CN108424124B - Spinel reinforced magnesium oxide base crucible synthesized in situ by magnesium oxide whisker and preparation method thereof - Google Patents
Spinel reinforced magnesium oxide base crucible synthesized in situ by magnesium oxide whisker and preparation method thereof Download PDFInfo
- Publication number
- CN108424124B CN108424124B CN201810307134.6A CN201810307134A CN108424124B CN 108424124 B CN108424124 B CN 108424124B CN 201810307134 A CN201810307134 A CN 201810307134A CN 108424124 B CN108424124 B CN 108424124B
- Authority
- CN
- China
- Prior art keywords
- magnesia
- magnesium oxide
- crucible
- nano
- oxide
- 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.)
- Active
Links
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 421
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 258
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 70
- 239000011029 spinel Substances 0.000 title claims abstract description 67
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000919 ceramic Substances 0.000 claims abstract description 107
- 238000005245 sintering Methods 0.000 claims abstract description 81
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 51
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002002 slurry Substances 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 235000015895 biscuits Nutrition 0.000 claims abstract description 28
- 238000000498 ball milling Methods 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 230000008595 infiltration Effects 0.000 claims abstract description 11
- 238000001764 infiltration Methods 0.000 claims abstract description 11
- 238000005498 polishing Methods 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 88
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 80
- 238000010438 heat treatment Methods 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 53
- 239000011787 zinc oxide Substances 0.000 claims description 43
- 229910052782 aluminium Inorganic materials 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 31
- 239000013078 crystal Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 24
- 239000010440 gypsum Substances 0.000 claims description 17
- 229910052602 gypsum Inorganic materials 0.000 claims description 17
- 229910052593 corundum Inorganic materials 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 12
- 238000007569 slipcasting Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 229920003086 cellulose ether Polymers 0.000 claims description 8
- 238000009423 ventilation Methods 0.000 claims description 8
- 239000000110 cooling liquid Substances 0.000 claims description 6
- 239000010431 corundum Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 6
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 6
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 6
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 4
- RFRMMZAKBNXNHE-UHFFFAOYSA-N 6-[4,6-dihydroxy-5-(2-hydroxyethoxy)-2-(hydroxymethyl)oxan-3-yl]oxy-2-(hydroxymethyl)-5-(2-hydroxypropoxy)oxane-3,4-diol Chemical compound CC(O)COC1C(O)C(O)C(CO)OC1OC1C(O)C(OCCO)C(O)OC1CO RFRMMZAKBNXNHE-UHFFFAOYSA-N 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 230000003014 reinforcing effect Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 19
- 230000035939 shock Effects 0.000 abstract description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract 1
- 235000012245 magnesium oxide Nutrition 0.000 description 206
- 239000011777 magnesium Substances 0.000 description 52
- 229910052749 magnesium Inorganic materials 0.000 description 48
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000012071 phase Substances 0.000 description 26
- 229910000861 Mg alloy Inorganic materials 0.000 description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- -1 fluorine ions Chemical class 0.000 description 17
- 238000003723 Smelting Methods 0.000 description 14
- 229910045601 alloy Inorganic materials 0.000 description 14
- 239000000956 alloy Substances 0.000 description 14
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 229910000838 Al alloy Inorganic materials 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 12
- 239000006104 solid solution Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000002131 composite material Substances 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 description 9
- 230000006378 damage Effects 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 238000009766 low-temperature sintering Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 238000005266 casting Methods 0.000 description 6
- 229910010293 ceramic material Inorganic materials 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 239000011858 nanopowder Substances 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910001195 gallium oxide Inorganic materials 0.000 description 3
- 238000000462 isostatic pressing Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000011153 ceramic matrix composite Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910003465 moissanite Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 210000002345 respiratory system Anatomy 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- 229910016384 Al4C3 Inorganic materials 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- 102000002274 Matrix Metalloproteinases Human genes 0.000 description 1
- 108010000684 Matrix Metalloproteinases Proteins 0.000 description 1
- 229910019752 Mg2Si Inorganic materials 0.000 description 1
- 229910017857 MgGa Inorganic materials 0.000 description 1
- 229910003112 MgO-Al2O3 Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 230000002308 calcification Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- MHKWSJBPFXBFMX-UHFFFAOYSA-N iron magnesium Chemical compound [Mg].[Fe] MHKWSJBPFXBFMX-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000005058 metal casting Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 210000004165 myocardium Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/03—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
- C04B35/04—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/03—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
- C04B35/04—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
- C04B35/053—Fine ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/6261—Milling
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62625—Wet mixtures
- C04B35/6263—Wet mixtures characterised by their solids loadings, i.e. the percentage of solids
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/6342—Polyvinylacetals, e.g. polyvinylbutyral [PVB]
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/636—Polysaccharides or derivatives thereof
- C04B35/6365—Cellulose or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5031—Alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5076—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with masses bonded by inorganic cements
- C04B41/508—Aluminous cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B2235/3218—Aluminium (oxy)hydroxides, e.g. boehmite, gibbsite, alumina sol
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5276—Whiskers, spindles, needles or pins
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6027—Slip casting
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/606—Drying
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/616—Liquid infiltration of green bodies or pre-forms
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/661—Multi-step sintering
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a spinel reinforced magnesia-based crucible which can realize sintering at low temperature and is excellent in chemical stability and thermal shock resistance and prepared by in-situ synthesis of magnesia whiskers, and a preparation method thereof, wherein the preparation method comprises the following steps: (1) preparing 15-25% of nano alumina sol, 0.8-1.5% of rheological agent and the balance of magnesia ceramic powder containing nano titanium dioxide sintering aid according to the mass percentage, adding absolute ethyl alcohol, ball-milling and mixing uniformly to prepare ceramic slurry with the solid content of 65-75%; (2) preparing a crucible biscuit; (3) preparing a crucible blank; (4) and (3) carrying out vacuum infiltration treatment on the magnesium oxide-based crucible blank in alumina sol, then carrying out surface polishing treatment, drying, carrying out high-temperature secondary sintering at the temperature of 1350-1550 ℃, and cooling to room temperature along with a furnace to obtain the magnesium oxide-based crucible.
Description
Technical Field
The invention relates to a magnesium oxide base crucible and a preparation method thereof, in particular to a spinel reinforced magnesium oxide base crucible synthesized in situ by magnesium oxide whiskers and a preparation method thereof, belonging to the field of metal materials and metallurgy. The magnesium oxide-based crucible prepared by the invention is particularly suitable for smelting magnesium and magnesium alloy.
Background
In recent years, the demand for light weight has led to rapid development of applications of magnesium alloys and aluminum alloys, and the production of both wrought magnesium alloys and cast magnesium alloys and aluminum alloys cannot be separated from casting equipment. Magnesium is active in chemical property, is easy to react with oxygen, nitrogen and water vapor, is easy to oxidize and burn during melting and refining, and the generated products remain in magnesium to deteriorate the internal quality and performance of products. For aluminum alloy, except large-scale manufacturing enterprises which adopt large-scale reverberatory furnaces, crucible furnaces are still the main equipment for casting aluminum alloy in small and medium-scale casting enterprises.
The crucible is the key for determining the smelting quality of the crucible furnace, and the metal casting crucible applied in industry mainly comprises an iron crucible (such as cast iron and stainless steel) and a non-metal crucible. Iron crucibles (carbon steel, stainless steel, etc.) are commonly used for casting magnesium and aluminum alloy at present, but molten alloy liquid and liquid flux easily corrode the crucibles during heating to reduce the service life of the crucibles, and iron easily enters the molten alloy liquid to pollute the alloy. Among the non-metallic crucibles, the graphite crucible is low in strength, the crucible is easily broken when it is not operated properly or heated unevenly, and the thermal conductivity is remarkably decreased after a long time, and therefore, the graphite crucible is rarely used at present.
The application of the ceramic crucible greatly promotes the development of the metallurgical industry, particularly the special smelting of nuclear materials. The adoption of a ceramic crucible or a ceramic lining in the magnesium alloy smelting process can furthest prevent an iron crucible from being mixed with harmful elements such as Fe, Cu, Cr and the like in the magnesium alloy casting process, and improve the corrosion resistance of a magnesium alloy product. Although the smelting temperature of the magnesium alloy is not high (similar to that of the aluminum alloy, about 700 ℃), the chemical property of the magnesium alloy is very active, the standard free enthalpy of MgO generation is very low, the magnesium alloy is very easy to oxidize in the smelting process, the generated loose magnesium oxide can not provide protection for a melt, and the generated heat can accelerate oxidation combustion; on the other hand, the vapor pressure of magnesium is quite high (1037 Pa at 727 ℃), magnesium alloy liquid and vapor are easy to permeate into the porous ceramic material and react with the porous ceramic material, and the physical properties of the reaction product, such as the thermal expansion coefficient, the elastic modulus and the like of the ceramic matrixIn contrast, stress is easily generated to cause the reaction product to fall off from the ceramic substrate, resulting in the deterioration, structural looseness and damage of the ceramic and contamination of the alloy melt, e.g., a highly reactive magnesium melt is very easy to react with Al which has been widely used at present2O3，ZrO2，SiC、SiO2The ceramic matrix crucible material undergoes the reactions of the formulas (1) to (4) to rapidly damage and pollute magnesium alloy melt, so the ceramic material for smelting the magnesium alloy is more strict, and the existing Al2O3，ZrO2，SiC、SiO2The ceramic crucible is not suitable for casting magnesium and magnesium alloy, and the related reports about the ceramic material for smelting magnesium alloy are less.
3Mg(l)+Al2O3(s)＝3MgO(s)+2Al(l) (1)
2Mg(l)+ZrO2(s)＝2MgO(s)+Zr(s) (2)
6Mg(l)+4Al(l)+3SiC(s)＝3Mg2Si(s)+Al4C3(s) (3)
4Mg(l)+SiO2(s)＝2MgO(s)+Mg2Si(s) (4)
MgO is a cubic NaCl type structure with a lattice constant of 0.411nm, belongs to an ionic bond compound, has a melting point of 2852 ℃, and is much higher than that of common Al2O3(2054 ℃ C.) and SiO2(1650 +/-50 ℃), so that the magnesium oxide product has the characteristics of good chemical stability, high resistivity, strong erosion resistance to metal, slag and alkaline solution and the like. Compared with the common ceramic material, MgO, magnesium and alloy melt thereof have good high-temperature chemical stability, the use temperature of the MgO, magnesium and alloy melt is as high as 1600-1850 ℃, the MgO, magnesium and alloy melt do not react with flux inclusion consisting of molten chloride and fluonate, and the MgO and flux inclusion have smaller wetting angle and are easy to absorb flux inclusion in the magnesium melt, so the MgO ceramic crucible is an ideal choice for smelting and purifying magnesium alloy liquid. Furthermore, dense MgO ceramics are also considered to be preferred smelting vessel materials for smelting high-purity iron and its alloys, and nickel, uranium, thorium, zinc, tin, aluminum and its alloys.
Firing below the melting point of the oxide composition is useful in the preparation of ceramic materialsThe essential, most critical step, and the sintering, grain growth, etc. that occurs at high temperatures determines the microstructure and properties of the ceramic material. The magnesium oxide ceramics prepared by pure magnesium oxide as raw material, such as Chinese patent document CN103030407B (a preparation method of high-strength, high-density and high-purity magnesium oxide crucible), Chinese patent document CN1011306B (pure magnesium oxide foam ceramic filter and preparation process thereof), etc., because MgO has very high melting point and thermal expansion coefficient (13.5 multiplied by 10)-6/° c), which results in difficulty in sintering (sintering temperature not lower than 0.8 times of its melting point) and poor thermal shock resistance, limiting the application and development of MgO ceramic.
The research shows that: the heat consumption of unit products can be reduced by more than 10 percent when the firing temperature is reduced by 100 ℃ in the ceramic sintering process, and the addition of the sintering aid is an important technical means for reducing the sintering temperature of the MgO ceramic. Addition of V2O5In the case of powder, MgO reacts with V at 1190 DEG C2O5Form an approximate composition of Mg3V2O8Can remarkably lower the sintering temperature of the MgO foamed ceramics, but V2O5Has damage to the respiratory system and the skin during the use process, and has strict limitation on the operation. And V2O5Similarly, cobalt oxide is a good low temperature sintering aid, but has limited application as a highly toxic substance and a scarce resource. Chinese patent documents CN100434390C (composition for manufacturing crucible and method thereof) and CN101785944B (method for preparing magnesium oxide foam ceramic filter for filtering magnesium and magnesium melt) are added with fluorite (melting point 1423 ℃) and magnesium fluoride (melting point 1248 ℃), solid solution of fluoride not only increases lattice distortion of matrix magnesium oxide in the sintering process, but also easily forms low-melting-point liquid phase, thereby reducing the sintering temperature of magnesium oxide ceramic; however, F in the fluoride is combined with Si, Al, Fe and Ca in the sintering process, most of the F (accounting for about 70 percent in the production of the ceramic tiles) volatilizes in a gaseous state, not only corrodes a blank body to damage the quality of the sintered ceramic, but also seriously causes the fluoride pollution when being discharged into the atmosphere, the fluoride can enter a human body through a respiratory tract, a digestive tract and the skin and has toxic effect on a central nervous system and cardiac muscle,the low concentration fluorine pollution can cause brittle calcification of teeth and bones, and the emission standard of fluoride is required to be lower than 5.0mg/m in the emission standard of pollutants in the ceramic industry (GB25464-2010)3The fluoride is used as the low-temperature sintering aid of the magnesium oxide ceramic, so that the emission of gaseous fluoride is increased inevitably, and the burden of environmental protection is increased; in addition, fluorine ions in solid-solution fluorides remaining in ceramics exist in the form of substituted oxygen ions, which causes a decrease in chemical stability of intergranular bonding, and makes it difficult to resist long-term erosion by flux in magnesium melt. In the slurry for preparing the ceramic foam filter disclosed in chinese patent document CN104496492B (a composite magnesia carbon refractory crucible and a method for preparing the same), silica sol and the like are used as a binder, and SiO (silicon dioxide) among sintered ceramic particles is used as a binder2The existence of the components makes the components easy to react with magnesium and magnesium alloy melt according to the formula (4), and the chemical stability of the ceramic is also reduced. In chinese patent documents CN100536986C (magnesia ceramic foam filter), CN103553686A (magnesium aluminate spinel ceramic foam filter and its preparation method), and the like, boron trioxide and borax are used as low temperature sintering aids for magnesia ceramics, and when the boron trioxide is higher than 450 ℃, it forms a liquid phase, and when the sintering temperature exceeds 1350 ℃, it reacts with magnesia to generate magnesium borate in the form of a liquid phase, thereby lowering the sintering temperature. However, boron trioxide is liable to react with magnesium and aluminum and is unstable in magnesium and aluminum alloy melts; meanwhile, as the diboron trioxide is dissolved in solvents such as water, ethanol and the like, the boric acid can be strongly absorbed in the air to generate boric acid, and the diboron trioxide added in the preparation process of the ceramic product is dissolved in water to form a boric acid aqueous solution, so that the boric acid aqueous solution is easy to react with magnesium oxide to form magnesium borate precipitate to reduce the effect of the magnesium borate precipitate. Gallium oxide is a family oxide of diboron trioxide, and forms spinel-shaped MgGa with magnesium oxide at a lower temperature2O4But the sintering temperature is reduced, but the resource amount of gallium is very small (gallium is a strategic reserve metal), and the application of gallium oxide in common ceramics is limited due to the higher price of gallium oxide.
The production method of the ceramic crucible industry adopts a dry pressing method, and besides the small crucible, slip casting and isostatic pressing are two common preparation technologies. Although the isostatic pressing crucible has the density and compositionThe method has the advantages of high product rate and difficult deformation of a crucible blank in the sintering process, but the problems of high cost, low efficiency, poor thermal stability, easy cracking and peeling of the crucible in the rapid heating and cooling processes, short service life and the like of the crucible formed by the isostatic pressing machine are found. The slip casting method is the most reasonable method for forming crucibles or other hollow products, and under the same conditions, the slip casting method can obtain green bodies with larger particle bulk density (more than 2000 kg/cm) than other forming methods3The article is also denser at the molding pressure) and the firing temperature required is also lower.
Disclosure of Invention
The invention aims to provide a preparation method of a spinel reinforced magnesia-based crucible which can realize sintering at low temperature and has excellent chemical stability and thermal shock resistance and is synthesized in situ by magnesia whiskers.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a spinel-reinforced magnesium oxide-base crucible for in-situ synthesis of magnesium oxide whisker is prepared through slip casting of light-burned magnesium oxide ceramic slurry containing nano iron oxide, nano zinc oxide and magnesium oxide whisker in gypsum mould, drying and sintering.
A preparation method of a spinel reinforced magnesia-based crucible for in-situ synthesis of magnesia whiskers comprises the following steps:
(1) according to the mass percentage, 15 to 25 percent of nano alumina sol, 0.8 to 1.5 percent of rheological agent and the balance of light-burned magnesia ceramic powder containing nano iron oxide, nano zinc oxide and magnesia crystal whisker are mixed, added with absolute ethyl alcohol, and ball-milled and mixed evenly to prepare ceramic slurry with the solid content of 65 to 75 percent.
The added nano aluminum sol can not only be added into the light-burned magnesium oxide particles and highly uniformly dispersed nano Fe2O3Forming gamma-Al on the surface of the powder and the magnesia crystal whisker2O3Coating the film to act as a binder, Al during sintering2O3With Fe2O3The magnesium and the alloy melt thereof are combined together with MgO in situ to form MA-MF composite spinel solid solution phase with chemical stabilityThe damage of the existing product added with the bonding agents such as silica sol, ethyl silicate and the like to the chemical stability of the ceramic is avoided; meanwhile, the ceramic component does not contain sodium salt (for example, sodium carboxymethylcellulose is not adopted in the rheological agent), so that residual Na with larger ionic radius is avoided+The resistance to sintering of the ceramic.
The solid content of the nano aluminum sol is 20-25%, and the PH value is more than or equal to 4.
The rheological agent is a mixture of polyvinyl butyral and cellulose ether, wherein the polyvinyl butyral accounts for 50% of the mass of the rheological agent, and the cellulose ether is one of industrial hydroxypropyl methyl cellulose and hydroxyethyl cellulose or a mixture thereof.
Cellulose ether and polyvinyl butyral are good dispersants for nano iron oxide, nano zinc oxide powder and magnesium oxide whisker, can prevent slurry from agglomerating, can play a role of a binder when preparing a biscuit to enable the biscuit to have higher strength, and are easy to escape in a sintering process to avoid polluting products.
The ceramic powder is a mixture of nano iron oxide, nano zinc oxide, magnesium oxide whiskers and light-burned magnesium oxide. The nano iron oxide accounts for 1-2% of the mass of the ceramic powder, the nano zinc oxide accounts for 0.5-1% of the mass of the ceramic powder, the magnesium oxide whisker accounts for 1.5-2.5% of the mass of the ceramic powder, and the balance is light-burned magnesium oxide. The particle size of the nano ferric oxide is 30-60 nm, the particle size of the nano zinc oxide is 20-30 nm, the magnesium oxide whisker is an industrialized product, the diameter of the magnesium oxide whisker is 2-5 mu m, the length of the magnesium oxide whisker is 200-1000 mu m, and the particle size of the light-burned magnesium oxide powder is 250-500 meshes (the middle diameter d5058 μm).
The light-burned magnesia fine powder has high sintering activity, and the nano alumina sol and the nano iron oxide can be dissolved into the crystal lattice of MgO in a solid solution mode in the sintering process to enable the crystal lattice of MgO to be distorted, activate the crystal lattice, and react with MgO particles and magnesia whiskers to sinter to generate an MA-MF composite spinel phase, so that the sintering and the combination of the particle phases are promoted. On the other hand, the nano powder has the characteristics of large specific surface area, high surface energy, high activity and the like, the low-temperature sintering aid is added in the form of nano alumina sol and nano iron oxide, the gradation and the mixing uniformity of ceramic particles are optimized, and meanwhile, due to the surface and interface effects of the nano powder, the reaction speed of spinel phase generation is rapidly increased due to the full contact between the nano sintering aid and MgO particles and magnesium oxide whiskers, so that the sintering temperature is further reduced, and the reduction of the sintering temperature is favorable for reducing the energy consumption and the production cost of a crucible.
The solid phase component in the aluminum sol is high-activity porous gamma-Al2O3The crystal structure is the same as that of the magnesium aluminate spinel MA crystal. The mechanical property of the ceramic matrix composite material can be improved by adopting the fibers and the whiskers as the reinforcement. Whiskers (whisker) are understood to have a certain length ratio (generally greater than 10) and an area of 5.2X 10-4cm2The single crystal fiber material of (1). The magnesia whisker has the characteristics of high melting point (2850 ℃), high strength and high elastic modulus. In the scheme provided by the invention, the nano zinc oxide plays a role in promoting densification in sintering; the surfaces of the light-burned magnesia particles with high sintering activity and the highly dispersed magnesia whiskers are surrounded by the nanometer alumina sol film and react in situ in the sintering process to generate the MA phase of the magnesium aluminate spinel. The solubility of iron in periclase MgO is far higher than that of aluminum, and Fe is generated at 1600 DEG C2O3And Al2O3The effective solubility in periclase was approximately 60% and 1%, respectively. Adding nano Fe2O3，Fe3+The diffusion speed into MgO is high, so that periclase MgO spinel is transformed into spinel, and Al is promoted2O3Diffusion into MgO, therefore, there is a close and continuous bonding interface between MA and MF generated by in situ reaction and periclase solid solution. Because MA and MF can be mutually dissolved, MgO particles are directly combined with MA-MF composite spinel phases formed around, the pinning effect of the composite spinel phases inhibits the growth of magnesium oxide particles, thereby refining the texture of ceramics and improving the density among ceramic crystal grains; meanwhile, the shape of the magnesium oxide whisker with certain directionality in the prepared biscuit is inherited by the formed magnesia-alumina spinel.
The preparation method of the ceramic slurry comprises the following steps: adding light-burned magnesium oxide powder into a ball milling tank according to the proportion, mixing nano aluminum sol, nano iron oxide, nano zinc oxide, magnesium oxide whiskers, a rheological agent and absolute ethyl alcohol, carrying out ultrasonic treatment for 30-60 min, fully dispersing the nano iron oxide, the nano zinc oxide and the magnesium oxide whiskers, adding into the ball milling tank, adding corundum balls according to the ball-to-material ratio of 2:1, and carrying out ball milling for 2-4 h at the rotating speed of 60-120 rpm to uniformly mix the materials.
(2) Pouring the ceramic slurry into a gypsum mold by a slip casting method, demolding, and removing the ethanol solvent in a ventilation chamber at 40-50 ℃ to obtain a crucible biscuit.
The preparation method of the crucible biscuit comprises the following steps: and (3) quickly injecting the ceramic slurry into a gypsum mold, placing the gypsum mold on a vibration forming machine for vibration forming, stopping vibration when the mold is completely filled with the slurry and the surface of the slurry is uniformly spread, flattening the surface of the spread slurry, demolding when no ethanol liquid escapes from the surface of the blank, and removing the ethanol solvent in a ventilation chamber at 40-50 ℃ to obtain the ceramic.
(3) And (3) putting the dried crucible biscuit into a sintering furnace, heating to 1350-1550 ℃ for high-temperature sintering, and cooling to room temperature along with the furnace to obtain the magnesium oxide-based crucible blank.
The high-temperature sintering process of the magnesium oxide-based crucible blank comprises the following steps: heating to 550 ℃ at a heating rate of 60 ℃/h to decompose and gasify organic matters (rheological agents and the like) in the biscuit and discharge the organic matters, heating to 1100 ℃ at a heating rate of 200 ℃/h, heating to 1350-1550 ℃ at a heating rate of 50 ℃/h, and preserving heat at the temperature for 2-3 h.
(4) And (3) carrying out vacuum infiltration treatment on the magnesium oxide-based crucible blank in alumina sol, then carrying out surface polishing treatment, drying, carrying out high-temperature secondary sintering at the temperature of 1350-1550 ℃, and cooling to room temperature along with a furnace to obtain the magnesium oxide-based crucible.
The vacuum infiltration treatment method of the magnesium oxide-based crucible blank in the alumina sol comprises the following steps: putting the magnesia-based crucible blank into alumina sol, carrying out vacuum infiltration treatment for 30min under the negative pressure of 0.02 MPa-0.05 MPa, baking the magnesia-based crucible blank in a baking oven at the temperature of 120 +/-10 ℃ for 24 hours, and then repeatedly carrying out twice according to the method; then, polishing the surface of the aluminum sol serving as cooling liquid on a grinding machine, and baking the aluminum sol in an oven at the temperature of 120 +/-10 ℃ for 24 hours; and finally, performing high-temperature secondary sintering on the dried crucible blank with the polished surface, wherein the secondary sintering process comprises the following steps: heating to 1100 ℃ at a heating rate of 200 ℃/h, then heating to 1350-1550 ℃ at a heating rate of 50 ℃/h, and preserving heat for 2-3 h at the temperature.
The lower temperature rise speed in the low-temperature sintering stage can prevent the biscuit collapse or deformation damage caused by the excessively high decomposition speed of the rheological agent, and after the sintering temperature exceeds 1100 ℃ in the high-temperature sintering stage, the lower temperature rise speed can ensure the temperature in the sintering body to be consistent, and meanwhile, the generation speed of the generated spinel is prevented from being uniform, and the deformation and cracking of the sintering body caused by the excessively fast generated phase change stress are avoided.
The magnesium oxide-based crucible is prepared by a slip casting method, and has the advantages of simple process equipment, uniform crucible wall thickness, low cost, high efficiency, suitability for large-scale production and the like; the prepared spinel reinforced magnesia-based crucible synthesized in situ by the magnesia whisker does not contain any component for reducing the chemical stability of the spinel reinforced magnesia-based crucible, the added nano alumina sol and nano iron oxide not only can play a role in reducing the sintering temperature, but also can be highly and uniformly dispersed into magnesia ceramic powder particles and react with the magnesia ceramic powder particles to generate a spinel solid solution phase with chemical stability to magnesium and magnesium alloy melt so as to weld the magnesia particles together, meanwhile, the form of the magnesia whisker with certain directionality is inherited by the formed magnesia-alumina spinel phase, and the nano zinc oxide plays a role in promoting densification in sintering, so the prepared magnesia-based crucible has good strength, chemical stability and thermal shock resistance, and is particularly suitable for smelting magnesium and aluminum alloy. The method specifically comprises the following steps:
firstly, the spinel reinforced magnesia-based crucible synthesized in situ by the magnesia whisker has excellent chemical stability. With Al2O3、Cr2O3In contrast, Fe2O3The solid solubility is greatest in the periclase MgO phase. Added nano Fe2O3Is easy to be dissolved in MgO phase and reacts to generate magnesium iron spinel (MgFe) with high temperature stability2O4MF) phase (melt)Point 2030 deg.C). Although the raw material alumina sol component contains gamma-Al which reacts with the magnesium liquid2O3But the added nano aluminum sol is added in the light-burned magnesium oxide particles and highly uniformly dispersed nano Fe2O3Forming gamma-Al on the surface of the powder and the magnesia crystal whisker2O3Coating film of gamma-Al in alumina sol during sintering2O3Reacts with light-burned MgO particles in situ and magnesia crystal whiskers to generate high-melting-point magnesia-alumina spinel (MgAl) with face-centered cubic lattice2O4MA) phase (melting point 2135 ℃ C.). MA and MF can be completely mutually dissolved, and the XRD analysis result shows that the sintering crucible prepared by the invention only has periclase MgO and MA-MF composite spinel solid solution phases.
In the magnesium melt and MgO-Al added with alumina2O3In addition to the reaction formula (1), the following reaction may be present in the reaction system for sintering ceramics:
3Mg(l)+4Al2O3(s)＝3MgAl2O4(s)+2Al(l) (5)
magnesium aluminate spinel MgAl generated by alumina and magnesia2O4The reaction of (a) is:
MgO(s)+Al2O3(s)＝MgAl2O4(s) (6)
magnesium melt and magnesium aluminate spinel MgAl2O4The reactions that occur are:
3Mg(l)+MgAl2O4(s)＝2Al(l)+4MgO(s) (7)
according to the pure substance thermochemistry data handbook (edited by Sudoku of Helh Sanger Valenchen, Chengmelin et al, Beijing: scientific Press, 2003), the Gibbs free energy data of the reaction system of magnesium melt and magnesium aluminate spinel at 900-1200K and the Gibbs free energy change delta G of the reactions (1), (5), (6) and (7)1、ΔG5、ΔG6、ΔG7The calculation results of (a) are shown in table 1.
TABLE 1 Gibbs free energy change delta G calculation results of each reaction in a 900-1200K magnesium melt and magnesium aluminate spinel reaction system
Reaction formula Gibbs free energy delta G of formula (5) for forming magnesium aluminate spinel by magnesium melt and alumina5The temperature difference is minimal, which indicates that the reaction can preferentially occur at the common melting temperature of magnesium alloy. Although the reaction formula (7) of the magnesium liquid and the magnesium aluminate spinel is thermodynamically feasible, the reaction is essentially a reaction between the magnesium liquid and alumina, which is a decomposition product of the magnesium aluminate spinel, but it is known from table 1 that the reaction of the magnesium aluminate spinel to alumina and magnesia is difficult to proceed at the melting temperature of the magnesium alloy (reverse reaction of the reaction formula (6)), and the residual alumina in the sintered ceramic and the magnesium liquid preferentially form the magnesium aluminate spinel according to the reaction formula (5); on the other hand, MgO-Al2O3In the phase diagram, the MgO side is a periclase solid solution and MA spinel solid solution eutectic phase diagram, and almost no O is generated in the process of generating MA through in-situ reaction2-Diffusion, only Mg2+And Al3+Through mutual diffusion of fixed oxygen lattices, Al with slower diffusion speed is generated3+Determined that the MA phase is mainly in Al2O3One side is grown by means of an epitaxial growth, resulting in the formation of a limited solid solution between the MA phase and MgO, while the MgO content in the MA outer layer in contact with the MgO particles is much higher than its average value, while MgO does not react with the magnesium melt, so that the magnesium aluminate spinel phase fusing together the magnesium oxide particles in the sintered ceramic structure is stable in the magnesium melt.
The spinel reinforced magnesia-based crucible synthesized in situ by the magnesia whisker does not contain any component for reducing the chemical stability, and the added nano alumina sol can not only be added in light-burned magnesia particles and highly uniformly dispersed nano Fe2O3Forming gamma-Al on the surface of the powder and the magnesia crystal whisker2O3Coated film to act as a binderOf Al during sintering2O3With Fe2O3The MA-MF composite spinel solid solution phase which has chemical stability to magnesium and alloy melt thereof is synthesized together with MgO in situ, so that the damage of the existing product on the chemical stability of ceramics caused by adding binders such as silica sol, ethyl silicate and the like is avoided; meanwhile, the ceramic component does not contain sodium salt (for example, sodium carboxymethylcellulose is not adopted in the rheological agent), so that residual Na with larger ionic radius is avoided+The resistance to sintering of the ceramic.
Because the reaction formulas (1) and (5) can spontaneously proceed at the common melting temperature of the magnesium alloy, and the melting temperature of the aluminum and the aluminum alloy is the same as that of the magnesium and the aluminum alloy, the reverse reactions of the reaction formulas (1) and (5) can not occur between the MgO spinel phase and the aluminum alloy melt; the same as that used for magnesium and alloy melt, avoids the damage of adding bonding agents such as silica sol, ethyl silicate and the like to the chemical stability of ceramics in aluminum and alloy melt (even if the material contains 1 percent of SiO)2The melt of aluminum and its alloy will also react with SiO in the ceramic at high temperature2Generation of Al + SiO2→Al2O3Reaction of + Si); therefore, the prepared spinel reinforced magnesia-based crucible synthesized in situ by the magnesia whisker can also be used for smelting and purifying aluminum and aluminum alloy. In addition, the grouting slurry for preparing the crucible can also be used as a brickwork and inner wall trowelling slurry of an aluminum alloy reflection smelting furnace.
Secondly, the spinel reinforced magnesia-based crucible synthesized in situ by the magnesia whisker has good low-temperature sintering performance. The light-burned magnesia fine powder adopted by the invention has high sintering activity, and the nano alumina sol and the nano iron oxide can be dissolved into the crystal lattice of MgO in a solid way in the sintering process to ensure that the crystal lattice distortion of MgO crystals occurs, activate the crystal lattice, and simultaneously react with MgO particles and magnesia whiskers to sinter and generate an MA-MF composite spinel phase, thereby promoting the combination of sintering and particle phases. On the other hand, the nano powder has the characteristics of large specific surface area, high surface energy, high activity and the like, the low-temperature sintering aid is added in the form of nano alumina sol and nano iron oxide, the gradation and the mixing uniformity of ceramic particles are optimized, and meanwhile, due to the surface and interface effects of the nano powder, the reaction speed of spinel phase generation is rapidly increased due to the full contact between the nano sintering aid and MgO particles and magnesium oxide whiskers, so that the sintering temperature is further reduced, and the reduction of the sintering temperature is favorable for reducing the energy consumption and the production cost of a crucible. The test result shows that the sintering temperature of the spinel reinforced magnesia-based crucible for in-situ synthesis of the magnesia whisker is only 1350-1550 ℃.
Thirdly, the spinel reinforced magnesia-based crucible synthesized in situ by the magnesia whisker has good thermal shock resistance. The solid phase component in the aluminum sol is high-activity porous gamma-Al2O3The crystal structure is the same as that of the magnesium aluminate spinel MA crystal. The mechanical property of the ceramic matrix composite material can be improved by adopting the fibers and the whiskers as the reinforcement. Whiskers (whisker) are understood to have a certain length ratio (generally greater than 10) and an area of 5.2X 10-4cm2The single crystal fiber material of (1). The magnesia whisker has the characteristics of high melting point (2850 ℃), high strength and high elastic modulus. In the scheme provided by the invention, the nano zinc oxide plays a role in promoting densification in sintering; the surfaces of the light-burned magnesia particles with high sintering activity and the highly dispersed magnesia whiskers are surrounded by the nanometer alumina sol film and react in situ in the sintering process to generate the MA phase of the magnesium aluminate spinel. The solubility of iron in periclase MgO is far higher than that of aluminum, and Fe is generated at 1600 DEG C2O3And Al2O3The effective solubility in periclase was approximately 60% and 1%, respectively. Adding nano Fe2O3，Fe3+The diffusion speed into MgO is high, so that periclase MgO spinel is transformed into spinel, and Al is promoted2O3Diffusion into MgO, therefore, there is a close and continuous bonding interface between MA and MF generated by in situ reaction and periclase solid solution. Because MA and MF can be mutually dissolved, MgO particles are directly combined with MA-MF composite spinel phases formed around, the pinning effect of the composite spinel phases inhibits the growth of magnesium oxide particles, thereby refining the texture of ceramics and improving the density among ceramic crystal grains; meanwhile, the form of the magnesia crystal whisker with certain directionality in the prepared biscuit is inherited by the formed magnesia-alumina spinel, so that the prepared magnesia-alumina spinel has good oxidation resistance and good heat resistanceThe spinel reinforced magnesia-based crucible synthesized in situ by the magnesium whisker has higher mechanical property, high-temperature impact resistance and thermal shock resistance.
In addition, the cellulose ether and polyvinyl butyral which are used as rheological agents in the preparation method are good dispersants for the nano iron oxide, the nano zinc oxide powder and the magnesium oxide whisker, can prevent slurry from agglomerating, can play a role of a binder when preparing the biscuit so that the biscuit has higher strength, and simultaneously are easy to escape in the sintering process without polluting products, thereby ensuring the quality of a sintering crucible.
Drawings
FIG. 1 is a flow chart of a preparation process of a spinel reinforced magnesia-based crucible in situ synthesized by magnesia whiskers.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
The spinel reinforced magnesia-based crucible is synthesized in situ by magnesia whiskers, light-burned magnesia ceramic slurry containing nano iron oxide, nano zinc oxide and magnesia whiskers is formed in a gypsum mold by slip casting, and the spinel reinforced magnesia-based crucible is obtained by drying and sintering. The specific preparation process is shown in figure 1.
Example 1
According to the proportion that nano iron oxide accounts for 1 percent of the mass of the ceramic powder, nano zinc oxide accounts for 0.5 percent, magnesium oxide whiskers accounts for 1.5 percent, and the balance is light-burned magnesium oxide, the nano iron oxide with the grain diameter of 30nm, the nano zinc oxide with the grain diameter of 20nm, commercial magnesium oxide whiskers (the diameter of which is 2 mu m to 5 mu m, and the length of which is 200 mu m to 1000 mu m) and the grain diameter of which is 250 meshes (the middle diameter d is5058 μm) of light burned magnesia powder to prepare ceramic powder; mixing polyvinyl butyral and hydroxypropyl methyl cellulose in the mass ratio of 1 to prepare the rheological agent.
According to the mass percentage, 25 percent of nano aluminum sol with the solid content of 25 percent (commercial nano aluminum sol with the pH value close to neutral is selected, the same is applied below), 0.8 percent of rheological agent and the balance of ceramic powder are mixed. Firstly, adding light-burned magnesium oxide powder into a ball milling tank according to a ratio, mixing nano alumina sol, nano iron oxide, nano zinc oxide, magnesium oxide whiskers, a rheological agent and a proper amount of absolute ethyl alcohol (the addition amount of the inorganic nano zinc oxide, the addition amount of the inorganic nano zinc oxide and the magnesium oxide whiskers is determined according to the solid content of ceramic slurry, and the same is applied below) and carrying out ultrasonic treatment for 30min to fully disperse the nano iron oxide, the nano zinc oxide and the magnesium oxide whiskers, then adding the mixture into the ball milling tank, adding corundum balls according to the ball-to-material ratio of 2:1, and carrying out ball milling at the rotating speed of 60rpm for 4h to uniformly mix the mixture to obtain the ceramic slurry.
And (3) quickly injecting the ceramic slurry into a gypsum mould, placing the gypsum mould on a vibration forming machine for vibration forming, stopping vibration when the mould is completely filled with the slurry and the slurry surface is uniformly overflowed, and flattening the overflowed surface. And demolding when no ethanol liquid escapes from the surface of the blank, and removing the ethanol solvent in a ventilation chamber at 40 ℃ to obtain a crucible biscuit.
And (2) putting the dried biscuit into a sintering furnace, heating to 550 ℃ at a heating rate of 60 ℃/h to decompose and gasify organic matters such as rheological agents in the biscuit and discharge the organic matters, heating to 1100 ℃ at a heating rate of 200 ℃/h, heating to 1550 ℃ at a heating rate of 50 ℃/h, preserving heat at the temperature for 2.5h, and cooling to room temperature along with the furnace to obtain the magnesia-based crucible blank.
Putting the magnesia-based crucible blank into alumina sol, carrying out vacuum infiltration treatment for 30min under the negative pressure of 0.02MPa, baking for 24 hours in a baking oven at the temperature of 120 +/-10 ℃, and then repeating the steps twice according to the method; then, polishing the surface of the aluminum sol serving as cooling liquid on a grinding machine, and baking the aluminum sol in an oven at the temperature of 120 +/-10 ℃ for 24 hours; and finally, performing high-temperature secondary sintering on the dried crucible blank with the polished surface, wherein the secondary sintering process comprises the steps of heating to 1100 ℃ at the heating rate of 200 ℃/h, then heating to 1550 ℃ at the heating rate of 50 ℃/h, preserving heat for 2.5h at the temperature, and cooling to room temperature along with the furnace to obtain the magnesium oxide-based crucible blank.
Example 2
According to the proportion that the nano iron oxide accounts for 2 percent of the ceramic powder by mass, the nano zinc oxide accounts for 1 percent of the ceramic powder by mass, the magnesia crystal whisker accounts for 2.5 percent of the ceramic powder by mass, and the rest is light-burned magnesia, the nano iron oxide with the grain diameter of 60nm, the nano zinc oxide with the grain diameter of 30nm and the commercialized magnesia crystal whisker (the diameter of the magnesia is 2-5 mu m,200 to 1000 μm in length) and a particle diameter of 500 mesh (median diameter d)5025 μm) of light burned magnesia powder to prepare ceramic powder; mixing polyvinyl butyral and hydroxypropyl methyl cellulose in the mass ratio of 1 to prepare the rheological agent.
According to the mass percentage, 15 percent of nano-alumina sol with the solid content of 20 percent, 1.5 percent of rheological agent and the balance of ceramic powder are mixed. Firstly, adding light-burned magnesium oxide powder into a ball milling tank according to a ratio, mixing nano alumina sol, nano iron oxide, nano zinc oxide, magnesium oxide whiskers, a rheological agent and a proper amount of absolute ethyl alcohol, carrying out ultrasonic treatment for 30min, fully dispersing the nano iron oxide, the nano zinc oxide and the magnesium oxide whiskers, then adding the mixture into the ball milling tank, adding corundum balls according to a ball-to-material ratio of 2:1, and carrying out ball milling at a rotating speed of 120rpm for 2h to uniformly mix the mixture to obtain ceramic slurry with a solid content of 70%.
And (3) quickly injecting the ceramic slurry into a gypsum mould, placing the gypsum mould on a vibration forming machine for vibration forming, stopping vibration when the mould is completely filled with the slurry and the slurry surface is uniformly overflowed, and flattening the overflowed surface. And demolding when no ethanol liquid escapes from the surface of the blank, and removing the ethanol solvent in a ventilation chamber at 50 ℃ to obtain a crucible biscuit.
And (2) putting the dried biscuit into a sintering furnace, heating to 550 ℃ at a heating rate of 60 ℃/h to decompose and gasify organic matters such as rheological agents in the biscuit and discharge the organic matters, heating to 1100 ℃ at a heating rate of 200 ℃/h, heating to 1350 ℃ at a heating rate of 50 ℃/h, preserving heat at the temperature for 3h, and cooling to room temperature along with the furnace to obtain the magnesia-based crucible blank.
Putting the magnesia-based crucible blank into alumina sol, carrying out vacuum infiltration treatment for 30min under the negative pressure of 0.05MPa, baking the magnesia-based crucible blank in a baking oven at the temperature of 120 +/-10 ℃ for 24 hours, and then repeatedly carrying out twice according to the method; then, polishing the surface of the aluminum sol serving as cooling liquid on a grinding machine, and baking the aluminum sol in an oven at the temperature of 120 +/-10 ℃ for 24 hours; and finally, performing high-temperature secondary sintering on the dried crucible blank with the polished surface, wherein the secondary sintering process comprises the steps of heating to 1100 ℃ at the heating rate of 200 ℃/h, then heating to 1350 ℃ at the heating rate of 50 ℃/h, preserving heat for 3h at the temperature, and cooling to room temperature along with a furnace to obtain the magnesium oxide-based crucible blank.
Example 3
According to the proportion that the nano iron oxide accounts for 1.5 percent of the mass of the ceramic powder, the nano zinc oxide accounts for 0.75 percent of the mass of the ceramic powder, the magnesia crystal whisker accounts for 2 percent of the mass of the ceramic powder, and the balance is the light burned magnesia, the nano iron oxide with the grain diameter of 50nm, the nano zinc oxide with the grain diameter of 25nm, the commercialized magnesia crystal whisker (the diameter of which is 2 mu m to 5 mu m and the length of which is 200 mu m to 1000 mu m) and the grain diameter of 325 meshes (the middle diameter d is5045 μm) of light burned magnesia powder to prepare ceramic powder; mixing the polyvinyl butyral and the hydroxyethyl methyl cellulose in a mass ratio of 1:1 to prepare the rheological agent.
According to the mass percentage, 20 percent of nano aluminum sol with the solid content of 22 percent, 1.0 percent of rheological agent and the balance of ceramic powder are mixed. Firstly, adding light-burned magnesium oxide powder into a ball milling tank according to a ratio, mixing nano alumina sol, nano iron oxide, nano zinc oxide, magnesium oxide whiskers, a rheological agent and a proper amount of absolute ethyl alcohol (the addition amount of the inorganic nano zinc oxide, the addition amount of the inorganic nano zinc oxide and the magnesium oxide whiskers is determined according to the solid content of ceramic slurry, and the same is applied below) and carrying out ultrasonic treatment for 30min to ensure that the nano iron oxide, the nano zinc oxide and the magnesium oxide whiskers are fully dispersed and then added into the ball milling tank, then adding corundum balls according to the ball-to-material ratio of 2:1, and carrying out ball milling at the rotating speed of 90rpm for 3h to uniformly mix the mixture to obtain.
And (3) quickly injecting the ceramic slurry into a gypsum mould, placing the gypsum mould on a vibration forming machine for vibration forming, stopping vibration when the mould is completely filled with the slurry and the slurry surface is uniformly overflowed, and flattening the overflowed surface. And demolding when no ethanol liquid escapes from the surface of the blank, and removing the ethanol solvent in a ventilation chamber at 45 ℃ to obtain a crucible biscuit.
And (2) putting the dried biscuit into a sintering furnace, heating to 550 ℃ at a heating rate of 60 ℃/h to decompose and gasify organic matters such as rheological agents in the biscuit and discharge the organic matters, heating to 1100 ℃ at a heating rate of 200 ℃/h, heating to 1400 ℃ at a heating rate of 50 ℃/h, preserving heat at the temperature for 2h, and cooling to room temperature along with the furnace to obtain the magnesia-based crucible blank.
Putting the magnesia-based crucible blank into alumina sol, carrying out vacuum infiltration treatment for 30min under the negative pressure of 0.03MPa, baking the magnesia-based crucible blank in a baking oven at the temperature of 120 +/-10 ℃ for 24 hours, and then repeating the steps twice according to the method; then, polishing the surface of the aluminum sol serving as cooling liquid on a grinding machine, and baking the aluminum sol in an oven at the temperature of 120 +/-10 ℃ for 24 hours; and finally, performing high-temperature secondary sintering on the dried crucible blank with the polished surface, wherein the secondary sintering process comprises the steps of heating to 1100 ℃ at the heating rate of 200 ℃/h, then heating to 1400 ℃ at the heating rate of 50 ℃/h, preserving heat for 2h at the temperature, and cooling to room temperature along with the furnace to obtain the magnesium oxide-based crucible blank.
Example 4
According to the proportion that the nano iron oxide accounts for 1.0 percent of the ceramic powder by mass, the nano zinc oxide accounts for 0.5 percent of the ceramic powder by mass, the magnesia crystal whisker accounts for 2 percent of the ceramic powder by mass, and the balance is light-burned magnesia, the nano iron oxide with the grain diameter of 60nm, the nano zinc oxide with the grain diameter of 20nm, the commercial magnesia crystal whisker (the diameter of the nano zinc oxide is 2-5 mu m, the length of the nano zinc oxide is 200-1000 mu m) and the grain diameter of 300 meshes (the middle diameter d is5048 μm) of light burned magnesia powder to prepare ceramic powder; according to the weight ratio of polyvinyl butyral: hydroxypropyl methylcellulose: the hydroxyethyl cellulose is mixed according to the mass ratio of 5:2:3 to prepare the rheological agent.
According to the mass percentage, 25 percent of nano-alumina sol with the solid content of 20 percent, 1.0 percent of rheological agent and the balance of ceramic powder are mixed. Firstly, adding light-burned magnesium oxide powder into a ball milling tank according to a ratio, mixing nano alumina sol, nano iron oxide, nano zinc oxide, magnesium oxide whiskers, a rheological agent and a proper amount of absolute ethyl alcohol, carrying out ultrasonic treatment for 45min, fully dispersing the nano iron oxide, the nano zinc oxide and the magnesium oxide whiskers, then adding the mixture into the ball milling tank, adding corundum balls according to a ball-to-material ratio of 2:1, and carrying out ball milling for 3h at a rotating speed of 100rpm to uniformly mix the mixture to obtain ceramic slurry with a solid content of 70%.
And (3) quickly injecting the ceramic slurry into a gypsum mould, placing the gypsum mould on a vibration forming machine for vibration forming, stopping vibration when the mould is completely filled with the slurry and the slurry surface is uniformly overflowed, and flattening the overflowed surface. And demolding when no ethanol liquid escapes from the surface of the blank, and removing the ethanol solvent in a ventilation chamber at 45 ℃ to obtain a crucible biscuit.
And (2) putting the dried biscuit into a sintering furnace, heating to 550 ℃ at a heating rate of 60 ℃/h to decompose and gasify organic matters such as rheological agents in the biscuit and discharge the organic matters, heating to 1100 ℃ at a heating rate of 200 ℃/h, heating to 1450 ℃ at a heating rate of 50 ℃/h, preserving heat at the temperature for 2h, and cooling to room temperature along with the furnace to obtain the magnesia-based crucible blank.
Putting the magnesia-based crucible blank into alumina sol, carrying out vacuum infiltration treatment for 30min under the negative pressure of 0.04MPa, baking for 24 hours in a baking oven at the temperature of 120 +/-10 ℃, and then repeating the steps twice according to the method; then, polishing the surface of the aluminum sol serving as cooling liquid on a grinding machine, and baking the aluminum sol in an oven at the temperature of 120 +/-10 ℃ for 24 hours; and finally, performing high-temperature secondary sintering on the dried crucible blank with the polished surface, wherein the secondary sintering process comprises the steps of heating to 1100 ℃ at the heating rate of 200 ℃/h, then heating to 1450 ℃ at the heating rate of 50 ℃/h, preserving heat for 2h at the temperature, and cooling to room temperature along with the furnace to obtain the magnesium oxide-based crucible blank.
In the embodiment, the prepared magnesia-based crucible has excellent thermal shock resistance and strength, and does not crack after being cooled in the air at 1000 ℃ for 100 times; the normal-temperature crushing strength of the sintering crucible is not lower than 150 MPa.
The above embodiments do not limit the present invention in any way, and all technical solutions obtained by means of equivalent substitution or equivalent transformation fall within the protection scope of the present invention.
Claims (9)
1. The utility model provides a magnesium oxide whisker normal position synthesis spinel reinforcing magnesium oxide base crucible which characterized in that: the light-burned magnesia ceramic slurry containing the nano iron oxide, the nano zinc oxide and the magnesia whisker is formed by slip casting in a gypsum mold, and is obtained by drying and sintering; the light-burned magnesia ceramic slurry containing the nano iron oxide, the nano zinc oxide and the magnesia whisker comprises, by mass, 15-25% of nano alumina sol, 0.8-1.5% of a rheological agent, and the balance of light-burned magnesia ceramic powder containing the nano iron oxide, the nano zinc oxide and the magnesia whisker; the rheological agent is a mixture of polyvinyl butyral and cellulose ether, wherein the polyvinyl butyral accounts for 50% of the mass of the rheological agent, and the cellulose ether is one or a mixture of industrial hydroxypropyl methyl cellulose and hydroxyethyl cellulose; the ceramic powder is a mixture of nano iron oxide, nano zinc oxide, magnesium oxide whiskers and light-burned magnesium oxide.
2. A preparation method of a spinel reinforced magnesia-based crucible for in-situ synthesis of magnesia whiskers is characterized by comprising the following steps:
(1) according to the mass percentage, 15 to 25 percent of nano alumina sol, 0.8 to 1.5 percent of rheological agent and the balance of light-burned magnesia ceramic powder containing nano iron oxide, nano zinc oxide and magnesia crystal whisker are mixed, added with absolute ethyl alcohol, ball-milled and mixed evenly to prepare ceramic slurry with the solid content of 65 to 75 percent; the rheological agent is a mixture of polyvinyl butyral and cellulose ether, wherein the polyvinyl butyral accounts for 50% of the mass of the rheological agent, and the cellulose ether is one or a mixture of industrial hydroxypropyl methyl cellulose and hydroxyethyl cellulose; the ceramic powder is a mixture of nano iron oxide, nano zinc oxide, magnesium oxide whiskers and light-burned magnesium oxide;
(2) pouring the ceramic slurry into a gypsum mold by a slip casting method, demolding, and removing an ethanol solvent in a ventilation chamber at 40-50 ℃ to obtain a crucible biscuit;
(3) putting the dried crucible biscuit into a sintering furnace, heating to 1350-1550 ℃ for high-temperature sintering, and cooling to room temperature along with the furnace to obtain a magnesium oxide-based crucible blank;
(4) and (3) carrying out vacuum infiltration treatment on the magnesium oxide-based crucible blank in alumina sol, then carrying out surface polishing treatment, drying, carrying out high-temperature secondary sintering at the temperature of 1350-1550 ℃, and cooling to room temperature along with a furnace to obtain the magnesium oxide-based crucible.
3. The method for preparing the spinel reinforced magnesia-based crucible in situ synthesized by magnesia whiskers, according to claim 2, is characterized in that: the solid content of the nano aluminum sol is 20-25%, and the PH value is more than or equal to 4.
4. The method for preparing the spinel reinforced magnesia-based crucible in situ synthesized by magnesia whiskers, according to claim 2, is characterized in that: the nano iron oxide accounts for 1-2% of the mass of the ceramic powder, the nano zinc oxide accounts for 0.5-1% of the mass of the ceramic powder, the magnesium oxide whisker accounts for 1.5-2.5% of the mass of the ceramic powder, and the balance is light-burned magnesium oxide.
5. The method for preparing the spinel reinforced magnesia-based crucible in situ synthesized by magnesia whiskers, according to claim 2, is characterized in that: the particle size of the nano ferric oxide is 30-60 nm, the particle size of the nano zinc oxide is 20-30 nm, the magnesium oxide whisker is an industrialized product, the diameter of the magnesium oxide whisker is 2-5 mu m, the length of the magnesium oxide whisker is 200-1000 mu m, and the particle size of the light-burned magnesium oxide powder is 250-500 meshes.
6. The method for preparing the spinel reinforced magnesia-based crucible in situ synthesized by magnesia whiskers according to claim 4, is characterized in that the method for preparing the ceramic slurry comprises the following steps: adding light-burned magnesium oxide powder into a ball milling tank according to the proportion, mixing nano aluminum sol, nano iron oxide, nano zinc oxide, magnesium oxide whiskers, a rheological agent and absolute ethyl alcohol, carrying out ultrasonic treatment for 30-60 min, fully dispersing the nano iron oxide, the nano zinc oxide and the magnesium oxide whiskers, adding into the ball milling tank, adding corundum balls according to the ball-to-material ratio of 2:1, and carrying out ball milling for 2-4 h at the rotating speed of 60-120 rpm to uniformly mix the materials.
7. The method for preparing the spinel reinforced magnesia-based crucible in situ synthesized by magnesia whiskers, according to claim 2, is characterized in that the method for preparing the biscuit of the crucible comprises the following steps: and (3) quickly injecting the ceramic slurry into a gypsum mold, placing the gypsum mold on a vibration forming machine for vibration forming, stopping vibration when the mold is completely filled with the slurry and the surface of the slurry is uniformly spread, flattening the surface of the spread slurry, demolding when no ethanol liquid escapes from the surface of the blank, and removing the ethanol solvent in a ventilation chamber at 40-50 ℃ to obtain the ceramic.
8. The method for preparing the spinel reinforced magnesia-based crucible as claimed in claim 2, wherein in the step (3), the sintering process comprises: heating to 550 ℃ at a heating rate of 60 ℃/h to decompose and gasify organic matters in the biscuit and discharge the organic matters, heating to 1100 ℃ at a heating rate of 200 ℃/h, heating to 1350-1550 ℃ at a heating rate of 50 ℃/h, and preserving heat at the temperature for 2-3 h.
9. The method for preparing the spinel reinforced magnesia-based crucible for in-situ synthesis of magnesia whiskers, according to claim 2, is characterized in that the vacuum infiltration treatment method of the magnesia-based crucible blank in alumina sol comprises the following steps: putting the magnesia-based crucible blank into alumina sol, carrying out vacuum infiltration treatment for 30min under the negative pressure of 0.02 MPa-0.05 MPa, baking the magnesia-based crucible blank in a baking oven at the temperature of 120 +/-10 ℃ for 24 hours, and then repeatedly carrying out twice according to the method; then, polishing the surface of the aluminum sol serving as cooling liquid on a grinding machine, and baking the aluminum sol in an oven at the temperature of 120 +/-10 ℃ for 24 hours; and finally, performing high-temperature secondary sintering on the dried crucible blank with the polished surface, wherein the secondary sintering process comprises the following steps: heating to 1100 ℃ at a heating rate of 200 ℃/h, then heating to 1350-1550 ℃ at a heating rate of 50 ℃/h, and preserving heat for 2-3 h at the temperature.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810307134.6A CN108424124B (en) | 2018-04-08 | 2018-04-08 | Spinel reinforced magnesium oxide base crucible synthesized in situ by magnesium oxide whisker and preparation method thereof |
| PCT/CN2018/089573 WO2019196182A1 (en) | 2018-04-08 | 2018-06-01 | Magnesium oxide whisker in-situ synthesis spinel-reinforced magnesium oxide-based crucible and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810307134.6A CN108424124B (en) | 2018-04-08 | 2018-04-08 | Spinel reinforced magnesium oxide base crucible synthesized in situ by magnesium oxide whisker and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108424124A CN108424124A (en) | 2018-08-21 |
| CN108424124B true CN108424124B (en) | 2020-12-08 |
Family
ID=63160503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810307134.6A Active CN108424124B (en) | 2018-04-08 | 2018-04-08 | Spinel reinforced magnesium oxide base crucible synthesized in situ by magnesium oxide whisker and preparation method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN108424124B (en) |
| WO (1) | WO2019196182A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110002854A (en) * | 2019-05-06 | 2019-07-12 | 辽宁科技大学 | A kind of preparation method of the magnesium oxide-based ceramics of high-compactness |
| CN110281359B (en) * | 2019-07-30 | 2020-09-08 | 福建省德化戴玉堂陶瓷有限公司 | Ceramic plate production process |
| CN115286411B (en) * | 2022-08-12 | 2024-01-02 | 辽宁科技大学 | Titanium dioxide whisker reinforced magnesium oxide ceramic substrate material and preparation method thereof |
| CN116217174B (en) * | 2023-03-09 | 2024-05-10 | 成都理工大学 | Preparation method of artificial stone |
| CN116751573B (en) * | 2023-08-21 | 2023-11-14 | 大庆科讯油田技术服务有限公司 | Petroleum nanometer blocking remover and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008266074A (en) * | 2007-04-20 | 2008-11-06 | Tosoh Corp | Method of firing formed body containing zinc oxide |
| CN101555150A (en) * | 2009-05-18 | 2009-10-14 | 郑州大学 | Low-carbon magnesia carbon brick containing nanometer zinc oxide |
| CN107140951A (en) * | 2017-07-11 | 2017-09-08 | 辽宁中镁高温材料有限公司 | A kind of whisker composite high-performance magnesia brick and its manufacture method |
| CN107382345A (en) * | 2017-08-18 | 2017-11-24 | 郑州大学 | A kind of MgO MA aggregate processing methods of micro-nano spinelle toughness reinforcing |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101498041B (en) * | 2009-01-23 | 2011-09-21 | 东北大学 | Preparation of magnesia crystal whisker |
| JP2014005173A (en) * | 2012-06-25 | 2014-01-16 | Mitsubishi Plastics Inc | Inorganic fiber molded body and insulation member |
| CN103601473B (en) * | 2013-11-04 | 2016-03-16 | 中国科学院合肥物质科学研究院 | A kind of high purity, high-compactness magnesia ceramics |
| CN105084916B (en) * | 2015-07-09 | 2017-12-05 | 徐玉玉 | A kind of anticorrosive magnesium-aluminium fire resistant materials and preparation method thereof |
| WO2017049047A1 (en) * | 2015-09-17 | 2017-03-23 | 3Dbotics, Inc. | Material system and method for fabricating refractory material-based 3d printed objects |
| CN105294127B (en) * | 2015-11-19 | 2017-09-01 | 长兴兴鹰新型耐火建材有限公司 | A kind of triple air hose of cement kiln castable |
-
2018
- 2018-04-08 CN CN201810307134.6A patent/CN108424124B/en active Active
- 2018-06-01 WO PCT/CN2018/089573 patent/WO2019196182A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008266074A (en) * | 2007-04-20 | 2008-11-06 | Tosoh Corp | Method of firing formed body containing zinc oxide |
| CN101555150A (en) * | 2009-05-18 | 2009-10-14 | 郑州大学 | Low-carbon magnesia carbon brick containing nanometer zinc oxide |
| CN107140951A (en) * | 2017-07-11 | 2017-09-08 | 辽宁中镁高温材料有限公司 | A kind of whisker composite high-performance magnesia brick and its manufacture method |
| CN107382345A (en) * | 2017-08-18 | 2017-11-24 | 郑州大学 | A kind of MgO MA aggregate processing methods of micro-nano spinelle toughness reinforcing |
Non-Patent Citations (2)
| Title |
|---|
| Al2O3对MgO 陶瓷微观结构和性能的影响;王蒙蒙等;《中国陶瓷》;20170331;第53卷(第3期);第45-50页 * |
| 镁合金熔炼用陶瓷材料的研究;苏叶清;《中国优秀博硕士学位论文全文数据库（硕士）工程科技I辑》;中国学术期刊（光盘版）电子杂志社;20041231(第4期);第1-66页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019196182A1 (en) | 2019-10-17 |
| CN108424124A (en) | 2018-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108424124B (en) | Spinel reinforced magnesium oxide base crucible synthesized in situ by magnesium oxide whisker and preparation method thereof | |
| CN108484182B (en) | Magnesium aluminate spinel reinforced magnesium oxide based foamed ceramic filter synthesized in situ by magnesium oxide whiskers and preparation method thereof | |
| CN108516803B (en) | Magnesium aluminate spinel reinforced magnesium oxide base foamed ceramic filter and preparation method thereof | |
| CN108546093B (en) | Alumina short fiber reinforced magnesium oxide base crucible and preparation method thereof | |
| CN108503378B (en) | Spinel reinforced magnesium oxide base foamed ceramic filter and preparation method thereof | |
| CN109422537A (en) | Continuous casting is with exempting to toast refractory material and preparation method thereof | |
| CN108439957B (en) | MA-M2T-spinel solid solution reinforced magnesium oxide base foamed ceramic filter and preparation method thereof | |
| CN111957951B (en) | Preparation method and application of modified aluminum powder for refractory castable | |
| JP4094353B2 (en) | Rare earth metal-containing amorphous refractory and construction body and kiln furnace lined with these | |
| CN108546094B (en) | MA-MF composite spinel reinforced magnesium oxide base foamed ceramic filter and preparation method thereof | |
| CN109020524A (en) | A kind of medium-frequency induction furnace furnace lining material and preparation method thereof | |
| CN108439959B (en) | Zirconium dioxide short fiber and magnesium oxysulfate whisker composite reinforced magnesium oxide-based crucible and preparation method thereof | |
| CN108530094B (en) | Basic magnesium sulfate whisker in-situ synthesized magnesium aluminate spinel reinforced magnesium oxide based foamed ceramic filter and preparation method thereof | |
| CN113979761B (en) | Ternary composite self-repairing baking-free sliding plate brick and preparation method thereof | |
| CN110452009A (en) | A kind of preparation method of in-situ preparation magnesium aluminate spinel whisker skeletal porous ceramics | |
| CN108484128B (en) | Mg (Al, Cr)2O4Composite spinel reinforced magnesium oxide base foamed ceramic filter and preparation method thereof | |
| CN112479729B (en) | High-strength silicon carbide-oxide composite material and preparation method thereof | |
| CN108484181B (en) | Alumina short fiber reinforced magnesium oxide based foamed ceramic filter and preparation method thereof | |
| CN111875393B (en) | Sintering aid, aluminum titanate ceramic precursor, aluminum titanate ceramic, and method for producing same | |
| CN112125692B (en) | Dispersed air brick of magnesia spinel-zirconia formed in situ by combustion and preparation process thereof | |
| CN114644525A (en) | Composite sagger added with waste materials and preparation method thereof | |
| CN113173780A (en) | Magnesia-bonded refractory castable containing in-situ spinel and preparation method thereof | |
| CN110407593A (en) | A kind of low-density alumina-magnesia castable and preparation method thereof | |
| CN116924781B (en) | High-temperature tin bath bottom brick for float glass production and preparation method thereof | |
| CN115073190B (en) | Aluminum-magnesium-zirconium castable for copper outlet chute of anode furnace and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |