CN107108256B - 多孔钛酸盐化合物颗粒及其制造方法 - Google Patents
多孔钛酸盐化合物颗粒及其制造方法 Download PDFInfo
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- CN107108256B CN107108256B CN201580057757.7A CN201580057757A CN107108256B CN 107108256 B CN107108256 B CN 107108256B CN 201580057757 A CN201580057757 A CN 201580057757A CN 107108256 B CN107108256 B CN 107108256B
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- titanate compound
- compound particle
- porous
- particle
- porous titanate
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- 239000002245 particle Substances 0.000 title claims abstract description 79
- -1 titanate compound Chemical class 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 239000002783 friction material Substances 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 35
- 239000010936 titanium Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 229910052783 alkali metal Inorganic materials 0.000 claims description 17
- 150000001340 alkali metals Chemical class 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 239000008187 granular material Substances 0.000 claims description 8
- 229920001187 thermosetting polymer Polymers 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 description 41
- 239000000835 fiber Substances 0.000 description 20
- 239000002002 slurry Substances 0.000 description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- 238000009826 distribution Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 238000012790 confirmation Methods 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 238000001000 micrograph Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000012798 spherical particle Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000010425 asbestos Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910052895 riebeckite Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 241000224489 Amoeba Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910020288 Na2Ti6O13 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000007670 carcinogenicity Effects 0.000 description 2
- 231100000260 carcinogenicity Toxicity 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- OQRWAMBQGTYSRD-UHFFFAOYSA-N dipotassium;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[K+].[K+].[Ti+4].[Ti+4].[Ti+4].[Ti+4] OQRWAMBQGTYSRD-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 240000007762 Ficus drupacea Species 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000008264 cloud Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- DKKXQTSDXGEATA-UHFFFAOYSA-N dipotassium oxido-(oxido(oxo)titanio)oxy-oxotitanium Chemical compound [K+].[K+].[O-][Ti](=O)O[Ti]([O-])=O DKKXQTSDXGEATA-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
- F16D69/00—Friction linings; Attachment thereof; Selection of coacting friction substances or surfaces
- F16D69/02—Composition of linings ; Methods of manufacturing
- F16D69/025—Compositions based on an organic binder
- F16D69/026—Compositions based on an organic binder containing fibres
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/001—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62695—Granulation or pelletising
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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Abstract
提供一种在用于摩擦材料时能够赋予优异的抗衰减性的多孔钛酸盐化合物颗粒、含有该多孔钛酸盐化合物颗粒的树脂组合物和摩擦材料、以及多孔钛酸盐化合物颗粒的制造方法。多孔钛酸盐化合物颗粒通过钛酸盐化合物的晶粒结合而成,其特征在于,在孔径为0.01~1.0μm的范围的累计孔容在5%以上。
Description
技术领域
本发明涉及多孔钛酸盐化合物颗粒及其制造方法。
背景技术
各种车辆、产业机械等的制动***所使用的摩擦材料需求摩擦系数高且安定、抗衰减性优异、耐磨损性优异、刹车片攻击性低。为了满足这些特性,由石棉、无机充填材料、有机充填材料等、将它们结合的酚醛树脂等热固性树脂(结合剂)的树脂组合物作为摩擦材料被使用。
但是,对于石棉来说,已经确认了其致癌性,并且容易粉尘化,因而由于操作时吸入而引起的环境卫生方面的问题,其使用受到限制,从而提出了将作为代替品的纤维状钛酸钾等的钛酸钾作为摩擦调节材料使用的摩擦材料。特别是钛酸钾纤维不具有石棉那样的致癌性,不会像金属纤维那样损伤刹车片、摩擦特性也优异,但是现有的钛酸钾纤维大多平均纤维径为0.1~0.5μm、平均纤维长度为10~20μm,不包括在世界卫生组织(WHO)所推荐的范围内(作为吸入性纤维的WHO纤维:平均短径在3μm以下、平均纤维长度在5μm以上并且长径比在3以上的纤维状化合物以外)。因此,在专利文献1中提出了具有阿米巴形状的钛酸钾。
另一方面,摩擦材料的衰减现象是伴随摩擦材料的高温化使得摩擦材料中的有机成分气化、在与圆盘的摩擦界面形成气层而引起的现象,通过抑制摩擦界面形成气层,能够改善抗衰减性(fade resistance)。在这方面,提高摩擦材料的孔隙率、使气体容易从摩擦界面排出是有效的。作为提高摩擦材料的孔隙率的方法,可以考虑将对原料混合物进行粘接成型的工序中的成型压力调节设定为较低的值,但如果降低成型压力,摩擦材料的强度和耐磨损性就会降低,无法获得摩擦特性。因此,在专利文献2中,提出了通过将具有棒状、柱状、圆柱状、条状、粒状和/或板状的形状的钛酸碱金属颗粒结合而成的中空体构成的钛酸碱金属的中空体粉末。
现有技术文献
专利文献
专利文献1:国际公开WO2008-123046号公报
专利文献2:日本特开2009-114050号公报
发明内容
发明所要解决的课题
但是,在专利文献1所使用的钛酸钾中,存在包含微量的WHO纤维的可能性。专利文献2所使用的钛酸碱金属无法获得充分的抗衰减性。
本发明的目的在于提供一种在用于摩擦材料时能够赋予优异的抗衰减性的多孔钛酸盐化合物颗粒、含有该多孔钛酸盐化合物颗粒的树脂组合物和摩擦材料、以及多孔钛酸盐化合物颗粒的制造方法。
用于解决课题的方法
本发明提供以下的多孔钛酸盐化合物颗粒、含有该多孔钛酸盐化合物颗粒的树脂组合物和摩擦材料、以及多孔钛酸盐化合物颗粒的制造方法。
项1一种多孔钛酸盐化合物颗粒,其是钛酸盐化合物的晶粒结合而成的多孔钛酸盐化合物颗粒,孔径0.01~1.0μm的范围的累计孔容在5%以上。
项2如项1所述的多孔钛酸盐化合物颗粒,上述多孔钛酸盐化合物颗粒的平均粒径为5~500μm。
项3如项1或2所述的多孔钛酸盐化合物颗粒,上述钛酸盐化合物由组成式A2TinO(2n+1)[式中,A为选自碱金属中的1种或2种以上、n=2~8]表示。
项4一种含有项1~3中任一项所述的多孔钛酸盐化合物颗粒和热固性树脂的树脂组合物。
项5一种含有项4所述的树脂组合物的摩擦材料。
项6一种多孔钛酸盐化合物颗粒的制造方法,用于制造项1~3中任一项所述的多孔钛酸盐化合物颗粒,该制造方法包括:将钛源和碱金属盐以机械方式粉碎、准备粉碎混合物的工序;将上述粉碎混合物干式造粒、准备造粒物的工序;和对上述造粒物进行烧制的工序。发明效果
本发明的多孔钛酸盐化合物颗粒在用于摩擦材料时能够赋予优异的抗衰减性。
附图说明
图1是表示实施例1的多孔钛酸盐化合物颗粒的全体像的扫描电子显微镜照片。
图2是表示实施例1的多孔钛酸盐化合物颗粒的内部构造的扫描电子显微镜照片。
图3是表示实施例2的多孔钛酸盐化合物颗粒的全体像的扫描电子显微镜照片。
图4是表示实施例2的多孔钛酸盐化合物颗粒的内部构造的扫描电子显微镜照片。
图5是表示比较例1的钛酸盐化合物颗粒的全体像的扫描电子显微镜照片。
图6是表示比较例1的钛酸盐化合物颗粒的内部构造的扫描电子显微镜照片。
图7是表示比较例2的钛酸盐化合物颗粒的扫描电子显微镜照片。
具体实施方式
以下,对优选实施方式进行说明。但以下的实施方式仅仅是例示,本发明不限于以下的实施方式。
本发明的多孔钛酸盐化合物颗粒是钛酸盐化合物的晶粒通过烧结和/或熔接等结合而成的多孔钛酸盐化合物颗粒,孔径0.01~1.0μm的范围的累计孔容在5%以上。
在本发明中,上述累计孔容优选在10%以上,更优选在15%以上。上述累计孔容的优选的上限值为40%,更优选为30%。在上述累计孔容过小时,有时在用于摩擦材料时无法获得优异的抗衰减性。在上述累计孔容过大时,钛酸盐化合物的晶粒间的结合部分变弱,有时无法维持多孔结构。上述累计孔容可以通过水银压入法测定。
另外,本发明的多孔钛酸盐化合物颗粒的BET比表面积优选在1~13m2/g的范围内,更优选在3~9m2/g的范围内。上述BET比表面积过小时,有时在用于摩擦材料时无法获得优异的抗衰减性。上述BET比表面积过大时,有时烧制工序中的化学反应未完结。
本发明的多孔钛酸盐化合物颗粒的颗粒形状优选为球状、不定形状等粉末状,优选为非纤维状。特别优选为球状。
本发明的多孔钛酸盐化合物颗粒的颗粒尺寸没有特别限制,优选平均粒径为5~500μm、更优选为10~300μm。本发明中平均粒径意味着,通过在不进行利用了超声波的分散的激光衍射、散射法求出的粒度分布中,累计值50%时的粒径。这些各种颗粒形状和颗粒尺寸可以通过制造条件、特别是原料组成、烧制条件、粉碎处理条件等任意地控制。
作为钛酸盐化合物,可以列举组成式A2TinO(2n+1)[式中,A为选自碱金属中的1种或2种以上、n=2~8]、MxAyTi(2-y)O4[式中,M为除锂外的碱金属,A为选自锂、镁、锌、镍、铜、铁、铝、镓、锰中的1种或2种以上,x=0.5~1.0、y=0.25~1.0]、K0.5~0.8Li0.27Ti1.73O3.85~4、K0.2~0.8Mg0.4Ti1.6O3.7~4等所示的钛酸盐化合物。
在上述钛酸盐化合物中,优选组成式A2TinO(2n+1)[式中,A为选自碱金属中的1种或2种以上、n=2~8]所示的钛酸盐化合物,更优选组成式A2Ti6O13[式中,A为选自碱金属中的1种或2种以上]所示的钛酸盐化合物。作为碱金属,有锂、钠、钾、铷、铯、钫,其中,从在经济方面有利的观点出发,优选锂、钠、钾。进一步具体而言,可以例示Li2Ti6O13、K2Ti6O13、Na2Ti6O13等。
本发明的多孔钛酸盐化合物颗粒的制造方法只要能够获得上述的特性就没有特别限制,例如可以例示通过将钛源和碱金属盐以机械方式粉碎获得粉碎混合物、将该粉碎混合物干式造粒并进行烧制而制造的方法等。
作为机械方式的粉碎,可以列举一边给予物理撞击一边进行粉碎的方法。具体可以列举利用振动磨的粉碎。可以认为通过进行利用振动磨的粉碎处理,利用混合粉体的摩擦带来的剪切应力,原子排列的混乱和原子间距离的减少会同时发生,引起不同种颗粒的接点部分的原子移动,结果,得到亚稳相。由此,能够得到反应活性高的粉碎混合物,即使降低后述的烧制温度对粉碎混合物进行造粒,也能够减少未反应物。机械方式的粉碎能够以良好的效率对原料赋予剪切应力,因而优选不使用水或溶剂的干式处理。
机械方式的粉碎的处理时间没有特别限制,通常优选在0.1~2小时的范围内。
粉碎混合物的造粒可以利用不使用水和溶剂的干式造粒进行。干式造粒可以以公知的方法进行,例如可以例示转动造粒、流动层造粒、搅拌造粒等。关于湿式造粒,伴随着造粒物的干燥工序中造粒物内部的液态物的气化,结果得到内部具有大空洞的多孔颗粒,粉体强度降低,因而不优选。另外,为了使水和溶剂气化需要加热,批量生产性也差。
作为对造粒物进行烧制的温度,可以根据目的钛酸盐化合物的组成适当选择,优选为650~1000℃的范围,更优选为800~950℃的范围。烧制时间优选为0.5~8小时,更优选为2~6小时。
作为钛源,只要是含有钛元素、不阻碍通过烧制生成氧化物的原材料就没有特别限定,例如存在通过在空气中进行烧制而形成氧化钛的化合物等。作为这样的化合物,例如可以列举氧化钛、金红石矿石、氢氧化钛湿滤饼、含水氧化钛等,优选氧化钛。
作为碱金属盐,有碱金属的碳酸盐、碳酸氢盐、氢氧化物、乙酸盐等的有机酸盐、硫酸盐、硝酸盐等,优选盐酸盐。
钛源与碱金属盐的混合比可以根据目的钛酸盐化合物的组成适当选择。
本发明的多孔钛酸盐化合物颗粒由于如上所述,其孔径小,所以能够抑制热固性树脂浸渗入多孔颗粒内。因此,在将含有本发明的多孔钛酸盐化合物颗粒的树脂组合物作为摩擦材料使用时,该多孔颗粒成为衰减气体的漏孔。因此,可以认为即使将对原料混合物进行粘接成型的工序中的成型压力调节设定为较低值,也能够获得优异的抗衰减性。并且,本发明的多孔钛酸盐化合物颗粒不仅能够提高抗衰减性,还是非纤维形状的多孔体,因而也可以期待作为不含WHO纤维的摩擦调节材料。
本发明的树脂组合物的特征在于含有上述多孔钛酸盐化合物颗粒和热固性树脂。作为热固性树脂,可以从公知的热固性树脂中适当选择任意的树脂使用。例如可以列举酚醛树脂、甲醛树脂、三聚氰胺树脂、环氧树脂、丙烯酸树脂、芳香族聚酯树脂、尿素树脂等,可以将它们的1种单独使用或将2种以上组合使用。其中,优选酚醛树脂。
本发明的多孔钛酸盐化合物颗粒中,为了提高分散性、与热固性树脂的密合性等,可以按照常规方法利用硅烷偶联剂、钛酸酯系偶联剂等实施表面处理后使用。本发明的多孔钛酸盐化合物颗粒在树脂组合物中的含量没有特别限制,优选为树脂组合物整体的3~30质量%,更优选为5~25质量%。
本发明的树脂组合物可以用于需要耐磨损性的制品,特别适合用于各种车辆或产业机械的制动垫、制动衬垫、离合器成片等的摩擦材料。并且,从考虑对自然环境的影响的观点出发,本发明的树脂组合物即使不含铜粉末、铜纤维等铜,也能够获得优异的耐磨损性和抗衰减性。
在将本发明的树脂组合物用作摩擦材料的情况下,可以根据所需的特性,适当配合公知的纤维基材、摩擦调节剂等,在常温下以规定压力成型、接着以规定温度进行热成型、进行热处理和精加工处理,从而制成摩擦材料的成型体。
作为纤维基材,有芳纶纤维、丙烯酸纤维等的有机纤维、钢纤维、铜纤维等的金属纤维;玻璃纤维、岩纤维、陶瓷纤维、生物分解性纤维、生物体溶解性纤维、硅灰石纤维等的无机纤维;碳纤维等,可以将它们的1种单独使用或将2种以上组合使用。
作为摩擦调节剂,有硫化或未硫化的天然橡胶或合成橡胶、槚如树屑、树脂屑等有机粉末;合成石墨或天然石墨、炭黑、硫化锡、二硫化钼、三硫化锑、硫酸钡、碳酸钙、粘土、云母、滑石等无机粉末;铜、铝、锌、铁等金属粉末;氧化铝、二氧化硅、氧化镁、氧化锆(zironia)、氧化铬、二氧化钼、硅酸锆、氧化钛、氧化铁等氧化物粉末;除本发明的多孔钛酸盐化合物颗粒以外的球状、层状、板状、柱状、块状、不定形状等颗粒形状的钛酸盐化合物粉末等,可以将它们的1种单独使用或将2种以上组合使用。
实施例
以下,基于具体的实施例,对本发明进行更为详细的说明。本发明完全不限定于以下的实施例,在不改变其要点的范围内可以适当变更实施。
<钛酸盐化合物颗粒的制造>
(实施例1)
将以Ti:K=3:1(摩尔比)称量的氧化钛和碳酸钾在振动磨中边粉碎边混合10分钟。利用高速混合机对所得到的粉碎混合物进行干式造粒后,在电炉中以850℃烧制4小时,由此得到粉末。
利用X射线衍射测定装置(Rigaku Corporation生产、Ultima IV)确认所得到的粉末是K2Ti6O13的单相。利用激光衍射式粒度分布测定装置(岛津制作所生产、SALD-2100)确认平均粒径为169μm。
使用电场放出型扫描电子显微镜(SEM)(日立高新技术株式会社生产、S-4800)观察所得到的粉末地形状。图1表示颗粒的全体像的SEM照片、图2表示颗粒的内部构造的SEM照片。由图1和图2可知,所得到的粉末是微粒间具有小于1μm的微细空隙的球状颗粒。
使用水银孔隙度计(Quanta Chrome公司生产、PoreMaster 60-GT)测定所得到的粉末的细孔,处于0.01~1.0μm的孔径范围内的累计孔容为21.1%、细孔分布的极大值为0.11μm。
另外,对所得到的粉末测定BET比表面积,结果为5.9m2/g。
(实施例2)
将以Ti:Na=3:1(摩尔比)称量的氧化钛和碳酸钠在振动磨中边粉碎边混合10分钟。利用高速混合机对所得到的粉碎混合物进行干式造粒后,在电炉中以850℃烧制4小时,由此得到粉末。
所得到的粉末的评价与实施例1同样地进行。结果确认是Na2Ti6O13的单相、平均粒径为56μm、处于0.01~1.0μm的孔径范围内的累计孔容为24.0%、细孔分布的极大值为0.34μm的球状颗粒。
图3表示颗粒的全体像的SEM照片,图4表示颗粒的内部构造的SEM照片。
另外,对所得到的粉末测定BET比表面积,结果为4.4m2/g。
(实施例3)
通过使用3-氨基丙基三乙氧基硅烷的甲醇溶液对实施例1中得到的钛酸盐化合物颗粒进行表面处理,得到粉末。表面处理以3-氨基丙基三乙氧基硅烷相对于钛酸盐化合物颗粒100质量%为0.5质量%的量进行。
(比较例1)
如上所述操作,制造上述专利文献2所公开的中空状的钛酸盐化合物颗粒。
将以Ti:K=3:1(摩尔比)的量称量的氧化钛和碳酸钾在振动磨中边粉碎边混合10分钟。在电炉中以1050℃对所得到的粉碎混合物烧制4小时,将烧制物用粉碎机粉碎,得到平均短径1.9μm、平均长径3.1μm、平均长径比1.7的柱状粉末。
使用所得到的柱状粉末、乙基纤维素系粘合剂、聚羧酸铵盐制造浆料,对所得到的浆料进行喷雾干燥。接着以900℃对喷雾干燥而得到的粉末进行2小时热处理。
所得到的粉末的评价与实施例1同样地进行。结果确认是K2Ti6O13的单相、平均粒径为141μm、处于0.01~1.0μm的孔径范围内的累计孔容为2.8%、细孔分布的极大值为1.9μm的球状颗粒。图5表示颗粒的全体像的SEM照片、图6表示颗粒的内部构造的SEM照片。由图5和图6可知是具有大量1~5μm的空隙的中空状球状颗粒。
另外,对所得到的粉末测定BET比表面积,结果为0.6m2/g。
(比较例2)
将比较例1中得到的粉末用研钵粉碎,得到柱状粉末。图7表示颗粒的全体像的SEM照片。
(比较例3)
将以Ti:K:Li=1.73:0.8:0.27(摩尔比)的量称量的氧化钛、碳酸钾和碳酸锂按照常规方法混合,将原料混合物在振动磨中边粉碎边混合30分钟。在电炉中以1000℃对所得到的粉碎混合物烧制4小时后,将烧制物粉碎,由此得到粉末。使所得到的粉末分散在水中,制备10质量%的浆料。通过将该浆料的固态成分过滤分离、干燥,得到钛酸锂钾(K0.8Li027Ti1.73O4)。
将所得到的钛酸锂钾分散在调节为3.5质量%的硫酸溶液中,制备5质量%的浆料。将该浆料的固态成分过滤分离、水洗、干燥,由此得到钛酸(H2Ti2O5)。
将所得到的钛酸分散在调节为5.3质量%的氢氧化钾溶液中,制备10质量%浆料。将该浆料的固态成分过滤分离、水洗、干燥。在电炉中以500℃对该物质烧制3小时,由此得到粉末。
使用X射线衍射测定装置确认所得到的粉末是8钛酸钾(K2Ti8O17)。使用激光衍射式粒度分布测定装置确认平均粒径为9μm。使用SEM确认粉末的形状是板状颗粒。
(比较例4)
将以Ti:K:Li=1.73:0.8:0.27(摩尔比)的量称量的氧化钛、碳酸钾和碳酸锂按照常规方法混合,将原料混合物在振动磨中边粉碎边混合30分钟。将所得到的粉碎混合物在电炉中以1000℃烧制4小时后,将烧制物粉碎,由此得到粉末。将所得到的粉末分散在水中,制成10质量%的浆料,在添加酸。将该浆料的固态成分过滤分离、干燥。干燥后,在电炉中以600℃烧制1小时,由此得到粉末。
使用X射线衍射测定装置确认所得到的粉末是纤铁矿型层状结晶的钛酸锂钾(K0.7Li0.27Ti1.73O3.95)。使用激光衍射式粒度分布测定装置确认平均粒径为15μm。使用SEM确认粉末的形状是板状颗粒。
(比较例5)
将以Ti:K:Mg=4:2:1(摩尔比)的量称量的氧化钛、碳酸钾和氢氧化镁按照常规方法混合,将原料混合物在振动磨中边粉碎边混合30分钟。将所得到的粉碎混合物在电炉中以1000℃烧制4小时后,将烧制物粉碎,得到粉末。使所得到的粉末分散在水中,制成10质量%的浆料,再添加酸。将该浆料的固态成分过滤分离、干燥。干燥后,在电炉中以600℃烧制1小时,由此得到粉末。
使用X射线衍射测定装置确认所得到的粉末是纤铁矿型层状结晶的钛酸镁钾(K0.7Mg0.4Ti1.6O3.95)。使用激光衍射式粒度分布测定装置确认平均粒径为4μm。使用SEM确认粉末的形状是板状颗粒。
(比较例6)
将以Ti:K=1:1(摩尔比)的量称量的氧化钛和碳酸钾按照常规方法混合,将原料混合物在振动磨中边粉碎边混合30分钟。将所得到的粉碎混合物在电炉中以780℃烧制4小时后,将烧制物粉碎,由此得到2钛酸钾(K2Ti2O5)。
使所得到的2钛酸钾分散在水中,制备15质量%的浆料,再添加酸。将该浆料的固态成分过滤分离、干燥。干燥后,在电炉中以600℃烧制1小时,将烧制物用锤击磨粉碎,由此得到粉末。
使用X射线衍射测定装置确认所得到的粉末是7.9钛酸钾(K2Ti7.9O16.8)。使用激光衍射式粒度分布测定装置确认平均粒径为11μm。使用SEM确认粉末的形状是具有不定形的形状、具有多条突起沿着不规则的方向延伸的形状(阿米巴形状)的颗粒。
<摩擦材料的制造>
(实施例3)
按照表1所示的配合比率配合材料,在Loedige Mixer中混合后,对所得到的混合物进行预成型(25MPa)、热成型(150℃、20MPa),再以220℃进行热处理,制造盘式制动用垫片。
<摩擦材料的评价>
摩擦试验使用通用的全尺寸动态模型试验机,依据JASO C-406进行测试。摩擦材料的孔隙率依据JIS D4418通过在油中浸渗进行测定。将结果示于表1。
[表1]
如表1所示可知,使用了按照本发明的实施例1~3的多孔钛酸化合物颗粒的实施例3~11与使用了比较例1~6的钛酸盐化合物颗粒的比较例7~14相比,在衰减试验项目中制动10次中的最低摩擦系数(μ)高,无论是否含有铜粉末,都显示出优异的抗衰减性。
Claims (7)
1.一种多孔钛酸盐化合物颗粒,其特征在于:
该多孔钛酸盐化合物颗粒是组成式A2Ti6O13所示的钛酸盐化合物的晶粒结合而成,孔径0.01~1.0μm的范围的累计孔容在5%以上,
式中,A为选自碱金属中的1种或2种以上。
2.如权利要求1所述的多孔钛酸盐化合物颗粒,其特征在于:
所述多孔钛酸盐化合物颗粒的平均粒径为5~500μm。
3.一种树脂组合物,其特征在于:
含有权利要求1或2所述的多孔钛酸盐化合物颗粒、和热固性树脂。
4.一种摩擦材料,其特征在于:
含有权利要求3所述的树脂组合物。
5.一种多孔钛酸盐化合物颗粒的制造方法,用于制造钛酸盐化合物的晶粒结合而成的、孔径0.01~1.0μm的范围的累计孔容在5%以上的多孔钛酸盐化合物颗粒,该制造方法的特征在于,包括:
将钛源和碱金属盐以机械方式粉碎,准备粉碎混合物的工序;
对所述粉碎混合物进行干式造粒,准备造粒物的工序;和
对所述造粒物进行烧制的工序。
6.如权利要求5所述的多孔钛酸盐化合物颗粒的制造方法,其特征在于:
所述多孔钛酸盐化合物颗粒的平均粒径为5~500μm。
7.如权利要求5或6所述的多孔钛酸盐化合物颗粒的制造方法,其特征在于:
所述钛酸盐化合物由组成式A2TinO(2n+1)表示,
式中,A为选自碱金属中的1种或2种以上,n=2~8。
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JP6563676B2 (ja) * | 2015-04-27 | 2019-08-21 | 曙ブレーキ工業株式会社 | 摩擦材組成物および摩擦材とその製造方法 |
JP6630095B2 (ja) * | 2015-09-17 | 2020-01-15 | 曙ブレーキ工業株式会社 | 摩擦材組成物及び摩擦材 |
US10233988B2 (en) | 2015-09-23 | 2019-03-19 | Akebono Brake Industry Co., Ltd | Friction material |
CN108137341B (zh) * | 2015-09-24 | 2020-03-31 | 大塚化学株式会社 | 多孔质钛酸盐化合物颗粒及其制造方法 |
JP6713392B2 (ja) * | 2016-09-28 | 2020-06-24 | 大塚化学株式会社 | 樹脂組成物、これを用いた摩擦材、摩擦部材、及びドラムブレーキ用ブレーキシュー |
JP6898078B2 (ja) | 2016-11-01 | 2021-07-07 | 曙ブレーキ工業株式会社 | 摩擦材 |
US20190358135A1 (en) * | 2017-02-07 | 2019-11-28 | Otsuka Chemical Co., Ltd. | Cosmetic composition |
WO2018164028A1 (ja) * | 2017-03-08 | 2018-09-13 | 大塚化学株式会社 | 摩擦材組成物、摩擦材及び摩擦部材 |
KR102148795B1 (ko) * | 2017-05-30 | 2020-08-27 | 주식회사 엘지화학 | 티탄산칼륨 제조방법 |
CN108516580A (zh) * | 2018-04-16 | 2018-09-11 | 张家港大塚化学有限公司 | 多孔空心球状钛酸钠制备方法 |
CN108328651A (zh) * | 2018-04-16 | 2018-07-27 | 张家港大塚化学有限公司 | 多孔空心球状钛酸钾制备方法 |
CN112020533A (zh) * | 2018-04-17 | 2020-12-01 | 住友电木株式会社 | 钛酸盐改性酚醛树脂组合物的制造方法、钛酸盐改性酚醛树脂组合物、摩擦材料用酚醛树脂组合物和摩擦材料 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1730432A (zh) * | 2005-07-07 | 2006-02-08 | 南京工业大学 | 六钛酸钾晶须多孔材料的制备方法 |
CN101616869A (zh) * | 2007-03-02 | 2009-12-30 | 大塚化学株式会社 | 固着有碱金属钛酸盐的钛酸盐、其制造方法、以及含有固着有碱金属钛酸盐的钛酸盐的树脂组合物 |
CN101631747A (zh) * | 2007-04-04 | 2010-01-20 | 大塚化学株式会社 | 钛酸钾及其制造方法、以及摩擦材料和树脂组合物 |
CN101679067A (zh) * | 2007-03-29 | 2010-03-24 | 东邦钛株式会社 | 碱金属钛酸盐和碱金属钛酸盐空心体粉末及其制法、以及含有碱金属钛酸盐和碱金属钛酸盐空心体粉末的摩擦材料 |
CN102820459A (zh) * | 2012-07-20 | 2012-12-12 | 合肥国轩高科动力能源有限公司 | 一种介孔二氧化钛合成高比能钛酸锂材料的制备方法 |
CN102958844A (zh) * | 2010-07-02 | 2013-03-06 | 大塚化学株式会社 | 多孔质钛酸锂的制造方法、多孔质钛酸锂和使用其的锂电池 |
CN103342571A (zh) * | 2013-07-10 | 2013-10-09 | 武汉理工大学 | 六钛酸钾晶须隔热保温材料的制备方法 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3393276B2 (ja) * | 1995-06-14 | 2003-04-07 | 株式会社クボタ | 複合チタン化合物粉末およびその製造方法 |
JPH10139894A (ja) | 1996-11-07 | 1998-05-26 | Kubota Corp | 耐フェード性にすぐれたブレーキ用摩擦材 |
TWI243169B (en) * | 1998-03-02 | 2005-11-11 | Nissan Chemical Ind Ltd | Optically active epoxy compound |
PL2098493T3 (pl) * | 2006-12-27 | 2017-03-31 | Hitachi Metals, Ltd. | Sposób wytwarzania ceramicznej struktury typu plastra miodu na bazie tytanianu glinu |
JP5261757B2 (ja) | 2007-06-08 | 2013-08-14 | 大塚化学株式会社 | 六チタン酸ナトリウム及びその製造方法 |
JP2009114050A (ja) * | 2007-10-15 | 2009-05-28 | Toho Titanium Co Ltd | チタン酸アルカリの中空体粉末及びその製造方法、並びにこれを含む摩擦材 |
CN101597476B (zh) | 2008-06-05 | 2014-04-30 | 比亚迪股份有限公司 | 一种微孔摩擦材料及其制备方法 |
JP5284400B2 (ja) * | 2011-03-18 | 2013-09-11 | 株式会社田中化学研究所 | カーボン複合チタン酸リチウム、その製造方法、非水電解質電池用活物質、及び非水電解質電池 |
JP6053325B2 (ja) | 2012-05-22 | 2016-12-27 | スリーエム イノベイティブ プロパティズ カンパニー | 焼成物、金属イオン吸着材、金属イオンの除去方法、及び金属イオン除去設備 |
EP3006403A4 (en) * | 2013-06-04 | 2017-01-25 | Ishihara Sangyo Kaisha, Ltd. | Lithium titanate, production method for same, and electrical storage device employing same |
-
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Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1730432A (zh) * | 2005-07-07 | 2006-02-08 | 南京工业大学 | 六钛酸钾晶须多孔材料的制备方法 |
CN101616869A (zh) * | 2007-03-02 | 2009-12-30 | 大塚化学株式会社 | 固着有碱金属钛酸盐的钛酸盐、其制造方法、以及含有固着有碱金属钛酸盐的钛酸盐的树脂组合物 |
CN101679067A (zh) * | 2007-03-29 | 2010-03-24 | 东邦钛株式会社 | 碱金属钛酸盐和碱金属钛酸盐空心体粉末及其制法、以及含有碱金属钛酸盐和碱金属钛酸盐空心体粉末的摩擦材料 |
CN101631747A (zh) * | 2007-04-04 | 2010-01-20 | 大塚化学株式会社 | 钛酸钾及其制造方法、以及摩擦材料和树脂组合物 |
CN102958844A (zh) * | 2010-07-02 | 2013-03-06 | 大塚化学株式会社 | 多孔质钛酸锂的制造方法、多孔质钛酸锂和使用其的锂电池 |
CN102820459A (zh) * | 2012-07-20 | 2012-12-12 | 合肥国轩高科动力能源有限公司 | 一种介孔二氧化钛合成高比能钛酸锂材料的制备方法 |
CN103342571A (zh) * | 2013-07-10 | 2013-10-09 | 武汉理工大学 | 六钛酸钾晶须隔热保温材料的制备方法 |
Non-Patent Citations (2)
Title |
---|
Alkali hexatitanates-A2Ti6O13(A = Na, K) as host structure for reversible lithium insertion;R.Dominko等;《Journal of Power Sources》;20070630;第174卷;第1172-1176页 * |
钛酸钾晶须研究现状及发展前景;景晓明等;《西南民族大学学报·自然科学版》;20080630;第34卷(第3期);第539-544页 * |
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JP6030277B2 (ja) | 2016-11-24 |
KR20170058986A (ko) | 2017-05-29 |
JPWO2016063688A1 (ja) | 2017-04-27 |
EP3210941B1 (en) | 2019-05-08 |
CN107108256A (zh) | 2017-08-29 |
US10106464B2 (en) | 2018-10-23 |
EP3210941A4 (en) | 2018-07-04 |
CA2959845C (en) | 2019-03-05 |
TWI631078B (zh) | 2018-08-01 |
CA2959845A1 (en) | 2016-04-28 |
EP3210941A1 (en) | 2017-08-30 |
MX2017004616A (es) | 2017-07-10 |
US20170291855A1 (en) | 2017-10-12 |
BR112017007544A2 (pt) | 2017-12-19 |
TW201619060A (zh) | 2016-06-01 |
KR101902720B1 (ko) | 2018-09-28 |
WO2016063688A1 (ja) | 2016-04-28 |
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