TW201713781A - Production method for zirconium tungsten phosphate - Google Patents
Production method for zirconium tungsten phosphate Download PDFInfo
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- TW201713781A TW201713781A TW105132119A TW105132119A TW201713781A TW 201713781 A TW201713781 A TW 201713781A TW 105132119 A TW105132119 A TW 105132119A TW 105132119 A TW105132119 A TW 105132119A TW 201713781 A TW201713781 A TW 201713781A
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- Prior art keywords
- slurry
- zirconium
- compound
- reaction precursor
- zirconium phosphate
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
- RWWJXIAEEFWUSU-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[W+4].[Zr+4] Chemical compound P(=O)([O-])([O-])[O-].[W+4].[Zr+4] RWWJXIAEEFWUSU-UHFFFAOYSA-K 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 103
- 239000002243 precursor Substances 0.000 claims abstract description 72
- 150000003658 tungsten compounds Chemical class 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 31
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000010521 absorption reaction Methods 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims description 132
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 80
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 46
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 40
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 34
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 31
- 238000005245 sintering Methods 0.000 claims description 27
- 150000003755 zirconium compounds Chemical class 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 25
- 238000010298 pulverizing process Methods 0.000 claims description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims description 19
- 229910019142 PO4 Inorganic materials 0.000 claims description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 16
- OJLGWNFZMTVNCX-UHFFFAOYSA-N dioxido(dioxo)tungsten;zirconium(4+) Chemical compound [Zr+4].[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O OJLGWNFZMTVNCX-UHFFFAOYSA-N 0.000 claims description 16
- 239000011574 phosphorus Substances 0.000 claims description 16
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 15
- 239000010452 phosphate Substances 0.000 claims description 15
- 238000001694 spray drying Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 50
- 238000002441 X-ray diffraction Methods 0.000 abstract description 34
- 239000000463 material Substances 0.000 abstract description 22
- 238000010304 firing Methods 0.000 abstract 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 25
- 239000011324 bead Substances 0.000 description 18
- 239000002270 dispersing agent Substances 0.000 description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 235000021317 phosphate Nutrition 0.000 description 15
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 9
- 150000003863 ammonium salts Chemical class 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 239000002612 dispersion medium Substances 0.000 description 7
- 239000011164 primary particle Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- 239000011163 secondary particle Substances 0.000 description 7
- 239000003125 aqueous solvent Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 6
- 239000000347 magnesium hydroxide Substances 0.000 description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- -1 organic acid salts Chemical class 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920005646 polycarboxylate Polymers 0.000 description 6
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000007561 laser diffraction method Methods 0.000 description 5
- 238000000790 scattering method Methods 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000005102 attenuated total reflection Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 3
- 239000004137 magnesium phosphate Substances 0.000 description 3
- 229960002261 magnesium phosphate Drugs 0.000 description 3
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 3
- 235000010994 magnesium phosphates Nutrition 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 0 CN*C=*C* Chemical compound CN*C=*C* 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 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 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- RRZKHZBOZDIQJG-UHFFFAOYSA-N azane;manganese Chemical compound N.[Mn] RRZKHZBOZDIQJG-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- LGRDPUAPARTXMG-UHFFFAOYSA-N bismuth nickel Chemical compound [Ni].[Bi] LGRDPUAPARTXMG-UHFFFAOYSA-N 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910000174 eucryptite Inorganic materials 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920003050 poly-cycloolefin Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
Description
本發明是有關於一種作為負熱膨脹材而有用的磷酸鎢酸鋯的製造方法。The present invention relates to a method for producing zirconium phosphate zirconate useful as a negative thermal expansion material.
若溫度上升，則多數物質會隨著熱膨脹而長度或體積增大。與此相對，亦已知若加溫則反而體積變小的顯示出負的熱膨脹的材料（以下有時亦稱為「負熱膨脹材」）。已知，顯示出負的熱膨脹的材料可與其他材料一起使用來抑制由溫度變化所引起的材料的熱膨脹的變化。If the temperature rises, most of the material will increase in length or volume as it expands. On the other hand, a material which exhibits a negative thermal expansion when the temperature is increased (hereinafter sometimes referred to as a "negative thermal expansion material") is also known. It is known that materials exhibiting negative thermal expansion can be used with other materials to inhibit changes in the thermal expansion of the material caused by temperature changes.
顯示出負的熱膨脹的材料例如已知：β-鋰霞石、鎢酸鋯（ZrW2 O8 ）、磷酸鎢酸鋯（Zr2 WO4 (PO4 )2 ）、Znx Cd1-x (CN)2 、二氮化三錳（manganese nitride）、鉍·鎳·鐵氧化物等。Materials exhibiting negative thermal expansion are known, for example, as β-eucryptite, zirconium tungstate (ZrW 2 O 8 ), zirconium tungstate phosphate (Zr 2 WO 4 (PO 4 ) 2 ), Zn x Cd 1-x ( CN) 2 , manganese nitride, bismuth nickel, iron oxide, and the like.
磷酸鎢酸鋯的線膨脹係數於0℃～400℃的溫度範圍內為-3.4 ppm/℃～-3.0 ppm/℃，負熱膨脹性大，可藉由與顯示出正的熱膨脹的材料併用使用來製造低熱膨脹的材料。The linear expansion coefficient of zirconium tungstate phosphate is -3.4 ppm/°C to -3.0 ppm/°C in the temperature range of 0°C to 400°C, and the negative thermal expansion property is large, and can be used by using a material which exhibits positive thermal expansion. Create low thermal expansion materials.
作為磷酸鎢酸鋯的製造方法，例如於下述專利文獻1中提出了如下方法：將結晶性的磷酸鋯、氧化鎢及MgO等反應促進劑於濕式球磨機中混合，對所獲得的混合物於1200℃下進行煅燒；下述專利文獻2中提出了如下方法：對磷酸銨等磷源、與鎢酸銨等鎢源以及氯化鋯等鋯源進行濕式混合後，進行預燒；下述非專利文獻1中提出了對包含氧化鋯、氧化鎢及磷酸二氫銨的混合物於1200℃下進行煅燒的方法等。 [現有技術文獻] [專利文獻]As a method for producing zirconium tungstate phosphate, for example, Patent Document 1 below proposes a method in which a reaction accelerator such as crystalline zirconium phosphate, tungsten oxide or MgO is mixed in a wet ball mill to obtain a mixture. Calcination is carried out at 1200 ° C. In the following Patent Document 2, a method is as follows: a phosphorus source such as ammonium phosphate, a tungsten source such as ammonium tungstate, and a zirconium source such as zirconium chloride are wet-mixed, followed by calcination; Non-Patent Document 1 proposes a method of calcining a mixture containing zirconia, tungsten oxide, and ammonium dihydrogen phosphate at 1200 ° C. [Prior Art Document] [Patent Literature]
[專利文獻1]日本專利特開2005-35840號公報，申請專利範圍第3項、第0035段。 [專利文獻2]日本專利特開2015-10006號公報，第0023～0025段。 [非專利文獻][Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-35840, the third and the s. [Patent Document 2] Japanese Patent Laid-Open Publication No. 2015-10006, paragraphs 0023 to 0025. [Non-patent literature]
[非專利文獻1]「材料研究通報（Materials Research Bulletin）」，44（2009），第2045-2049頁。[Non-Patent Document 1] "Materials Research Bulletin", 44 (2009), pp. 2045-2049.
[發明所欲解決的課題] 作為負熱膨脹材，磷酸鎢酸鋯被認為有希望作為用以進行超精密加工的構件，進而亦期望開發出利用工業上有利的方法來獲得磷酸鎢酸鋯的方法。[Problems to be Solved by the Invention] As a negative thermal expansion material, zirconium phosphotungstate is considered to be a member for ultra-precision processing, and it is also desired to develop a method for obtaining zirconium phosphate tungstate by an industrially advantageous method. .
因此，本發明的目的在於提供一種利用工業上有利的方法來獲得作為負熱膨脹材而有用的於X射線繞射中為單相的磷酸鎢酸鋯的方法。 [解決課題的手段]Accordingly, it is an object of the present invention to provide a method for obtaining zirconium phosphotungstate which is a single phase in X-ray diffraction useful as a negative thermal expansion material by an industrially advantageous method. [Means for solving the problem]
本發明者等人鑒於所述實情而反覆進行銳意研究，結果發現，於相對於水為不溶性或難溶性的鎢化合物的存在下進行磷酸與特定的鋯化合物的反應而獲得的鎢化合物、與包含磷及鋯的無定形化合物的混合物成為反應性優異的反應前驅物，藉由使用該反應前驅物而容易獲得於X射線繞射中為單相的磷酸鎢酸鋯，從而完成本發明。The inventors of the present invention have conducted intensive studies in view of the above-mentioned facts, and have found that a tungsten compound obtained by reacting phosphoric acid with a specific zirconium compound in the presence of a tungsten compound which is insoluble or poorly soluble in water is contained and contained. The mixture of the amorphous compound of phosphorus and zirconium is a reaction precursor excellent in reactivity, and the use of the reaction precursor makes it easy to obtain zirconium phosphotungstate which is a single phase in X-ray diffraction, thereby completing the present invention.
即，本發明所欲提供的磷酸鎢酸鋯的製造方法的特徵在於：將鎢化合物、與包含磷及鋯的不定形化合物的混合物作為反應前驅物，對該反應前驅物進行煅燒。 [發明的效果]That is, the method for producing zirconium phosphate zirconate to be provided by the present invention is characterized in that a mixture of a tungsten compound and an amorphous compound containing phosphorus and zirconium is used as a reaction precursor, and the reaction precursor is calcined. [Effects of the Invention]
依據本發明，可利用工業上有利的方法來獲得作為負熱膨脹材而有用的於X射線繞射中為單相的磷酸鎢酸鋯。According to the present invention, an industrially advantageous method can be used to obtain a zirconium phosphate tungstate which is useful as a negative thermal expansion material and which is single phase in X-ray diffraction.
以下，基於本發明的較佳實施形態對本發明進行說明。 本發明的磷酸鎢酸鋯的製造方法的特徵在於：將鎢化合物、與包含磷及鋯的不定形化合物的混合物作為反應前驅物，對該反應前驅物進行煅燒。Hereinafter, the present invention will be described based on preferred embodiments of the present invention. The method for producing zirconium phosphotungstate according to the present invention is characterized in that a mixture of a tungsten compound and an amorphous compound containing phosphorus and zirconium is used as a reaction precursor, and the reaction precursor is calcined.
本發明者等人發現，藉由磷酸與鋯化合物的反應而獲得的包含磷及鋯的無定形化合物為微細的一次粒子，是以所需的莫耳比包含磷原子及鋯原子者。另外，於鎢化合物均勻分散的漿料中，藉由進行所述反應，而獲得鎢化合物、與包含磷及鋯的無定形化合物均勻分散的漿料。進而，若對其進行乾燥處理，則各原料均勻分散，成為以所需的莫耳比包含Zr、W、P的反應性優異的反應前驅物。The present inventors have found that an amorphous compound containing phosphorus and zirconium obtained by a reaction of phosphoric acid with a zirconium compound is fine primary particles, and contains a phosphorus atom and a zirconium atom at a desired molar ratio. Further, in the slurry in which the tungsten compound is uniformly dispersed, a tungsten compound and a slurry uniformly dispersed with an amorphous compound containing phosphorus and zirconium are obtained by performing the reaction. Further, when the drying treatment is carried out, the respective raw materials are uniformly dispersed, and a reaction precursor excellent in reactivity including Zr, W, and P at a desired molar ratio is obtained.
例如，於使用氫氧化鋯作為鋯化合物的情況下，當對所獲得的反應前驅物進行X射線繞射分析時，僅確認到鎢化合物的繞射峰（參照圖1），未觀察到氫氧化鋯的繞射峰。另外，當對該反應前驅物進行FT-IR分析時，氫氧化鋯與磷酸顯示出不同的紅外線吸收峰的圖案（參照圖2（a）、（b）、（c）及（d）），由此可確認添加於漿料中的氫氧化鋯與磷酸進行反應。For example, when zirconium hydroxide is used as the zirconium compound, when X-ray diffraction analysis is performed on the obtained reaction precursor, only the diffraction peak of the tungsten compound is confirmed (refer to FIG. 1), and no hydroxide is observed. A diffraction peak of zirconium. Further, when the reaction precursor is subjected to FT-IR analysis, zirconium hydroxide and phosphoric acid exhibit patterns of different infrared absorption peaks (see FIGS. 2(a), (b), (c), and (d)). From this, it was confirmed that zirconium hydroxide added to the slurry reacted with phosphoric acid.
此外，本發明者等人推測，藉由磷酸與鋯化合物的反應而獲得的包含磷及鋯的無定形化合物為無定形的磷酸鋯。Further, the inventors of the present invention presumed that the amorphous compound containing phosphorus and zirconium obtained by the reaction of phosphoric acid with a zirconium compound is amorphous zirconium phosphate.
本製造方法中，所述反應前驅物較佳為至少於950 cm-1 ～1150 cm-1 具有紅外線吸收峰，且該範圍內的紅外線吸收峰的極大值位於1030（±20）cm-1 者。In the production method, the reaction precursor preferably has an infrared absorption peak of at least 950 cm -1 to 1150 cm -1 , and the maximum value of the infrared absorption peak in the range is 1030 (±20) cm -1 . .
另外，所述反應前驅物中的Zr、W、P的莫耳比為Zr/W=1.7～2.3，較佳為1.9～2.1，P/W=1.7～2.3，較佳為1.9～2.1。Further, the molar ratio of Zr, W, and P in the reaction precursor is Zr/W = 1.7 to 2.3, preferably 1.9 to 2.1, and P/W = 1.7 to 2.3, preferably 1.9 to 2.1.
本發明中，所述反應前驅物較佳為利用下述兩種方法而獲得者。 （1）包括以下步驟的方法（以下稱為「第一方法」）：第一步驟，製備包含鎢化合物的漿料；第二步驟，繼而於該漿料中添加磷酸、以及選自氫氧化鋯及碳酸鋯中的鋯化合物；以及第3步驟，繼而對所獲得的漿料進行總量乾燥。 （2）包括以下步驟的方法（以下稱為「第二方法」）：第A步驟，對包含鎢化合物、磷源及鋯源的漿料進行加熱處理；第B步驟，繼而利用介質磨機對該漿料進行濕式粉碎處理；以及第C步驟，繼而對所獲得的漿料進行總量乾燥。In the present invention, the reaction precursor is preferably obtained by the following two methods. (1) A method comprising the following steps (hereinafter referred to as "first method"): a first step of preparing a slurry containing a tungsten compound; a second step, followed by adding phosphoric acid to the slurry, and being selected from zirconium hydroxide And a zirconium compound in the zirconium carbonate; and a third step, followed by drying the total amount of the obtained slurry. (2) A method comprising the following steps (hereinafter referred to as "second method"): in the step A, heat-treating a slurry containing a tungsten compound, a phosphorus source, and a zirconium source; and a step B, followed by using a media mill The slurry is subjected to a wet pulverization treatment; and a C step, and then the obtained slurry is subjected to total amount drying.
＜第一方法＞ 以下，對利用第一方法來製造所述反應前驅物的方法進行說明。<First Method> Hereinafter, a method of producing the reaction precursor by the first method will be described.
第一方法的第一步驟為製備將鎢化合物均勻分散於成為分散介質的水溶媒中而得的漿料的步驟。The first step of the first method is a step of preparing a slurry obtained by uniformly dispersing a tungsten compound in an aqueous solvent which is a dispersion medium.
第一步驟的鎢化合物較佳為相對於水為不溶性或難溶性的化合物，例如可列舉三氧化鎢、鎢酸銨、氯化鎢等鎢化合物。該些化合物中，就可於工業上容易獲取純度高者，另外處理亦容易的觀點而言，較佳為三氧化鎢。The tungsten compound in the first step is preferably a compound which is insoluble or poorly soluble with respect to water, and examples thereof include a tungsten compound such as tungsten trioxide, ammonium tungstate or tungsten chloride. Among these compounds, tungsten trioxide is preferred because it is industrially easy to obtain a high purity, and the treatment is also easy.
就獲得反應性優異的反應前驅物的觀點而言，可使用的鎢化合物的較佳物性較佳為：雷射繞射·散射法所要求的平均粒徑為100 μm以下、較佳為0.1 μm～50 μm。From the viewpoint of obtaining a reaction precursor excellent in reactivity, a preferable physical property of a tungsten compound which can be used is preferably an average particle diameter required for the laser diffraction/scattering method of 100 μm or less, preferably 0.1 μm. ~50 μm.
使第一步驟的鎢化合物分散的溶媒並非僅限於水，亦可為水與親水性溶媒的混合溶媒。 就成為操作性及處理容易的黏度的漿料的觀點而言，第一步驟的漿料濃度較佳為設為5質量%～50質量%、較佳為10質量%～30質量%。The solvent for dispersing the tungsten compound in the first step is not limited to water, and may be a mixed solvent of water and a hydrophilic solvent. The slurry concentration in the first step is preferably from 5% by mass to 50% by mass, preferably from 10% by mass to 30% by mass, from the viewpoint of the slurry having operability and easy-to-handle viscosity.
就獲得反應性優異的反應前驅物的觀點而言，第一步驟較佳為製備利用雷射繞射·散射法來求出的固體成分的平均粒徑為5 μm以下、較佳為2 μm以下的漿料。From the viewpoint of obtaining a reaction precursor excellent in reactivity, in the first step, it is preferable to prepare an average particle diameter of a solid component obtained by a laser diffraction/scattering method to be 5 μm or less, preferably 2 μm or less. Slurry.
第一步驟中，使鎢化合物均勻分散於水溶媒中的方法若為可將鎢化合物均勻分散於水溶媒中的方法，則可無特別限制地使用，但鎢化合物的粒子由於凝聚性特別強，故而亦可為將分散劑添加於漿料中的方法，就獲得反應性更優異的反應前驅物的觀點而言，特佳為以固體成分的平均粒徑成為所述範圍的方式，藉由利用可同時進行粉碎與分散的介質磨機的濕式粉碎處理來進行。In the first step, the method of uniformly dispersing the tungsten compound in the aqueous solvent is a method in which the tungsten compound can be uniformly dispersed in the aqueous solvent, and it can be used without particular limitation, but the particles of the tungsten compound are particularly strong in cohesiveness. Therefore, in order to obtain a reaction precursor which is more excellent in reactivity, the method of adding a dispersing agent to the slurry is particularly preferably used in such a manner that the average particle diameter of the solid component is within the above range. The wet pulverization treatment of the pulverizing and dispersing media mill can be carried out simultaneously.
所使用的分散劑只要根據分散介質的種類來選擇適當者即可。於分散介質例如為水的情況下，可使用各種界面活性劑、聚羧酸銨鹽等作為分散劑。就分散效果提高的觀點而言，漿料中的分散劑的濃度較佳為設為0.01重量%～10重量%，特佳為設為0.1重量%～5重量%。The dispersing agent to be used may be selected as appropriate depending on the type of the dispersion medium. In the case where the dispersion medium is, for example, water, various surfactants, polycarboxylate ammonium salts and the like can be used as the dispersant. The concentration of the dispersant in the slurry is preferably from 0.01% by weight to 10% by weight, particularly preferably from 0.1% by weight to 5% by weight, from the viewpoint of improving the dispersion effect.
介質磨機可使用珠磨機、球磨機、塗料振盪器、磨碎機、砂磨機等。特佳為使用珠磨機。該情況下，運轉條件或珠的種類及大小只要根據裝置的尺寸或處理量來適當選擇即可。The media mill can use a bead mill, a ball mill, a paint shaker, a grinder, a sand mill, or the like. It is especially good to use a bead mill. In this case, the operating conditions or the type and size of the beads may be appropriately selected depending on the size of the apparatus or the amount of processing.
就更有效率地使用介質磨機進行處理的觀點而言，亦可於漿料中添加分散劑。所使用的分散劑只要根據分散介質的種類來選擇適當者即可。於分散介質例如為水的情況下，可使用各種界面活性劑、聚羧酸銨鹽等作為分散劑。就分散效果提高的觀點而言，漿料中的分散劑的濃度較佳為設為0.01重量%～10重量%，特佳為設為0.1重量%～5重量%。From the viewpoint of more efficient treatment using a media mill, a dispersant may also be added to the slurry. The dispersing agent to be used may be selected as appropriate depending on the type of the dispersion medium. In the case where the dispersion medium is, for example, water, various surfactants, polycarboxylate ammonium salts and the like can be used as the dispersant. The concentration of the dispersant in the slurry is preferably from 0.01% by weight to 10% by weight, particularly preferably from 0.1% by weight to 5% by weight, from the viewpoint of improving the dispersion effect.
就可獲得反應性更優異的反應前驅物的觀點而言，使用介質磨機的粉碎處理較佳為進行至利用雷射繞射·散射法來求出的固體成分的平均粒徑成為1 μm以下、較佳為0.1 μm～1 μm為止。 藉由所述方式，可製備鎢化合物均勻分散於水溶媒中的漿料。From the viewpoint of obtaining a reaction precursor having a more excellent reactivity, the pulverization treatment using a media mill is preferably performed until the average particle diameter of the solid component obtained by the laser diffraction/scattering method is 1 μm or less. Preferably, it is from 0.1 μm to 1 μm. By the means, a slurry in which a tungsten compound is uniformly dispersed in an aqueous solvent can be prepared.
繼而，第二步驟中，於第一步驟中獲得的漿料中添加磷酸、以及選自氫氧化鋯及碳酸鋯中的鋯化合物（以下，有時簡稱為「鋯化合物」）來製備反應前驅物。Then, in the second step, phosphoric acid and a zirconium compound selected from zirconium hydroxide and zirconium carbonate (hereinafter sometimes simply referred to as "zirconium compound") are added to the slurry obtained in the first step to prepare a reaction precursor. .
第二步驟中，藉由在鎢化合物的存在下進行磷酸與鋯化合物的反應，而獲得含有鎢化合物、與包含磷及鋯的無定形化合物的混合物的漿料。In the second step, a slurry containing a mixture of a tungsten compound and an amorphous compound containing phosphorus and zirconium is obtained by performing a reaction of phosphoric acid with a zirconium compound in the presence of a tungsten compound.
第二步驟的磷酸若為可於工業上獲取者，則可無特別限制地使用，另外，磷酸可作為磷酸水溶液而添加於第一步驟中獲得的漿料中。The phosphoric acid in the second step can be used without any particular limitation if it is industrially obtainable, and phosphoric acid can be added to the slurry obtained in the first step as an aqueous phosphoric acid solution.
第二步驟的鋯化合物為氫氧化鋯及/或碳酸鋯。 碳酸鋯可為鹼性鹽，亦可為氨或鈉、鉀等的複鹽。 鋯化合物若為可於工業上獲取者，則可無特別限制地使用，另外，鋯化合物可為無水鹽或含水鹽。 鋯化合物可直接作為粉體而添加於第一步驟中獲得的漿料中，亦可作為分散於水溶媒中的懸浮液或者溶解於水溶媒中的溶液來添加。The zirconium compound of the second step is zirconium hydroxide and/or zirconium carbonate. The zirconium carbonate may be an alkaline salt or a double salt of ammonia or sodium or potassium. The zirconium compound is not particularly limited as long as it is industrially obtainable, and the zirconium compound may be an anhydrous salt or an aqueous salt. The zirconium compound may be added as a powder directly to the slurry obtained in the first step, or may be added as a suspension dispersed in an aqueous solvent or a solution dissolved in an aqueous solvent.
就獲得負的熱膨脹大者的觀點而言，磷酸於漿料中的添加量較佳為設為以漿料中的磷酸中的P元素相對於鎢化合物中的W元素的莫耳比（P/W）計為1.7～2.3，較佳為1.9～2.1。From the viewpoint of obtaining a large negative thermal expansion, the amount of phosphoric acid added to the slurry is preferably set to the molar ratio of the P element in the phosphoric acid in the slurry to the W element in the tungsten compound (P/ W) is 1.7 to 2.3, preferably 1.9 to 2.1.
就獲得負的熱膨脹大者的觀點而言，鋯化合物於漿料中的添加量較佳為設為以漿料中的鋯化合物中的Zr元素相對於鎢化合物中的W元素的莫耳比（Zr/W）計為1.7～2.3，較佳為1.9～2.1。From the viewpoint of obtaining a large negative thermal expansion, the amount of the zirconium compound added to the slurry is preferably set to a molar ratio of the Zr element in the zirconium compound in the slurry to the W element in the tungsten compound ( Zr/W) is 1.7 to 2.3, preferably 1.9 to 2.1.
另外，就獲得負的熱膨脹大者的觀點而言，添加於漿料中的鎢化合物與磷酸的調配比例較佳為設為以磷酸中的P元素相對於鎢化合物中的W元素的莫耳比（P/W）計為1.7～2.3，較佳為1.9～2.1。Further, from the viewpoint of obtaining a large negative thermal expansion, the blending ratio of the tungsten compound to the phosphoric acid added to the slurry is preferably set to a molar ratio of the P element in the phosphoric acid to the W element in the tungsten compound. (P/W) is 1.7 to 2.3, preferably 1.9 to 2.1.
就成為操作性及處理容易的黏度的漿料的觀點而言，漿料中的磷酸與鋯化合物的反應條件較佳為設為反應溫度為5℃～100℃，較佳為10℃～50℃。The reaction conditions of the phosphoric acid and the zirconium compound in the slurry are preferably from 5 ° C to 100 ° C, preferably from 10 ° C to 50 ° C, from the viewpoint of the workability and the viscosity of the slurry which is easy to handle. .
第二步驟中的反應時間於本製造方法中並非臨界性的，只要進行充分時間的反應直至生成包含磷及鋯的無定形化合物為止即可。於多數情況下，能夠以0.5小時以上、較佳為1小時～4小時，來生成令人滿意的諸物性的鎢化合物、與包含磷及鋯的無定形化合物均勻分散的漿料。The reaction time in the second step is not critical in the present production method as long as the reaction is carried out for a sufficient period of time until an amorphous compound containing phosphorus and zirconium is formed. In many cases, a tungsten compound having satisfactory physical properties and a slurry uniformly dispersed with an amorphous compound containing phosphorus and zirconium can be produced in an amount of 0.5 hour or longer, preferably 1 hour to 4 hours.
反應結束後，第2步驟後的漿料並不進行固液分離，而是於第3步驟中對該漿料進行總量乾燥，藉此可利用第一方法來獲得本發明中使用的反應前驅物。對漿料進行總量乾燥的方法並無特別限制，若藉由噴霧乾燥來進行乾燥處理，則獲得原料粒子密集地聚集的狀態的造粒物，因此就更容易獲得於粉末X射線繞射中為單相的磷酸鎢酸鋯的觀點而言較佳。After the completion of the reaction, the slurry after the second step is not subjected to solid-liquid separation, but the total amount of the slurry is dried in the third step, whereby the first method can be used to obtain the reaction precursor used in the present invention. Things. The method of drying the total amount of the slurry is not particularly limited, and if the drying treatment is carried out by spray drying, granules in a state in which the raw material particles are densely aggregated are obtained, and thus it is more easily obtained in powder X-ray diffraction. It is preferred from the viewpoint of single-phase zirconium tungstate phosphate.
噴霧乾燥法中，藉由利用既定方法將漿料霧化，使由此產生的微細液滴乾燥而獲得反應前驅物。漿料的霧化中例如有使用旋轉圓盤的方法、以及使用壓力噴嘴的方法。第3步驟中可使用任一種方法。In the spray drying method, the slurry is atomized by a predetermined method, and the fine droplets thus produced are dried to obtain a reaction precursor. Examples of the atomization of the slurry include a method of using a rotating disk and a method of using a pressure nozzle. Any method can be used in the third step.
噴霧乾燥法中，經霧化的液滴的大小並無特別限定，較佳為1 μm～40 μm，特佳為5 μm～30 μm。於噴霧乾燥裝置中的漿料的供給量理想為考慮該觀點來決定。In the spray drying method, the size of the atomized droplets is not particularly limited, but is preferably 1 μm to 40 μm, particularly preferably 5 μm to 30 μm. The supply amount of the slurry in the spray drying device is desirably determined in consideration of this viewpoint.
此外，就防止粉體的吸濕，粉體的回收變得容易的方面而言，噴霧乾燥裝置中的熱風溫度較佳為調整為100℃～270℃，較佳為150℃～230℃。Further, the hot air temperature in the spray drying device is preferably adjusted to 100 ° C to 270 ° C, preferably 150 ° C to 230 ° C, in terms of preventing moisture absorption of the powder and facilitating recovery of the powder.
＜第二方法＞ 以下，對利用第二方法來製造所述反應前驅物的方法進行說明。<Second Method> Hereinafter, a method of producing the reaction precursor by the second method will be described.
第二方法的第A步驟是對包含選自氫氧化鋯及碳酸鋯中的鋯化合物、磷酸以及鎢化合物的漿料進行加熱處理的步驟。The third step of the second method is a step of heat-treating a slurry containing a zirconium compound selected from zirconium hydroxide and zirconium carbonate, phosphoric acid, and a tungsten compound.
若於製備使鎢化合物預先均勻分散而成的漿料後，未添加磷酸及鋯化合物，則由於鎢化合物而使漿料的黏性提高，存在難以對各原料進行均勻混合處理的傾向，但本發明者等人發現，藉由對包含鎢化合物、磷酸及鋯化合物的漿料進行加熱處理，黏性降低，獲得可利用介質磨機進行濕式粉碎處理的漿料。因此，第二方法中，藉由實施第A步驟，可一邊進行磷酸與鋯化合物的反應，一邊一下子獲得鎢化合物、與包含磷及鋯的無定形化合物均勻分散的漿料。When the slurry obtained by uniformly dispersing the tungsten compound in advance is prepared, the phosphoric acid and the zirconium compound are not added, and the viscosity of the slurry is improved by the tungsten compound, and it is difficult to uniformly mix the raw materials. The inventors have found that by heat-treating a slurry containing a tungsten compound, a phosphoric acid, and a zirconium compound, the viscosity is lowered, and a slurry which can be subjected to wet pulverization treatment by a media mill is obtained. Therefore, in the second method, by carrying out the first step, a reaction between phosphoric acid and a zirconium compound can be carried out, and a tungsten compound and a slurry uniformly dispersed with an amorphous compound containing phosphorus and zirconium can be obtained at once.
第A步驟的鎢化合物、磷酸及鋯化合物可使用與所述第一方法的第1步驟及第2步驟相同的化合物。As the tungsten compound, the phosphoric acid, and the zirconium compound in the first step, the same compounds as in the first step and the second step of the first method can be used.
就獲得負的熱膨脹大者的觀點而言，鋯化合物於漿料中的添加量較佳為設為以漿料中的鋯化合物中的Zr元素相對於鎢化合物中的W元素的莫耳比（Zr/W）計為1.7～2.3，較佳為1.9～2.1。From the viewpoint of obtaining a large negative thermal expansion, the amount of the zirconium compound added to the slurry is preferably set to a molar ratio of the Zr element in the zirconium compound in the slurry to the W element in the tungsten compound ( Zr/W) is 1.7 to 2.3, preferably 1.9 to 2.1.
就獲得負的熱膨脹大者的觀點而言，磷酸於漿料中的添加量較佳為設為以漿料中的磷酸中的P元素相對於鎢化合物中的W元素的莫耳比（P/W）計為1.7～2.3，較佳為1.9～2.1。From the viewpoint of obtaining a large negative thermal expansion, the amount of phosphoric acid added to the slurry is preferably set to the molar ratio of the P element in the phosphoric acid in the slurry to the W element in the tungsten compound (P/ W) is 1.7 to 2.3, preferably 1.9 to 2.1.
使第A步驟的鎢化合物、磷酸及鋯化合物分散的溶媒並非僅限於水，亦可為水與親水性溶媒的混合溶媒。 就成為操作性及處理容易的黏度的漿料的觀點而言，第A步驟的漿料濃度較佳為設為5質量%～50質量%，較佳為10質量%～30質量%。The solvent for dispersing the tungsten compound, the phosphoric acid, and the zirconium compound in the step A is not limited to water, and may be a mixed solvent of water and a hydrophilic solvent. The slurry concentration in the first step is preferably from 5% by mass to 50% by mass, and preferably from 10% by mass to 30% by mass, from the viewpoint of the slurry having operability and easy-to-handle viscosity.
此外，第A步驟中，各原料的添加順序並無特別限制，較佳為考慮反應裝置等來進行，就操作性變得更容易的觀點而言，較佳為於製備包含鎢化合物的漿料後，於該漿料中添加磷酸及鋯化合物。Further, in the step A, the order of addition of the respective raw materials is not particularly limited, but it is preferably carried out in consideration of a reaction apparatus or the like, and from the viewpoint of facilitating workability, it is preferred to prepare a slurry containing a tungsten compound. Thereafter, phosphoric acid and a zirconium compound are added to the slurry.
就一邊進行磷酸與鋯化合物的反應，一邊成為操作性及處理容易的黏度的漿料的觀點而言，第A步驟的漿料加熱處理溫度較佳為設為40℃～110℃，較佳為60℃～90℃。The slurry heat treatment temperature in the step A is preferably 40 to 110 ° C from the viewpoint of the reaction of the phosphoric acid with the zirconium compound and the viscosity of the slurry which is easy to handle and handle. 60 ° C ~ 90 ° C.
第A步驟中的加熱處理時間於本製造方法中並非臨界性的，只要進行充分時間的反應，直至生成包含磷及鋯的無定形化合物，並且漿料黏度適度下降為止即可。於多數情況下，能夠以0.5小時以上，較佳為1小時～4小時，來生成令人滿意的諸物性的鎢化合物、與包含磷及鋯的無定形化合物均勻分散的黏性低的漿料。The heat treatment time in the first step is not critical in the present production method, and it is sufficient that the reaction is carried out for a sufficient period of time until an amorphous compound containing phosphorus and zirconium is formed, and the viscosity of the slurry is appropriately lowered. In many cases, a tungsten compound having satisfactory physical properties and a low-viscosity slurry uniformly dispersed with an amorphous compound containing phosphorus and zirconium can be produced in an amount of 0.5 hours or longer, preferably 1 hour to 4 hours. .
繼而，第B步驟中，利用介質磨機對第A步驟中獲得的漿料進行濕式粉碎處理。Then, in the step B, the slurry obtained in the step A is subjected to wet pulverization treatment using a media mill.
第B步驟是利用介質磨機對第A步驟後的漿料進行濕式粉碎處理，獲得微細且均勻地分散有各原料的漿料的步驟。In the step B, the slurry after the step A is subjected to wet pulverization treatment using a media mill to obtain a slurry in which the raw materials are finely and uniformly dispersed.
介質磨機可使用珠磨機、球磨機、塗料振盪器、磨碎機、砂磨機等。特佳為使用珠磨機。該情況下，運轉條件或珠的種類及大小只要根據裝置的尺寸或處理量來適當選擇即可。The media mill can use a bead mill, a ball mill, a paint shaker, a grinder, a sand mill, or the like. It is especially good to use a bead mill. In this case, the operating conditions or the type and size of the beads may be appropriately selected depending on the size of the apparatus or the amount of processing.
就更有效率地使用介質磨機進行處理的觀點而言，亦可於漿料中添加分散劑。所使用的分散劑只要根據分散介質的種類來選擇適當者即可。於分散介質例如為水的情況下，可使用各種界面活性劑、聚羧酸銨鹽等作為分散劑。就分散效果提高的觀點而言，漿料中的分散劑的濃度較佳為設為0.01重量%～10重量%，特佳為設為0.1重量%～5重量%。From the viewpoint of more efficient treatment using a media mill, a dispersant may also be added to the slurry. The dispersing agent to be used may be selected as appropriate depending on the type of the dispersion medium. In the case where the dispersion medium is, for example, water, various surfactants, polycarboxylate ammonium salts and the like can be used as the dispersant. The concentration of the dispersant in the slurry is preferably from 0.01% by weight to 10% by weight, particularly preferably from 0.1% by weight to 5% by weight, from the viewpoint of improving the dispersion effect.
使用介質磨機的粉碎處理若進行至利用雷射繞射·散射法來求出的固體成分的平均粒徑成為2 μm以下、較佳為1 μm以下、特佳為0.1 μm～0.5 μm為止，則就獲得反應性更優異的反應前驅物的觀點而言較佳。In the pulverization treatment using the media mill, the average particle diameter of the solid component obtained by the laser diffraction/scattering method is 2 μm or less, preferably 1 μm or less, and particularly preferably 0.1 μm to 0.5 μm. It is preferable from the viewpoint of obtaining a reaction precursor which is more excellent in reactivity.
藉由所述方式，可製備微細的鎢化合物、與包含磷及鋯的無定形化合物均勻分散的黏性低的漿料。By the means described above, a fine tungsten compound and a low-viscosity slurry which is uniformly dispersed with an amorphous compound containing phosphorus and zirconium can be prepared.
反應結束後，第B步驟後的漿料並不進行固液分離，而是於第C步驟中將該漿料進行總量乾燥，藉此可利用第二方法來獲得本發明中使用的反應前驅物。對漿料進行總量乾燥的方法並無特別限制，若藉由噴霧乾燥來進行乾燥處理，則獲得原料粒子密集地聚集的狀態的造粒物，因此就更容易獲得於X射線繞射中為單相的磷酸鎢酸鋯的觀點而言較佳。After the completion of the reaction, the slurry after the step B is not subjected to solid-liquid separation, but the total amount of the slurry is dried in the step C, whereby the second method can be used to obtain the reaction precursor used in the present invention. Things. The method of drying the total amount of the slurry is not particularly limited, and if the drying treatment is carried out by spray drying, a granulated product in a state in which the raw material particles are densely aggregated is obtained, and thus it is more easily obtained in X-ray diffraction. From the viewpoint of single-phase zirconium tungstate phosphate, it is preferred.
噴霧乾燥法中，藉由利用既定方法將漿料霧化，使由此產生的微細液滴乾燥而獲得反應前驅物。漿料的霧化中例如有使用旋轉圓盤的方法、以及使用壓力噴嘴的方法。第C步驟中可使用任一種方法。In the spray drying method, the slurry is atomized by a predetermined method, and the fine droplets thus produced are dried to obtain a reaction precursor. Examples of the atomization of the slurry include a method of using a rotating disk and a method of using a pressure nozzle. Any of the methods can be used in the step C.
噴霧乾燥法中，經霧化的液滴的大小並無特別限定，較佳為1 μm～40 μm，特佳為5 μm～30 μm。於噴霧乾燥裝置中的漿料的供給量理想為考慮到該觀點來決定。In the spray drying method, the size of the atomized droplets is not particularly limited, but is preferably 1 μm to 40 μm, particularly preferably 5 μm to 30 μm. The supply amount of the slurry in the spray drying device is desirably determined in consideration of this viewpoint.
此外，就防止粉體的吸濕，粉體的回收變得容易的方面而言，噴霧乾燥裝置中的熱風溫度較佳為調整為100℃～270℃，較佳為150℃～230℃。Further, the hot air temperature in the spray drying device is preferably adjusted to 100 ° C to 270 ° C, preferably 150 ° C to 230 ° C, in terms of preventing moisture absorption of the powder and facilitating recovery of the powder.
本製造方法中，可使第一方法及第二方法中獲得的反應前驅物中含有燒結助劑成分。In the production method, the reaction precursor obtained in the first method and the second method may contain a sintering aid component.
燒結助劑成分例如可列舉：選自Mg、Zn、Cu、Fe、Cr、Mn、Ni、V、Li、Al、B、Na、K、F、Cl、Br、I、Ca、Sr、Ba、Ti、Hf、Nb、Ta、Y、Yb、Si、S、Mo、Co、Bi、Te、Pb、Ag、Cd、In、Sn、Sb、Te、Ga、Ge、La、Ce、Nd、Sm、Eu、Tb、Dy及Ho等中的元素，該些元素可使用一種或者兩種以上。該些元素中，較佳為選自Mg及/或V中的元素。The sintering aid component may, for example, be selected from the group consisting of Mg, Zn, Cu, Fe, Cr, Mn, Ni, V, Li, Al, B, Na, K, F, Cl, Br, I, Ca, Sr, Ba, Ti, Hf, Nb, Ta, Y, Yb, Si, S, Mo, Co, Bi, Te, Pb, Ag, Cd, In, Sn, Sb, Te, Ga, Ge, La, Ce, Nd, Sm, An element in Eu, Tb, Dy, Ho, or the like may be used alone or in combination of two or more. Among these elements, those selected from Mg and/or V are preferred.
所述燒結助劑成分較佳為作為含有該燒結助劑成分的化合物，而於第一方法中添加於第二步驟～第三步驟前的漿料中。 另外，第二方法中，較佳為第A步驟～第B步驟前的漿料，具體而言，於進行第A步驟之前、進行第A步驟的中途、第A步驟完畢後、進行第B步驟之前、以及進行第B步驟的中途中的至少一種情景下，添加含有該燒結助劑成分的化合物。The sintering aid component is preferably added as a compound containing the sintering aid component to the slurry before the second step to the third step in the first method. Further, in the second method, it is preferably the slurry before the steps A to B, specifically, before the step A, the middle of the step A, the step A, and the step B. A compound containing the sintering aid component is added in at least one of the previous and the middle of the step B.
含有燒結助劑成分的化合物可列舉：包含所述燒結助劑成分的氧化物、氫氧化物、碳酸鹽、有機酸鹽、銨鹽、硝酸鹽、磷酸鹽、硫酸鹽、氯化物、溴化物、碘化物等，該些化合物中，就容易控制製品的純度，容易獲得高純度品的觀點而言，較佳為使用包含燒結助劑成分的氧化物、氫氧化物。Examples of the compound containing a sintering aid component include oxides, hydroxides, carbonates, organic acid salts, ammonium salts, nitrates, phosphates, sulfates, chlorides, bromides, and the like. Among these compounds, from the viewpoint of easily controlling the purity of the product and easily obtaining a high-purity product, it is preferred to use an oxide or a hydroxide containing a sintering aid component.
此外，第一方法及第二方法中，為了使所添加的含有燒結助劑成分的化合物於漿料中溶解或析出，可視需要利用鹼或酸來調整pH值。Further, in the first method and the second method, in order to dissolve or precipitate the added compound containing the sintering aid component in the slurry, the pH may be adjusted by using an alkali or an acid as needed.
含有燒結助劑成分的化合物於漿料中的添加量較佳為以由燒結助劑成分計成為0.05質量%～5.0質量%、較佳為0.1質量%～3.0質量%的方式添加於所獲得的反應前驅物中。The amount of the compound containing the sintering aid component to be added to the slurry is preferably such that it is added in an amount of 0.05% by mass to 5.0% by mass, preferably 0.1% by mass to 3.0% by mass, based on the sintering aid component. Reaction precursor.
燒結助劑成分可作為所添加的含有燒結助劑成分的化合物而直接含有於反應前驅物中，所添加的含有燒結助劑成分的化合物亦可於漿料中進行反應，轉換為其他的含有燒結助劑成分的化合物而含有於反應前驅物中。 例如，於使用氫氧化物來作為含有燒結助劑成分的化合物的情況下，存在如下情況：於漿料中與磷酸進行反應，轉換為含有燒結助劑成分的磷酸鹽而含有於反應前驅物中。 此外，反應前驅物中所包含的含有燒結助劑成分的化合物可為結晶質或不定形者。The sintering aid component may be directly contained in the reaction precursor as a compound containing a sintering aid component, and the added compound containing the sintering aid component may be reacted in the slurry to be converted into other sintering-containing components. The compound of the auxiliary component is contained in the reaction precursor. For example, when a hydroxide is used as the compound containing a sintering aid component, the slurry is reacted with phosphoric acid, converted into a phosphate containing a sintering aid component, and contained in the reaction precursor. . Further, the compound containing the sintering aid component contained in the reaction precursor may be crystalline or amorphous.
本發明中，可藉由設置對所述反應前驅物進行煅燒的煅燒步驟而獲得作為目標的磷酸鎢酸鋯。In the present invention, the intended zirconium phosphate tungstate can be obtained by providing a calcination step of calcining the reaction precursor.
煅燒步驟中，對反應前驅物進行煅燒的煅燒溫度為900℃～1300℃。其原因在於：若煅燒溫度小於900℃，則未反應的氧化物等殘存，而存在難以獲得於X射線繞射中為單相的磷酸鎢酸鋯的傾向，另一方面，若煅燒溫度高於1300℃，則成為粒子彼此固結的狀態的塊，存在難以獲得粉末的傾向。 此外，本製造方法中，由於可於低溫下獲得於X射線繞射中為單相的磷酸鎢酸鋯，故而為了有效利用該優點，較佳為將煅燒溫度設為900℃～1100℃來進行。In the calcination step, the calcination temperature at which the reaction precursor is calcined is from 900 ° C to 1300 ° C. The reason for this is that if the calcination temperature is less than 900 ° C, unreacted oxide or the like remains, and it is difficult to obtain zirconium phosphate zirconate which is single phase in X-ray diffraction, and on the other hand, if the calcination temperature is higher than At 1300 ° C, the particles are in a state of being consolidated with each other, and it is difficult to obtain a powder. Further, in the present production method, since zirconium phosphate zirconate which is single-phase in X-ray diffraction can be obtained at a low temperature, in order to effectively utilize the advantage, it is preferred to carry out the calcination temperature at 900 ° C to 1100 ° C. .
煅燒時間於本製造方法中並非臨界性的，進行充分時間的反應直至生成於X射線繞射中為單相的磷酸鎢酸鋯為止。於多數情況下，能夠以1小時以上、較佳為2小時～20小時來生成令人滿意的諸物性的磷酸鎢酸鋯。另外，煅燒環境並無特別限制，可為惰性氣體環境下、真空環境下、氧化性氣體環境下、大氣中的任一者。The calcination time is not critical in the present production method, and the reaction is carried out for a sufficient period of time until it is formed into a single-phase zirconium phosphate zirconate during X-ray diffraction. In many cases, a satisfactory physical property of zirconium phosphotungstate can be produced for 1 hour or longer, preferably 2 hours to 20 hours. Further, the calcination atmosphere is not particularly limited, and may be any of an inert gas atmosphere, a vacuum atmosphere, an oxidizing gas atmosphere, and an atmosphere.
煅燒可視需要進行多次。或者，出於使粉體特性均勻的目的，亦可將一次煅燒者粉碎，繼而進行再煅燒。Calcination can be carried out as many times as necessary. Alternatively, for the purpose of making the powder characteristics uniform, the primary calciner may be pulverized and then re-calcined.
煅燒後，適當冷卻，視需要進行粉碎、壓碎、分級等，可獲得作為目標的於X射線繞射中為單相的磷酸鎢酸鋯。After the calcination, it is appropriately cooled, and if necessary, pulverized, crushed, classified, or the like, and a target single-phase zirconium tungstate phosphate which is a single phase in X-ray diffraction can be obtained.
本製造方法中獲得的磷酸鎢酸鋯除了是由Zr2 (WO4 )(PO4 )2 所表示，且為於X射線繞射中為單相的磷酸鎢酸鋯以外，就當將該磷酸鎢酸鋯用作在樹脂或玻璃等中的填料用途時，處理變得容易的觀點而言，較佳為：藉由掃描型電子顯微鏡觀察來求出的平均一次粒徑為5 μm以下，較佳為0.1 μm～4 μm，平均二次粒徑為1 μm～40 μm，較佳為4 μm～30 μm，布厄特（Brunauer-Emmett-Teller，BET）比表面積為0.1 m2 /g～20 m2 /g，較佳為0.1 m2 /g～10 m2 /g。The zirconium phosphotungstate obtained in the present production method is represented by Zr 2 (WO 4 )(PO 4 ) 2 and is a single-phase zirconium phosphate zirconate in X-ray diffraction. When zirconium tungstate is used as a filler in a resin or glass, and the handling is easy, it is preferable that the average primary particle diameter obtained by observation by a scanning electron microscope is 5 μm or less. Preferably, it is from 0.1 μm to 4 μm, the average secondary particle diameter is from 1 μm to 40 μm, preferably from 4 μm to 30 μm, and the Brunauer-Emmett-Teller (BET) specific surface area is 0.1 m 2 /g. 20 m 2 /g, preferably 0.1 m 2 /g to 10 m 2 /g.
本製造方法中獲得的磷酸鎢酸鋯尤其可用作顯示出負的熱膨脹的負熱膨脹材，本製造方法中獲得的磷酸鎢酸鋯於0℃～400℃的溫度範圍內的線膨脹係數為-3.4 ppm/℃～-2.6 ppm/℃、較佳為-3.4 ppm/℃～-2.8 ppm/℃。The zirconium tungstate phosphate obtained in the present production method is particularly useful as a negative thermal expansion material exhibiting negative thermal expansion, and the linear expansion coefficient of the zirconium phosphate zirconate obtained in the present production method in the temperature range of 0 ° C to 400 ° C is - 3.4 ppm/°C to -2.6 ppm/°C, preferably -3.4 ppm/°C to -2.8 ppm/°C.
本製造方法中獲得的磷酸鎢酸鋯可用作粉體或糊料。於用作糊料的情況下，能夠以與黏性低的液狀樹脂的糊料的狀態來使用。或者，亦可以含有溶解，進而視需要含有黏合劑、助熔材及分散劑等的糊料的狀態來使用。The zirconium tungstate phosphate obtained in the present production method can be used as a powder or a paste. When it is used as a paste, it can be used in the state of the paste of the liquid resin with low viscosity. Alternatively, it may be used in a state of being dissolved, and if necessary, a paste containing a binder, a fluxing material, a dispersing agent, or the like.
本製造方法中獲得的磷酸鎢酸鋯可與各種有機化合物或者無機化合物併用來用作複合材料。所述有機化合物或者無機化合物並無特別限定，有機化合物可列舉：橡膠、聚烯烴、聚環烯烴、聚苯乙烯、丙烯腈丁二烯苯乙烯（acrylonitrile butadiene styrene，ABS）、聚丙烯酸酯、聚苯硫醚、酚樹脂、聚醯胺樹脂、聚醯亞胺樹脂、環氧樹脂、矽酮樹脂、聚碳酸酯樹脂、聚乙烯樹脂、聚丙烯樹脂、聚對苯二甲酸乙二酯樹脂（polyethylene terephthalate resin，PET樹脂）及聚氯乙烯樹脂等。另外，無機化合物可列舉：二氧化矽、石墨、藍寶石、各種玻璃材料、混凝土材料、各種陶瓷材料等。The zirconium tungstate phosphate obtained in the present production method can be used as a composite material with various organic compounds or inorganic compounds. The organic compound or inorganic compound is not particularly limited, and examples of the organic compound include rubber, polyolefin, polycycloolefin, polystyrene, acrylonitrile butadiene styrene (ABS), polyacrylate, and poly Phenyl sulfide, phenol resin, polyamide resin, polyimide resin, epoxy resin, fluorenone resin, polycarbonate resin, polyethylene resin, polypropylene resin, polyethylene terephthalate resin (polyethylene) Terephthalate resin, PET resin, and polyvinyl chloride resin. Further, examples of the inorganic compound include cerium oxide, graphite, sapphire, various glass materials, concrete materials, various ceramic materials, and the like.
所述複合材料由於含有成為本發明的負熱膨脹材的磷酸鎢酸鋯，故而可根據與其他化合物的調配比率來實現負熱膨脹率、零熱膨脹率或者低熱膨脹率。 [實施例]Since the composite material contains zirconium phosphate tungstate which is a negative thermal expansion material of the present invention, a negative thermal expansion coefficient, a zero thermal expansion coefficient, or a low thermal expansion coefficient can be achieved according to a compounding ratio with other compounds. [Examples]
以下，藉由實施例來對本發明進行說明，但本發明並不限定於該些實施例。 ＜評價裝置＞ 1. X射線繞射分析：磷酸鎢酸鋯與反應前驅物的X射線繞射分析是使用理學（Rigaku）公司的阿爾奇馬（Ultima）IV。使用Cu-Kα作為輻射源。測定條件設為管電壓40 kV、管電流40 mA、掃描速度0.1°/sec。 2. 紅外吸收光譜（FT-IR）分析：反應前驅物的紅外吸收光譜分析是利用賽默飛世爾科技（Thermo Fisher Scientific）公司製造的尼高力（NICOLET）6700，以分解能力：4 cm-1 、累計數：256次、測定波數區域：400 cm-1 ～4000 cm-1 的條件來測定。利用衰減全反射（attenuated total reflection，ATR）法來測定，進行ATR校正及光譜的平滑化處理（smoothing processing）。 3. 平均粒徑：各原料及漿料中的固體成分的平均粒徑是利用雷射繞射·散射法，使用麥奇克（Microtrac）MT3300EXII粒度分析計（麥奇克拜爾（MicrotracBEL）公司製造）來測定。Hereinafter, the present invention will be described by way of examples, but the invention is not limited thereto. <Evaluation device> 1. X-ray diffraction analysis: X-ray diffraction analysis of zirconium tungstate phosphate and reaction precursor was carried out using Rigaku's Ultima IV. Cu-Kα was used as a radiation source. The measurement conditions were a tube voltage of 40 kV, a tube current of 40 mA, and a scanning speed of 0.1°/sec. 2. Infrared Absorption Spectroscopy (FT-IR) Analysis: The infrared absorption spectrum analysis of the reaction precursor was performed using a NICOLET 6700 manufactured by Thermo Fisher Scientific, with a decomposition capacity of 4 cm - 1 , cumulative number: 256 times, measured wave number area: 400 cm -1 ~ 4000 cm -1 conditions to determine. The ATR correction and the smoothing processing of the spectrum were performed by an attenuated total reflection (ATR) method. 3. Average particle size: The average particle size of the solid components in each raw material and slurry is laser diffraction/scattering method using Microtrac MT3300EXII particle size analyzer (MicrotracBEL) Manufacture) to determine.
{實施例1} 將15質量份的市售的三氧化鎢（WO3 ；平均粒徑1.2 μm）加入至燒杯中，進而添加84重量份的純水，投入1重量份的作為分散劑的聚羧酸銨鹽。 於室溫（25℃）下使用三一馬達（Three-One Motor）攪拌機來攪拌120分鐘，製備包含三氧化鎢的15質量%漿料。漿料中的固體成分的平均粒徑為1.2 μm。 繼而，於該漿料中，以漿料中的Zr：W：P的莫耳比成為2.00：1.00：2.00的方式，於室溫（25℃）下添加氫氧化鋯、及85質量%磷酸水溶液，一邊攪拌一邊反應2小時。 反應結束後，對漿料的總量於200℃、大氣下進行24小時乾燥，獲得反應前驅物。對所獲得的反應前驅物進行X射線繞射，結果僅觀察到三氧化鎢的繞射峰（參照圖1（a））。另外，以FT-IR進行分析的結果為，於950 cm-1 ～1150 cm-1 具有紅外線吸收峰，此間的紅外線吸收峰的極大值出現於1027 cm-1 （參照圖2（a）、（b）、（c）及（d））。 繼而，對所獲得的反應前驅物於950℃下，於大氣中進行2小時的煅燒反應，獲得白色的煅燒品。 對所獲得的煅燒品進行X射線繞射分析的結果為，煅燒品為單相的Zr2 (WO4 )(PO4 )2 （參照圖3）。{Example 1} 15 parts by mass of commercially available tungsten trioxide (WO 3 ; average particle diameter 1.2 μm) was placed in a beaker, and further 84 parts by weight of pure water was added, and 1 part by weight of a polydispersant was charged. Ammonium carboxylate. The mixture was stirred at room temperature (25 ° C) using a Three-One Motor mixer for 120 minutes to prepare a 15% by mass slurry containing tungsten trioxide. The solid content of the solid content in the slurry was 1.2 μm. Then, in the slurry, zirconium hydroxide and an 85 mass% phosphoric acid aqueous solution were added at room temperature (25 ° C) so that the molar ratio of Zr:W:P in the slurry was 2.00:1.00:2.00. The reaction was carried out for 2 hours while stirring. After completion of the reaction, the total amount of the slurry was dried at 200 ° C for 24 hours in the air to obtain a reaction precursor. X-ray diffraction of the obtained reaction precursor was carried out, and as a result, only a diffraction peak of tungsten trioxide was observed (refer to Fig. 1 (a)). In addition, as a result of analysis by FT-IR, an infrared absorption peak is obtained at 950 cm -1 to 1150 cm -1 , and the maximum value of the infrared absorption peak appears at 1027 cm -1 (refer to Fig. 2 (a), b), (c) and (d)). Then, the obtained reaction precursor was calcined in the air at 950 ° C for 2 hours to obtain a white calcined product. As a result of performing X-ray diffraction analysis on the obtained calcined product, the calcined product was a single-phase Zr 2 (WO 4 )(PO 4 ) 2 (see Fig. 3).
{實施例2} 秤量15質量份的市售的三氧化鎢（WO3 ；平均粒徑25 μm），投入至槽中。於槽中投入84重量份的純水、1重量份的作為分散劑的聚羧酸銨鹽。 繼而，將漿料一邊攪拌，一邊供給至投入有直徑為0.5 mm的氧化鋯珠的介質攪拌型珠磨機中，混合15分鐘來進行濕式粉碎。濕式粉碎後的漿料中的固體成分的平均粒徑為0.3 μm。 繼而，於該漿料中，以漿料中的Zr：W：P的莫耳比成為2.00：1.00：2.00的方式，於室溫（25℃）下添加氫氧化鋯、及85質量%磷酸水溶液，一邊攪拌一邊反應2小時。 反應結束後，於設定為220℃的噴射乾燥機中，以2.4 L/h的供給速度來供給漿料，獲得反應前驅物。對所獲得的反應前驅物進行X射線繞射，結果僅觀察到三氧化鎢的繞射峰。另外，以FT-IR進行分析的結果為，於950 cm-1 ～1150 cm-1 具有紅外線吸收峰，此間的紅外線吸收峰的極大值出現於1030 cm-1 。 繼而，對所獲得的反應前驅物於950℃下，於大氣中進行2小時的煅燒反應，獲得白色的煅燒品。 對所獲得的煅燒品進行X射線繞射分析的結果為，煅燒品為單相的Zr2 (WO4 )(PO4 )2 。{Example 2} 15 parts by mass of commercially available tungsten trioxide (WO 3 ; average particle diameter: 25 μm) was weighed and placed in a tank. 84 parts by weight of pure water and 1 part by weight of a polycarboxylic acid ammonium salt as a dispersing agent were charged into the tank. Then, the slurry was supplied to a medium agitating bead mill in which zirconia beads having a diameter of 0.5 mm were placed while being stirred, and mixed for 15 minutes to carry out wet pulverization. The average particle diameter of the solid content in the slurry after the wet pulverization was 0.3 μm. Then, in the slurry, zirconium hydroxide and an 85 mass% phosphoric acid aqueous solution were added at room temperature (25 ° C) so that the molar ratio of Zr:W:P in the slurry was 2.00:1.00:2.00. The reaction was carried out for 2 hours while stirring. After completion of the reaction, the slurry was supplied at a supply rate of 2.4 L/h in a spray dryer set at 220 ° C to obtain a reaction precursor. X-ray diffraction of the obtained reaction precursor was carried out, and as a result, only a diffraction peak of tungsten trioxide was observed. Further, as a result of analysis by FT-IR, an infrared absorption peak was observed at 950 cm -1 to 1150 cm -1 , and the maximum value of the infrared absorption peak at this time appeared at 1030 cm -1 . Then, the obtained reaction precursor was calcined in the air at 950 ° C for 2 hours to obtain a white calcined product. As a result of performing X-ray diffraction analysis on the obtained calcined product, the calcined product was a single phase of Zr 2 (WO 4 )(PO 4 ) 2 .
{比較例1} 秤量7質量份的市售的三氧化鎢（WO3 ；平均粒徑25 μm）與市售的氧化鋯（ZrO2 ；平均粒徑6.5 μm），以W：Zr的莫耳比成為2.00：1.00的方式投入至槽中。於槽中添加84重量份的純水、1重量份的作為分散劑的聚羧酸銨鹽，製備固體成分濃度為15%的漿料。 繼而，將漿料一邊攪拌，一邊供給至投入有直徑為0.5 mm的氧化鋯珠的介質攪拌型珠磨機中，混合15分鐘來進行濕式粉碎。濕式粉碎後的漿料中的固體成分的平均粒徑為0.3 μm。 繼而，於該漿料中，以漿料中的Zr：W：P的莫耳比成為2.00：1.00：2.00的方式添加85質量%磷酸水溶液，於室溫（25℃）下進行2小時攪拌。 反應結束後，對漿料的總量於200℃、大氣下進行24小時乾燥，獲得反應前驅物。對所獲得的反應前驅物進行X射線繞射，結果，觀察到三氧化鎢與氧化鋯的繞射峰（參照圖4）。 繼而，對所獲得的反應前驅物於950℃下，於大氣中進行2小時的煅燒反應，獲得綠白色的煅燒品。 對所獲得的煅燒品進行X射線繞射分析的結果為，煅燒品為包含大量異相者，且稍微生成Zr2 (WO4 )(PO4 )2 （參照圖5）。{Comparative Example 1} 7 parts by mass of commercially available tungsten trioxide (WO 3 ; average particle diameter 25 μm) and commercially available zirconia (ZrO 2 ; average particle diameter 6.5 μm) were weighed in a W:Zr molar It is put into the slot in a way that becomes 2.00:1.00. 84 parts by weight of pure water and 1 part by weight of a polycarboxylic acid ammonium salt as a dispersing agent were added to the tank to prepare a slurry having a solid concentration of 15%. Then, the slurry was supplied to a medium agitating bead mill in which zirconia beads having a diameter of 0.5 mm were placed while being stirred, and mixed for 15 minutes to carry out wet pulverization. The average particle diameter of the solid content in the slurry after the wet pulverization was 0.3 μm. Then, in the slurry, an 85 mass% phosphoric acid aqueous solution was added so that the molar ratio of Zr:W:P in the slurry was 2.00:1.00:2.00, and the mixture was stirred at room temperature (25 ° C) for 2 hours. After completion of the reaction, the total amount of the slurry was dried at 200 ° C for 24 hours in the air to obtain a reaction precursor. X-ray diffraction of the obtained reaction precursor was carried out, and as a result, diffraction peaks of tungsten trioxide and zirconium oxide were observed (refer to Fig. 4). Then, the obtained reaction precursor was calcined in the air at 950 ° C for 2 hours to obtain a greenish white calcined product. As a result of performing X-ray diffraction analysis on the obtained calcined product, the calcined product contained a large amount of heterogeneous phase, and Zr 2 (WO 4 )(PO 4 ) 2 was slightly formed (see Fig. 5).
＜物性評價＞ 對於實施例1～實施例2及比較例1中獲得的磷酸鎢酸鋯，測定平均一次粒徑、平均二次粒徑、BET比表面積及熱膨脹係數。將其結果示於表1中。另外，將實施例2中獲得的磷酸鎢酸鋯的SEM照片示於圖6中。<Evaluation of Physical Properties> The average primary particle diameter, the average secondary particle diameter, the BET specific surface area, and the thermal expansion coefficient of the zirconium phosphate zirconate obtained in Examples 1 to 2 and Comparative Example 1 were measured. The results are shown in Table 1. Further, an SEM photograph of zirconium phosphate zirconate obtained in Example 2 is shown in Fig. 6 .
（平均一次粒徑的評價） 磷酸鎢酸鋯的平均一次粒徑是根據於掃描型電子顯微鏡觀察中，以倍率5千倍任意抽出的50個以上的粒子的平均值來求出。 （平均二次粒徑的評價） 磷酸鎢酸鋯的平均二次粒徑是根據於掃描型電子顯微鏡觀察中，以倍率400倍任意抽出的50個以上的粒子的平均值來求出。 （線膨脹係數的評價） 利用帶有升溫功能的X射線繞射（X-Ray Diffractometer，XRD）裝置（理學（Rigaku）公司，阿爾奇馬（Ultima）IV），以升溫速度20℃/min達到目標溫度10分鐘後，測定試樣的相對於a軸、b軸、c軸的晶格常數，對晶格體積變化（長方體）進行線換算來求出線膨脹係數（參照「材料科學雜誌（Journal of Materials Science，J. Mat. Sci.）」，35（2000）第2451-2454頁）。(Evaluation of Average Primary Particle Diameter) The average primary particle diameter of zirconium tungstate phosphate is determined from the average value of 50 or more particles arbitrarily extracted at a magnification of 5,000 times in scanning electron microscope observation. (Evaluation of Average Secondary Particle Diameter) The average secondary particle diameter of zirconium tungstate phosphate is determined from the average value of 50 or more particles which are arbitrarily extracted at a magnification of 400 times in scanning electron microscope observation. (Evaluation of coefficient of linear expansion) Using an X-ray Diffractometer (XRD) apparatus with a temperature rising function (Rigaku Corporation, Ultima IV), the temperature rise rate was 20 ° C / min. After the target temperature was 10 minutes, the lattice constant of the sample with respect to the a-axis, the b-axis, and the c-axis was measured, and the linear volume conversion was obtained by linearly converting the lattice volume change (cuboid) (refer to Journal of Materials Science (Journal) Of Materials Science, J. Mat. Sci.)", 35 (2000) pp. 2451-2454).
[表1]
{實施例3} 將15質量份的市售的三氧化鎢（WO3 ；平均粒徑1.2 μm）加入至燒杯中，進而添加84重量份的純水。 於室溫（25℃）下攪拌120分鐘，製備包含三氧化鎢的15質量%漿料。漿料中的固體成分的平均粒徑為1.2 μm。 繼而，於該漿料中，以漿料中的Zr：W：P：Mg的莫耳比成為2.00：1.00：2.00：0.1的方式，於室溫（25℃）下添加氫氧化鋯、85質量%磷酸水溶液及氫氧化鎂後，升溫至80℃，一邊攪拌一邊反應4小時。 反應結束後，投入1重量份的作為分散劑的聚羧酸銨鹽，將漿料一邊攪拌，一邊供給至投入有直徑為0.5 mm的氧化鋯珠的介質攪拌型珠磨機中，混合15分鐘來進行濕式粉碎。濕式粉碎後的漿料中的固體成分的平均粒徑為0.3 μm。 繼而，於設定為220℃的噴射乾燥機中，以2.4 L/h的供給速度來供給漿料，獲得反應前驅物。對所獲得的反應前驅物進行X射線繞射，結果僅觀察到三氧化鎢的繞射峰（參照圖7）。另外，以FT-IR進行分析的結果為，於950 cm-1 ～1150 cm-1 具有紅外線吸收峰，此間的紅外線吸收峰的極大值出現於1042 cm-1 （參照圖8）。 此外推測，燒結助劑成分的Mg是藉由漿料中的磷酸與氫氧化鎂的反應，作為不定形的磷酸鎂而存在於反應前驅物中。 繼而，對所獲得的反應前驅物於1050℃下，於大氣中進行2小時的煅燒反應，獲得白色的煅燒品。 對所獲得的煅燒品進行X射線繞射分析的結果為，煅燒品為單相的Zr2 (WO4 )(PO4 )2 （參照圖9）。{Example 3} 15 parts by mass of commercially available tungsten trioxide (WO 3 ; average particle diameter 1.2 μm) was placed in a beaker, and further 84 parts by weight of pure water was added. The mixture was stirred at room temperature (25 ° C) for 120 minutes to prepare a 15% by mass slurry containing tungsten trioxide. The solid content of the solid content in the slurry was 1.2 μm. Then, in the slurry, zirconium hydroxide and 85 mass are added at room temperature (25 ° C) so that the molar ratio of Zr:W:P:Mg in the slurry becomes 2.00:1.00:2.00:0.1. After the % phosphoric acid aqueous solution and magnesium hydroxide, the temperature was raised to 80 ° C, and the reaction was carried out for 4 hours while stirring. After completion of the reaction, 1 part by weight of a polycarboxylate ammonium salt as a dispersing agent was charged, and the slurry was supplied to a medium agitating bead mill in which zirconia beads having a diameter of 0.5 mm were placed, and mixed for 15 minutes while stirring. To carry out wet pulverization. The average particle diameter of the solid content in the slurry after the wet pulverization was 0.3 μm. Then, in a spray dryer set at 220 ° C, the slurry was supplied at a supply rate of 2.4 L/h to obtain a reaction precursor. X-ray diffraction of the obtained reaction precursor was carried out, and as a result, only a diffraction peak of tungsten trioxide was observed (refer to Fig. 7). Further, as a result of analysis by FT-IR, an infrared absorption peak was observed at 950 cm -1 to 1150 cm -1 , and the maximum value of the infrared absorption peak at this time appeared at 1042 cm -1 (see Fig. 8). Further, it is presumed that Mg of the sintering aid component is present in the reaction precursor as an amorphous magnesium phosphate by the reaction of phosphoric acid and magnesium hydroxide in the slurry. Then, the obtained reaction precursor was calcined in the air at 1,050 ° C for 2 hours to obtain a white calcined product. As a result of performing X-ray diffraction analysis on the obtained calcined product, the calcined product was a single-phase Zr 2 (WO 4 )(PO 4 ) 2 (see Fig. 9).
{實施例4} 將15質量份的市售的三氧化鎢（WO3 ；平均粒徑1.2 μm）加入至燒杯中，進而添加84重量份的純水，投入1重量份的作為分散劑的聚羧酸銨鹽。 於室溫（25℃）下攪拌120分鐘，製備包含三氧化鎢的15質量%漿料。漿料中的固體成分的平均粒徑為1.2 μm。 繼而，於該漿料中，以漿料中的Zr：W：P：Mg：V的莫耳比成為2.00：1.00：2.00：0.1：0.05的方式，於室溫（25℃）下添加氫氧化鋯、85質量%磷酸水溶液、氫氧化鎂及五氧化二釩後，升溫至80℃，一邊攪拌一邊反應4小時。 反應結束後，將漿料一邊攪拌，一邊供給至投入有直徑為0.5 mm的氧化鋯珠的介質攪拌型珠磨機中，混合15分鐘來進行濕式粉碎。濕式粉碎後的漿料中的固體成分的平均粒徑為0.3 μm。 繼而，於設定為220℃的噴射乾燥機中，以2.4 L/h的供給速度來供給漿料，獲得反應前驅物。對所獲得的反應前驅物進行X射線繞射，結果僅觀察到三氧化鎢的繞射峰。另外，以FT-IR進行分析的結果為，於950 cm-1 ～1150 cm-1 具有紅外線吸收峰，此間的紅外線吸收峰的極大值出現於1030 cm-1 。 此外推測，燒結助劑成分的Mg是藉由漿料中的磷酸與氫氧化鎂的反應，作為不定形的磷酸鎂而存在於反應前驅物中。另一方面推測，燒結助劑成分的V雖於X射線繞射中，由於為檢測極限以下而未檢測出繞射峰，但作為五氧化二釩而存在於反應前驅物中。 繼而，對所獲得的反應前驅物於1050℃下，於大氣中進行2小時的煅燒反應，獲得白色的煅燒品。 對所獲得的煅燒品進行X射線繞射分析的結果為，煅燒品為單相的Zr2 (WO4 )(PO4 )2 。{Example 4} 15 parts by mass of commercially available tungsten trioxide (WO 3 ; average particle diameter 1.2 μm) was placed in a beaker, and further 84 parts by weight of pure water was added, and 1 part by weight of a polydispersant was charged. Ammonium carboxylate. The mixture was stirred at room temperature (25 ° C) for 120 minutes to prepare a 15% by mass slurry containing tungsten trioxide. The solid content of the solid content in the slurry was 1.2 μm. Then, in the slurry, hydrogen peroxide was added at room temperature (25 ° C) so that the molar ratio of Zr:W:P:Mg:V in the slurry was 2.00:1.00:2.00:0.1:0.05. Zirconium, an 85 mass% phosphoric acid aqueous solution, magnesium hydroxide, and vanadium pentoxide were heated to 80 ° C, and reacted for 4 hours while stirring. After completion of the reaction, the slurry was supplied to a medium agitating bead mill into which zirconia beads having a diameter of 0.5 mm were placed, and mixed for 15 minutes to carry out wet pulverization. The average particle diameter of the solid content in the slurry after the wet pulverization was 0.3 μm. Then, in a spray dryer set at 220 ° C, the slurry was supplied at a supply rate of 2.4 L/h to obtain a reaction precursor. X-ray diffraction of the obtained reaction precursor was carried out, and as a result, only a diffraction peak of tungsten trioxide was observed. Further, as a result of analysis by FT-IR, an infrared absorption peak was observed at 950 cm -1 to 1150 cm -1 , and the maximum value of the infrared absorption peak at this time appeared at 1030 cm -1 . Further, it is presumed that Mg of the sintering aid component is present in the reaction precursor as an amorphous magnesium phosphate by the reaction of phosphoric acid and magnesium hydroxide in the slurry. On the other hand, it is estimated that the V of the sintering aid component is not detected as a diffraction peak in the X-ray diffraction, but is present as a vanadium pentoxide in the reaction precursor. Then, the obtained reaction precursor was calcined in the air at 1,050 ° C for 2 hours to obtain a white calcined product. As a result of performing X-ray diffraction analysis on the obtained calcined product, the calcined product was a single phase of Zr 2 (WO 4 )(PO 4 ) 2 .
{實施例5} 將15質量份的市售的三氧化鎢（WO3 ；平均粒徑1.2 μm）加入至燒杯中，進而添加84重量份的純水。 於室溫（25℃）下攪拌120分鐘，製備包含三氧化鎢的15質量%漿料。漿料中的固體成分的平均粒徑為1.2 μm。 繼而，於該漿料中，以漿料中的Zr：W：P：Mg的莫耳比成為2.00：1.00：2.00：0.1的方式，於室溫（25℃）下添加氫氧化鋯、85質量%磷酸水溶液及氫氧化鎂後，升溫至80℃，一邊攪拌一邊反應4小時。 反應結束後，投入1重量份的作為分散劑的聚羧酸銨鹽，將漿料一邊攪拌，一邊供給至投入有直徑為0.5 mm的氧化鋯珠的介質攪拌型珠磨機中，混合15分鐘來進行濕式粉碎。濕式粉碎後的漿料中的固體成分的平均粒徑為0.3 μm。 繼而，於設定為220℃的噴射乾燥機中，以2.4 L/h的供給速度來供給漿料，獲得反應前驅物。對所獲得的反應前驅物進行X射線繞射，結果僅觀察到三氧化鎢的繞射峰。另外，以FT-IR進行分析的結果為，於950 cm-1 ～1150 cm-1 具有紅外線吸收峰，此間的紅外線吸收峰的極大值出現於1030 cm-1 。 此外推測，燒結助劑成分的Mg藉由漿料中的磷酸與氫氧化鎂的反應，作為不定形的磷酸鎂而存在於反應前驅物中。 繼而，對所獲得的反應前驅物於960℃下，於大氣中進行2小時的煅燒反應，獲得白色的煅燒品。將其以氣流式粉碎機加以粉碎而獲得粉碎品。 對所獲得的煅燒品進行X射線繞射分析的結果為，煅燒品為單相的Zr2 (WO4 )(PO4 )2 。{Example 5} 15 parts by mass of commercially available tungsten trioxide (WO 3 ; average particle diameter 1.2 μm) was placed in a beaker, and further 84 parts by weight of pure water was added. The mixture was stirred at room temperature (25 ° C) for 120 minutes to prepare a 15% by mass slurry containing tungsten trioxide. The solid content of the solid content in the slurry was 1.2 μm. Then, in the slurry, zirconium hydroxide and 85 mass are added at room temperature (25 ° C) so that the molar ratio of Zr:W:P:Mg in the slurry becomes 2.00:1.00:2.00:0.1. After the % phosphoric acid aqueous solution and magnesium hydroxide, the temperature was raised to 80 ° C, and the reaction was carried out for 4 hours while stirring. After completion of the reaction, 1 part by weight of a polycarboxylate ammonium salt as a dispersing agent was charged, and the slurry was supplied to a medium agitating bead mill in which zirconia beads having a diameter of 0.5 mm were placed, and mixed for 15 minutes while stirring. To carry out wet pulverization. The average particle diameter of the solid content in the slurry after the wet pulverization was 0.3 μm. Then, in a spray dryer set at 220 ° C, the slurry was supplied at a supply rate of 2.4 L/h to obtain a reaction precursor. X-ray diffraction of the obtained reaction precursor was carried out, and as a result, only a diffraction peak of tungsten trioxide was observed. Further, as a result of analysis by FT-IR, an infrared absorption peak was observed at 950 cm -1 to 1150 cm -1 , and the maximum value of the infrared absorption peak at this time appeared at 1030 cm -1 . Further, it is presumed that Mg of the sintering aid component is present in the reaction precursor as an amorphous magnesium phosphate by the reaction of phosphoric acid in the slurry with magnesium hydroxide. Then, the obtained reaction precursor was subjected to a calcination reaction at 960 ° C for 2 hours in the atmosphere to obtain a white calcined product. This was pulverized by a jet mill to obtain a pulverized product. As a result of performing X-ray diffraction analysis on the obtained calcined product, the calcined product was a single phase of Zr 2 (WO 4 )(PO 4 ) 2 .
{實施例6} 將15質量份的市售的三氧化鎢（WO3 ；平均粒徑1.2 μm）加入至燒杯中，進而添加84質量份的純水。 於室溫（25℃）下攪拌120分鐘，製備包含三氧化鎢的15質量%漿料。漿料中的固體成分的平均粒徑為1.2 μm。 繼而，於該漿料中，以漿料中的Zr：W：P的莫耳比成為2.00：1.00：2.00的方式，於室溫（25℃）下添加氫氧化鋯、及85質量%磷酸水溶液後，升溫至80℃，一邊攪拌一邊反應4小時。 反應結束後，投入1質量份的作為分散劑的聚羧酸銨鹽，將漿料一邊攪拌，一邊供給至投入有直徑為0.5 mm的氧化鋯珠的介質攪拌型珠磨機中，混合15分鐘來進行濕式粉碎。濕式粉碎後的漿料中的固體成分的平均粒徑為0.3 μm。 繼而，於設定為220℃的噴射乾燥機中，以2.4 L/h的供給速度來供給漿料，獲得反應前驅物。對所獲得的反應前驅物進行X射線繞射，結果僅觀察到三氧化鎢的繞射峰。另外，以FT-IR進行分析的結果為，於950 cm-1 ～1150 cm-1 具有紅外線吸收峰，此間的紅外線吸收峰的極大值出現於1042 cm-1 。 繼而，對所獲得的反應前驅物於1220℃下，歷經8小時於大氣中進行煅燒反應，獲得白色的煅燒品。 對所獲得的煅燒品進行X射線繞射分析的結果為，煅燒品為單相的Zr2 (WO4 )(PO4 )2 。{Example 6} 15 parts by mass of commercially available tungsten trioxide (WO 3 ; average particle diameter 1.2 μm) was placed in a beaker, and further 84 parts by mass of pure water was added. The mixture was stirred at room temperature (25 ° C) for 120 minutes to prepare a 15% by mass slurry containing tungsten trioxide. The solid content of the solid content in the slurry was 1.2 μm. Then, in the slurry, zirconium hydroxide and an 85 mass% phosphoric acid aqueous solution were added at room temperature (25 ° C) so that the molar ratio of Zr:W:P in the slurry was 2.00:1.00:2.00. Thereafter, the temperature was raised to 80 ° C, and the reaction was carried out for 4 hours while stirring. After completion of the reaction, 1 part by mass of a polycarboxylate ammonium salt as a dispersing agent was charged, and the slurry was supplied to a medium agitating bead mill in which zirconia beads having a diameter of 0.5 mm were placed while stirring, and mixed for 15 minutes. To carry out wet pulverization. The average particle diameter of the solid content in the slurry after the wet pulverization was 0.3 μm. Then, in a spray dryer set at 220 ° C, the slurry was supplied at a supply rate of 2.4 L/h to obtain a reaction precursor. X-ray diffraction of the obtained reaction precursor was carried out, and as a result, only a diffraction peak of tungsten trioxide was observed. Further, as a result of analysis by FT-IR, an infrared absorption peak was observed at 950 cm -1 to 1150 cm -1 , and the maximum value of the infrared absorption peak at this time appeared at 1042 cm -1 . Then, the obtained reaction precursor was calcined in the atmosphere at 1220 ° C for 8 hours to obtain a white calcined product. As a result of performing X-ray diffraction analysis on the obtained calcined product, the calcined product was a single phase of Zr 2 (WO 4 )(PO 4 ) 2 .
＜物性評價＞ 對於實施例3～實施例6中獲得的磷酸鎢酸鋯，以與實施例1～實施例2及比較例1相同的方式，測定平均一次粒徑、平均二次粒徑、BET比表面積及線熱膨脹係數。將其結果示於表2中。另外，將實施例3中獲得的磷酸鎢酸鋯的SEM照片示於圖10（上：30000倍，下：400倍）中。<Evaluation of physical properties> The average primary particle diameter, the average secondary particle diameter, and BET were measured in the same manner as in Examples 1 to 2 and Comparative Example 1 for the zirconium phosphate zirconate obtained in Examples 3 to 6. Specific surface area and coefficient of linear thermal expansion. The results are shown in Table 2. Further, an SEM photograph of zirconium phosphate zirconate obtained in Example 3 is shown in Fig. 10 (top: 30,000 times, bottom: 400 times).
[表2]
無no
圖1為實施例1中獲得的反應前驅物的X射線繞射圖。 圖2（a）、（b）、（c）及（d）為傅立葉轉換-紅外（Fourier Transform-Infrared，FT-IR）光譜圖。圖2（a）為實施例1中獲得的反應前驅物的FT-IR光譜圖。圖2（b）為氫氧化鋯的FT-IR光譜圖。圖2（c）為磷酸的FT-IR光譜圖。圖2（d）為三氧化鎢的FT-IR光譜圖。 圖3為實施例1中獲得的磷酸鎢酸鋯的X射線繞射圖。 圖4為比較例1中獲得的反應前驅物的X射線繞射圖。 圖5為比較例1中獲得的磷酸鎢酸鋯的X射線繞射圖。 圖6為實施例2中獲得的磷酸鎢酸鋯的掃描式電子顯微鏡（Scanning Electron Microscope，SEM）照片。 圖7為實施例3中獲得的反應前驅物的X射線繞射圖。 圖8為實施例3中獲得的反應前驅物的FT-IR光譜圖。 圖9為實施例3中獲得的磷酸鎢酸鋯的X射線繞射圖。 圖10為實施例3中獲得的磷酸鎢酸鋯的SEM照片。 （上）：30000倍、（下）：400倍1 is an X-ray diffraction diagram of a reaction precursor obtained in Example 1. 2(a), (b), (c), and (d) are Fourier Transform-Infrared (FT-IR) spectra. Fig. 2(a) is a FT-IR spectrum chart of the reaction precursor obtained in Example 1. Fig. 2(b) is an FT-IR spectrum of zirconium hydroxide. Figure 2 (c) is a FT-IR spectrum of phosphoric acid. Fig. 2(d) is an FT-IR spectrum of tungsten trioxide. 3 is an X-ray diffraction diagram of zirconium phosphate zirconate obtained in Example 1. 4 is an X-ray diffraction chart of the reaction precursor obtained in Comparative Example 1. Fig. 5 is an X-ray diffraction diagram of zirconium phosphate zirconate obtained in Comparative Example 1. Fig. 6 is a scanning electron microscope (SEM) photograph of zirconium phosphate zirconate obtained in Example 2. Fig. 7 is an X-ray diffraction diagram of the reaction precursor obtained in Example 3. Fig. 8 is a FT-IR spectrum chart of the reaction precursor obtained in Example 3. Fig. 9 is an X-ray diffraction diagram of zirconium phosphate zirconate obtained in Example 3. Fig. 10 is a SEM photograph of zirconium tungstate phosphate obtained in Example 3. (top): 30,000 times, (bottom): 400 times
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| CN112384471A (en) * | 2018-06-26 | 2021-02-19 | 日本化学工业株式会社 | Negative thermal expansion material, method for producing same, and composite material |
| TWI836228B (en) * | 2020-06-22 | 2024-03-21 | 日商三井金屬鑛業股份有限公司 | Compound and method for manufacturing the same, and composite material |
| TWI843814B (en) * | 2019-03-07 | 2024-06-01 | 日商日本化學工業股份有限公司 | Modified zirconium tungstate phosphate, negative thermal expansion filler and polymer composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6105140B1 (en) * | 2015-10-07 | 2017-03-29 | 日本化学工業株式会社 | Negative thermal expansion material and composite material containing the same |
| JP7239608B2 (en) * | 2018-11-05 | 2023-03-14 | 日本化学工業株式会社 | Modified zirconium tungstate phosphate, negative thermal expansion filler and polymer composition |
| CN115260958A (en) * | 2022-08-29 | 2022-11-01 | 厦门理工学院 | Preparation process of packaging adhesive for Micro-LED |
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| US6187700B1 (en) * | 1998-05-19 | 2001-02-13 | Corning Incorporated | Negative thermal expansion materials including method of preparation and uses therefor |
| JP2005035840A (en) * | 2003-07-15 | 2005-02-10 | Kcm Corp | Sealing material |
| CN101484396B (en) * | 2006-07-11 | 2012-07-25 | 日本电气硝子株式会社 | Glass composition and sealing material for sealing |
| JP5552743B2 (en) * | 2008-03-28 | 2014-07-16 | 旭硝子株式会社 | Frit |
| WO2009127889A1 (en) * | 2008-04-16 | 2009-10-22 | Arkema France | Process for manufacturing acrolein from glycerol |
| CN102433454B (en) * | 2011-09-22 | 2013-01-16 | 郑州大学 | A sintering synthesis method of metal-based ceramic material Al-Zr2P2WO12 with controllable thermal expansion coefficient |
| CN102432292A (en) * | 2011-09-22 | 2012-05-02 | 郑州大学 | A kind of sintering synthesis method of nanometer negative expansion ceramic Zr2(WO4)(PO4)2 |
| JP6035938B2 (en) * | 2012-07-20 | 2016-11-30 | 日本特殊陶業株式会社 | Low thermal expansion ceramic, exposure apparatus stage, and method of manufacturing low thermal expansion ceramic |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112384471A (en) * | 2018-06-26 | 2021-02-19 | 日本化学工业株式会社 | Negative thermal expansion material, method for producing same, and composite material |
| CN112384471B (en) * | 2018-06-26 | 2023-08-04 | 日本化学工业株式会社 | Negative thermal expansion material, its manufacturing method and composite material |
| TWI843814B (en) * | 2019-03-07 | 2024-06-01 | 日商日本化學工業股份有限公司 | Modified zirconium tungstate phosphate, negative thermal expansion filler and polymer composition |
| TWI836228B (en) * | 2020-06-22 | 2024-03-21 | 日商三井金屬鑛業股份有限公司 | Compound and method for manufacturing the same, and composite material |
| CN112079587A (en) * | 2020-09-09 | 2020-12-15 | 贵州石博士科技有限公司 | Preparation method of low-expansion high-heat-conductivity emergency repair additive for nuclear power facilities |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017061402A1 (en) | 2017-04-13 |
| TWI750137B (en) | 2021-12-21 |
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