CN106164013A - 制造瓷砖的工艺 - Google Patents
制造瓷砖的工艺 Download PDFInfo
- Publication number
- CN106164013A CN106164013A CN201580016108.2A CN201580016108A CN106164013A CN 106164013 A CN106164013 A CN 106164013A CN 201580016108 A CN201580016108 A CN 201580016108A CN 106164013 A CN106164013 A CN 106164013A
- Authority
- CN
- China
- Prior art keywords
- weight
- water
- water paste
- salt
- ceramic tile
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000004927 clay Substances 0.000 claims abstract description 36
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- 150000001768 cations Chemical class 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 20
- 239000000440 bentonite Substances 0.000 claims description 13
- 229910000278 bentonite Inorganic materials 0.000 claims description 13
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 13
- 229920001732 Lignosulfonate Polymers 0.000 claims description 10
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 6
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 150000002772 monosaccharides Chemical class 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- TVHALOSDPLTTSR-UHFFFAOYSA-H hexasodium;[oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O TVHALOSDPLTTSR-UHFFFAOYSA-H 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims 2
- 229920001282 polysaccharide Polymers 0.000 claims 2
- 239000005017 polysaccharide Substances 0.000 claims 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims 1
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 claims 1
- 235000002639 sodium chloride Nutrition 0.000 description 23
- 229940092782 bentonite Drugs 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
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- 239000004014 plasticizer Substances 0.000 description 6
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- 238000012360 testing method Methods 0.000 description 6
- 239000011449 brick Substances 0.000 description 5
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- 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 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000007787 solid 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
- 150000001340 alkali metals Chemical class 0.000 description 3
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- 239000004567 concrete Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- 229920001542 oligosaccharide Polymers 0.000 description 3
- 150000002482 oligosaccharides Chemical class 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 235000019743 Choline chloride Nutrition 0.000 description 2
- 229920001353 Dextrin Polymers 0.000 description 2
- 239000004375 Dextrin Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 241001597008 Nomeidae Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 2
- 229960003178 choline chloride Drugs 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 235000019425 dextrin Nutrition 0.000 description 2
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical group [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052615 phyllosilicate Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000005846 sugar alcohols Chemical class 0.000 description 2
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 241000158728 Meliaceae Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010427 ball clay Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical group 0.000 description 1
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
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- 239000008121 dextrose Substances 0.000 description 1
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 235000013681 dietary sucrose Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
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- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
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- 229920000620 organic polymer Polymers 0.000 description 1
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- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
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- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
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- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000269 smectite group Inorganic materials 0.000 description 1
- 229940080314 sodium bentonite Drugs 0.000 description 1
- 229910000280 sodium bentonite Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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Abstract
本文涉及制造瓷砖的工艺，其特征在于向陶瓷原材料添加水性浆料，所述水性浆料包含蒙脱石类可膨胀粘土、粘合剂和单价阳离子的水溶性盐。
Description
技术领域
本文涉及制造瓷砖的工艺，其特征在于，向陶瓷原材料添加水性浆料，所述水性浆料包含蒙脱石类可膨胀粘土、粘合剂和单价阳离子的水溶性盐。
现有技术
瓷砖的生产通常涉及以下步骤：
I)混合陶瓷原材料；
II)对陶瓷原材料进行湿研磨；
III)对由此获得的陶瓷粉浆进行喷雾干燥；
IV)通过压制粉状中间体形成生坯片；
V)对生坯片进行干燥；
VI)对经干燥的生坯片的上表面进行上釉；
VII)对经上釉的生坯片进行烧制。
可用于制备陶瓷粉浆的陶瓷原材料是典型的陶瓷原材料，并且是如下两种基本类型：
·粘土状材料(通常是陶土(china clay)和红色可玻璃化粘土)；
·补充材料(通常是长石、似长石、长石砂、石英、伟晶岩等)，其具有熔融和/或惰性特征。
研磨的目的是实现陶瓷原材料的尺寸减小并且使得它们均质化，直到实现最终恒定的粒度分布；通常来说，在研磨之后的残留物在63微米(230目)筛上是约为0.5-10重量％(wt％)，这取决于陶瓷材料的特性。
湿研磨提供了经湿研磨的陶瓷原材料，也称作陶瓷粉浆，含有约30-40重量％的水。
后续步骤是对陶瓷粉浆进行喷雾干燥。喷雾干燥的目的是实现粉浆中所含水的部分蒸发(将水含量降低至4-7重量％)，同时形成球形颗粒。
用于玻璃化单次烧制瓷砖的喷雾干燥粉末的典型粒度分布是70-80重量％的颗粒落在425-180微米的范围内。
通过压制形成瓷砖体的目的是获得生坯片上尽可能致密化的粉末，兼容烧制过程中可能出现的黑心斑或脱气问题；通常来说，形成瓷砖体的具体压力约为200-450kg/cm2。
干燥是加工相，其消除了新形成的瓷砖中的残留压制水分；通过辊道线收集来自压制的瓷砖体并输送到提供在通道内的干燥器，其向干燥区散发热空气。
可以使用常用的干法或湿法施涂技术来进行上釉。
在窑中采用预先限定的烧制循环来进行烧制；烧制循环和温度通常分别落在20-60’和1100-1250℃的范围内，这取决于待烧制的陶瓷物质的特性以及瓷砖自身的尺寸。
陶瓷生坯片体的形成和干燥代表了制品制造中的关键操作。在前述步骤中通常加入添加剂来减少压制和干燥过程中产生的缺陷。常见的添加剂是粘合剂和塑化剂。
加入粘合剂的具体目的是与粉状原材料粘牢(cement)在一起，并增加经干燥的生坯片的机械抗性。它们通常是有机特性的(例如，磨拉石、木质素磺酸盐、淀粉及其衍生物)；无机粘合剂也是已知且可用的(粘合剂粘土)。
添加塑化剂的具体目的是增加粉浆在形成瓷砖过程中尺寸和形状发生改变的能力。已知的有机塑化剂是二醇，例如聚乙二醇、聚乙烯醇和聚丙烯酸酯。
不幸的是，添加大量有机添加剂增加了陶瓷体中的有机物质含量，并且经验表明，采用过多有机物的经压制的瓷砖体非常容易发生黑心斑问题。
无机塑化剂也是已知的。无机塑化剂的例子是特定的粘土，例如球粘土或属于伊利石-绿泥石和/或伊利石-高岭石粘土类的粘土，但是它们的较高成本和周期性短缺限制了它们的使用。
已知蒙脱石类膨胀粘土(例如膨润土)展现出塑性和粘结性质，并且在瓷砖的制造中将它们加入到陶瓷原材料会同时增加生坯强度和干燥强度。出于这些原因，在研磨之前，陶瓷原材料偶尔结合作为粉末的少量膨润土。但是，膨润土类的化学性质变化很大，并且在将它们加入到粉浆之前，必须在实验室中对它们进行测试并且在工厂进行小心控制，因为它们对于陶瓷混合物的粘度和流变性特性的强烈影响会对研磨过程产生剧烈影响。除此之外，膨润土在干燥过程中收缩更为厉害，从而它们开裂的可能性更高，因此仅可以添加有限量的膨润土。
现在发现可以将蒙脱石类膨胀粘土、单价阳离子的水溶性盐和特定的有机粘合剂配制成液体形式，作为特定的可浇注水性浆料，其可以无难度地添加到陶瓷原材料。本发明的水性浆料作为塑化剂和粘合剂，不会引起黑心斑问题，具有可预测的性能，并且由于其对于陶瓷原材料混合物或者陶瓷粉浆的粘度的小影响，不需要任何预先实验室测试以及同时增加了生坯体和干燥瓷砖体的强度。此外，浆料作为易于浇注的液体，不仅可以在原材料的混合过程中添加，还可以在研磨步骤之后的下放阶段期间进行添加，不会导致形成会需要进一步的长时间且存在困难的过滤步骤的凝胶或残留物。
膨胀粘土的浆料是已知的，并且被用于例如造纸部门。
美国专利US 5,0153,34描述了一种组合物，其包含水可分散性胶状硅质材料(例如膨胀粘土)，紧密结合低分子量水可溶性高电荷密度有机聚合物(例如聚丙烯酸或聚胺)。以硅质材料的干重计，聚合物浓度为0.5-25％。
美国专利US 5,266,538提供了蒙脱石粘土的提升固体水性浆料，例如高至50重量％的固体，含有有效浓度的单价盐。单价盐优选是氯化钠。
US2007131372提供了含页硅酸盐材料和胶粘剂的水性浆料，其具有低于100cps的最终赫科勒斯表观粘度。这些浆料可含有20-55重量％的固体页硅酸盐材料含量。胶粘剂的例子包括各种形式的松脂(单独使用或者结合其他材料)，例如木质素磺酸盐、妥尔油脂肪酸、苯乙烯化合物、含氟烃、丙烯酸乳液和苯乙烯丙烯酸酯、硬脂酸酯和硬脂酸。EP1329484描述了一种粘土浆料，其包含蒙脱石类粘土、限定的膦酸酯添加剂和水，其特别适用于作为混凝土的抗渗添加剂。蒙脱石粘土浆料含有至少2重量％的粘土以及约0.5-15重量％的一种或多种膦酸酯，以蒙脱石粘土的重量计。
就本申请的申请人所知道的是，没有描述将本文的浆料用于生产瓷砖或者它们的具体配方。
发明内容
本发明的主要目的是提供一种水性浆料组合物，其包含：
a)5-30重量％的蒙脱石类膨胀粘土；
b)10-30重量％的粘合剂，其选自：木质素磺酸盐、萘磺酸盐-甲醛缩合物盐、单糖和低聚糖、水可溶性淀粉、水可溶性纤维素衍生物，及其混合物；
c)0.1-10重量％的单价阳离子的水可溶性盐。
本发明的另一个目的是制造瓷砖的方法，其包括如下步骤：
I)混合陶瓷原材料；
II)对陶瓷原材料进行湿研磨；
III)对由此获得的陶瓷粉浆进行喷雾干燥；
该方法的特征在于，在步骤I)期间或者在步骤II)之后并且在步骤III)之前，加入0.2-3重量％，优选0.4-2重量％的所述水性浆料。
具体实施方式
优选地，水性浆料包含：
a)10-20重量％的蒙脱石类膨胀粘土；
b)15-25重量％的所述粘合剂；
c)0.5-5重量％的所述单价阳离子的盐。
通常来说，本发明的水性浆料包含35-84.5重量％的水。
蒙脱石类膨胀粘土属于众所周知的三层粘土矿物质类，其含有夹在两层二氧化硅四面体之间的氧化铝或氧化镁八面体中心层，并且具有基于叶腊石的理想化学式，其通过用更低价态的阳离子取代部分Al+3、Si+4或Mg+2进行改性，得到整体阴离子晶格电荷。蒙脱石类膨胀粘土包括蒙脱土，其包括膨润土、贝得石、绿脱石、皂石和锂蒙脱石。膨胀粘土通常具有80-150毫当量/100g干矿物质的阳离子交换能力，并且可以较为容易地分散在水中。
根据本发明的用途，蒙脱石类膨胀粘土优选是钠或锂形式(其可以是天然存在的，但是更通常来说，通过对天然存在的碱土粘土进行阳离子交换获得)或者是氢形式(其可以通过碱金属或者碱土金属粘土的无机酸处理获得)。此类钠、锂或氢形式的粘土当水合时通常具有增加它们的基面距离的性质，以促进被称为膨胀的现象。
为了实现本发明，膨润土是优选的蒙脱石类膨胀粘土，钠膨润土是特别优选的。
适用于实现本发明的粘合剂b)是：木质素磺酸盐、萘磺酸盐-甲醛缩合物盐、单糖和低聚糖、水可溶性淀粉、水可溶性纤维素衍生物，例如羧甲基纤维素和羟乙基纤维素，及其混合物。单糖和低聚糖的例子是糖类，例如葡萄糖和蔗糖；糖醇，例如山梨糖醇；糊精和麦芽糊精。这些粘合剂是本领域常用的，并且是本领域技术人员众所周知的。
用于实现本发明的特别优选的粘合剂是木质素磺酸钠或木质素磺酸钾。
木质素磺酸盐是生产木纸浆的副产物。当有机木质素分子与强极性磺酸基团在亚硫酸盐化制浆期间结合时，木质素磺酸盐以它们的钠盐、钙盐或铵盐的形式容易地溶解在水中。木质素磺酸盐可以是泛黄色的粉末，具有可变的组成并且还具有可变的分子尺寸。木质素磺酸盐的典型重均分子量约为30,000道尔顿(Da)，其典型的数均分子量约为3000道尔顿。
萘磺酸盐-甲醛缩合物盐，也称作NSF，已知有一段时间了，还被广泛地描述作为不同部门中的分散剂。通常来说，这些材料是通过熔融萘与发烟硫酸缩合形成具有不同位置异构体的萘磺酸衍生物制得的。然后在约为90℃的温度使得磺酸衍生物与水和甲醛缩合，之后通过添加碱金属或铵的氢氧化物或碳酸盐转变成盐。适用于实现本发明的萘磺酸盐甲醛缩合物盐的重均分子量优选约为10,000Da。
适合于实施本发明的羧甲基纤维素可选自在陶瓷领域常用的且本领域技术人员已知的那些。优选用于实现本发明的羧甲基纤维素的取代度包括0.5-1.5，更优选0.6-1.2。优选地，在水中2重量％，60rpm以及20℃时，其布氏LVT粘度为5-300mPa*s，更优选为5-50mPa*s。
优选的粘合剂是木质素磺酸盐、萘磺酸盐-甲醛缩合物盐、糖、糖醇、羧甲基纤维素，及其混合物。
水性浆料还包括单价阳离子的水溶性盐c)，其降低了蒙脱石粘土的膨胀能力并且降低了浆料的粘度，因而降低了陶瓷粉浆的粘度。在一些情况下，可以使用含二价或更高价态阳离子(例如钙)的盐，但是这些二价离子倾向于与初始存在于可膨胀粘土中的单价离子发生交换，并且这会抑制粘土的后续膨胀。因此，通常优选盐的阳离子是单价的，例如，铵或碱金属。可用的盐的例子是铵盐(具体来说，NH4 +、四-C1-C4-烷基铵和四-C1-C4-烯基铵盐，其中，一个或多个烷基或烯基基团被-OH基团所取代)或者氯、溴、磷酸(一元、二元和三元磷酸)的碱金属盐，及其混合物。具体地例子是氯化钠或氯化钾、溴化钠或溴化钾、磷酸二氢钠或磷酸二氢钾、磷酸一氢钠或磷酸一氢钾、四烷基氯化铵、氯化胆碱，及其混合物。
优选地，单价阳离子是钠、钾或胆碱。
盐优选是氯化钠、氯化钾、氯化胆碱，更优选是氯化钾。
在一个优选的实施方式中，本发明的水性浆料还包含0.5-5重量％，优选1-3重量％的分散剂，其选自本领域常用的那些。分散剂的例子是(甲基)丙烯酸聚合物，通常以钠盐形式提供；磷酸盐和聚磷酸盐，例如三聚磷酸钠、偏硅酸钠；二硅酸钠；液体硅酸钠；及其混合物。特别优选的分散剂是重均分子量低于20,000Da，优选低于10,000Da，例如1000-6000Da的(甲基)丙烯酸聚合物。
本发明的水性浆料中还可存在常用的陶瓷添加剂。添加剂的例子是消泡剂、香味剂、防腐剂以及染料等。
通过如下方式制备水性浆料：首先将盐c)、粘合剂b)和任选的添加剂溶解在水中，之后分散于蒙脱石类可膨胀粘土a)的溶液中。粘土-粘合剂混合物以最小剪切进行搅拌，优选是在加入粘土时进行。发现混合的剪切越低，可以实现的固体含量越高。可以采用能够产生低剪切混合的任何混合装置。
通常来说，最终水性浆料的布氏粘度(25℃，20rpm)低于3000mPa*s，优选为500-1500mPa*s。
重要的是，要注意到本发明的浆料具有低粘度和高固体含量。它们还是稳定的，特征在于延长的使用寿命。
上文所述的水性浆料可用于根据本发明的方法来制造瓷砖。如上文所述，可以在步骤I)中加入浆料。
根据该实施方式，陶瓷原材料与水性浆料的结合通常是通过使得陶瓷原材料和其他添加剂(例如，抗絮凝剂)与浆料小心混合形成均匀混合物所实现的。
然后使得陶瓷原材料的混合物经受湿研磨。可以使用连续工艺或者不连续工艺进行该步骤。
在研磨结束时，对粉浆进行筛分并输送到贮槽，由此将它们泵送到喷雾器。还可在研磨和喷雾干燥之间的任意时刻将本发明的水性浆料添加到粉浆，甚至是直接在贮槽和雾化器之间的传输线中。
在步骤III)中，当粉浆在雾化器中加热时，通过升温热空气柱对其进行干燥，形成小的、自由流动的颗粒，产生适用于成形的粉末。
用于生产瓷砖的工艺还包括如下步骤：对粉状中间体进行压制以形成生坯片，对生坯片进行干燥，对经干燥的生坯片的上表面上釉，以及最终对经过上釉的瓷砖体进行烧制。可以通过常规技术和程序来完成制备瓷砖的这些后续步骤。
相比于直接采用蒙脱石类可膨胀粘土来制造瓷砖的现有技术工艺，本发明的瓷砖制造工艺具有数个优势。具体来说，性能优于采用粉末形式的相应蒙脱石可获得的情况，但是没有对粉末进行处理的不便性。
本发明的工艺适用于生产任何种类的瓷砖，例如，墙砖、地砖、瓷器、瓷制瓷器、粗瓷器、瓦片、贴面砖，其可以是单次烧制或者两次烧制。
以下非限制性实施例显示了采用根据本发明的浆料的示例性水性浆料和工艺。
实施例
实施例1-3
采用表1所记载的市售可得组分来制备根据本发明的三种水性浆料。
表1
| 组分(％w/w) | 实施例1 | 实施例2 | 实施例3 |
| KCl | 0.4 | 0.4 | 1.5 |
| 木质素磺酸钠 | 25 | - | 15 |
| NSF | - | 20 | |
| 膨润土 | 20 | 30 | 20 |
| Reotan HS | - | - | 5.0 |
| 杀生物剂 | 0.1 | 0.1 | 0.1 |
| 香料 | 0.3 | - | 0.2 |
| 染料 | 0.1 | 0.1 | 0.1 |
| 消泡剂 | - | - | 0.1 |
| 水 | 至100 | 至100 | 至100 |
根据以下过程制备浆料：
·将盐溶解在水中；
·加入粘合剂；
·在搅动下溶解，然后添加分散剂和其他添加剂(如果存在的话)；
·在5分钟后，在搅动下，将膨润土逐渐倒入混合物中；
·在均质化10分钟后，将浆料过筛100微米筛。
溶解测试
在研磨之前，对陶瓷原材料混合物评估浆料的效果。用表2中记载的瓷砖4的市售可得的陶瓷原材料来制备混合物。
通过确定没有任何添加剂制备的混合物(空白)、用1重量％的实施例3的浆料制备的混合物(实施例3A)以及用0.2重量％的实施例3的相同膨润土粉末制备的混合物(实施例B，具有与实施例3A的浆料相同量的膨润土)的福特粘度(ASTM标准方法D1200-10)来评估悬浮液的作用。通过装有八个叶片叶轮的高速机械搅拌器在320rpm下将混合物搅拌10分钟的方式进行均质化。
得到以下结果：
| 空白* | 实施例3A | 实施例B* | |
| 福特粘度(秒) | 27 | 28 | >60 |
*比较例
结果显示包含实施例3的浆料的陶瓷原材料混合物的粘度的优异稳定性。
使用根据本发明的浆料能够避免高粘度以及由此可能会产生的问题，例如难以研磨，以及使得粉浆移动通过各个工艺步骤。
对于表2所述的瓷砖1的陶瓷原材料研磨所获得的陶瓷粉浆进行类似测试。
对没有添加剂的粉浆(空白)、具有1重量％的实施例3的浆料(实施例3B)以及具有0.2重量％的实施例3的相同膨润土粉末的粉浆(实施例C，具有与实施例3B的浆料相同量的膨润土)进行测试。通过装有八个叶片叶轮的高速机械搅拌器在320rpm下将混合物搅拌10分钟的方式进行均质化。
在均质化之后，在配衡的63微米ASTM筛(100目)上过筛250g的每种粉浆，不溶材料(残留物)的量通过在105℃的烘箱中下干燥2小时后的重量差来测定。
得到以下结果：
| 空白* | 实施例3B | 实施例C* | |
| 残留物(重量％) | 0.4 | 0.4 | 1 |
*比较例
结果显示，含有实施例3的浆料的陶瓷原材料混合物具有较低的残留物含量。
存在高浓度的残留物在工艺的后续步骤中产生问题，并且迫使用户在喷雾干燥之前对粉浆进行二次过滤。
强度测试
对于用根据表2所记载的市售可得陶瓷原材料制备的瓷砖体来确定本发明的浆料的性能，其中，(份数)表示(重量份数)以及(重量％)表示重量百分比。
表2
将实施例1-3的浆料添加到通过研磨陶瓷原材料获得的陶瓷粉浆中，并采用机械搅拌器小心地均质化。
在均质化之后，粉浆在75-80℃烘箱中调节过一夜，再次研磨得到尺寸小于0.75mm的颗粒。
在研磨过程结束时，陶瓷粉浆的水含量约为6重量％。
生坯瓷砖体(5cm x10cm，0.5cm厚)采用如下方式制备：实验室液压机(南尼蒂，Mod.Mignon SS/EA(Nannetti,Mod.Mignon SS/EA))对墙砖体(瓷砖1-3)施加约300kg/cm2的压力，以及对标准生坯瓷砖体(瓷砖4-7)施加约400kg/cm2的压力。
采用相同程序和单独的陶瓷原材料来制备对比生坯片。
根据国际标准测试方法ISO 10545-4，采用实验室挠度计(南尼蒂，Mod.FM96(Nannetti,Mod.FM96))来确定生坯片体的断裂模量(MOR)。
在110℃的烘箱干燥过一夜之后，对余下的瓷砖体确定干燥瓷砖体的MOR。
断裂模量是瓷砖体的强度指数。结果表示为根据本发明制备的瓷砖体相比于对比瓷砖体的强度的％增加，见表3。
表3
| 瓷砖1 | 瓷砖2 | 瓷砖3 | 瓷砖4 | 瓷砖5 | 瓷砖6 | 瓷砖7 | |
| ％生坯强度 | +14,1 | +35,3 | +70,6 | +11,1 | +13,1 | +5,0 | +6,0 |
| ％干燥强度 | +41,8 | +49,1 | +75,3 | +19,4 | +43,5 | +11,4 | +16,8 |
Claims (8)
1.制造瓷砖的方法，该方法包括以下步骤：
I)混合陶瓷原材料；
II)对所述陶瓷原材料进行湿研磨；
III)对由此获得的粉浆进行喷雾干燥；
其特征在于，在步骤I)中或者在步骤II)之后并且在步骤III)之前，加入0.2-3重量％的水性浆料，所述水性浆料包含：
a)5-30重量％的蒙脱石类膨胀粘土；
b)10-30重量％的粘合剂，其选自：木质素磺酸盐、萘磺酸盐-甲醛缩合物盐、单糖和低聚糖、水可溶性淀粉、水可溶性纤维素衍生物，及其混合物；
c)0.1-10重量％的单价阳离子的水可溶性盐。
2.如权利要求1所述的方法，其特征在于，加入0.4-2重量％的所述水性浆料。
3.水性浆料，其包含：
a)5-30重量％的蒙脱石类膨胀粘土；
b)10-30重量％的粘合剂，其选自：木质素磺酸盐、萘磺酸盐-甲醛缩合物盐、单糖和低聚糖、水可溶性纤维素衍生物，及其混合物；
c)0.1-10重量％的单价阳离子的水可溶性盐。
4.如权利要求3所述的水性浆料，其包含：
a)10-20重量％的蒙脱石类膨胀粘土；
b)15-25重量％的所述粘合剂；
c)0.5-5重量％的所述单价阳离子的盐。
5.如权利要求3所述的水性浆料，其特征在于，所述水性浆料还包括0.5-5重量％的分散剂，其选自：(甲基)丙烯酸聚合物、磷酸盐和聚磷酸盐、偏硅酸钠、二硅酸钠、液体硅酸钠，及其混合物。
6.如权利要求5所述的水性浆料，其特征在于，所述分散剂是重均分子量低于20,000Da的(甲基)丙烯酸聚合物。
7.如权利要求3所述的水性浆料，其特征在于，所述单价阳离子的盐c)选自：铵或碱金属的氯化物、溴化物或磷酸盐，或其混合物。
8.如权利要求3-7中任一项所述的水性浆料，其特征在于，所述蒙脱石类膨胀粘土a)是膨润土。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITVA20140013 | 2014-04-07 | ||
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| PCT/EP2015/057297 WO2015155110A1 (en) | 2014-04-07 | 2015-04-02 | Process for making tiles |
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| CN106164013A true CN106164013A (zh) | 2016-11-23 |
| CN106164013B CN106164013B (zh) | 2020-10-23 |
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| MX (1) | MX355889B (zh) |
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| PT (1) | PT3129335T (zh) |
| WO (1) | WO2015155110A1 (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107879724A (zh) * | 2017-11-09 | 2018-04-06 | 佛山恒泰红狮陶瓷有限公司 | 一种防裂磨面砖及其制备方法 |
| CN112920461A (zh) * | 2021-01-27 | 2021-06-08 | 江苏汉卿新材料科技研究院有限公司 | 一种成瓷填料及其制备方法和epdm复合材料 |
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|---|---|---|---|---|
| IT201600079966A1 (it) | 2016-07-29 | 2018-01-29 | Lamberti Spa | Processo per produrre piastrelle |
| CN106320622B (zh) * | 2016-08-08 | 2019-01-04 | 佛山市东鹏陶瓷有限公司 | 一种干压注浆成型的陶瓷砖及其生产方法 |
| US10346943B2 (en) * | 2017-01-03 | 2019-07-09 | Microsoft Technology Licensing, Llc | Prefetching for a graphics shader |
| US11905211B2 (en) | 2018-09-12 | 2024-02-20 | Eth Zurich | Construction material without a hydraulic binder |
| FR3093513B1 (fr) | 2019-03-06 | 2022-12-09 | Materrup | Procédé de sélection de la composition d’un matériau de construction comportant une terre argileuse excavée, procédé et système de préparation d’un tel matériau de construction |
| IT202100028286A1 (it) * | 2021-11-05 | 2023-05-05 | Lamberti Spa | Processo per produrre piastrelle |
| FR3128954A1 (fr) * | 2022-11-07 | 2023-05-12 | Materrup | Procédé de sélection de la composition d’un matériau de construction comportant une terre argileuse excavée, procédé et système de préparation d’un tel matériau de construction |
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- 2015-04-02 CN CN201580016108.2A patent/CN106164013B/zh active Active
- 2015-04-02 BR BR112016023165-1A patent/BR112016023165B1/pt active IP Right Grant
- 2015-04-02 US US15/302,546 patent/US10858291B2/en active Active
- 2015-04-02 ES ES15718151.2T patent/ES2668025T3/es active Active
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| US5972263A (en) * | 1995-06-13 | 1999-10-26 | Ecc International Ltd. | Process for producing clay compositions for use in slip casting |
| CN1213420A (zh) * | 1996-03-08 | 1999-04-07 | 联合胶体有限公司 | 溶胀粘土的活化和使用活化粘土的方法 |
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| CN107879724B (zh) * | 2017-11-09 | 2018-10-19 | 佛山恒泰红狮陶瓷有限公司 | 一种防裂磨面砖及其制备方法 |
| CN112920461A (zh) * | 2021-01-27 | 2021-06-08 | 江苏汉卿新材料科技研究院有限公司 | 一种成瓷填料及其制备方法和epdm复合材料 |
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Also Published As
| Publication number | Publication date |
|---|---|
| PL3129335T3 (pl) | 2018-07-31 |
| MX355889B (es) | 2018-05-02 |
| US10858291B2 (en) | 2020-12-08 |
| BR112016023165A2 (zh) | 2017-08-15 |
| ES2668025T3 (es) | 2018-05-16 |
| WO2015155110A1 (en) | 2015-10-15 |
| US20170029334A1 (en) | 2017-02-02 |
| CN106164013B (zh) | 2020-10-23 |
| EP3129335A1 (en) | 2017-02-15 |
| EP3129335B1 (en) | 2018-01-31 |
| PT3129335T (pt) | 2018-05-10 |
| BR112016023165B1 (pt) | 2022-01-04 |
| MX2016013104A (es) | 2017-02-02 |
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