、铜、银、钽、钨、硅、磷、锡、钒、锆、钙、钡或铕。
基材可包括铝合金、钢合金、镍合金、钛合金、聚合物、多糖或纤维素材料(例如,木材、棉花)或玻璃。
在各种实施方案中,与在相同基材上不包括聚合物、蜡和/或树脂的相同陶瓷材料相比,聚合物、蜡和/或树脂可赋予复合材料一种或多种选自以下的功能特性:增强的硬度、弹性、粘弹性、粘附性、热性能、美学外观、拒液性、声音衰减、光散射和耐腐蚀性。
在一个实施方案中,陶瓷材料是无粘结剂陶瓷材料。在一些实施方案中,聚合物、蜡和/或树脂包括天然聚合物,诸如衍生自桐油、亚麻子油、核桃油、天然橡胶、纤维素或壳多糖的聚合物。在一些实施方案中,聚合物、蜡和/或树脂包括合成聚合物,诸如聚乙烯、聚丙烯、聚苯乙烯、聚四氟乙烯、聚酯如聚对苯二甲酸乙二酯、聚丙烯酸酯如聚(甲基丙烯酸甲酯)、聚乙酸乙烯酯、聚醚、聚氯丁二烯、聚(氯乙烯)、聚氨酯、聚酰胺、聚酰亚胺、硅氧树脂、聚(二甲基硅氧烷)或聚环氧化物聚合物。在一些实施方案中,聚合物、蜡和/或树脂包括硅烷、硅酸盐(例如,硅酸钾、硅酸钠)、硅醇盐(例如,甲基硅醇钾盐、甲基硅醇钠盐)、有机三乙氧基硅烷或有机三甲氧基硅烷、聚硅氮烷(例如,Durazane 1500、Durazane 1800或Durazane 2200)。在一些实施方案中,聚合物、蜡和/或树脂包括石油蜡(例如,石蜡)、动物产生的蜡(例如,蜂蜡、羊毛脂、虫胶)、植物衍生的蜡(例如,棕榈蜡、加诺巴蜡、大豆蜡)或矿物衍生的蜡(例如,地蜡、褐煤蜡)。
在一些实施方案中,聚合物、蜡和/或树脂包括一种或多种附加添加剂,诸如但不限于润滑剂、增塑剂、阻燃剂、染料、UV稳定剂、自由基清除剂或交联剂。例如,添加剂可赋予复合材料一种或多种结构或功能性质,诸如但不限于粘度、柔韧性、可燃性、颜色、UV稳定性、化学反应性和/或交联度。
在一些实施方案中,陶瓷材料的至少约1%,例如约1%至约99%的孔隙体积填充有聚合物、蜡和/或树脂,如通过水银孔隙率测定法测试所确定的。
在一些实施方案中,聚合物、树脂和/或蜡的厚度小于陶瓷材料的厚度的约1.5倍。
在一些实施方案中,陶瓷材料与聚合物、蜡和/或树脂材料相互作用,从而改变聚合物、蜡和/或树脂的一种或多种性质。在一个实例中,与当将聚合物、蜡和/或树脂直接施加至不包含陶瓷材料的相同基材时的交联速率和/或交联度相比,相互作用可增加所述聚合物、蜡和/或树脂的交联速率和/或交联度,例如碳链的交联。在另一个实例中,与当将聚合物、蜡和/或树脂材料直接施加至不包含陶瓷材料的相同基材时的结晶度相比,相互作用可增加聚合物、蜡和/或树脂材料的结晶度。在另一个实例中,与直接施加至不包含陶瓷材料的相同基材的聚合物、蜡和/或树脂材料的UV降解速率相比,相互作用可降低聚合物、蜡和/或树脂材料的UV降解速率。在一个非限制性实例中,陶瓷材料中的氧化锌可充当UV吸收剂。
在一些实施方案中,陶瓷材料包括镁、锰、氧化锌或氧化铝或氢氧化铝,并且聚合物、蜡和/或树脂包括干性油,诸如桐油或石蜡。
在一些实施方案中,陶瓷材料包括镁、锰、氧化锌或氧化铝或氢氧化铝,并且聚合物、蜡和/或树脂与陶瓷材料发生化学反应以改变聚合物、蜡和/或树脂的一种或多种性质。例如,改变聚合物、蜡和/或树脂的性质的化学反应可包括聚合物、蜡和/或树脂的交联、硬化和/或聚合。
在一些实施方案中,如本文所述的复合材料用于为基材提供一种或多种功能性质,诸如但不限于:对基材的腐蚀保护;用于粘附和/或结垢表面的耐久性改性剂;粘附促进或阻滞构造;触觉改性表面;拒液性应用;光学性质改变;机械改性,诸如硬度、弹性和粘弹性;表面和划痕自愈和修复目的;分离应用;电性质改变或电性质应用;冰、冷凝物和霜的减轻和/或改变;或美学性质,其中功能性质比在相同基材上没有聚合物、树脂和/或蜡的相同多孔陶瓷材料得到改善或具有更大量级,或者比直接施加至相同基材的聚合物、树脂和/或蜡得到改善或具有更大量级。
在一些实施方案中,复合材料包含超过油漆的临界颜料或陶瓷体积浓度。在一些实施方案中,颜料或陶瓷的体积浓度大于复合材料的总体积的约40%、约50%、约60%、约70%、约80%或约90%中的任一者。
附图说明
图1示出实施例1中描述的陶瓷材料的X射线衍射光谱。
图2A至图2C示出如实施例11中所述的多孔陶瓷涂覆的铝板、复合材料涂覆的铝板和未涂覆的铝板的比较。图2A:多孔陶瓷表面;图2B:部分填充有RTV硅氧树脂的多孔陶瓷表面;图2C;顶部涂覆有RTV硅氧树脂的铝板。
图3A至图3C示出如实施例12中所述的多孔陶瓷涂覆的铝板、复合材料涂覆的铝板和未涂覆的铝板的比较。图3A:多孔陶瓷表面;图3B:顶部涂覆有PDMS的多孔陶瓷表面;图3C:顶部涂覆有PDMS的铝板。
图4A至4C示出如实施例16中所述的多孔陶瓷涂覆的铝板、复合材料涂覆的铝板和未涂覆的铝板经受腐蚀性盐雾的比较。图4A:多孔陶瓷表面;图4B:涂覆有聚氨酯表面处理的铝板;4C:填充有聚氨酯面漆的多孔陶瓷。
图5A至图5C示出如实施例17中所述的多孔陶瓷涂覆的铝板、复合材料涂覆的铝板和未涂覆的铝板进行交叉影线粘附测试的比较。图5A:多孔陶瓷表面;图5B:涂覆有聚丙烯酸密封剂的铝板;图5C:填充有聚丙烯酸密封剂的多孔陶瓷。
图6A至图6B示出当涂覆有丙烯酸密封剂时在铝板上观察到的流挂、视觉涂层缺陷的比较。图6A:涂覆有丙烯酸密封剂的铝板显示出流挂;图6B:涂覆有丙烯酸密封剂的多孔陶瓷表面没有流挂缺陷。
图7A至图7C示出与裸铝基材相比多孔陶瓷基材上的自流平效果随时间进展的比较。与裸铝板(图7A)相比,环氧基树脂在氧化锌基(图7B)和氧化锰基(图7C)多孔陶瓷基材上在10分钟内实现了较低的接触角。
图8示出在多孔陶瓷基材上观察到的自流平效果的比较。与裸铝基材相比,环氧基树脂在锌基和锰基涂覆的多孔陶瓷基材上表现出较低的接触角,并且因此自流平性更好。
图9示出如实施例22中所述的涂覆有混合锌/铝氧化物和混合锰/铝氧化物陶瓷的铝板上的石蜡的芯吸行为。
图10示出与裸铝相比,在Zn和Mn基多孔陶瓷涂覆的基材上的石蜡随时间推移的芯吸行为。与裸铝板相比,在5分钟内在多孔陶瓷涂覆的基材上实现了更多的芯吸,并因此实现了改善的(更均匀的)覆盖。
具体实施方式
本文提供了陶瓷复合材料。该复合材料包括含有互连陶瓷网络的多孔陶瓷材料。可及孔隙体积的至少一部分至少部分填充有聚合物、树脂和/或蜡。陶瓷复合材料沉积在基材上。本文所述的复合材料提供有益的特性,诸如对基材的良好粘附性,并且可用于将均匀的外部涂层施加到基材如金属基材,和/或赋予所需的美学性质,诸如但不限于最小化或消除通常与如本文所述直接施加至基材的聚合物、树脂和/或蜡相关的滴落物、流痕和斑点。
定义
本文提供的数值范围包括限定该范围的数值。
“一个”、“一种”和“所述”包括多个指代物,除非上下文中另有明确规定。
本文在说明书和权利要求书中使用的短语“和/或”应该被理解为意指如此结合的要素中的“任一者或两者”,即在一些情况下结合存在而在其他情况下分离存在的要素。除了由“和/或”从句具体指明的要素之外,还可以任选地存在其他要素,无论与具体指明的那些要素相关或不相关,除非明确地相反指示。因此,作为非限制性实例,当与诸如“包括”的开放式语言结合使用时,对“A和/或B”的引用在一个实施方案中可以指A而不是B(任选地包括除B之外的要素);在另一个实施方案中,可以指B而不是A(任选地包括除A之外的要素);在又一实施方案中,可以指A和B两者(任选地包括其他要素);等等。”
“粘结剂(Binder)”或粘结剂(binding agent)是通过粘附或内聚以机械、化学方式将其他材料保持或牵引在一起以形成粘结整体的任何材料或物质。
“无粘结剂”是指不存在可外源添加到主要材料中以改善结构完整性的粘结剂,特别是关于有机粘结剂或树脂(例如,聚合物、胶、粘合剂、沥青)或无机粘结剂(例如,石灰、水泥玻璃、石膏等)。
“毛细管爬升”是指由于多孔基材而在与液体的自由表面接触时表面张力驱动液体沿样品向上流动(毛细管爬升与由于重力引起的力(矢量)的方向平行并与之相反)。
“纤维素”材料是指由纤维素或纤维素衍生物(例如纤维素的醚或酯)构成或含有纤维素或纤维素衍生物的材料。
“陶瓷”或“陶瓷材料”是指包括具有离子键或共价键的金属或准金属和非金属的无机化合物的固体材料。“非金属”可以包括氧(氧化物陶瓷),或碳(碳化物)或氮(氮化物)(非氧化物陶瓷)。“金属”可以包括周期表第1族的非氢元素、周期表第2-12族的元素或来自p区(周期表第12-17族)的元素,例如Al、Ga、In、Tl、Sn、Pb、Bi或其组合。“准金属”可以包括B、Si、Ge、As、Sb、Se、Te或Po或其组合。
“接触角”是指通过表面和接触表面处的液-气界面之间的液体测得的角度。
“连续的”或“邻接的”是指包含彼此直接接触的壁和特征,或者在相对于单个孔或结构较大的区域或尺寸上共享公共壁的孔和结构。
“转化涂层”是指表面层,其中反应物与待处理的表面发生化学反应,这将基材转化为不同的化合物。该过程通常不是添加或沉积,但可能导致较小的质量变化。
“第一四分位数孔径”是指在增加孔径的方向上测定的累积孔表面积等于通过BJH气体吸附/解吸测量测定的总累积孔表面积的25%时的孔径值。
“功能性材料层”是指可用作与周围环境相互作用的最上表面层或可用作后续材料的界面层(两个其他材料层之间的中间层)的材料层。功能材料层赋予下面的基材和/或其上沉积的材料一种或多种所需的功能性质。
“梯度”在本文中是指材料的一种或多种物理或化学性质的定量增加或降低,其通过沿着材料位于或固定于其上的基材表面从空间上的一个点传递到另一个点来观察,并且在材料上或通过材料的笛卡尔坐标中在x、y或z方向上变化来观察。梯度性质的非限制性实例包括厚度、密度、硬度、延展性、孔径、孔径分布、孔隙填充率或化学或物理组成,包括但不限于氧化态、金属浓度或交联密度,例如导致等电点、电导率、热导率、电容等的变化。
“亲水的”是指对水具有高亲和力的表面。接触角可以非常低(例如,在空气的存在下从表面通过液态水测量时小于30度)和/或不可测量。
“浸渍的”聚合物、树脂和/或蜡是指分散在如本文所述的多孔陶瓷材料的孔隙内的聚合物、树脂和/或蜡。
“互连陶瓷网络”或“陶瓷的互连网络”是指陶瓷材料的网络或基体,其中网络中的陶瓷材料与网络中的其他陶瓷材料物理接触(连接)。这与包含陶瓷颗粒的悬浮液如油漆形成对比,其中各个陶瓷颗粒悬浮在介质如粘结剂、树脂、油或蜡中,并且其中陶瓷颗粒彼此不固定接触。本文所述的互连陶瓷网络是宏观区域或体积上的连续陶瓷相,并且可以在陶瓷网络内包含具有可及孔隙体积的孔(开放空间),所述可及孔隙体积可填充或部分填充有另一种材料。
“层状双氢氧化物”是指一类离子固体,其特征在于具有一般顺序[AcB Z AcB]n的层状结构,其中c表示金属阳离子层,A和B是氢氧根阴离子层,并且Z是其他阴离子和/或中性分子(诸如水)层。在PCT申请第PCT/US2017/052120号中也描述了层状双氢氧化物,其全部内容通过引用并入本文。
“大孔隙”是指固体内的几何空间,其特征尺寸基本上大于单个孔或特征的特征尺寸(例如,厚度),例如,比特征尺寸大至少约5x至约10x或约10x至约100x。
“平均值”是指算术平均值或平均值。
“平均孔径”是使用来自Barrett-Joyner-Halenda(BJH)吸附/解吸方法的总表面积和总体积测量值计算的,即4倍总孔体积除以总表面积(4V/A),假定是圆柱形孔。
“多峰”是指包含多于一种不同模式的分布,其表现为多于一种不同的峰。
流体力学中的“渗透性”是多孔材料允许流体通过其的能力的量度。介质的渗透性与孔隙率有关,但也与介质中孔的形状和它们的连通程度有关。
“孔径分布”是指通过压汞孔隙率测定法(MIP)和Washburn方程测定的每个孔径或孔径范围的相对丰度。
“孔隙率”是材料中空隙(即,“空的”)空间的量度,并且是空隙(即,大空隙)的体积的分数。在总体积上,在0和1之间,或作为在0%和100%之间的百分比。本文公开的孔隙率通过压汞孔隙率测定法测量。
“多孔”是指固体材料内的空间、孔或空隙。
“树脂”在本文中指包含植物或合成来源的化合物的混合物的固体或高粘度物质,该混合物是或可以部分或完全转化成聚合物。
“超疏水”是指非常难以润湿的表面。水滴在超疏水材料上的接触角在此是指固着的液滴接触角>150°。高度疏水接触角>120°。这里提到的接触角是通过液体的表面之间形成的角度。
“每平方米投影基材面积的表面积”是指实际测量的表面积(通常以平方米测量)除以基材的表面积(如果基材是原子级平滑的(没有表面粗糙度)),通常也以平方米测量。
“协同作用”或“协同作用的”是指两种或更多种物质、材料或试剂之间的相互作用或协同作用,以产生比其单独的单独作用的总和更大(正协同作用)或更小(负协同作用)的组合作用。
“厚度”是指基材表面和表面改性(例如,陶瓷)材料顶部之间的长度。
“第三四分位数孔径”是指在增加孔径的方向上测定的累积孔表面积等于通过BJH气体吸附/解吸测量测定的总累积孔表面积的75%时的孔径值。
“迂曲度”是指通过多孔结构的最短路径的分数Δl以及该路径的起点和终点之间的欧几里德(Euclidean)距离Δx。
“可调谐”是指材料的功能、特性或质量被改变或修改的能力。
“蜡”在本文中是指天然或合成产生的有机化合物,其包括在中等温度下通常为亲脂性、可延展的固体并且在高温下为低粘度液体的烃。蜡通常包括长脂族烷基链,并且还可含有多种官能团,包括脂肪酸、脂质、烷烃、伯醇和仲醇、酮、醛和脂肪酸酯。合成蜡通常包括缺少官能团的同系列长链脂族烃(烷烃或石蜡)。
陶瓷复合材料
本文提供了陶瓷复合材料。该复合材料包括浸渍在互连陶瓷网络的孔隙内的聚合物、蜡和/或树脂。聚合物、蜡和/或树脂至少部分填充陶瓷网络的可及孔隙体积的至少一部分。陶瓷网络包括陶瓷基础材料网络内的孔隙集合。这些孔隙可以是互连的(通常为开孔)、独立的(通常为闭孔)或互连和独立的组合(混合孔)。这些孔隙可以由陶瓷壁流体分隔,但由其间的陶瓷连结或连接。例如,至少约20质量%、30质量%、40质量%、50质量%、60质量%、70质量%、75质量%、80质量%、85质量%、90质量%、95质量%、98质量%、99质量%或99.5质量%的陶瓷中的任一者是互连的(与其他陶瓷材料接触的孔隙之间的陶瓷材料),即,与被另一种材料例如聚合物、树脂和/或蜡包围的未连接的陶瓷颗粒相反。
本文所述的陶瓷复合材料与油漆的不同之处在于,颜料或陶瓷颗粒悬浮在油漆中,并且一旦将油漆施加到表面,相对于油漆内的其他陶瓷颗粒或颜料,颜料或陶瓷颗粒通常被树脂、聚合物、蜡或油包围并且主要与树脂、聚合物、蜡或油物理接触。油漆中的颜料或陶瓷颗粒悬浮在油漆制剂中,并且彼此不固定接触,这与本文所述的包含互连陶瓷网络的陶瓷组合物材料相反。油漆通常在临界颜料体积浓度以下配制,以确保粘结剂可涂覆所有颜料,以防止形成互连颜料或陶瓷网络,并防止空隙。本文所述的陶瓷复合材料包括在不存在使陶瓷或颜料与其他陶瓷颗粒或颜料分离的树脂、聚合物、蜡或油的情况下互连的陶瓷材料。在一些实施方案中,复合材料内的大部分互连陶瓷网络互连成单个网络。在其他实施方案中,将互连的陶瓷网络施加到基材的离散部分。在一些实施方案中,互连陶瓷网络的连续性可以被互连陶瓷网络内的裂纹中断,形成互连陶瓷网络的岛。在一些实施方案中,复合材料内的互连陶瓷网络的岛具有投影在相关基材的标称平均平面上的算术平均值或中值面积,其为约10平方微米至约1平方厘米、约1000平方微米至约10,000平方毫米、约5000平方微米至约50,000平方毫米、约20,000平方毫米至约100,000平方毫米、约250,000平方毫米至约1平方厘米,或大于约10平方微米、约50平方微米、约100平方微米、约200平方微米、约500平方微米、约1000平方微米、约2000平方微米、约5000平方微米、约10,000平方毫米、约20,000平方毫米、约50,000平方毫米、约100,000平方毫米、约500,000平方毫米或约1平方厘米中的任一者。在一些实施方案中,复合材料内基本上所有的陶瓷是互连的。
陶瓷材料可以包括稀土元素、过渡金属、碱土金属和/或铝。陶瓷材料可以是金属氧化物、金属氢氧化物或层状双氢氧化物或其组合的形式。例如,陶瓷可以包括但不限于一种或多种选自铁、铝、镁、铈、锌、锰、钛、铬、镍、钴、铜、银、钽、钨、硅、磷、锡和铕的元素。
陶瓷材料可以是导电的、绝缘的或半导电的。在一些实施方案中,陶瓷材料比基材更具电阻性。在其他实施方案中,陶瓷材料比基材更导电。在一些实施方案中,陶瓷材料是带隙在约0.1eV与约4eV之间的半导体。在一些实施方案中,陶瓷材料是光活性的、压电活性的,或者能够在施加压力或热梯度时产生电。在一些实施方案中,陶瓷材料是热绝缘体。在其他实施方案中,陶瓷材料是热导体。
将互连的陶瓷网络材料沉积在基材上。在一些实施方案中,将互连陶瓷网络材料固定在基材上。在一些实施方案中,互连陶瓷网络材料是基材上的无粘结剂多孔陶瓷材料。在一些实施方案中,互连陶瓷网络材料可以与基材直接接触。在其他实施方案中,互连陶瓷网络材料可以与基材间接接触,例如,与基材表面上的表面改性或处理接触。基材可以包括金属或金属合金(诸如但不限于铝、钢、钛或其合金)、聚合物、多糖、纤维素材料、木材、棉花或玻璃。在一些实施方案中,基材包括一种或多种金属,并且基材中的原生金属不同于陶瓷材料中的原生金属。
基材上复合材料的厚度可以为约1微米至约100微米。例如,复合材料的厚度可以为约1μm至约10μm、约5μm至约25μm、约10μm至约50μm、约25μm至约75μm、约50μm至约100μm、约1μm至约25μm、约10μm至约100μm,或至少约1μm、5μm、10μm、15μm、20μm、25μm、30μm、35μm、40μm、45μm、50μm、55μm、60μm、65μm、70μm、75μm、80μm、90μm、95μm或100μm中的任一者。
在一些实施方案中,陶瓷材料的约1%至约99%的可及孔隙体积填充有聚合物、树脂和/或蜡,例如,如通过水银孔隙率测定法测试所确定的。例如,约1%至约5%、约5%至约20%、约10%至约30%、约20%至约40%、约30%至约50%、约40%至约60%、约50%至约70%、约60%至约80%、约70%至约90%、约80%至约99%、约1%至约20%、约10%至约50%、约25%至约75%、约50%至约99%、约10%至约90%、约1%至约99.9%,或至少约1%、5%、10%、15%、20%、25%、30%、40%、45%、50%、55%、60%、65%、70%、75%、80%、85%、90%或95%至约99%的孔隙体积中的任一者填充有聚合物、树脂和/或蜡。
在一个实例中,聚合物、树脂和/或蜡填充可及陶瓷孔隙体积的一部分,但也比多孔陶瓷结构(互连陶瓷网络)的厚度更厚(例如,从多孔陶瓷结构的孔隙中突出)。在另一个实例中,聚合物、树脂和/或蜡填充可及孔隙体积的一部分,但是不厚于多孔陶瓷结构(例如,包含在多孔陶瓷结构的孔隙(互连陶瓷网络)内)。
在一些实施方案中,聚合物、树脂和/或蜡是小于陶瓷材料厚度约1.5倍的层的形式。在一些实施方案中,聚合物、树脂和/或蜡呈层的形式,其厚度高达陶瓷材料厚度的约2、5、10、15、20、25、30、35、40、45或50倍中的任一者。
如本文所述的复合材料中的天然聚合物的非限制性实例包括:桐油、亚麻籽油、核桃油、天然橡胶、纤维素和壳多糖。如本文所述的复合材料中的合成聚合物的非限制性实例包括:聚乙烯、聚丙烯、聚苯乙烯、聚四氟乙烯、聚对苯二甲酸乙二酯、聚(甲基丙烯酸甲酯)、聚乙酸乙烯酯、聚氯丁二烯、聚(氯乙烯)、聚氨酯、聚酰胺、聚酰亚胺、聚(二甲基硅氧烷)、聚硅氮烷和聚环氧化物,以及其共聚物。
如本文所述的复合材料中的聚合物或树脂的非限制性实例包括:硅烷、硅酸盐(诸如硅酸钠或硅酸钾)、硅醇盐(诸如甲基硅醇钠盐或甲基硅醇钾盐)、聚硅氮烷、有机三乙氧基硅烷和有机三甲氧基硅烷以及虫胶。
如本文所述的复合材料中的蜡的非限制性实例包括:石油、动物生产的、植物衍生的和矿物衍生的蜡,例如石蜡、蜂蜡、羊毛脂、棕榈蜡、加诺巴蜡、大豆蜡、地蜡和褐煤蜡。
聚合物、树脂和/或蜡可以包括一种或多种赋予功能或化学/物理性质的添加剂,诸如但不限于润滑剂(例如,赋予粘度)、增塑剂(例如,赋予柔韧性)、阻燃剂(赋予耐燃性)、染料或颜料(赋予颜色)、紫外线(UV)稳定剂(赋予UV稳定性)、自由基清除剂(例如,赋予抗化学反应性)或交联剂(赋予交联度)。
在本文所述的复合材料的一些实施方案中,聚合物、树脂和/或蜡可以与陶瓷材料化学或物理相互作用,从而提供期望的功能或结构特征。例如,与当直接施加或沉积到不包括陶瓷材料的相同基材时的聚合物、树脂和/或蜡的交联相比,相互作用可以增加聚合物、树脂和/或蜡的交联速率和/或交联度。在另一个实例中,与当直接施加或沉积到不包括陶瓷材料的相同基材时的聚合物、蜡和/或树脂的结晶度相比,相互作用可以增加聚合物、树脂和/或蜡的结晶度。在另一个实例中,与当直接施加或沉积到不包括陶瓷材料的相同基材时的聚合物、树脂和/或蜡的UV降解相比,相互作用可以降低聚合物、树脂和/或蜡的UV降解速率。在一些实施方案中,陶瓷材料和聚合物、蜡和/或树脂协同地相互作用,提供一种或多种相对于单独沉积在相同基材上的任一种材料得到改善或增强的功能性质。
在一些实施方案中,多孔或结构化陶瓷材料用于增强聚合物、蜡或树脂的输送或芯吸,以帮助其围绕边缘流动和/或形成厚度更均匀的层。在一些实施方案中,结构化陶瓷层允许将聚合物,蜡或树脂均匀喷涂在具有复杂几何形状或紧密间隔的基材上,诸如在热交换器中。在一些实施方案中,复合材料提供与不具有结构化陶瓷层的油漆或聚合物、蜡或树脂涂覆的基材相当的性能,同时使用较少的材料。在一些实施方案中,复合材料减少或消除缺陷,诸如但不限于裂口、渗色、起泡、起霜、雾浊、桥接、鼓泡、粉化、龟裂、网纹、成坑、裂纹、爪形皱纹、剥落、大龟裂、油漆皱皮、针孔、波纹、流动、流挂、溶剂咬底和/或应力开裂。
在一些实施方案中,多种聚合物、蜡和/或树脂用于产生复合材料。在一些实施方案中,第一聚合物层用于部分填充结构化陶瓷材料层的孔隙。在一些实施方案中,第二聚合物层用于进一步填充陶瓷材料的孔隙。在一些实施方案中,相对于在没有互连的结构化陶瓷层的基材上沉积多个聚合物、树脂和/或蜡层,不需要在层之间进行砂磨步骤,或者减少砂磨步骤的数量。
用途的应用
本文所述的复合材料可用于多种应用,包括对基材的腐蚀保护、针对粘附和结垢表面的耐久性改性剂、粘附促进或阻滞构造、触觉改性表面、拒液性、微生物、病毒和真菌性质的改性、光学性质改变、机械改性如硬度、弹性和粘弹性、表面和划痕自愈和修复、分离、电性质改变、冰、冷凝物和霜的减轻和改变、或美学性质。与在相同基材上不包括聚合物、蜡和/或树脂的相同多孔陶瓷材料相比,或与直接施加到相同基材的相同聚合物、蜡和/或树脂相比,复合材料可以提供上述功能性质中的任一种或任何组合的改进。
结构化陶瓷材料
本文所述的连续或离散涂料或表面改性材料可以是结构化陶瓷,例如无粘结剂(例如表面固定的)陶瓷,诸如结晶度大于约20%的无粘结剂陶瓷。结构化陶瓷是多孔的,即互连陶瓷网络材料含有空隙或孔隙。在PCT/US19/65978中提供了陶瓷材料的非限制性实例,其全部内容通过引用并入本文。
陶瓷材料可以包括金属氧化物和/或氢氧化物陶瓷,例如单一金属或混合金属氧化物和/或氢氧化物陶瓷。在一些实施方案中,陶瓷材料包括金属氢氧化物和/或氢氧化物陶瓷,例如单一金属或混合金属氧化物和/或氢氧化物陶瓷。在一些实施方案中,陶瓷材料包括金属氧化物和金属氢氧化物陶瓷,其中金属氧化物和金属氢氧化物包括相同或不同的单一金属或混合金属。在一些实施方案中,陶瓷材料包括金属氧化物和/或金属氢氧化物陶瓷,其中基材被水或其他化合物水合,导致表面能的变化并潜在地改变陶瓷的金属氧化物与金属氢氧化物组成的比率。在一些实施方案中,陶瓷材料包括金属氢氧化物,其中至少一部分的金属氢氧化物为层状双氢氧化物的形式,例如至少约5%、10%、15%、20%、25%、30%、35%、40%、45%、50%、55%、60%、65%、70%、75%、80%、85%、90%或95%的金属氢氧化物为层状双氢氧化物。
在一些实施方案中,“金属氧化物”或“金属氢氧化物”可以分别是金属氧化物或金属氢氧化物的水合物的形式,或者金属氧化物或金属氢氧化物的一部分可以分别是金属氧化物或金属氢氧化物的水合物的形式。
混合金属氧化物或混合金属氢氧化物可以分别包括例如多于一种金属的氧化物或氢氧化物,所述金属诸如但不限于铁、钴、镍、铜、锰、铬、钛、钒、锆、钼、钽、锌、铅、锡、钨、铈、镨、钐、钆、镧、镁、铝或钙。
在一些实施方案中,陶瓷材料是无粘结剂的陶瓷材料,即,在没有粘结剂的情况下沉积到基材上。在一些实施方案中,将陶瓷材料固定在基材上。
在一些实施方案中,互连陶瓷网络材料具有开孔多孔结构,例如,其特征在于以下中的一种或多种:能够在1小时内在封闭容器中实现具有大于约5mm的低表面张力的液体(例如,小于约25mN/m,诸如异丙醇)逆着重力沿表面向上的毛细管爬升;约0.1m2/g至约10,000m2/g的表面积;约10nm至约1000nm或约1nm至约1000nm的平均孔径;约0至约1cc/g的通过汞(Hg)侵入孔隙率测定法测量的孔隙体积;以及约1至约1000的曲折度,所述曲折度定义为流体路径的长度与最短距离的“弧线比”;和/或约1至约10,000毫达西的渗透率。
在一些实施方案中,互连陶瓷网络具有约5%至约95%的孔隙率。在一些实施方案中,孔隙率可以是至少约或大于约5%、10%、15%、20%、25%、30%、35%、40%、50%、55%、60%、65%、70%、75%、80%、85%、90%或95%中的任一者。在一些实施方案中,孔隙率为约10%至约90%、约30%至约90%、约40%至约80%、或约50%至约70%。
在一些实施方案中,互连陶瓷网络材料具有约1至10,000毫达西的渗透性。在一些实施方案中,渗透性可以是至少约1、10、100、500、1000、5000或10,000毫达西中的任一者。在一些实施方案中,渗透性为约1至约100、约50至约250、约100至约500、约250至约750、约500至约1000、约750至约2000、约1000至约2500、约2000至约5000、约3000至约7500、约5000至约10,000、约1至约1000、约1000至约5000、或约5000至约10,000毫达西。
在一些实施方案中,互连陶瓷网络材料包括通过压汞孔隙率测定法测定的约100mm3/g至约7500mm3/g的空隙体积。在一些实施方案中,空隙体积为至少约100、200、300、400、500、600、700、800、900、1000、1500、2000、2500、3000、3500、4000、4500、5000、5500、6000、6500、7000或7500mm3/g中的任一者。在一些实施方案中,空隙体积为约100至约500、约200至约1000、约400至约800、约500至约1000、约800至约1500、约1000至约2000、约1500至约3000、约2000至约5000、约3000至约7500、约250至约5000、约350至约4000、约400至约3000、约250至约1000、约250至约2500、约2500至约5000或约500至约4000mm3/g中的任一者。
本文公开的互连陶瓷网络材料的特征可以在于其与液体材料的相互作用。如前所述,陶瓷材料的特征可以在于能够在1小时内在封闭容器中实现具有大于约5mm的低表面张力的液体(例如,小于约25mN/m,诸如异丙醇)逆着重力沿表面向上的毛细管爬升。可以使用在20℃下表面张力小于约25mN/m的其他溶剂,包括但不限于全氟己烷、全氟庚烷、全氟辛烷、正己烷(HEX)、聚二甲基硅氧烷(Baysilone M5)、叔丁基氯、正庚烷、正辛烷(OCT)、异丁基氯、乙醇、甲醇、异丙醇、1-氯丁烷、异戊基氯、丙醇、正癸烷(DEC)、乙基溴、甲基乙基酮(MEK)、正十一烷、环己烷。可以使用在20℃下表面张力>25mN/m的其他溶剂,包括:丙酮(2-丙酮)、正十二烷(DDEC)、异戊腈、四氢呋喃(THF)、二氯甲烷、正十四烷(TDEC)、均四氯甲烷、正十六烷(HDEC)、氯仿、1-辛醇、丁腈、对伞花烃、异丙苯、甲苯、二丙二醇单甲醚、1-癸醇、乙二醇单乙醚(乙基溶纤剂)、1,3,5-三甲苯(均三甲苯)、苯、间二甲苯、正丙基苯、乙基苯、正丁基苯、1-硝基丙烷、邻二甲苯、十二烷基苯、富马酸二乙酯、萘烷、硝基乙烷、二硫化碳、环戊醇、1,4-二噁烷、1,2-二氯乙烷、氯苯、二丙二醇、环己醇、六氯丁二烯、溴苯、吡咯(PY)、N,N-二甲基乙酰胺(DMA)、硝基甲烷、邻苯二甲酸二乙酯、N,N-二甲基甲酰胺(DMF)、吡啶、甲基萘、苄醇、邻氨基苯甲酸乙酯、碘苯、N-甲基-2-吡咯烷酮、磷酸三甲苯酯(TCP)、间硝基甲苯、溴仿、邻硝基甲苯、异硫氰酸苯酯、a-氯萘、糠醛(2-糠醛)、喹啉、1,5-戊二醇、苯胺(AN)、聚乙二醇200(PEG)、邻氨基苯甲酸甲酯、硝基苯、a-溴萘(BN)、二乙二醇(DEG)、1,2,3-三溴丙烷、苯甲酸苄酯(BNBZ)、1,3-二碘丙烷、3-吡啶甲醇(PYC)、乙二醇(EG)、2-氨基乙醇、均四溴乙烷、二碘甲烷(DI)、硫二甘醇(2,2'-硫代二乙醇)(TDG)、甲酰胺(FA)、甘油(GLY)、水(WA)和汞。
互连陶瓷网络材料可以具有在各种温度下实现水毛细管爬升的能力。这些材料可以具有分离可混溶材料和二元共沸物(例如乙醇-水、乙酸乙酯-乙醇或丁醇-水)以破坏三元共沸物或从包括乙醇和水的混合物中去除戊醇的能力。
互连陶瓷网络材料的孔隙可以包括填充有一种或多种气体的开孔,可以包括部分填充的孔隙(例如,部分填充有一种或多种固体材料),或可以包括完全或基本上填充的孔隙(例如,完全或基本上填充有一种或多种液体和/或固体材料)。在一些实施方案中,孔隙部分地、基本上或完全填充有气体、液体或固体物质或其组合。
在一些实施方案中,孔隙部分填充有第一材料,并且然后部分或完全填充有第二材料。在一个非限制性实施方案中,第一材料是树脂并且第二材料是蜡。在另一个非限制性实施方案中,第一材料是树脂并且第二材料是密封剂、保护性面漆、保护性面漆或油漆。在一些实施方案中,第二材料作为部分填充的孔隙上的材料层添加。在一些实施方案中,第一材料是气体、固体或液体,或者气体、液体和/或固体物质的组合。在一些实施方案中,第二材料是气体、固体和/或液体物质,或者是环境(例如,空气)。实例包括并且由此赋予的功能包括孔隙率、芯吸、排斥性和/或润湿行为的变化;复合材料(包括多孔材料和第二材料)的变化,以改变电/介电性质,改变机械性质如耐磨性、硬度、韧性、触感、弹性模量、屈服强度、屈服应力、杨氏模量、表面(压缩或拉伸)应力和/或弹性;热性质如热扩散率、电导率、热膨胀系数、热界面应力和/或热各向异性的变化;光学性质如发射率、颜色、反射率和/或吸收系数的改变;化学性质如腐蚀、催化、反应性、惰性、相容性、耐结垢性、离子泵阻塞、耐微生物性和/或微生物相容性的改变;和/或作为生物催化的底物。
在一些实施方案中,第一材料以正或负协同方式与第二材料相互作用以改变陶瓷材料的一种或多种功能特性,诸如但不限于润湿性、硬度、弹性、机械、电、压电、光学、粘附或热性质、微生物亲和力或耐受性、生物膜生长的改变、催化活性、渗透性、美学外观、拒液性和/或耐腐蚀性。
在一些实施方案中,本文所述的复合材料具有超过油漆的临界颜料体积浓度的陶瓷或颜料与树脂的比率。在一些实施方案中,陶瓷或颜料浓度大于复合材料的总体积的约40%、约50%、约60%、约70%、约80%或约90%。
如本文所述的聚合物、树脂和/或蜡材料也可以沉积到孔隙中,部分或基本上完全填充孔隙。陶瓷材料可以包括例如锌、铝、锰、镁、铈、钆和钴的一种或多种氧化物。此外,陶瓷材料可以包括可添加到表面改性材料中的任何固体材料,包括主要以离子键和共价键保持的金属、非金属或准金属原子的无机化合物,例如粘土、二氧化硅和玻璃。聚合物可以包括例如天然聚合物材料,诸如大麻、虫胶、琥珀、羊毛、丝、天然橡胶、纤维素和其他天然纤维、糖、半纤维素和全纤维素、多糖和生物衍生材料如胞外蛋白、DNA、壳多糖。合成聚合物包括例如含有聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、合成橡胶、酚醛树脂(或酚醛塑料)、氯丁橡胶、尼龙、聚丙烯腈、PVB、硅氧树脂、聚异丁烯、PEEK、PMMA和PTFE的聚合物和共聚物。
在一些实施方案中,孔隙被薄复合聚合物层部分填充,以产生具有由聚合物提供的孔隙率和功能性的表面改性材料。在其他实施方案中,孔隙被厚聚合物层完全填充,以产生具有厚聚合物层的表面改性材料,所述厚聚合物层具有多孔基体材料和聚合物层的复合性质。本文的组合物中描述的聚合物包括共聚物。
在一些实施方案中,沉积向表面改性材料中添加一个或多个官能团的材料层,所述官能团诸如但不限于铵基(例如季铵基)、烷基、全氟烷基、氟烷基。在一些实施方案中,沉积聚合物或陶瓷层。由此赋予的官能团和功能的实例包括用于抗微生物功能的季铵基团、用于斥水性和烃亲和性的烷基链、用于防水和防油功能的全氟烷基、用于机械性能功能的聚合物、用于美学功能、光电功能或防腐功能的其他陶瓷。
在一些实施方案中,孔隙基本上或完全被聚合物或陶瓷材料填充。
在一些实施方案中,孔隙中的材料与陶瓷材料相互作用。此类材料和由此赋予的功能的实例包括通过环境液体或蒸气对表面改性材料的氧化、微量组分(例如,环境污染物)的冷凝、从环境空气中捕获或氧化有害环境材料如CO或H2S以及/或在环境中收集和保留材料。
在一些实施方案中,环境中或添加到孔隙中的水分与孔隙中的材料相互作用,以改性孔隙中的材料或表面改性材料。此类材料和由此赋予的功能的实例包括润湿行为的变化、光学性质的变化、氧化态或反应性的变化、蒸发速率的变化、结霜、结冰或冷凝。
在一些实施方案中,孔隙中的材料可以被设计成与陶瓷材料相互作用以“调整”整个表面的性质。可调性质的实例包括但不限于润湿性、硬度、耐微生物性、催化活性、耐腐蚀性、声学性质、光反射率、颜色和/或光化学活性。
在一些实施方案中,陶瓷表面改性材料和孔隙中的材料以协同方式相互作用,例如,仅与表面改性材料和/或孔隙中的材料的功能相比,增强或降低表面改性材料和/或孔隙中的材料的至少一种功能。在一些实施方案中,孔隙中的两种或更多种材料以协同方式相互作用,例如,仅与材料的功能相比,增强或降低孔隙中的至少一种材料的至少一种功能。
在一些实施方案中,陶瓷表面改性材料是不对称的,例如,不是球形、圆柱形、立方形或以其他方式有序的孔隙形态,所述孔隙形态具有明确的、相对恒定的表面积与体积的正态分布,其特征在于第一四分位数处的孔径与第三四分位数处的孔径的比率作为无粘结剂陶瓷表面改性的厚度的函数。特别地,当与球形、圆柱形或立方体结构相比时,孔隙形态围绕其中心不对称。不对称孔隙的非限制性实例描述于PCT申请第PCT/US19/39743号中,其全文以引用方式并入本文。
多孔陶瓷材料(互连陶瓷网络)的特征可在于随着与基材的距离而变化的宽孔径分布。特别地,在距基材给定距离处的孔隙结构可以局部表征,例如如本文所述,并且在不同距离处具有不同的表征。所得不对称性由基材、离子迁移率、加工条件如温度、压力和浓度的组合原位确定。不对称度可以通过本体方法如混合、搅拌、电场调制和槽式过滤,或通过表面定向的处理方法如剪切速率、撞击流或表面电荷改性和调制来进一步改性。不对称性可以通过各种方法如蚀刻、径迹蚀刻、离子束研磨、氧化、光催化或通过另外的方法非原位确定。这些方法是指具有厚度和/或孔隙深度的较窄或对称孔隙结构的材料,诸如沸石、径迹蚀刻膜或膨胀PTFE膜。
在一些实施方案中,互连陶瓷网络材料包括范围为约2nm至约50nm的中孔平均孔径。在其他实施方案中,平均孔径范围为约50nm至约1000nm。在一些实施方案中,无粘结剂多孔陶瓷材料包括约2nm至约20nm的平均孔径。在一些实施方案中,平均孔径为至少约2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19或20nm中的任一者。在一些实施方案中,平均孔径为约2至约5、约4至约9、约5至约10、约7至约12、约9至约15、约12至约18、约15至约20、约4至约11、约5至约9、约4至约8、或约7至约11nm中的任一者。
互连陶瓷网络材料可以包括一种或多种金属氧化物和/或金属氢氧化物(和/或其水合物)。可包含在本文公开的陶瓷组合物中的金属的非限制性实例包括:锌、铝、锰、镁、铈、铜、钆、钨、锡、铅和钴。在一些实施方案中,陶瓷材料包括过渡金属、第II族元素、稀土元素(例如,镧、铈、钆、镨、钪、钇、钐或钕)、铝、锡或铅。在一些实施方案中,陶瓷材料包括两种或多种金属氧化物(例如,混合金属氧化物),包括但不限于锌、铝、锰、镁、铈、镨和钴。
在一些实施方案中,互连陶瓷网络材料包括:锌和铝的氧化物和/或氢氧化物的混合物;ZnO和Al2O3的混合物,以及Zn-铝酸盐;包含含有Zn、Al和氧的任何/所有相的材料的混合物;锰和镁的氧化物和/或氢氧化物的混合物;氧化锰;氧化铝;混合金属锰氧化物和/或氢氧化物;镁和铝的氧化物和/或氢氧化物的混合物;镁、铈和铝的氧化物和/或氢氧化物的混合物;锌、钆和铝的氧化物和/或氢氧化物的混合物;钴和铝的氧化物和/或氢氧化物的混合物;锰和铝的氧化物和/或氢氧化物的混合物;铈和铝的氧化物和/或氢氧化物的混合物;铁和铝的氧化物和/或氢氧化物的混合物;钨和铝的氧化物和/或氢氧化物的混合物;锡和铝氧化物的混合物;氧化钨和/或氢氧化钨;氧化镁和/或氢氧化镁;氧化锰和/或氢氧化锰;氧化锡和/或氢氧化锡;或氧化锌和/或氢氧化锌。
在一些实施方案中,陶瓷材料中的至少一种金属处于2+氧化态。
在一些实施方案中,互连陶瓷网络材料包括锌、铝、锰、镁、铈、钆和钴的一种或多种氧化物和/或氢氧化物,并且基材是铝或铝合金。
在一些实施方案中,互连陶瓷网络材料是超疏水的。在一些实施方案中,表面改性材料是高度疏水的。在一些实施方案中,与不包括陶瓷材料的基材相比,表面改性材料包括选自以下的一种或多种功能特性:润湿性、硬度、弹性、机械、电、压电、电磁、光学、粘附或热性质、微生物亲和力或耐受性、生物膜生长的改变、催化活性、渗透性、美学外观和耐腐蚀性。
在一些实施例中,功能材料层(例如,顶层材料)沉积在陶瓷材料上。此类材料的实例包括但不限于用于抗微生物功能的季铵基团、用于斥水性和烃亲和性的烷基链、用于防水和防油功能的全氟烷基、用于机械性能功能的聚合物、用于美学功能、光电功能或防腐功能的其他陶瓷。由此类材料赋予的功能的实例包括但不限于孔隙率、芯吸、排斥性和/或润湿行为的变化;复合材料(包括多孔材料和第二材料)的变化,以改变电/介电性质,改变机械性质如耐磨性、硬度、韧性、触感、弹性模量、屈服强度、屈服应力、杨氏模量、表面(压缩或拉伸)应力、拉伸强度、压缩强度和/或弹性;热性质如热扩散率、电导率、热膨胀系数、热界面应力、热各向异性的变化,以改变光学性质,诸如发射率、颜色、反射率和/或吸收系数,以改变化学性质,诸如腐蚀、催化、反应性、惰性、相容性、耐污性、离子泵阻塞、耐微生物性和/或微生物相容性、促进后续材料层的粘附以及/或作为生物催化的底物。
在一些实施方案中,与基材材料如聚合物或本文公开的任何基材材料相比,互连陶瓷网络材料具有抗紫外线辐射降解性。
在一些实施方案中,互连陶瓷网络材料包括约0.5微米至约20微米的厚度。在一些实施方案中,陶瓷材料包括约0.2微米至约25微米的厚度。在一些实施方案中,厚度为至少约0.2、0.5、1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24或25微米中的任一者。在一些实施方案中,厚度为约0.2至约0.5、约0.5至约1、约1至约5、约3至约7、约5至约10、约7至约15、约10至约15、约12至约18、约15至约20、约18至约25、约0.5至约15、约2至约10、约1至约10、约3至约13、约0.5至约15、约0.5至约5、约0.5至约10或约5至约15微米中的任一者。
在一些实施方案中,互连陶瓷网络材料的特征在于约0°至约180°的水接触角。在其他实施方案中,水接触角小于约30度。在其他实施方案中,水接触角大于约150度。
在一些实施方案中,互连陶瓷网络材料包括每平方米投影基材面积约1.1m2至约100m2的表面积。在一些实施方案中,陶瓷材料包括每平方米投影基材面积约10m2至约1500m2的表面积。在一些实施方案中,表面积为每平方米投影基材面积至少约10、50、100、150、200、250、300、350、400、450、500、550、600、650、700、750、800、850、900、950、1000、1050、1100、1150、1200、1250、1300、1350、1400、1450或1500m2中的任一者。在一些实施方案中,表面积为每平方米投影基材面积约10至约100、约50至约250、约150至约500、约250至约750、约500至约1000、约750至约1200、约1000至约1500、约70至约1000、约150至约800、约500至约900、或约500至约1000m2中的任一者。
在一些实施方案中,互连陶瓷网络材料包括每克陶瓷材料约15m2至约1500m2的表面积。在一些实施方案中,表面积为每克陶瓷材料至少约15、50、100、150、200、250、300、350、400、450、500、550、600、650、700、750、800、850、900、950、1000、1050、1100、1150、1200、1250、1300、1350、1400、1450或1500m2中的任一者。在一些实施方案中,表面积为每克陶瓷材料约15至约100、约50至约250、约150至约500、约250至约750、约500至约1000、约750至约1200、约1000至约1500、约50至约700、约75至约600、约150至约650、或约250至约700m2中的任一者。
基材
在其上施加或沉积如本文所述的多孔陶瓷材料(互连陶瓷网络)的基材可以由适用于结构或功能特性或功能应用的任何材料组成,例如,在诸如热交换器的装置中。在一些实施方案中,基材是铝或含有铝(例如,铝合金)、铁合金、锌、锌合金、铜、铜合金、镍合金、镍、钛合金、钛、含钴-铬的合金、玻璃、聚合物、共聚物、天然材料(例如,含纤维素的天然材料)或塑料。
在一些实施方案中,基材包括金属,并且如本文所述的互连陶瓷网络材料中的原生金属不同于基材中的原生金属。原生金属是占基材或陶瓷材料中总金属的至少约50%、60%、70%、80%、90%或95%的金属,例如如通过基于原子金属的x射线衍射所测定。基材原生金属的实例包括但不限于铝、铁、铜、锌、镍、钛和镁。陶瓷原生金属的实例包括但不限于锌、铝、锰、镁、铈、铜、钆、钨、锡、铅和钴。
在一些实施方案中,基材包括能够在允许基材金属局部溶解的反应条件下反应(例如溶解)的金属,并且基材金属被掺入到基材改性材料中,诸如陶瓷材料,例如无粘结剂多孔陶瓷材料。例如,铝基材可以提供铝(例如,Al3+),当陶瓷材料沉积在基材上时,铝掺入到陶瓷材料中。
以下实施例旨在说明而非限制本发明。
实施例
如下制备如以下实施例中所述的表面改性材料。用异丙醇(IPA)和毛巾清洁零件、基材或组件,以去除任何残留油。聚合物基材或具有pH灵敏性的基材通常仅用IPA清洁,并且不经历以下苛性碱和酸处理步骤。接着,在约20℃至约60℃的温度下将金属零件或基材浸没在pH>11的苛性蚀刻浴中约5分钟至约20分钟。然后将组件在水中漂洗以去除任何残留的苛性碱或松散粘附的材料。接着,将零件浸没在pH低于1并且温度为约20℃至约40℃的硝酸溶液中以去除污垢和/或使基材脱氧。然后将组件置于含有20-250mM的金属硝酸盐或硫酸盐或混合的金属硝酸盐或硫酸盐以及允许在50-85℃的反应温度下反应和沉降的类似摩尔量的二胺、三胺或四胺的生产浴中。将零件、基材或组件在浴中保持约5分钟至约3小时范围内的时间段。将基材取出并且排干并置于烘箱中以在足以将陶瓷材料转化成高度氧化物的温度下干燥和/或煅烧,诸如但不限于约65%或更高(例如,改变氢氧化物/氧化物的比率,同时保留一些氢氧化物),例如约50℃至约600℃热处理持续数分钟至数小时。如果需要,则该沉积步骤可以任选地在干燥步骤之前或之后重复,随后是另一个任选的干燥步骤。冷却后,如下文实施例中所述进一步加工和/或测试零件。
实施例1
清洁的3003铝板涂覆有基于氧化镁和氧化铝的混合物的互连多孔陶瓷表面。在约50℃至80℃的温度下,在25至100mM的硝酸镁水溶液和类似量的六亚甲基四胺中沉积互连多孔陶瓷表面持续约15至90分钟的时间段。然后将盘管在约300℃至约500℃的温度下煅烧约1小时。样品的扫描电子显微术(SEM)横截面通过如下制备:首先用环氧树脂覆盖陶瓷表面的顶部,并且然后将聚焦的离子束导向样品的顶部,直到去除足够的材料以暴露互连多孔陶瓷层的侧面。在垂直于铝基材表面的方向上测量互连多孔陶瓷层的厚度,并且发现厚度为约5微米。使用水银孔隙率测定法、X射线衍射(XRD)、差示扫描量热法、纳米压痕法和极化电阻对样品进行分析。水银孔隙率测定法显示样品具有1400mm3/g的孔隙体积和84%的总孔隙率。图1中的XRD光谱在35.6°、43.4°和62.7°处显示清晰的峰,表明晶体MgO沉积物结构。
实施例2
清洁的3003铝板以与实施例1中所述的程序类似的程序涂覆有基于氧化镁和氧化铝的混合物的互连多孔陶瓷表面。将聚苯乙烯于甲苯中的溶液浇注到保持在20℃和35℃之间的沉积物表面上。蒸发溶剂,直到样品完全干燥。
实施例3
清洁的3003铝板以与实施例1中所述的程序类似的程序涂覆有基于氧化镁和氧化铝的混合物的互连多孔陶瓷表面。然后将板浸入保持在20℃和35℃之间的聚苯乙烯于甲苯中的溶液中。几小时后,从溶液中取出样品,并且保留在表面上的溶剂蒸发,直到样品完全干燥。
实施例4
清洁的3003铝板涂覆有基于氧化锌的互连多孔陶瓷表面。单独地,清洁的3003铝板涂覆有互连多孔陶瓷表面,该多孔陶瓷表面由大约66质量%的氧化锌和34质量%的氧化镁组成。单独地,清洁的3003铝板涂覆有基于氧化镁的互连多孔陶瓷表面。将所有三个样品浸入聚氯丁二烯于乙酸叔丁酯中的溶液中90分钟。然后将样品从溶液中取出并在氮气气氛下在160℃下固化40分钟。
使用含甲苯溶剂溶胀技术和傅立叶变换红外光谱(Fourier-transform infraredspectroscopy)(FTIR)分析每个样品以确定聚氯丁二烯的交联度。仅基于氧化锌的样品具有最高的交联度,仅基于氧化镁的样品具有最低的交联度,并且由氧化锌和氧化镁两者组成的样品具有在其他两个样品的值之间的交联度。
实施例5
清洁的3003铝板涂覆有基于氧化锌和氧化铝的混合物的多孔互连陶瓷表面改性物。在约50℃至80℃的温度下,在25至100mM的硝酸锌水溶液和类似量的六亚甲基四胺中沉积多孔陶瓷表面改性物约15至120分钟的时间段。然后将盘管在约350℃至550℃的温度下煅烧约1小时。然后将样品保持在100℃,并且滴铸石蜡熔体并使其芯吸进入表面。然后使样品冷却至室温。冷却至室温后24小时,对样品进行电化学测试。对样品进行极化电阻测试,并且发现耐腐蚀性为2.3x106欧姆。然后,按照ASTM G85-A3方案将样品在腐蚀性环境中浸泡3小时,按照ASTM D4587方案UV暴露115小时,并且按照ASTM D870方案在水中浸泡180小时。对样品再次进行极化电阻测试,并且发现耐腐蚀性为4.2x105欧姆。相比之下,在清洁的3003铝板上进行极化电阻测试,该铝板涂覆有基于氧化锌和氧化铝的混合物的互连多孔陶瓷表面且没有石蜡层,并且发现耐腐蚀性为4.3x104欧姆。
实施例6
清洁的3003铝板以与实施例1中所述的程序类似的程序涂覆有基于氧化镁和氧化铝的混合物的互连多孔陶瓷表面。然后将样品保持在100℃,并且滴铸石蜡熔体并使其芯吸进入表面。然后使样品冷却至室温。冷却至室温后24小时,对样品进行电化学测试。对样品进行极化电阻测试,并且发现耐腐蚀性为1.3x106欧姆。然后,按照ASTM G85-A3方案将样品在腐蚀性环境中浸泡3小时,按照ASTM D4587方案UV暴露115小时,并且按照ASTM D870方案在水中浸泡159小时。对样品再次进行极化电阻测试,并且发现耐腐蚀性为1.7x105欧姆。相比之下,在清洁的3003铝板上进行极化电阻测试,该铝板涂覆有基于氧化镁和氧化铝的混合物的互连多孔陶瓷表面,没有石蜡层,并且发现耐腐蚀性为2.2x104欧姆。
实施例7
以与实施例1中所述的程序类似的程序,但使用硝酸锰或硫酸锰代替硝酸镁,用基于氧化锰和氧化铝的混合物的互连多孔陶瓷表面涂覆清洁的3003铝板。然后将样品保持在100℃,并且滴铸石蜡熔体并使其芯吸进入表面。然后使样品冷却至室温。冷却至室温后24小时,对样品进行电化学测试。对样品进行极化电阻测试,并且发现耐腐蚀性为3.7x106欧姆。然后,按照ASTM G85-A3方案将样品在腐蚀性环境中浸泡3小时,按照ASTM D4587方案UV暴露115小时,并且按照ASTM D870方案在水中浸泡159小时。对样品再次进行极化电阻测试,并且发现耐腐蚀性为1.1x106欧姆。相比之下,在清洁的3003铝板上进行极化电阻测试,该铝板涂覆有基于氧化锰和氧化铝的混合物的互连多孔陶瓷表面且没有石蜡层,并且发现耐腐蚀性为4.6x104欧姆。
实施例8
清洁的3003铝板以与实施例7中所述的程序类似的程序涂覆有基于氧化锰和氧化铝的混合物的互连多孔陶瓷表面。然后用50%(按体积计)桐油和50%柠檬烯的溶液通过滴铸向样品上涂覆一层桐油。在溶液芯吸通过整个样品后,将样品在室温下悬挂干燥3天。
干燥后,对样品进行极化电阻测试,并且发现耐腐蚀性为3.4x105欧姆。然后,按照ASTM G85-A3方案将样品在腐蚀性环境中浸泡3小时,按照ASTM D4587方案UV暴露115小时,并且按照ASTM D870方案在水中浸泡158小时。对样品再次进行极化电阻测试,并且发现耐腐蚀性为7.6x105欧姆。相比之下,在清洁的3003铝板上进行极化电阻测试,该铝板涂覆有基于氧化锰和氧化铝的混合物的互连多孔陶瓷表面且没有桐油层,并且发现耐腐蚀性为4.6x104欧姆。
实施例9
清洁的3003铝板以与实施例5中所述的程序类似的程序涂覆有基于氧化锌和氧化铝的混合物的互连多孔陶瓷表面。然后用50%(按体积计)桐油和50%柠檬烯的溶液通过滴铸向样品涂覆一层桐油。在溶液芯吸通过整个样品后,将样品在室温下悬挂干燥3天。
干燥后,对样品进行极化电阻测试,并且发现耐腐蚀性为8.0x105欧姆。相比之下,在清洁的3003铝板上进行极化电阻测试,该铝板涂覆有基于氧化锌和氧化铝的混合物的互连多孔陶瓷表面且没有桐油层,并且发现耐腐蚀性为4.3x104欧姆。
实施例10
清洁的3003铝板以与实施例1中所述的程序类似的程序涂覆有基于氧化镁和氧化铝的混合物的互连多孔陶瓷表面。然后用50%(按体积计)桐油和50%柠檬烯的溶液通过滴铸向样品涂覆一层桐油。在溶液芯吸通过整个样品后,将样品在室温下悬挂干燥3天。
干燥后,对样品进行极化电阻测试,并且发现耐腐蚀性为6.1x105欧姆。相比之下,在清洁的3003铝板上进行极化电阻测试,该铝板涂覆有基于氧化镁和氧化铝的混合物的互连多孔陶瓷表面且没有桐油层,并且发现耐腐蚀性为2.2x104欧姆。
实施例11
两块清洁的3003铝板以与实施例5中所述的程序类似的程序涂覆有基于氧化锌和氧化铝的混合物的互连多孔陶瓷表面。将互连多孔陶瓷涂覆的铝板和另外的裸露的未涂覆的3003铝板浸渍在分散于乙酸叔丁酯中的1%至5%室温硫化(RTV)的氟硅氧树脂溶液中,并回收以形成连续膜。蒸发溶剂,直至两个样品完全干燥。将板在室温下在周围环境中湿固化48小时。在所有三块板上进行接触角测量,即:a)互连多孔陶瓷表面,b)部分填充有RTV硅氧树脂的互连多孔陶瓷表面,以及c)顶部涂覆有RTV硅氧树脂的3003铝板。图1示出了在板(b)上具有151°的最高接触角的所有三块板的SEM图像,其中互连陶瓷多孔结构部分填充有RTV硅氧树脂。在板(c)和(b)上观察到的接触角分别为114°和<15°。将板(b)再次浸入分散在乙酸叔丁酯中的RTV硅氧树脂溶液中,以完全填充互连多孔陶瓷结构,并且测量的接触角为117°。结果显示在图2A-2C中。
实施例12
两块清洁的3003铝板以与实施例7中所述的程序类似的程序涂覆有基于氧化锰和氧化铝的混合物的互连多孔陶瓷表面。将互连多孔陶瓷涂覆的铝板和另外的裸露的未涂覆的3003铝板浸渍在分散于甲苯中的1%-5%聚二甲基硅氧烷(PDMS)(Sylgard 182)溶液中,并回收以形成连续膜。蒸发溶剂,直到两个样品都完全干燥,并且将板在80℃下固化2小时。对所有三个板进行接触角测量,即:a)互连多孔陶瓷表面,b)顶部涂覆有PDMS的互连多孔陶瓷表面以及c)顶部涂覆有PDMS的3003铝板。图3A-3C示出了在板(b)上具有141°的最高接触角的所有三个板的SEM图像,其中互连陶瓷多孔结构部分填充有面漆。在板(c)和(b)上观察到的接触角分别为117°和<15°。
实施例13
用基于a)聚氨酯(Varathane),b)聚醚基硅烷封端的聚合物(Geniosil WP1)以及和c)溶剂基丙烯酸(Krylon晶体透明丙烯酸)的三种密封剂涂覆三块清洁的3003铝板。相对于所有三块板上的开路电位,在3.5%NaCl溶液中从-0.15mV至0.15mV进行极化电阻测试。对于聚氨酯、聚醚基硅烷封端的和丙烯酸基表面处理,耐腐蚀性分别测量为5.9x107欧姆、3.7x102欧姆和9.7x103欧姆。相比之下,在互连多孔陶瓷表面上进行极化电阻测试,该表面基于氧化锌和氧化铝的混合物且没有面漆,使用与实施例6中描述的程序类似的程序制备,并且发现为1.1x103欧姆。相比之下,三块清洁的3003铝板涂覆有基于氧化锌和氧化铝的混合物的互连多孔陶瓷表面。三块板再次涂覆有与上述相同的聚合物,即a)聚氨酯,b)聚醚基硅烷封端的聚合物,以及c)溶剂基丙烯酸。耐腐蚀性分别测量为1.4x108欧姆、1.4x107欧姆和1.0x107欧姆。
实施例14
三块清洁的3003铝板涂覆有基于氧化锰和氧化铝的混合物的互连多孔陶瓷表面(使用与实施例7中所述的程序类似的程序制备),并且进一步填充有基于以下的不同密封剂:a)聚氨酯(Varathane ultimate spar),b)水基聚丙烯酸(Minwax Polyacrylic),以及c)聚醚基硅烷封端的聚合物(Geniosil WP1)。测量耐腐蚀性并且发现为9.8x107欧姆、5.7x107欧姆和6.5x105欧姆。相比之下,对涂覆在清洁的3003铝板上的水基聚丙烯酸密封剂进行极化电阻测试,并且发现其为9.6x103欧姆。基于氧化锰和氧化铝的混合物的互连多孔陶瓷表面在清洁的3003铝板上的耐腐蚀性为1.7x104欧姆。实施例13中列出了裸铝板上的密封剂耐受性。
实施例15
两块清洁的3003铝板涂覆有基于氧化镁和氧化铝的混合物的互连多孔陶瓷表面(使用以与实施例1中所述的程序类似的程序制备)。板之一浸涂有水基Minwax聚丙烯酸表面处理剂,并保持在室温下,以使表面处理剂芯吸到表面内。对板进行极化电阻测试,并且发现耐腐蚀性为2.1x105欧姆。相比之下,发现以相同程序涂覆在清洁的3003铝板上的水基聚丙烯酸密封剂的耐腐蚀性为1.1x104欧姆。
实施例16
两块清洁的3003铝板涂覆有基于氧化锌和氧化铝的混合物的互连多孔陶瓷表面(使用以与实施例5中所述的程序类似的程序制备)。用气溶胶基聚氨酯密封剂(Varathane)喷涂样品之一,使其芯吸到表面中,并在室温下固化48小时。以类似的程序用气溶胶基聚氨酯表面处理剂涂覆另一块清洁的3003铝板。然后将所有三个样品按照ASTM G85-A3的方案在腐蚀环境中经受100小时的盐雾,并在用去离子(DI)水轻轻清洗,在DI水中超声处理10分钟并在室温下干燥一小时后成像。图4A-4C示出了所有三个样品上的腐蚀程度:a)用仅基于氧化锌和氧化铝的混合物的互连多孔陶瓷表面改性的板,b)用基于气溶胶的聚氨酯面漆涂覆的清洁3003铝板,以及c)用基于氧化锌和氧化铝的混合物的互连多孔陶瓷表面涂覆并填充有气溶胶基聚氨酯表面处理剂的板。与样品(b)不同,复合材料(c)防止了边缘周围的腐蚀。凹坑密度在图4A-4C中列出。
实施例17
两块清洁的3003铝板涂覆有基于氧化镁和氧化铝的混合物的互连多孔陶瓷表面(使用以与实施例1中所述的程序类似的程序制备)。将样品之一浸入水基聚丙烯酸密封剂(Minwax聚丙烯酸)中,使其芯吸到表面中,并在室温下固化24小时。另一块清洁的3003铝板涂覆有水基聚丙烯酸密封剂作为对照。然后按照ASTM D3359的方案对所有三个样品进行交叉影线粘附测试。图5A-5C示出了所有三个样品上的相应涂层的分层程度:a)涂覆有基于氧化镁和氧化铝的混合物的互连多孔陶瓷表面的板(ASTM等级:5B),b)涂覆有水基聚丙烯酸密封剂的3003铝板(ASTM等级:1B),和c)涂覆有基于氧化镁和氧化铝的混合物的互连多孔陶瓷表面并填充有水基聚丙烯酸密封剂的板(5B)。陶瓷改善了聚合物的粘合性能。
实施例18
清洁的3003铝板涂覆有基于氧化锌和氧化铝的混合物的互连多孔陶瓷表面(使用以与实施例5中所述的程序类似的程序制备)。随后,用丙烯酸基密封剂喷涂样品,并在室温下干燥24小时。然后按照ASTM D3363方法的方案对样品进行铅笔硬度测试,并且发现刮痕和圆凿硬度分别为HB和4H。相比之下,根据上述程序用丙烯酸基面漆喷涂、干燥的清洁的3003铝板的刮痕和圆凿硬度分别为5B和3B。
实施例19
清洁的3003铝板涂覆有基于氧化锌和氧化铝的混合物的互连多孔陶瓷表面(使用以与实施例5中所述的程序类似的程序制备)。随后,具有清洁的3003铝板的样品涂覆有丙烯酸基密封剂,并且目视检查两个样品的任何涂层缺陷。如图6A-6B所示,在涂覆有丙烯酸基密封剂的清洁的3003铝板上观察到流挂(图6A),而在涂覆有互连多孔陶瓷表面且然后填充有丙烯酸基密封剂的板上没有缺陷(图6B)。在涂覆有丙烯酸基密封剂的清洁的3003铝板上观察到流挂,而在涂覆有互连多孔陶瓷表面且然后填充有丙烯酸基密封剂的板上没有缺陷。
实施例20
将环氧基树脂滴在清洁的3003铝板的表面上,并测量接触角随时间的进展(样品A)。相比之下,清洁的3003铝板涂覆有基于氧化锌和氧化铝的混合物的互连多孔陶瓷表面,使用与实施例5中所述的程序类似的程序制备,并且测量接触角随时间的进展(样品B)。另一块清洁的3003铝板涂覆有基于氧化锰和氧化铝的混合物的互连多孔陶瓷表面,使用与实施例7中所述的程序类似的程序制备,并且按照相同的前述方案,通过测量相对于环氧基树脂(样品C)接触角随时间的进展来检查自流平特性。图7A-7C示出了所有三块板的自流平现象比较。
实施例21
两块清洁的3003铝板涂覆有基于氧化锌/氧化铝和氧化锰/氧化铝的混合物的互连多孔陶瓷表面(分别使用与实施例5和7中描述的程序类似的程序制备)。使用一滴水基聚丙烯酸表面处理剂在两块板上进行接触角测量,并且发现分别为大约57°和<15°。为了比较展示自流平现象,如图8所示,水基聚丙烯酸表面处理剂在清洁的3003铝板上的接触角为73°。
实施例22
两块清洁的3003铝板(2X 4in2)涂覆有基于氧化锌/氧化铝和氧化锰/氧化铝的混合物的互连多孔陶瓷表面(分别使用与实施例5和7中描述的程序类似的程序制备)。将180mg的熔点低于70℃的石蜡滴在保持在100℃的热板上的每个样品的中部,以检查芯吸行为。相比之下,也将180mg石蜡滴在清洁的3003Al板的中部,该板也保持在100℃的热板上。图9展示了所有样品的比较和5分钟后在样品上实现的石蜡聚合。使用ImageJ的目标功能区域确定每个样品上的石蜡覆盖面积%,并且测得锌/铝基表面为93.1%,锰/铝基表面为66.4%并且3003铝板为23.5%。图10展示了石蜡在所有三种基材上的芯吸行为。在锌/铝基陶瓷表面中,石蜡也能够通过边缘芯吸到板的背面。在板的背面上测量石蜡从边缘的渗透,并且在背面朝向样品的中部大约2mm。
实施例23
厚度为约3厘米的钎焊铝热交换器涂覆有基于氧化锰和氧化铝的无粘结剂结构陶瓷材料(使用与实施例7中所述的程序类似的程序制备)。将样品在干燥烘箱中加热,然后在两侧喷涂热石蜡。通过结构化陶瓷层向内芯吸蜡,产生比没有结构化陶瓷材料的热交换器更均匀涂覆的部件。
实施例24
两块清洁的3003铝板涂覆有基于氧化锰和氧化铝的混合物的互连多孔陶瓷表面(使用以与实施例7中所述的程序类似的程序制备)。将分散在乙酸正丁酯中的200μL的2重量%聚硅氮烷(Durazane 1500)溶液滴铸在互连多孔陶瓷涂覆的铝板(板A)上和另外的裸露的未涂覆的3003铝板(板B)上。按照类似的程序,将200μL的20重量%聚硅氮烷溶液滴铸在另一个互连多孔陶瓷涂覆的铝板(板C)上和另外的裸露的未涂覆的3003铝板(板D)上。蒸发溶剂,直至所有四个样品完全干燥并在200℃下固化8小时。使用2μL的DI水滴在所有板上进行接触角测量。板A、板B、板C和板D的测量接触角分别为141°、97°、150°和81°。然后按照ASTM D3363方法的方案对样品进行铅笔硬度测试,并且测量划痕和圆凿硬度并发现板A的划痕和圆凿硬度为4B和3H,板B的划痕和圆凿硬度为2B和2H,板C的划痕和圆凿硬度为4B和4H,并且板D的划痕和圆凿硬度为2B和5H。
实施例25
按照与实施例24中所述的程序类似的程序,用2重量%(板E)和20重量%(板G)的Durazane 1800基制剂涂覆并固化两块互连多孔陶瓷涂覆的铝板。用2重量%(板F)和20重量%(板H)的Durazane 1800基制剂涂覆并固化另外两块裸露的未涂覆的3003铝板。使用2μL的DI水滴在所有板上进行接触角测量。板E、板F、板G和板H的测量接触角分别为141°、87°、108°和75°。然后按照ASTM D3363方法的方案对样品进行铅笔硬度测试,并且测量划痕和圆凿硬度并发现板E的划痕和圆凿硬度为HB和3H,板F的划痕和圆凿硬度为H和4H,板G的划痕和圆凿硬度为2H和5H,并且板H的划痕和圆凿硬度为3HB和6H。
实施例26
用基于氧化锌的互连多孔陶瓷涂层涂覆乙酸纤维素薄膜。使用过硫酸钾的稀释水溶液氧化该膜。然后使用与上述实施例中描述的方法类似的方法,用氧化锌基互连多孔陶瓷表面改性剂涂覆该膜。通过线性4点探针测量所测量的乙酸纤维素裸膜的电阻超出仪器的范围(大于10^10欧姆)。氧化锌涂覆的乙酸纤维素膜经测量具有约10^6至约10^7欧姆的电阻。在用互连的多孔氧化锌陶瓷层涂覆该膜后,膜的电阻降低。
尽管出于清楚理解的目的,已经通过说明和实施例的方式相当详细地描述了前述发明,但是对于本领域技术人员显而易见的是,在不脱离本发明的精神和范围的情况下,可以实施某些改变和修改。因此,该描述不应被解释为限制本发明的范围。
本文所引用的所有出版物、专利和专利申请均出于所有目的以引用的方式整体并入本文中,并且并入的程度如同每个单独的出版物、专利或专利申请被具体地和单独地以引用的方式并入本文中一般。
Claims (31)
1.一种组合物,其包含:
(i)复合材料,所述复合材料包括:
浸渍到多孔陶瓷材料中的聚合物、蜡和/或树脂,
其中所述多孔陶瓷材料包括陶瓷的互连网络和至少部分填充有所述聚合物、蜡和/或树脂的可及孔隙体积;
和
(ii)基材,
其中所述复合材料与所述基材接触。
2.根据权利要求1所述的组合物,其中所述基材和所述陶瓷材料各自包含原生金属,并且其中所述陶瓷材料中的所述原生金属不同于所述基材中的所述原生金属。
3.根据权利要求1所述的组合物,其中所述复合材料包含约1微米至约100微米的厚度。
4.根据权利要求1所述的组合物,其中所述复合材料中总陶瓷含量的至少约20质量%是互连的。
5.根据权利要求1所述的组合物,其中陶瓷材料的所述互连网络大于约10平方微米。
6.根据权利要求1所述的组合物,其中所述复合材料包含多个陶瓷材料的互连网络。
7.根据权利要求6所述的组合物,其中所述多个陶瓷材料的互连网络内的陶瓷材料的互连网络的中值面积大于约10平方微米。
8.根据权利要求1至7中任一项所述的组合物,其中所述陶瓷材料包括稀土元素、过渡金属元素、碱土金属元素或铝。
9.根据权利要求1至7中任一项权利要求所述的组合物,其中所述陶瓷材料包括氧化物、氢氧化物和/或层状双氢氧化物。
10.根据权利要求9所述的组合物,其中所述氧化物、氢氧化物和/或层状双氢氧化物包括铁、铝、镁、铈、锌、锰、钛、铬、镍、钴、铜、银、钽、钨、硅、磷、锡、钒、锆、钙、钡或铕。
11.根据权利要求1至7中任一项所述的组合物,其中所述基材包括铝合金、钢合金、镍合金、钛合金、聚合物、纤维素材料、多糖、木材、棉花或玻璃。
12.根据权利要求1至7中任一项所述的组合物,其中与在相同基材上不包括所述聚合物、树脂和/或蜡的相同陶瓷材料相比,所述聚合物、蜡和/或树脂赋予一种或多种选自以下的功能特性:增强的硬度、弹性、粘弹性、粘附性、热性质、美学外观、拒液性和耐腐蚀性。
13.根据权利要求1至7中任一项所述的组合物,其中所述陶瓷材料是无粘结剂陶瓷材料。
14.根据权利要求1至7中任一项所述的组合物,其中所述聚合物、蜡和/或树脂包括衍生自桐油、亚麻子油、核桃油、天然橡胶、纤维素或壳多糖的聚合物。
15.根据权利要求1至7中任一项所述的组合物,其中所述聚合物、蜡和/或树脂包括聚乙烯、聚丙烯、聚苯乙烯、聚四氟乙烯、聚对苯二甲酸乙二酯、聚丙烯酸酯、聚(甲基丙烯酸甲酯)、聚乙酸乙烯酯、聚醚、聚氯丁二烯、聚(氯乙烯)、聚氨酯、聚酰胺、聚酰亚胺、硅氧树脂、聚(二甲基硅氧烷)或聚环氧化物聚合物。
16.根据权利要求1至7中任一项所述的组合物,其中所述聚合物、蜡和/或树脂包括硅烷、硅酸盐、硅醇盐、聚硅氮烷、有机三乙氧基硅烷或有机三甲氧基硅烷。
17.根据权利要求16所述的组合物,其中所述聚合物、蜡和/或树脂包括甲基硅醇钾盐、硅酸钠、硅酸钾或甲基硅醇钠盐。
18.根据权利要求1至7中任一项所述的组合物,其中所述聚合物、蜡和/或树脂包括石油蜡、动物产生的蜡、植物衍生的蜡或矿物衍生的蜡。
19.根据权利要求18所述的组合物,其中所述聚合物、蜡和/或树脂包括石蜡、蜂蜡、羊毛脂、虫胶、棕榈蜡、加诺巴蜡、大豆蜡、地蜡或褐煤蜡。
20.根据权利要求1至7中任一项所述的组合物,其中所述聚合物、蜡和/或树脂包括选自以下各项的一种或多种附加添加剂:润滑剂、增塑剂、阻燃剂、染料、UV稳定剂、自由基清除剂和交联剂。
21.根据权利要求20所述的组合物,其中所述添加剂赋予所述复合材料一种或多种选自粘度、柔韧性、可燃性、颜色、UV稳定性、化学反应性和交联度的性质。
22.根据权利要求1至7中任一项所述的组合物,其中大于约1%的所述可及孔隙体积填充有所述聚合物、蜡和/或树脂,如通过水银孔隙率测定法测试所确定。
23.根据权利要求1至7中任一项所述的组合物,其中所述聚合物、树脂和/或蜡的厚度小于所述陶瓷材料的厚度的约1.5倍。
24.根据权利要求1至7中任一项所述的组合物,其中所述陶瓷材料与所述聚合物、蜡和/或树脂材料相互作用,从而与当将所述聚合物、蜡和/或树脂直接施加至不包含所述陶瓷材料的相同基材时的交联速率和/或交联度相比,增加所述聚合物、蜡和/或树脂的交联速率和/或交联度。
25.根据权利要求1至7中任一项所述的组合物,其中所述陶瓷材料与所述聚合物、蜡和/或树脂材料相互作用,从而与当将所述聚合物、蜡和/或树脂材料直接施加至不包含所述陶瓷材料的相同基材时的结晶度相比,增加所述聚合物、蜡和/或树脂材料的结晶度。
26.根据权利要求1至7中任一项所述的组合物,其中所述陶瓷材料与所述聚合物、蜡和/或树脂材料相互作用,从而与直接施加至不包含所述陶瓷材料的相同基材上的所述聚合物、蜡和/或树脂材料的UV降解速率相比,降低所述聚合物、蜡和/或树脂材料的UV降解速率。
27.根据权利要求1至7中任一项所述的组合物,其中所述陶瓷材料包括镁、锰、氧化锌或氧化铝或氢氧化铝,并且所述聚合物、蜡和/或树脂包括干性油,诸如桐油或石蜡。
28.根据权利要求1至7中任一项所述的组合物,其中所述陶瓷材料包括镁、锰、氧化锌或氧化铝或氢氧化铝,并且所述聚合物、蜡和/或树脂与所述陶瓷材料发生化学反应以改变所述聚合物、蜡和/或树脂的性质。
29.根据权利要求28所述的组合物,其中改变所述聚合物、蜡和/或树脂的性质的所述化学反应包括交联、硬化和/或聚合。
30.根据权利要求1至7中任一项所述的组合物,其中施加所述复合材料以赋予所述基材以选自以下各项的一种或多种功能性质:对所述基材的腐蚀保护;用于粘附和/或结垢表面的耐久性改性剂;粘附促进或阻滞构造;触觉改性表面;拒液性应用;光学性质改变;机械改性,诸如硬度、弹性和粘弹性;表面和划痕自愈和修复目的;分离应用;电性质改变或电性质应用;冰、冷凝物和霜的减轻和/或改变;表面均匀性;缺陷减少;以及美学性质,并且
其中与在相同基材上没有所述聚合物、树脂和/或蜡的相同多孔陶瓷材料相比,或者与其上直接施加所述聚合物、树脂和/或蜡的相同基材相比,所述功能性质得到改善或具有更大量级。
31.根据权利要求1至7中任一项所述的组合物,其中所述复合材料包含大于所述复合材料的总体积的约40%的陶瓷体积浓度。
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PCT/US2019/065978 WO2020123804A1 (en) | 2018-12-12 | 2019-12-12 | Ceramic surface modification materials and methods of use thereof |
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US63/039,965 | 2020-06-16 | ||
PCT/US2020/064649 WO2021119514A1 (en) | 2019-12-12 | 2020-12-11 | Ceramic composite materials |
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