CN1031701C - Reflector and reflection road-sign contg. transparent non-vitreous zirconia microspheres - Google Patents
Reflector and reflection road-sign contg. transparent non-vitreous zirconia microspheres Download PDFInfo
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- CN1031701C CN1031701C CN90107390A CN90107390A CN1031701C CN 1031701 C CN1031701 C CN 1031701C CN 90107390 A CN90107390 A CN 90107390A CN 90107390 A CN90107390 A CN 90107390A CN 1031701 C CN1031701 C CN 1031701C
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- microsphere
- oxide
- zirconium white
- sheet material
- microspheres
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000004005 microsphere Substances 0.000 title abstract description 145
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000919 ceramic Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 28
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 20
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 19
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims description 26
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229960001866 silicon dioxide Drugs 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 28
- 235000019483 Peanut oil Nutrition 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 8
- 239000000312 peanut oil Substances 0.000 abstract description 8
- 239000000654 additive Substances 0.000 abstract description 7
- 230000000996 additive effect Effects 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001879 gelation Methods 0.000 abstract description 2
- 150000007942 carboxylates Chemical class 0.000 abstract 1
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 abstract 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 32
- 239000002245 particle Substances 0.000 description 20
- 229910004298 SiO 2 Inorganic materials 0.000 description 18
- 239000010410 layer Substances 0.000 description 18
- 238000000605 extraction Methods 0.000 description 16
- 239000011521 glass Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 11
- 229910052726 zirconium Inorganic materials 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 238000010304 firing Methods 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 235000019198 oils Nutrition 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000011324 bead Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- -1 pottery Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 235000019580 granularity Nutrition 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- 238000003980 solgel method Methods 0.000 description 5
- 150000003755 zirconium compounds Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000001246 colloidal dispersion Methods 0.000 description 4
- 239000011222 crystalline ceramic Substances 0.000 description 4
- 229910002106 crystalline ceramic Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000002310 reflectometry Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 241000490567 Pinctada Species 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000011224 oxide ceramic Substances 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 241001014698 Phacoides Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 239000010987 cubic zirconia Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000012780 transparent material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- OAKURXIZZOAYBC-UHFFFAOYSA-N 3-oxopropanoic acid Chemical compound OC(=O)CC=O OAKURXIZZOAYBC-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004821 Contact adhesive Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 238000005848 Knoop reaction Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- ZPRWYEFEBXYEEJ-UHFFFAOYSA-K aluminum formaldehyde triacetate Chemical compound C(C)(=O)[O-].[Al+3].C=O.C(C)(=O)[O-].C(C)(=O)[O-] ZPRWYEFEBXYEEJ-UHFFFAOYSA-K 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical group O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000010499 rapseed oil Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000003763 resistance to breakage Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010496 thistle oil Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Solid, transparent, non-vitreous, zirconia and zirconia-silica ceramic microspheres, useful as lens elements in retroreflective pavement markings. The microspheres are characterized by: (a) containing at least one additive metal oxide selected from alumina, magnesia, yttria and mixtures thereof; (b) an index of refraction greater than 1.6; and (c) being virtually free of cracks. These microspheres are formed by a sol-gel technique of extractive gelation (extracting carboxylic acid away from zirconyl carboxylate) of a sol in liquid medium such as hot peanut oil.
Description
The present invention relates to microsphere ceramic as making with Zirconia-alumina-aktivton and so on material.It also relates to the road sign industrial circle that comprises the transparent beads body that is used to do reflecrtive mark.On the other hand, it also relates to the method for preparing this ceramic.
Road sign industry is for a long time one to the transparent solid microsphere of expecting brighter and more competent mirror portion or thin pearl.The transparent beads body that is widely used as most now road sign all be some glass from system, these glass all are the transparent materials of non-crystalline state.General these glass all are soda lime systems, and specific refractory power is only about 1.5, and this specific refractory power has limited their reflecting brightness.4,367, proposed to improve weather resistance in No. 919 United States Patent (USP)s and had the more glass microspheres of high refractive index.
3,709, No. 706 United States Patent (USP)s have proposed a profit from the compound of silicon-dioxide and the zirconium crystalline ceramics microsphere with the sol-gel method preparation.In general, sol-gel method is the method that a kind of colloidal dispersions, colloidal sol, water-sol with metal oxide (or their parent) is transformed into gel.Gel is such one sharp state of matter, and wherein to a certain degree chemistry or the physical crosslinking formation that reaches three-dimensional network take place for a profit or various ingredients.The formation of this network causes the increase of mixture viscosity, and causes the machinery location of liquid phase in this network.Usually carry out after this gelling operation dry and continue calcining to obtain stupalith.
In order to guarantee that the microsphere optically focused that protrudes road sign is not partly covered by the dust on the road, the microsphere average diameter that is used for road sign is between about 100～1000 microns.
Be used to transparent beads body specific refractory power as the such reflector of landmarks board between about 1.5～2.5.Under drying conditions, at least 1.7 specific refractory power (N
D) just can provide good reflectivity, (best N
DBe 1.9), if require wet reflection, some or all of microspheres should have 2.2 specific refractory power at least.
At zirconium white-silicon oxide (ZrO
2-SiO
2) in the ceramic microspheres, for known to us, we believe that zirconium white is to give toughness, the component of weather resistance, intensity and high refractive index.But, work as ZrO
2To SiO
2Mol ratio be increased to far above 1.3: 1 o'clock, will cause that in the course of processing microsphere disruptive increases.
The objective of the invention is: 1) a kind of ceramic microspheres is provided, and it is not only transparent, and can make macrobead (greater than 100 microns), has specific refractory power and high scratch resistance, shatter-resistant and resistance to rupture greater than 1.6; 2) providing a kind of does not crack or the reliable method of this kind of production microsphere of inclusion.
The invention provides novel transparent solid ceramic particle (thin pearl or microsphere), they can make have enough transparencies, specific refractory power and other performance so that make it be used as senior phacoid in the reflector marker.This new ceramics particle can be summarized as follows
A kind of spheres of ceramic of non-vitreous densification of flawless substantially solid transparent has greater than 1.6 specific refractory power and comprises zirconium white and at least a other metal oxide, and this metal oxide is selected from one group by aluminum oxide (Al
2O
3), magnesium oxide (MgO), yttrium oxide (Y
2O
3) and their mixture.Oxide compound contains in those spheroids of silicon oxide in forming, zirconium white to the mol ratio of silicon oxide greater than 1.8, be preferably greater than 2.0, be more preferably greater than 2.2.
Another aspect of the present invention comprises identical solid-state, transparent, the non-vitrified spheres of ceramic with narration just now; if just in conjunction with 30% of weight, they can contain the silicon oxide to the arbitrary ratio of zirconium white to the weight of other metal oxide of bonded greater than zirconium white in the spheroid and silicon oxide.
Usually, zirconium white to the ratio of the total mole number of other metal oxide component in 1.0: 0.005 to 1.0: 5.0 scopes.
By in zirconium white, adding these other metal oxide or additives, prepared complete the crystalline ceramics spheroid or the microsphere of the macrobead (diameter is greater than 125 microns) of zirconium white-magnesium oxide, Zirconia-alumina-magnesium oxide, Zirconia-alumina-silicon oxide, zirconium white-silicon oxide-magnesium oxide, Zirconia-alumina-silicon oxide-yttrium oxide, Zirconia-alumina-magnesium oxide-silicon oxide, zirconium white-silicon oxide-yttrium oxide and zirconium white-yttrium oxide.In most of the cases, zirconium white is main (by volume) phase.The use of additive metal oxide reduces (for example to improve specific refractory power silica content in zirconium white-silicon oxide ceramics microsphere, bring up to greater than 1.83), and after burning till, do not crack or the reduction of transparency, otherwise under big like this size, will crack or transparent reduction.Under the microsphere situation of big like this (diameter is greater than 125 microns), as above represented not restriction of content to silicon oxide in this sharp spheroid.
Other composition that may comprise in the present composition has: 1) fusing assistant, and as B
2O
3, Na
2O, K
2O and P
2O
5With 2) other colloidal state or other oxide compound of state, as Cr
2O
3, CaO, NiO, TiO
2, SnO
2And Fe
2O
3
As used in describing at this; the meaning of " solid " speech is meant a kind of particle or entity, and it is not hollow, does not for example promptly exist about 4 of ceramic metal oxide micro-capsule; any essence cave defective in the microballoon of narrating in 349, No. 456 United States Patent (USP)s.
In the narration of this case, " non-vitrified " speech meaning is that this pottery is not that the liquid state that at high temperature produces from molten state or raw mix obtains.Purpose with this speech is to make ceramic microspheres of the present invention to be different from the granulated glass sphere made from scorification.
In the discussion of this case, " transparent " speech meaning is this spheres of ceramic, when opticmicroscope (for example under 100 times) is observed down, performance with visible light transmissive ray, when the result is dipped in specific refractory power and the approximately equalised oil of microsphere as the object both that microsphere is identical with a kind of character, can know the object of seeing below it by this microsphere, though this oil should have and the approximately equalised specific refractory power of this microsphere, can not be too near so that this microballon body as if disappear (when their specific refractory power equates fully).Clearly pick out profile, periphery or the edge of the object below this microsphere with this opticmicroscope.
Microsphere of the present invention can be made into fine and close fully." fully fine and close " speech meaning refers to by standard method of analysis, as B.E.T. nitrogen method (based on from gas that sample contacts the N that absorbs
2Molecule) analyze and to draw, it is near theoretical density, and does not have the open pores defective substantially.Can be with the surface area data (as meters squared per gram) of this unit weight sample that measures the surface-area of the desirable microsphere unit weight identical with a large amount of globule sizes compare and measure open porosity.High more surface imperfection degree and/or the porosity of meaning of unit surface (meters squared per gram) is high more.This measurement can be carried out on the Quantasorb equipment that the Quantachrome of New York Syossett company produces.Density measurement can carry out with air or water specific gravity hydrometer.
Microsphere of the present invention can be real globular, but also can be oblate spheroid shape or prolate shape.The general also available following character of best ceramic microspheres is given expression: average hardness is greater than the hardness of road surface sand; Have the toughness, resistance to crushing, sphericity and the reflectivity that are equal to or greater than the granulated glass sphere that has same particle size and about 1.5 specific refractory poweres usually; And has a specific refractory power between about 1.8 to 2.2.Obtained greater than known ceramics microsphere (for example, ZrO
2-SiO
2) resistance to crushing and brightness, and greater than the average hardness of known vitreosol-gel ceramic microspheres.Microsphere of the present invention also has subsurface defect and the impurity littler than the glass microballon of common identical size.
The present invention also provides a kind of sol-gel method of producing ceramic microspheres of the present invention.One sharp improved sol-gel method is extraction heat gelling process (is different from dehydration gelling process), and in the method, carboxylic acid (for example acetate) caused by extracting from carboxylic acid oxygen zirconium in the gelling of smart glue.When producing ceramic particle with the extraction heat gelling process, this carboxylic acid oxygen zirconium is the parent of the zirconium white component of ceramic particle of the present invention.This extraction agent is a kind of such liquid medium of oil that resembles.Rapid gelling takes place by losing acid in spissated zirconyl acetate collosol intermixture, just can produce the agglomerative microballon in this colloidal sol in the time about several minutes.Sneak in the soluble salt, in some cases when additive metal oxide, sneak in the colloidal dispersion, in the time of in thin pearl oyster liquid solution or the colloidal sol, at the agglomerative microsphere dry and burn till during, they play the disruptive effect that prevents." the not thin pearl of sintering " of this novel composition taken out from extraction agent with standard method, carry out drying and burn till (for example, under 900～1350 ℃)
This method provides the flawless sintered ceramic particle of the large size (diameter is greater than 125 microns) of the over-all properties with the not available reflecting brightness of known glass microsphere and weather resistance.This sol-gel method also has than the lower processing temperature of glass microsphere shaping processing, makes that thus production unit weight product energy expenditure is less.
When additive metal oxide is aluminum oxide, can observe than not containing Al
2O
3Or the gelling of the easier generation extraction heat of carboxylic acid oxygen zirconium system of its parent.
Ceramic microspheres of the present invention not only is used as the road sign material, and is used for others, as: blasting materials (because cause of their toughness); The high temperature spot contact bearing; As make filler and toughener in the materials such as glass, refractory materials, pottery, metal_based material and polymkeric substance; Reflector; Medium with the runner milling that is used to resemble sand milling and so on.Ceramic microspheres of the present invention can grind efflorescence, and the particulate product can be used as abrasive material.After particle was reduced, the particles no longer that obtains was a globular, and is irregularly shaped.
The glass microspheres as tamper in the prior art generally has evenly, the successive glass structure; and there is not crystallization (being often referred to the degree of crystallinity that has less than 5%) substantially; and microsphere of the present invention have again divide or grain pattern character; and comprise the particle or the crystal of many amorphousness resistatess that resemble colloidal silica particles and so on, in the colloidal sol of this colloidal silica particles from preparation microsphere of the present invention.
Will be below " particle " speech as the collective term of zone in microcrystallite in the crystalline material and the non-crystalline material or colloidal particles.In order to obtain best reflecting brightness, the particulate size in this microsphere preferably is not more than 1000 dusts (microcrystal is generally 50～400 dusts, and 150 dusts are following better), so that make granular boundary narrow down to minimum degree to the influence of scattering of light.(for example, crystal ZrO when particularly refringence is big between the two-phase
2And Al
2O
3With non-crystalline state SiO
2).In order to make scattering of light narrow down to minimum value, the overall dimension of the crystallite of light transmitting material is preferably less than 1/4th of transmitted light wavelength.1000 dusts be enough to be lower than about 5500 dusts the visible light mean wavelength 1/4th.The crystallite granularity that as if the best microsphere of invention have feature, its about 100～150 dusts, and as if the size-grade distribution of this crystallite than other vitreosol-gel micro-ball body (for example, ZrO
2-SiO
2) more even.
By being burnt till, agglomerative microsphere parent is fine and close state, avoided the space in the microsphere of the present invention ideally, thus, improved transparency, avoided (for example owing to freeze-dissolve circulation occurs) structure crack caused rapid wear effect and avoided making moisture or other liquid-absorbent of this microsphere degradation.
Ceramic particle of the present invention with the colloidal sol production that contains silicon oxide has a non-crystalline state silicon oxide phase.Most of metal oxides form polycrystalline or crystallite phase, and ZrO
2And Al
2O
3To form different product phases.As Y
2O
3, MgO and CaO and so on additive can form sosoloid with zirconium white, produce stable or partially stabilized four directions or cubic oxide cobalt thus.
Silicon oxide can be enhanced the transparency to the size that reduces the silicon oxide micelle that studies show that of zirconium white-silicon oxide microsphere body influence.The size of the colloidal silica particles in the raw material can change, and for example overall dimension is from 10～1000 dusts.Be the zirconium white-silicon oxide ceramics microsphere that generation is had better transparency less than the silicon oxide micelle of about 200 dusts (0.020 micron) in general.Zirconium white to the mol ratio of silicon oxide generally in 1: 0.1 to 1: 2 scope.
From the x-ray analysis of Zirconia-alumina of the present invention-silicon oxide ceramics microsphere, as if in air, burn till after 700～900 ℃, generally observed zirconium white is at first mainly with false cube form crystallization.When improving firing temperature, this zirconium white changes the tetragonal crystal state into.The temperature that this transformation takes place depends on its composition.When to observe mole ratio with extraction heat gelling process preparation be 1: 0.27: 0.33 Zirconia-alumina-silicon oxide microsphere body sample by x-ray analysis, the sample after burning till 15 minutes under 1100 ℃ only demonstrated the tetragonal crystal zirconium white.Generally this microballoon is burnt till 1050～1100 ℃ and will produce highest hardness, keep high-clarity simultaneously.When burning till higher temperature, usually produce higher hardness, transparency and thus the reflectivity of microsphere of the present invention begin to reduce.When improving more than the firing temperature to 1100 ℃, can follow the growth of crystal of zirconium oxide.The increase of crystal of zirconium oxide size will cause the increase of monoclinic zirconia amount in the refrigerative microsphere.
The existence of yttrium oxide can cause burning till the formation of back stabilizing zirconia in Zirconia-alumina-silicon oxide system.For example, have zirconium white: aluminum oxide: silicon oxide: the mole ratio of yttrium oxide is 1: 0.43: 0.53: 0.08 microsphere only burns till after 1000 ℃, demonstrates and has a cubic zirconia (Y that stablizes yttrium oxide
0.15Zr
0.85O
1.73) consistent X-ray figure.When making it be heated to 1300 ℃, this zirconium white component still remaines in the stable cubic structure.
At Zirconia-alumina-magnesium oxide is in the ceramics sample, determines the existence of tetragonal zircite and magnesium oxide-alumina spinel by x-ray analysis.
The microsphere of silicon oxide-containing of the present invention can and can be sintered into ZrO with the colloidal dispersion aqueous solution that comprises silicon oxide (that is, the colloidal sol or the water-sol)
2Two phase systems of oxygen containing zirconium compounds prepare.This colloided silica generally concentration in silica sol is about 1～50% (weight).Can be used for a lot of colloided silica colloidal sol of the present invention is that market is supplied in a large number, and has different micelle granularities, sees " Surfce Colloid Science ", Vol.6, ed.Matijevic, E., Wiley Interscience, 1973.Being best suited for silicon oxide of the present invention is that those silicon oxide that provide with the dispersion of the amorphous silicon oxide in water medium are (as the Nalcoag of Nalco Chemical company production
Colloided silica) and those concentration of sodium carbonate low, and can come acidifying silicon oxide (for example, E.I.Dupont de Nemors ﹠amp by sneaking into appropriate amount of acid; The Ludox that Co produces
The Nalco that LS colloided silica or Nalco Chemical company produce
2326).
Being used to produce the zirconium compounds that contains zirconic sol-gel spheres of ceramic of the present invention can be organic acid or mineral acid or water-soluble salt, the zirconates of for example aliphatic list or dicarboxylic acid (for example, formic acid, acetate, oxalic acid, citric acid, tartrate and lactic acid).The zirconyl acetate compound is useful especially.Can be used for colloidal zirconia colloidal sol of the present invention is a large amount of supplies in market, for example, stablizes the zirconium white (containing 0.83 mole nitrate in every mole of zirconium white that Nyacol.Inc.of Ashland, Massachusetts nitre sell) of nitrate.Applicable inorganic zirconium compound has zirconium oxynitride and basic zirconium chloride.See United States Patent (USP) 3,709, No. 706, the 4th row, the 61st row are to the 5th row, and the 5th row has been done to be described in more detail to can be used for zirconium white of the present invention source.
With extraction heat gelling process gelling microsphere the time, should there be carboxylic acid oxygen zirconium compounds.It can mix use with other zirconia source, also can be without other oxide compound (for example, Al
2O
3Or SiO
2) prepare zirconia sol-gelled product.Although following most of narration relates to and other oxide matrix blended carboxylic acid oxygen zirconium, treatment step is equally applicable to the gelling of general carboxylic acid oxygen zirconium.
Aforementioned other metal oxide (for example, Al
2O
3, Y
2O
3Or MgO) can form supply with parent, as water-soluble salt: nitrate, fontanelle compound, fontanel oxide compound, phosphoric acid salt, borate, carbonate, or the salt of organic acid (one or two-carboxylic acid, oxygen acid, hydroxy acid, amino acid or their mixture), or to Al
2O
3And Y
2O
3, supply with the form of colloidal dispersions.
About zirconium white of the present invention-silica-based microsphere, these two kinds of main raw materials are present in the original colloidal sol usually, the ZrO in the aqueous dispersions that its quantity is enough to provide equivalent
2: SiO
2Mole ratio in 10: 1 to 1: 2 scope.Along with having high index material (ZrO
2) the increase of ratio, the specific refractory power of resultant microsphere also increases, and regulates specific refractory power thus and is suitable for different purposes.
Can be by under agitation condition, the method in the water-soluble night of silicon oxide water-sol tramp m. oxide matrix salt being prepared dispersion liquid for some raw material, put upside down addition sequence (promptly, metal oxide solution under agitation condition, is added in the silicon oxide water-sol) can cause the inhomogeneous dispersion of noncrystal particulate in the final microsphere.Stir this mixture so that obtain not produce flocculation or sedimentary homogeneous dispersion liquid, also can remove by filter excess material.The aqueous mixture of colloided silica suspension and zirconium compounds generally should be that rarer (for example, heavy per-cent is 15～3 (% (solids)).
In the extraction heat gelling process, extraction phase or extraction agent are characterised in that: to the low solubility (as less than 1% (weight)) of zirconium compounds (as zirconyl acetate) and other colloidal sol component; Under the temperature (as greater than 70 ℃) that corresponding carboxylic acid (as acetate) discharges, arrive high-dissolvability (at least 1% (weight)) in having from contain carboxylic acid oxygen zirconium mixture; In the use temperature scope, has adequate stability; Chemical parent to this pottery has inertia; And has a reusable possibility.This proves unsaturated oil, all satisfy these requirements as the various derivatives of rape oil, Semen Maydis oil, Thistle oil, soya-bean oil, Oleum Helianthi, peanut oil and these oil, and peanut oil has been proved to be a kind of extraction agent easily and gel formation medium.In order to prepare big microsphere (greater than 100 microns), the temperature of gel formation medium will remain on water destruct ground and break away from below the temperature spot of the microsphere of coming into being, and for containing the zirconyl acetate original stock in the peanut oil, optimum temps is about 70～99 ℃.Between gelation time, the acetate that discharges from the thin pearl of original colloidal sol is absorbed by deep fat at microsphere.Part acetate may be run away by evaporation.Can remove remaining acetate more than 118 ℃ by being heated to simply, this sharp shaping medium (as peanut oil) of regenerating.
Before introducing shaping medium, generally to make zirconyl acetate silicon monoxide colloidal sol masterbatch concentrate (generally contain and burn till about 20～50% (weight) of solid), so that obtain the viscosity of suitable density and the thin pearl of formation, still, concentration is reached cause too early agglomerative degree.Concentrate and carry out with rotary evaporation, comprise in this process that the liquid that evaporates enters the cooling receiving flask from the rotary container of heating, this operation is normally under reduced pressure carried out.
Can parent be added in the shaping medium of heating by the equipment that in shaping medium, forms thin pearl.This equipment should be included in before the gelling, the parent of refinement pearl and make its gelling or it is added with form of liquid flow and produce thin pearl by stirring to shear.Under these conditions, the rapid gelling of the thin pearl of zirconyl acetate based sols according to microballoon size difference, promptly can produce hard microsphere about several minutes.
This sharp extraction heat gelatinization process can be controlled by changing following parameter: a) composition of carboxylic acid zirconyl masterbatch, concentration and temperature; B) character of spe medium is as the solubleness and the temperature of acetate; With c) extraction gelling also may be included in some different extraction step of operating under the differing temps, improve temperature gradually and expose to microsphere.The mixture of microsphere and extraction agent should or overflow to each subsequent step from a step cascading.The residence time of each step and temperature also can be controlled.
After the microsphere gelling forms, they are collected (as by filtering), then it is burnt till or expose at high temperature, generally under 500～1350 ℃, in the oxidizing atmosphere (as, air).We wish that most of zirconium white component reaches high-crystallinity, therefore, preferably burn till (being higher than 900 ℃) under higher temperature.Firing temperature should be too not high so that because the growth of crystal of zirconium oxide causes the reduction of transparency.Add other metal oxide and also may change optimum burning temperature-forming in zirconium white, this can determine by experience.In general, higher firing temperature also helps to obtain fine and close fully microsphere.In sintering process, in order to obtain the product that burns till of even high workability, the ceramic microspheres that does not burn till should be by fluff packing.
The hardness of microsphere of the present invention is generally greater than 800 Knoops (knoop).Measured the Knoop hardness (50 and 100g load) of ceramic microspheres of the present invention and some comparative sample.The mean value of 10 impression measurements is carried out in the representative hardness measurement value representative that provides in following table 1 and embodiment at least to microsphere, this microsphere is fixed in the Resins, epoxy, and polishing obtains a plane.
Table 1
Knoop hardness sample number main component mol ratio firing temperature (on average) N
D
ZrO
2∶SiO
2∶Al
2O
3
A 1∶0.53∶0.43 1010℃ 1291 1.83-1.84
B 1∶0.33∶0.27 1100℃ 1291 1.89-1.90
ZrO
2∶SiO
2∶Al
2O
3∶Y
2O
3
C 1∶0.42∶0.34∶0.04 1100℃ 1389 1.87-1.88
D 1∶0.33∶0.27∶0.04 1100℃ 1407 1.91-1.92
ZrO
2∶SiO
2∶MgO
E 1∶0.45∶005 950℃ 965 ～1.90
Comparative sample
1.5N
D: granulated glass sphere * * 770
1.75N
DGranulated glass sphere * * 602
1.9N
DGlass is from pearl * * 566
Road surface sand 573
Sandblast sand 1117ZS1 ZrO
2: SiO
2* 1,000 800 1.75
1∶1ZS2 ZrO
2∶SiO
2* 1030 955 1.83
1.3∶1.0
1: 0.77* uses with sample A-E same procedure preparation.The * granularity is 150～210 microns.
Measured the resistance to crusing performance of microsphere of the present invention on a device, the principal character of this device is to pacify has the parallel plate that two stone non-deformable materials (for example, sapphire or wolfram varbide) of usefulness are made.The microsphere of a known diameter is placed on the following plate, reduces upper plate then till microsphere breaks.Resistance to breakage is that microsphere is applied to power on the microsphere when breaking divided by cross-sectional area (the π r of microsphere
2).Test ten microspheres of given composition, write down the resistance to crushing of its mean value as the microsphere of this composition.Generally approximately greater than 250000 pounds/square inch (1720 megapascal (MPa)s), the resistance to crushing of sample is greater than 300000 pounds/square inch (2064 megapascal (MPa)s) for the resistance to crushing of microsphere of the present invention after measured.Granulated glass sphere generally has the resistance to crushing of about 50000～75000 pounds/square inch (350～525 megapascal (MPa)s).
With photometer measurement brightness or reflectivity, its unit is milli candle light/ft-c/square feet (mcd/fc/ft
2).Usually using the reflector planar angle that is combined into from the normal to the microsphere is 86.5 incident light, and 1.0 ° flare angle is measured between light source and the phototube.The relative brightness of the relative brightness of sample A and comparative sample ZS1 and ZS2 value 1.40 and 1.85 and 1.75N in last table 1
DThe relative brightness value 1.00 of glass sphere is in a ratio of 2.00.
Research the present invention by following examples will be clearer, and these embodiment are only as pure demonstration.In these embodiments, used following raw materials according:
The Nalco that Nalco Chemical company provides
2326 products, promptly original particle size is about 50 dusts, and pH value is about 9 the SiO that contains
2It is the stable ammonia colloided silica of 14.5% (weight).
The general formula that contains that Harshaw Chemical company provides is ZrO
2(O
2CCH
3)
2XH
2The complex compound of O (suitable ZrO
2Concentration is 25%) and the zirconyl acetate aqueous solution of water.
The trade mark that Union Carbide company limited provides is Niacet
Formaldehyde aluminum acetate solid (34.44%Al
2O
3).
The trade mark that Nalco Chemical company provides is that the original particle size of Nalco614 is about 20 dusts, and pH value is about 5.1, contains Al
2O
3It is the steady oxide colloidal alumina of 10% (weight).
Here used " burning till solid " speech meaning is meant the equivalent of actual oxide compound, weight percent by the acquisition of weighing sample, with sample drying with burn till high temperature (being higher than 900 ℃) and remove and to anhydrate and organism and any other volatile matter, the weighing firing sample, burn till the weight of weight divided by initial sample like this, the merchant multiply by 100 with gained.
Embodiment 1
With the colloided silica water-sol of 90.0 grams, when stirring rapidly, add 0.75 milliliter of concentrated nitric acid and make its acidifying.The acidifying colloided silica is joined in the zirconyl acetate solution of the 200 rapid stirrings that restrain.The Niacet malonaldehydic acid aluminium (34.44% burns till solid) of 52.05 grams are sneaked in 300 ml deionized water, and be heated to 80 ℃ and make its dissolving.When this solution cools off, it is mixed with the mixture of aforesaid zirconyl acetate/silicon oxide.The mixture that obtains is concentrated to the rotary evaporation method contains that to burn till solid be 35%.This spissated thin pearl oyster liquid solution drop by drop is added in heat (88～90 ℃) peanut oil of stirring.Stirring by oil reduces and gelling this sharp parent droplet granularity.
Almost will realize smell of acetate after this sharp adding beginning at once.For the gelling droplet major part that makes gained is suspended in the oil, proceed to stir.Stopped later in about one hour stirring, and separate the agglomerative microsphere with filtration method.Before burning till, the gelling microsphere of collection is placed in the baking oven under 78 ℃, dry 5 hours, the exsiccant microsphere is placed in the quartz disk, and by furnace temperature slowly was raised in 10 hours 900 ℃, 900 ℃ down insulation 1 hour and in stove the naturally cooling microsphere, it is burnt till in air.Initially burning till of all samples is to carry out in a box-type furnace of opening fire door a little.With microscope the check of microsphere being demonstrated diameter is that complete sum is transparent at most of microsphere of 200～300 microns.The sample that burnt till under 1100 ℃ 15 minutes through X-ray powder diffraction analysis revealed contains the zirconium white of tetragonal.This microsphere consist of ZrO
2Al
2O
3: SiO
2Mol ratio be 1: 0.43: 0.53.
Example II
Prepare microsphere with the described same way as of example I, but use the zirconyl acetate solution of 256.68 grams and burn till the gelling microballon: in 10 hours, temperature risen to 900 ℃, 900 ℃ of insulations 1 hour and at stove internal cooling sample down according to follow procedure.The sample of these microballons was burnt till under 1100 ℃ 15 minutes.Demonstrating major part by microscopical determination, to have diameter be that 300～350 microns microballon is that complete sum is very transparent.Find the hardness average out to 1355knoop of this microballon, x-ray analysis shows zirconium white and the false cubic structure zirconium white very in a small amount that has tetragonal.By comparing with the high refractive index oil-soaked, the specific refractory power of finding this microballon is 1.87～1.88.This microsphere consist of ZrO
2: Al
2O
3: SiO
2Mol ratio be 1: 0.34: 0.42.
With with zirconium white/silicon oxide microsphere body of extraction heat gel method preparation relatively, oxidation of the present invention/silica microsphere solidify or gelling very fast, and can make harder.
EXAMPLE III
Under agitation, with 8.81 gram magnesium acetate (Mg (OAc)
24H
2O) join in the 200 gram zirconyl acetate solution.After Mg (OAc) the 4HO dissolving, this mixture is concentrated to contain that to burn till solid be 34.9% by rotary evaporation (37 ℃, pressure of inspiration(Pi)).This thin pearl oyster body enriched material is drop by drop joined in the peanut oil (83～85 ℃) of stirring.Before gelling, stirring makes thin ball mother solution be broken into littler microballon rapidly.In this sharp mixing Once you begin, can find the acetate smell at once.The mixture that stirs was kept 15 minutes down at 83～85 ℃, form microsphere " fresh " or that do not burn till state during this period.After filtration this microsphere is separated from deep fat, placed in the quartz disk, burn till according to follow procedure: in 9 hours, make it be heated to 600 ℃ from 85 ℃; In 2 hours, be heated to 800 ℃ from 600 ℃; Be incubated 30 minutes down at 800 ℃.This microsphere is together cooled off with stove.And then make it burn till (in 2 hours, make it reach 850 ℃, and under this temperature, be incubated 30 minutes) under 850 ℃.The diameter that obtains is that 100～200 microns microsphere major part is muddy a little, but complete sum is reflective.The mole of this microsphere is formed and is about ZrO
2: MgO equals 1.0: 0.1.Opposite with this result, there are not the goods of the EXAMPLE III of MgO then to produce granularity greater than 50 microns incomplete reflective microsphere.And many breakages are black.
Do at magnesium oxide under the situation of additive, prepared and have that to measure complete compact zirconia-silicon oxide-magnesium oxide that specific refractory power is about 1.90 very transparent macrobead (diameter is greater than 300 microns) be ceramic microspheres.But needs are careful when using magnesium oxide in containing zirconium white and silicon oxide system, if magnesium oxide is excessive, will cause the precipitation of zirconium, and this precipitation is accompanied by the growth of oversized particles usually, and it is opaque therefore can to cause that microsphere becomes.The following examples will illustrate the condition that obtains the transparent beads body.
EXAMPLE IV
When stirring rapidly, to 75 gram NalCO
Add about 0.3 milliliter dense HNO in the stable colloided silica of 2326 ammonia
3Make its rapid acidifying.This sharp acidifying silica sol is joined lentamente in the 200 gram zirconyl acetate solution of rapid stirring.The Mg (OAc) that adds 8.81 grams again
24HO, the mixture that stirring obtains is till all solids all dissolves.The gained mixture is concentrated to contain that to burn till solid about 36% through rotary evaporation, as the use peanut oil of narrating in the example I, at 85～88 ℃ of preparation microspheres down.The microsphere that obtains is burnt till, and method is in 11 hours time firing temperature to be elevated to 800 ℃ gradually; Insulation is 30 minutes under this temperature; Make the microsphere cooling then.The sample that the sample of this microsphere and some were burnt till under 950 ℃ of firing temperatures afterwards is many all to be complete, transparent in reflective, and diameter is in 200～300 microns scope.The microsphere that burns till under 950 ℃ has the hardness of 846knoop.This sharp microsphere consist of ZrO
2: SiO
2: the mol ratio of MgO is about 1.0: 0.45: 0.1.
EXAMPLE V
Remove the Mg (OAc) that uses 4.40 grams at this
24H
2O rather than use 8.81 the gram Mg (OAc)
24H
2O and became to contain to burn till solid with solution concentration and is about beyond 39% before forming microsphere, prepare microsphere with same procedure described in the EXAMPLE IV.After burning till under 850 ℃, this microsphere is all very transparent, and many particulate diameters surpass 300 microns, and the profile that is kept perfectly.After burning till under 950 ℃, has about 1.9～1.91 the hardness of drawing specific refractory power and 965knoop through measuring this sharp microsphere.X-ray analysis shows that cubic cobalt oxide is main phase.The approximate molar ratio that this microsphere is formed is ZrO
2: SiO
2: MgO equals 1.0: 0.45: 0.05.If it should be noted that the firing temperature that uses in this embodiment more than 970 ℃, this sharp microsphere will become opaque.
Example VI
Y with 2.29 grams
2O
3Be dissolved in 10 milliliters water and be the required a small amount of dense HNO of acquisition solvency action
3In.This solution is joined in the 200 gram zirconyl acetate colloidal sols.Prepare microsphere from this solution described in the EXAMPLE III, the position needs to adopt following firing condition: raised the temperature to 1000 ℃ in 7 hours, and make the microsphere furnace cooling in insulation under 1000 ℃ after 30 minutes.Most diameter be 200 microns microsphere and littler all be that complete sum is transparent especially.The constitutive molar ratio of this microsphere is ZrO
2: Y
2O
3Equal 1.0: 0.02.
Example VII A
Prepare microsphere with the same procedure described in the example I, different is: use 70.1 grams to use about 0.5 milliliter of concentrated nitric acid acidifying Nalco
2326 colloided silicas and 140.25 gram Nalco
_614 colloidal aluminas are made silicon oxide and alumina source, and are that 21.41% yttrium nitrate solution joins in colloided silica-zirconyl acetate mixture with burning till solid containing of 17.06 grams.In deep fat, form before the microsphere, the mixture that obtains is concentrated into to contain burns till solid about 33%.The oily temperature that is shaped is 92 ℃.After after filtration microsphere being separated, they are placed in the quartz disk, then by temperature was risen to 900 ℃ gradually in 10 hours, and 900 ℃ of insulations 1 hour down.It is burnt till.Sample is together cooled off with stove.Be heated to after 900 ℃, a microsphere sample was burnt till under 1100 ℃ 15 minutes.Micrography shows the very transparent microsphere of the complete sum of many diameters in 200～400 micrometer ranges.Measuring main crystallization phases through x-ray analysis is false cubic zirconia, and is 1389knoop through measuring its hardness.This microsphere consist of ZrO
2: Al
2O
3: SiO
2: Y
2O
3Than equaling 1: 0.34: 0.42: 0.04
Example VII A I
Prepare microsphere with the same procedure described in the example VII A I, different be to use 56.09 grams use 0.5 milliliter of concentrated nitric acid acidifying Nalco
2326 colloided silicas, 112.18 gram Nalco
_The containing of 614 colloidal aluminas and 21.33 grams burning till solid is 21.41% yttrium nitrate solution.Be heated to after 900 ℃, a microsphere sample was burnt till under 1100 ℃ 15 minutes.Micrography shows that the microballoon of most diameter in 150～300 micrometer ranges is that complete sum is very transparent.By comparing with high refractive index oil, the specific refractory power that records this microsphere is 1.91～1.92.Find that its hardness is 1407knoop, and show in microsphere the zirconium white that has false cube and tetragonal through x-ray analysis.This microsphere sets becomes ZrO
2: Al
2O
3: SiO
2: Y
2O
3Mol ratio be 1: 0.27: 0.33: 0.04.
Making this crystalline ceramics microsphere painted is within the scope of the present invention.The aqueous dispersions that is used to form pottery of the present invention can contain various other water soluble metallic compounds, and this metallic compound will make the pottery of making have inherent color, not sacrifice transparency.Adding tinting material in pottery of the present invention can be according to 3,795, the 4th row in No. 524 United States Patent (USP)s, and the 72nd row is listed as the carrying out that the 72nd row is narrated to the 5th.The tinting material that resembles iron nitrate (red or orange) and so on can be joined in the dispersion liquid, add-on is about 1～5% of used aggregate metal oxide.Color also can produce (for example, TiO by the interaction of two kinds of compounds under certain processing conditions
2And ZrO
2Can interacting, it is yellow to produce).
Crystalline ceramics microsphere of the present invention is used for landmarks board material (that is the thin slice that, is used for the road surface).This microsphere of the present invention also can be sneaked into coating composition, and this coating composition generally comprises the film forming material of many microspheres that wherein distribute, and wherein is dispersed with the microsphere (for example, seeing 2,963, No. 378 United States Patent (USP)s of Palmquist) of size fractionated.This sharp microsphere also can be used for spreading in the multiple application, as is used for motorway lines place, in the case the microballoon pearl is layered on simply wet paint or heat thermoplast on, and with its bonding.
Several reflectors that can use microsphere of the present invention are arranged, for example expose eyeglass (as 2,326,634 and 2, propose in 354, No. 018 United States Patent (USP)s), interlayer eyeglass (for example, 2,407, No. 680 United States Patent (USP)s) and the sealing eyeglass (seeing United States Patent (USP) 4,025, No. 159).The type of these eyeglasses and production method thereof all are known technologies.The front mentions 4,025, and 159,2,407,680 and 2,326, the accompanying drawing in No. 634 United States Patent (USP)s has been represented various templates, is incorporated herein by reference.
The reflection plate material that is used for traffic signals comprises a polymer bonding layer, embeds individual layer microsphere of the present invention in this layer, its insert depth be diameter half or darker.These microspheres and reflection unit are the optics banded, coat aluminum coating as inlaying the surface at them.This reflection sheet material can be produced by following method; ⅰ) partly individual layer microsphere of the present invention is embedded in the solidified carrier nethike embrane (for example, polyethylene coating paper); ⅱ) on microsphere, coat layer of aluminum with the vacuum vaporization sedimentation; ⅲ) use adhesive coated (solution that for example, contains 68% solid alcohol acid resin in the aromatic solvent); ⅳ) cured binders (for example, solidifying 30 minutes down) at 95 ℃; ⅴ) on binding agent, use transparent polymer base layer (for example, with the hexichol butanols being the polyvinyl chloride butyral solution of 20% (weight) of solvent); ⅵ) dry-basis layer (for example, following dry 30 minutes) at 95 ℃; And ⅶ) peels off the carrier nethike embrane.
4,248, No. 932 United States Patent (USP) has been narrated a kind of typical landmarks board, and is for reference in this narration.This sheet material is that a kind of being applicable to is layered on or is fixed on the precoated plate of using as road surface boundary on the road surface, and it comprises:
1. a sole plate, as be suitable for the soft aluminium flake on road surface;
2. a upper layer (also claiming supporting course or tack coat) that adheres to sole plate lip-deep and very soft and resistance to fracture; With
3. to disperse or the mode of stochastic distribution is partially submerged into individual layer of upper layer such as transparent beads body phacoid and so on particle.
This landmarks board structure also may comprise a kind of bonding agent (for example, pressure sensitive adhesive, hot glue stick or solvent-activated adhesive, or contact adhesive) on the sole plate bottom surface, see the Fig. 1 in the United States Patent (USP) 4,248, No. 932.
This sole plate also may be used elastic material (as acrylic nitrile-butadiene-benzene polymer, polyurethane or chloroprene rubber).
The upper layer that wherein is embedded with the transparent beads body generally can be polymkeric substance (as a vinyl polymer, polyurethane, epoxy derivative and polyester).This on the other hand microsphere lens can embed in the road sign flaggy fully.4,117, No. 192 United States Patent (USP) has been narrated this landmarks board material, is described in that this is for reference.
Landmarks board can be made with currently known methods and (for example see, 4,248, No. 932 United States Patent (USP)s), an example comprises the following steps: ⅰ) a soft aluminium sheet (50 micron thickness) go up the coated resin (as, Resins, epoxy and acrylic nitrile-butadiene-benzene polymer elastomer blends), pigment (TiO
2) and the mixture of solvent (as methyl ethyl ketone) form supporting course; ⅱ) on the wet surface of supporting course, put into many so-gel microspheres of the present invention (diameter is 160 microns or bigger); With supporting course was solidified about 10 minutes down at 150 ℃.Then, usually binder layer is coated on the sole plate bottom surface.
This microsphere can be handled with improving between they and the upper layer fusible reagent, perhaps this reagent can be included in upper layer and microsphere contact position.What be used for this purpose has a silane linking agent.
Pigment or other tinting material can be contained in the upper layer enough to be used in the painted amount of this sheet material of traffic control target.General titanium dioxide will be used for obtaining white, and general lead chromate will be used to provide yellow.
In useful embodiments more of the present invention, specular-reflection unit is to be provided by the evaporation deposition metal level (as aluminium) on the microsphere.Another kind of useful specular-reflection unit is one to comprise the dielectric reflections plate of one or more layers transparent material of microsphere back, and wherein the specific refractory power of each layer is higher or lower than about 0.3 of adjoining course or microballon specific refractory power. and the thickness of each layer is equivalent to quarter-wave approximately odd-multiple in the visible-range.More detailed description to this dielectric reflections plate sees 3,700, No. 305 United States Patent (USP)s.
Through the research to specification sheets disclosed herein and embodiment, other embodiment of the present invention will be conspicuous for the professional and technical personnel.Under the situation of not leaving true scope of the present invention and spirit, may make various omission of the present invention, improvement and variant, true scope of the present invention is shown in following claim.
Claims (3)
1. sheet material; this sheet material comprises the polymeric binder layer; wherein be embedded with the non-vitrified spheres of ceramic of many flawless substantially solid transparent; said spheres of ceramic has the specific refractory power greater than 1.6; comprise crystallization zirconium white and at least a other metal oxide; this metal oxide is selected from aluminum oxide, magnesium oxide, yttrium oxide and their mixture, can contain silicon-dioxide in addition, wherein:
A. the spheroid that contains silicon-dioxide for those, zirconium white is greater than 1.8 to the mol ratio of silicon-dioxide, is no more than 10; Or
B. in the spheroid gross weight of other metal oxides greater than zirconium white and dioxy through 30% of silicon gross weight.
2. the sheet material described in the claim 1 is as the application of a landmarks board part, and said landmarks board comprises:
A. substrate that can be bonded on the road surface; With
B. adhere to the described sheet material of lip-deep claim 1 of said substrate.
3. the application of the sheet material described in the claim 1 in reflector, this application are by add a reflection unit that is connected with said spheres of ceramic optics on said sheet material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/800,688 US4772511A (en) | 1985-11-22 | 1985-11-22 | Transparent non-vitreous zirconia microspheres |
| US800,688 | 1985-11-22 | ||
| CN86107671A CN1014786B (en) | 1985-11-22 | 1986-11-08 | Solid transparent non-vitrified zirconia microspheres and method for preparing same |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86107671A Division CN1014786B (en) | 1985-11-22 | 1986-11-08 | Solid transparent non-vitrified zirconia microspheres and method for preparing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1054963A CN1054963A (en) | 1991-10-02 |
| CN1031701C true CN1031701C (en) | 1996-05-01 |
Family
ID=25742262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90107390A Expired - Lifetime CN1031701C (en) | 1985-11-22 | 1986-11-08 | Reflector and reflection road-sign contg. transparent non-vitreous zirconia microspheres |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1031701C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023170516A1 (en) * | 2022-03-09 | 2023-09-14 | 3M Innovative Properties Company | Microspheres comprising zirconia and alumina suitable for retroreflective articles |
| WO2023170515A1 (en) * | 2022-03-09 | 2023-09-14 | 3M Innovative Properties Company | Microspheres comprising alumina and zirconia suitable for retroreflective articles |
-
1986
- 1986-11-08 CN CN90107390A patent/CN1031701C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023170516A1 (en) * | 2022-03-09 | 2023-09-14 | 3M Innovative Properties Company | Microspheres comprising zirconia and alumina suitable for retroreflective articles |
| WO2023170515A1 (en) * | 2022-03-09 | 2023-09-14 | 3M Innovative Properties Company | Microspheres comprising alumina and zirconia suitable for retroreflective articles |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1054963A (en) | 1991-10-02 |
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