CN108546094B - MA-MF composite spinel reinforced magnesium oxide base foamed ceramic filter and preparation method thereof - Google Patents
MA-MF composite spinel reinforced magnesium oxide base foamed ceramic filter and preparation method thereof Download PDFInfo
- Publication number
- CN108546094B CN108546094B CN201810307627.XA CN201810307627A CN108546094B CN 108546094 B CN108546094 B CN 108546094B CN 201810307627 A CN201810307627 A CN 201810307627A CN 108546094 B CN108546094 B CN 108546094B
- Authority
- CN
- China
- Prior art keywords
- ceramic
- nano
- sintering
- magnesia
- template
- 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 265
- 239000000919 ceramic Substances 0.000 title claims abstract description 144
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 137
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 62
- 239000011029 spinel Substances 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 title claims abstract 6
- 238000005245 sintering Methods 0.000 claims abstract description 69
- 239000000843 powder Substances 0.000 claims abstract description 49
- 239000002002 slurry Substances 0.000 claims abstract description 37
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 36
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 235000015895 biscuits Nutrition 0.000 claims abstract description 32
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920003023 plastic Polymers 0.000 claims abstract description 24
- 239000004033 plastic Substances 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 235000019441 ethanol Nutrition 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000009423 ventilation Methods 0.000 claims abstract description 7
- 238000007654 immersion Methods 0.000 claims abstract description 3
- 239000006260 foam Substances 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 12
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 11
- 229920003086 cellulose ether Polymers 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000080 wetting agent Substances 0.000 claims description 8
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 6
- 229940060296 dodecylbenzenesulfonic acid Drugs 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
- 238000005406 washing Methods 0.000 claims description 6
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 5
- 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
- 239000000126 substance Substances 0.000 abstract description 20
- 230000035939 shock Effects 0.000 abstract description 7
- 235000012245 magnesium oxide Nutrition 0.000 description 116
- 239000011777 magnesium Substances 0.000 description 52
- 229910052749 magnesium Inorganic materials 0.000 description 50
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 33
- 239000012071 phase Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 26
- 229910000861 Mg alloy Inorganic materials 0.000 description 22
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 20
- 230000000694 effects Effects 0.000 description 19
- 230000004907 flux Effects 0.000 description 17
- -1 fluorine ions Chemical class 0.000 description 16
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 16
- 239000000956 alloy Substances 0.000 description 15
- 229910045601 alloy Inorganic materials 0.000 description 15
- 229910052593 corundum Inorganic materials 0.000 description 15
- 238000000746 purification Methods 0.000 description 15
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 239000013078 crystal Substances 0.000 description 12
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 239000006104 solid solution Substances 0.000 description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910000838 Al alloy Inorganic materials 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
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000010431 corundum Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000011858 nanopowder Substances 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- 239000007767 bonding agent Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 230000008859 change Effects 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
- 238000007598 dipping method Methods 0.000 description 3
- 229910001195 gallium oxide Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000011734 sodium Substances 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 2
- 229940071161 dodecylbenzenesulfonate Drugs 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
- 238000010304 firing Methods 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
- 229910052742 iron Inorganic materials 0.000 description 2
- MHKWSJBPFXBFMX-UHFFFAOYSA-N iron magnesium Chemical compound [Mg].[Fe] MHKWSJBPFXBFMX-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 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
- 210000002345 respiratory system Anatomy 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910016384 Al4C3 Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019752 Mg2Si Inorganic materials 0.000 description 1
- 229910020056 Mg3N2 Inorganic materials 0.000 description 1
- 229910017857 MgGa Inorganic materials 0.000 description 1
- 229910003112 MgO-Al2O3 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007664 blowing Methods 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
- 210000003169 central nervous system Anatomy 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
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 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
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 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
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003754 machining Methods 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
- 239000007769 metal material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 210000004165 myocardium Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000161 steel melt Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 238000009736 wetting Methods 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 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
- C04B35/053—Fine ceramics
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
- B01D39/2068—Other inorganic materials, e.g. ceramics
- B01D39/2093—Ceramic foam
-
- 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
- C04B35/6303—Inorganic additives
-
- 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
- C04B35/63416—Polyvinylalcohols [PVA]; Polyvinylacetates
-
- 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
- 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
- C04B35/64—Burning or sintering processes
-
- 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
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
-
- 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
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/0615—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances the burned-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a porous polyurethane sheet or a prepreg obtained by bonding together resin particles
-
- 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
- C04B2235/322—Transition aluminas, e.g. delta or gamma aluminas
-
- 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
- C04B2235/327—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
- C04B2235/50—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
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
-
- 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
- C04B2235/65—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
- C04B2235/656—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
- C04B2235/6567—Treatment time
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Filtering Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses an MA-MF composite spinel reinforced magnesium oxide based foamed ceramic filter which can realize sintering at low temperature and has excellent chemical stability and thermal shock resistance and a preparation method thereof, wherein the preparation method comprises the following steps: (1) preparing 15-25% of nano aluminum sol, 0.8-1.5% of rheological agent and the balance of magnesium oxide ceramic powder containing nano ferric oxide 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 60-70%; (2) immersing a polyurethane foam plastic template into the ceramic slurry, extruding the polyurethane foam plastic template through a roller press to remove redundant immersion slurry to prepare a biscuit, and then removing an ethanol solvent in a ventilation chamber at the temperature of 40-50 ℃ to dry the biscuit; (3) and (3) putting the dried 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 magnesia-based foamed ceramic filter.
Description
Technical Field
The invention relates to a magnesium oxide based foamed ceramic filter and a preparation method thereof, in particular to an MA-MF composite spinel reinforced magnesium oxide based foamed ceramic filter and a preparation method thereof, belonging to the field of metal materials and metallurgy. The filter prepared by the invention is particularly suitable for filtering and purifying magnesium and magnesium alloy melts, and can also be used for filtering and purifying aluminum and aluminum alloy melts.
Background
According to the type and property of inclusions in magnesium alloy, the inclusions are generally divided into two main categories of metal inclusions and non-metal inclusions, (1) metal inclusions, namely metal simple substances or metal compound inclusions which are inevitably introduced into the magnesium alloy in the production and later processing of original magnesium and remain on a matrix or a crystal boundary of the magnesium alloy in the forms of particles, clusters and the like, and mainly comprise α -Fe particles of the metal simple substances, metal compounds of manganese-iron such as (Fe, Mn)3Si，(Fe,Mn)5Si3Etc.; (2) non-metallic inclusions: the non-metallic inclusions in the magnesium alloy are mainly based on magnesium oxynitrides, such as MgO, Mg3N2Etc.; the magnesium alloy is added with chloride (KCl, NaCl, MgCl) in the smelting process2Etc.) as the main refining agent, the flux can not be completely removed in the refining process, and a small amount of flux remains in the magnesium melt, causing the inclusion of magnesium metal flux. The suspended oxide inclusions are pushed from the crystallization front to the grain boundary during crystallization, and are trapped by the grain boundaryThe impurities generally remain in the form of a film, particles, or clusters at the grain boundaries of the magnesium alloy. Statistical data show that MgO accounts for more than 80% of all inclusions in the magnesium alloy, and the distribution form is film, particle and cluster. The inclusion produced in the process of casting the magnesium alloy not only seriously deteriorates the mechanical property and the corrosion resistance of the alloy, but also reduces the surface quality of the alloy after machining and anodic oxidation treatment. For die-cast magnesium alloy, the content of film-like and particle-like oxides in the alloy needs to be controlled to 100cm2Kg and 100mm3The normal use requirements can be met only when the dosage is less than/kg. Therefore, a purification process for removing inclusions in a magnesium melt to improve the purity of the melt during the casting process becomes a key to the production of magnesium alloys.
The melt purification process can be divided into two main categories of flux purification and non-flux purification. The flux purification process is a purification process commonly adopted in the production of magnesium alloy due to high impurity removal efficiency, low cost and convenient operation, but the flux purification also has the defects of increased metal loss, inclusion of flux, incapability of degassing and the like, and particularly when the rare earth magnesium alloy is smelted, the flux can also consume a large amount of rare earth elements in the alloy. The non-flux purification process not only can make up the defects of the flux purification process, but also has excellent purification effect, becomes an important melt purification process applied and developed at present, and develops a plurality of non-flux purification technologies such as filtration purification, rotary blowing purification, electromagnetic purification, ultrasonic treatment and the like in succession. Compared with simple metal mesh melt filtration, the three-dimensional porous ceramic foam ceramic filter with the three-dimensional porous ceramic structure has the advantages of high porosity (70-90%), strong adsorption capacity, chemical corrosion resistance and the like, and can have good filtering effect on impurity particles in the alloy melt through filter cake effect, adsorption effect and rectification effect. The foamed ceramic filtering method can not only filter out fine inclusion particles as small as 10-20 microns in the alloy melt, but also filter out liquid flux inclusions which are difficult to filter out by common filter media.
U.S. Pat. No. 4, 3962081A (Ceramic foam filter), U.S. Pat. No. 4024212A (Ceramic foam and method of preparation), and Chinese patent document CN103787691A (a method for preparing alumina Ceramic foam) Etc. all disclose some Al for filtering inclusions in aluminum alloy and steel melts2O3，ZrO2，SiC、SiO2However, the standard free enthalpy of formation of MgO is very low, and the magnesium melt with high activity is very easy to react with the foam ceramic matrix material to dissolve rapidly, thereby blocking the filtration pores or corroding into the magnesium and its alloy melt to become harmful components, therefore, these prior art foam filters are not suitable for filtering magnesium and magnesium alloy melts.
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 common ceramic materials, MgO, magnesium and alloy melt thereof have good high-temperature chemical stability, do not react with flux inclusion slag formed by molten chloride and fluonate, have small wetting angle with the flux and are easy to adsorb the flux inclusion in the magnesium melt, so the MgO foamed ceramic is an ideal material for smelting and purifying magnesium alloy liquid.
Firing below the melting point of the oxide composition is the most critical step necessary for the preparation of the ceramic material, and the sintering, grain growth, etc. that occurs at high temperatures determines the microstructure and properties of the ceramic material. Chinese patent documents CN1011306B (pure magnesium oxide foamed ceramic filter and preparation process thereof), CN101138691A (preparation method of magnesium foamed ceramic filter for casting) and the like taking pure magnesium oxide as raw materialThe raw materials are used for preparing the foamed ceramic, and the 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 foam 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 foamed 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. Fluoride is a strong cosolvent and a mineralizer which are commonly used in the industrial sintering of ceramics, fluorite (melting point 1423 ℃) and magnesium fluoride (melting point 1248 ℃) are added into Chinese patent documents CN100536986C (a magnesia foam ceramic filter), CN1473947A (a foam ceramic for purifying magnesium and magnesium alloy melts) and CN101785944B (a preparation method of a magnesium oxide foam ceramic filter for filtering magnesium and magnesium melts), and solid solution of the fluoride not only increases lattice distortion of matrix magnesium oxide in the sintering process, but also easily forms a low-melting-point liquid phase, so that the sintering temperature of the magnesium oxide ceramic is reduced; however, F in 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 ceramic tiles) volatilizes in a gaseous state to erode a blank body and damage the quality of the sintered ceramic, more serious the F pollution is caused by the emission of the fluoride into the atmosphere, the fluoride can enter a human body through respiratory tract, digestive tract and skin, has toxic effect on the central nervous system and cardiac muscle, the low-concentration fluorine pollution can cause brittle calcification of teeth and bones, and the emission standard of the fluoride is required to be lower than 5.0mg/m in the emission standard of ceramic industrial pollutants (GB25464-2010)3With fluoride as the magnesia ceramicThe low-temperature sintering aid inevitably increases the emission of gaseous fluoride and increases the burden of environmental protection investment; 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 inclusion in a magnesium melt. In the slurry for producing the ceramic foam filter disclosed in Chinese patent document CN101138691A or the like, water glass, silica sol and ethyl silicate are used as a binder, and SiO is formed between sintered ceramic foam particles2The 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 foamed 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 foamed ceramic is dissolved in water to form a boric acid aqueous solution, and is easy to react with magnesium oxide to form magnesium borate precipitate so as 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.
Disclosure of Invention
The invention aims to provide an MA-MF composite spinel reinforced magnesia-based foamed ceramic filter which can be sintered at low temperature and has excellent chemical stability and thermal shock resistance and a preparation method thereof.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
an MA-MF composite spinel reinforced magnesium oxide-base foam ceramic filter is prepared through coating the light-burnt magnesium oxide-base ceramic slurry containing nano iron sesquioxide as sintering aid on the foam polyurethane carrier, drying and sintering.
A preparation method of an MA-MF composite spinel reinforced magnesia-based foamed ceramic filter 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 magnesia ceramic powder containing nano ferric oxide sintering aid are mixed, added with absolute ethyl alcohol, ball milled and mixed evenly to prepare ceramic slurry with the solid content of 60 to 70 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 powder2O3Coating the film to act as a binder, Al during sintering2O3With Fe2O3The MgO and the MA-MF composite spinel solid solution phase which has chemical stability to magnesium and alloy melt are synthesized together in situ, so that the damage of the prior product added with bonding agents such as silica sol, ethyl silicate and the like to the chemical stability of the foamed ceramic is avoided.
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 polyacrylic acid are good dispersing agents of nano titanium oxide powder, can prevent slurry from agglomerating, can also play a role of an adhesive when a biscuit is prepared, and the impregnated slurry can be firmly attached to a polyurethane foam template, so that the biscuit has high strength, and meanwhile, the impregnated slurry can easily escape in a sintering process without polluting products, thereby ensuring the quality of the foam ceramic filter. Sodium carboxymethyl cellulose and other sodium-containing salts are not adopted in the rheological agent, so that residual Na with larger ionic radius is avoided+The resistance to sintering of the ceramic.
The ceramic powder is a mixture of light-burned magnesia and nano ferric oxide. Wherein the nano ferric oxide accounts for ceramic powder material1-2% of the nano ferric oxide, and the particle size of the nano ferric oxide is 30-60 nm. The particle diameter of the light-burned magnesium oxide powder is 250-500 meshes (medium diameter d)5025 to 58 μm).
The adopted light-burned magnesia fine powder has high sintering activity, the nano alumina sol and the nano ferric 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 the MgO to generate crystal lattice distortion and activate the crystal lattice, and meanwhile, the MA-MF composite spinel phase is generated through reaction and sintering between the nano alumina sol and the MgO particles, so that the combination of sintering and the particle phases is 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 ferric 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 for generating a spinel phase is rapidly increased due to the full contact between the nano sintering aid and MgO particles, 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 the foamed ceramic filter.
Added nano Fe2O3Is easy to be dissolved in MgO phase and reacts to generate magnesium iron spinel (MgFe) with high temperature stability2O4MF) phase (melting point 2030 ℃ C.). The light-burned magnesia particles with high sintering activity are surrounded by the nanometer alumina sol film and react in situ in the sintering process to generate the magnesium aluminate spinel MA phase. Fe2O3The solubility in periclase MgO is far higher than that of Al2O31600 ℃ Fe2O3And 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 phase formed around, and the pinning effect of the composite spinel phase inhibits the growth of magnesium oxide particles, thereby refiningThe structure of the foamed ceramic improves the density among ceramic grains.
Preferably, the solid content of the nano-alumina sol is 20-25%, and the PH value of the nano-alumina sol is more than or equal to 4.
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 sesquioxide, a rheological agent and a proper amount of absolute ethyl alcohol, performing ultrasonic treatment for 30-60 min to ensure that nano lanthanum oxide powder is fully dispersed, then adding into the ball milling tank, adding corundum balls according to the ball-to-material ratio of 2:1, and performing ball milling for 2-4 h at the rotating speed of 60-120 rpm to uniformly mix the materials.
(2) Immersing the polyurethane foam plastic template into the ceramic slurry, extruding the polyurethane foam plastic template through a roller press to remove the redundant immersed slurry to prepare a biscuit, and then removing the ethanol solvent in a ventilation chamber at the temperature of 40-50 ℃ to dry the biscuit.
The polyurethane foam plastic template is prepared by the following steps of soaking a polyurethane foam plastic template in a 15-20% NaOH aqueous solution at 40-50 ℃ before use, etching the surface for 40-60 min, washing with clear water, naturally drying, soaking in an aqueous solution of 2-4% dodecylbenzene sulfonic acid wetting agent, taking out and drying, wherein the specification of the polyurethane foam plastic template is 10 PPI-20 PPI (Pores per inch, average number of Pores per unit length). The surface of the ceramic slurry is roughened by NaOH etching, and then the ceramic slurry is treated by the aqueous solution of the dodecyl benzene sulfonate wetting agent, so that the ceramic slurry is easily and uniformly coated and hung on a polyurethane foam template.
(3) And (3) putting the dried 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 magnesia-based foamed ceramic filter.
The sintering process is that organic matters (polyurethane foam, rheological agent and the like) in a biscuit of the foam ceramic filter are decomposed, gasified and discharged by heating to 550 ℃ at a temperature rise speed of 30 ℃/h, and then heated to 1100 ℃ at the temperature rise speed of 200 ℃/h, and in a low-temperature sintering stage, the biscuit collapse or deformation damage caused by the excessively high decomposition speed of the polyurethane foam and the rheological agent can be prevented due to a low temperature rise speed. And finally heating to 1350-1550 ℃ at a heating rate of 50 ℃/h and preserving heat for 2-3 h at the temperature. In the high-temperature sintering stage, after the sintering temperature exceeds 1100 ℃, the temperature in the sintered body can be ensured to be consistent by the lower temperature rise speed, the uniform generation speed of the generated spinel is avoided, and the deformation and the cracking of the sintered body caused by the phase change stress generated too fast are avoided.
The preparation method of the magnesium oxide based foamed ceramic filter provided by the invention has the advantages of simple process, low cost, high efficiency, suitability for large-scale production and the like, the prepared magnesium oxide based foamed ceramic filter does not contain any component for reducing the chemical stability of the magnesium oxide based foamed ceramic filter, the added nano aluminum sol and nano ferric oxide not only can play a role of reducing the sintering temperature, but also are highly and uniformly dispersed into magnesium oxide ceramic powder particles and react with the magnesium oxide ceramic powder particles to generate MgAl with chemical stability to magnesium and magnesium alloy melt2O4And MgFe2O4The composite spinel phase fuses the magnesia particles together, therefore, the foam ceramic filter has good strength, chemical stability and thermal shock resistance, is particularly suitable for filtering and purifying the inclusion in magnesium and alloy melt thereof, and can also be used for filtering and purifying aluminum and alloy melt thereof. Compared with the prior art, the invention has the technical effects that:
firstly, the MA-MF composite spinel reinforced magnesia ceramic foam filter 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 (melting point 2030 ℃ 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 powder2O3Coating film of gamma-Al in alumina sol during sintering2O3Reacts with light-burned MgO particles in situ 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 XRD analysis results show that the foam ceramic filter 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. Reaction of magnesium liquor with magnesium aluminate spinel equation (7), although thermodynamically feasible, is essentially of the nature of the reaction between magnesium liquor and magnesium aluminate spinelThe decomposition product, alumina, is reacted with each other, but it is known from table 1 that the reaction of decomposing the magnesium aluminate spinel into alumina and magnesia is difficult to proceed (reverse reaction of reaction formula (6)) at the melting temperature of the magnesium alloy, and the residual alumina in the sintered ceramics and the magnesium solution preferentially form magnesium aluminate spinel according to 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 MA-MF composite spinel reinforced magnesia foam ceramic filter does not contain any component for reducing the chemical stability of the filter, and the added nano alumina sol can not only be dispersed in light-burned magnesia particles and highly uniformly dispersed nano Fe2O3Forming gamma-Al on the surface of the powder2O3Coating the film to act as a binder, Al during sintering2O3With Fe2O3The MA-MF composite spinel solid solution phase which has chemical stability to magnesium and alloy melt is synthesized together with MgO in situ, so that the damage of the prior product on the chemical stability of the foamed ceramic 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.
Since the reaction formulas (1) and (5) can spontaneously proceed at the common melting temperature of the magnesium alloy, the melting temperature of the aluminum and the aluminum alloy is the same as that of the magnesium and the aluminum alloy, the reverse reaction of the reaction formulas (1) and (5) can not occur between the MgO spinel phase and the aluminum alloy melt(ii) a 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 the foamed 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 MA-MF composite spinel reinforced magnesia ceramic foam filter can also be used for smelting and purifying aluminum and aluminum alloy.
Secondly, the MA-MF composite spinel reinforced magnesia foam ceramic filter 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 ferric oxide can be dissolved into the crystal lattice of MgO in a solid solution manner 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 to sinter to 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 ferric 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 for generating a spinel phase is rapidly increased due to the full contact between the nano sintering aid and MgO particles, 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 the foamed ceramic filter. The test result shows that when the sintering temperature is lower than 1350 ℃, the sintering structure combination among magnesium oxide particles is insufficient, so that the strength is low, and the sintering temperature of the MA-MF composite spinel reinforced magnesium oxide foamed ceramic filter with good structure combination is 1350-1550 ℃.
And thirdly, the MA-MF composite spinel reinforced magnesia foam ceramic filter 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. In the scheme provided by the invention, the light calcined magnesia particles with high sintering activity are surrounded by the nano-alumina sol film in the sintering processThe in-situ reaction generates a magnesium aluminate spinel MA phase. Fe2O3The solubility in periclase MgO is far higher than that of Al2O31600 ℃ Fe2O3And 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, and the pinning effect of the composite spinel phases inhibits the growth of magnesium oxide particles, thereby refining the structure of the foam ceramic and improving the density among ceramic crystal grains, and the prepared MA-MF composite spinel reinforced magnesium oxide foam ceramic filter has higher mechanical property, high-temperature impact resistance and thermal shock resistance.
In addition, in the preparation method, the polyurethane foam plastic template is roughened by NaOH etching, and then is treated by the aqueous solution of the dodecylbenzene sulfonate wetting agent, so that the ceramic slurry is easily and uniformly coated on the polyurethane foam template; meanwhile, the cellulose ether and the polyvinyl butyral which are used as rheological agents are good dispersants for the nano ferric oxide powder, can prevent slurry from generating agglomeration phenomenon, can play a role of a bonding agent when a biscuit is prepared, and the slurry after being soaked can be firmly attached to a polyurethane foam template so that the biscuit has great strength, and can easily escape in a sintering process without polluting products, thereby ensuring the quality of the foam ceramic filter.
Drawings
FIG. 1 is a flow chart of a process for preparing an MA-MF composite spinel reinforced magnesia-based ceramic foam filter.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
The MA-MF composite spinel reinforced magnesia-based foamed ceramic filter is prepared by coating light-burned magnesia-based ceramic slurry containing nano ferric oxide sintering aid on a polyurethane foam carrier, drying and sintering. The specific preparation process is shown in figure 1.
Example 1
According to the proportion that the nano ferric oxide accounts for 1 percent of the mass of the ceramic powder, the nano ferric oxide with the grain diameter of 30nm and the grain diameter of 250 meshes (the intermediate diameter d)5058 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 sesquioxide, a rheological agent and a proper amount of absolute ethyl alcohol (the addition amount is determined according to the solid content of ceramic slurry, the same is applied below) and carrying out ultrasonic treatment for 30min to ensure that nano lanthanum oxide powder is fully dispersed and then added into the ball milling tank, adding corundum balls according to the ball-to-material ratio of 2:1, and carrying out ball milling for 4h at the rotating speed of 60rpm to uniformly mix the materials to obtain the ceramic slurry with the solid content of 60%.
Selecting a 10PPI polyurethane foam plastic template, soaking the template in a 15% NaOH aqueous solution at 40 ℃ for 60min, washing the template with clear water, naturally drying the template, then soaking the template in a 2% dodecylbenzene sulfonic acid wetting agent aqueous solution, and taking out and drying the template. Then, the polyurethane foam plastic template is immersed into the ceramic slurry, the polyurethane foam plastic template is extruded by a roller press to remove redundant immersion slurry to prepare a biscuit, and then the ethanol solvent is removed in a ventilation chamber at 40 ℃ to dry the biscuit, and the ethanol solvent can be recovered by a recovery device.
And (2) putting the dried biscuit into a sintering furnace, heating to 550 ℃ at a heating rate of 30 ℃/h to decompose and gasify organic matters such as polyurethane foam, rheological agent and the like in the biscuit of the foam ceramic filter, discharging, 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 magnesium oxide-based foam ceramic filter.
Example 2
According to the proportion that the nano ferric oxide accounts for 2 percent of the mass of the ceramic powder, the nano ferric oxide with the grain diameter of 60nm and the grain diameter of 500 meshes (the intermediate 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 aluminum sol, nano iron sesquioxide, a rheological agent and a proper amount of absolute ethyl alcohol, performing ultrasonic treatment for 60min to fully disperse nano lanthanum oxide powder, adding the nano lanthanum oxide powder into the ball milling tank, adding corundum balls according to a ball-to-material ratio of 2:1, and performing ball milling at a rotating speed of 120rpm for 2h to uniformly mix the mixture to obtain ceramic slurry with a solid content of 65%.
Selecting a 20PPI polyurethane foam plastic template, soaking the template in a 20% NaOH aqueous solution at 50 ℃ for 40min, washing the template with clear water, naturally drying the template, then soaking the template in a 4% dodecylbenzene sulfonic acid wetting agent aqueous solution, and taking out and drying the template. Then, the polyurethane foam plastic template is immersed into the ceramic slurry, the polyurethane foam plastic template is extruded by a roller press to remove the redundant dipping slurry to prepare a biscuit, and then the ethanol solvent is removed in a ventilation chamber at 50 ℃ to dry the biscuit.
And (2) putting the dried biscuit into a sintering furnace, heating to 550 ℃ at a heating rate of 30 ℃/h to decompose and gasify organic matters such as polyurethane foam, rheological agent and the like in the biscuit of the foam ceramic filter, discharging, 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 magnesium oxide-based foam ceramic filter.
Example 3
According to the proportion that the nano ferric oxide accounts for 1.5 percent of the mass of the ceramic powder, the grain diameter is 50nm nano ferric oxide and particle size of 325 mesh (medium diameter d)5045 μm) of light burned magnesia powder to prepare ceramic powder; mixing the polyvinyl butyral and the hydroxyethyl cellulose according to the 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 aluminum sol, nano iron sesquioxide, a rheological agent and a proper amount of absolute ethyl alcohol, performing ultrasonic treatment for 45min to fully disperse nano lanthanum oxide powder, adding the nano lanthanum oxide powder into the ball milling tank, adding corundum balls according to a ball-to-material ratio of 2:1, and performing ball milling at a rotating speed of 90rpm for 3h to uniformly mix the mixture to obtain ceramic slurry with a solid content of 70%.
Selecting a 15PPI polyurethane foam plastic template, soaking the template in a 45 ℃ 18% NaOH aqueous solution, etching the surface for 50min, washing the template with clear water, naturally drying the template, then soaking the template in a 3% dodecylbenzene sulfonic acid wetting agent aqueous solution, and taking out and drying the template. Then, the polyurethane foam plastic template is immersed into the ceramic slurry, the polyurethane foam plastic template is extruded by a roller press to remove the redundant dipping slurry to prepare a biscuit, and then the ethanol solvent is removed in a ventilation chamber at the temperature of 45 ℃ to dry the biscuit.
And (2) putting the dried biscuit into a sintering furnace, heating to 550 ℃ at a heating rate of 30 ℃/h to decompose and gasify organic matters such as polyurethane foam, rheological agent and the like in the biscuit of the foam ceramic filter, discharging, 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 magnesium oxide-based foam ceramic filter.
Example 4
According to the proportion that the nano ferric oxide accounts for 1 percent of the mass of the ceramic powder, the nano ferric oxide with the grain diameter of 60nm and the grain diameter of 300 meshes (medium diameter d) are mixed5048 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 sesquioxide, a rheological agent and a proper amount of absolute ethyl alcohol, performing ultrasonic treatment for 45min to fully disperse nano lanthanum oxide powder, adding the nano lanthanum oxide powder into the ball milling tank, adding corundum balls according to a ball-to-material ratio of 2:1, and performing ball milling at a rotating speed of 100rpm for 3h to uniformly mix the mixture to obtain ceramic slurry with a solid content of 65%.
Selecting a 15PPI polyurethane foam plastic template, soaking the template in a 15% NaOH aqueous solution at 45 ℃ for 50min, washing the template with clear water, naturally drying the template, then soaking the template in a 4% dodecylbenzene sulfonic acid wetting agent aqueous solution, and taking out and drying the template. Then, the polyurethane foam plastic template is immersed into the ceramic slurry, the polyurethane foam plastic template is extruded by a roller press to remove the redundant dipping slurry to prepare a biscuit, and then the ethanol solvent is removed in a ventilation chamber at the temperature of 45 ℃ to dry the biscuit.
And (2) putting the dried biscuit into a sintering furnace, heating to 550 ℃ at a heating rate of 30 ℃/h to decompose and gasify organic matters such as polyurethane foam, rheological agent and the like in the biscuit of the foamed ceramic filter, discharging, 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 magnesium oxide-based foamed ceramic filter.
In the embodiment, experiments show that the prepared foamed ceramic has excellent thermal shock resistance and strength, and does not crack after being cooled in air at 900 ℃ for 50 times; 75mm is multiplied by 25mm, and the normal temperature strength of the foamed ceramic filter of 10PPI is not lower than 2 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 (8)
1. An MA-MF composite spinel reinforced magnesia-based foamed ceramic filter is characterized in that a light-burned magnesia-based ceramic slurry containing a nano ferric oxide sintering aid is coated on a polyurethane foam carrier and is obtained by drying and sintering, wherein the light-burned magnesia-based ceramic slurry containing the nano ferric oxide sintering aid comprises 15-25% of nano aluminum sol, 0.8-1.5% of rheological agent, and the balance is magnesia ceramic powder containing the nano ferric oxide sintering aid; 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 light-burned magnesia and nano ferric oxide.
2. A preparation method of an MA-MF composite spinel reinforced magnesia-based foamed ceramic filter is characterized by comprising the following steps:
(1) preparing 15-25% of nano aluminum sol, 0.8-1.5% of rheological agent and the balance of magnesium oxide ceramic powder containing nano ferric oxide 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 60-70%; 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 light-burned magnesium oxide and nano ferric oxide;
(2) immersing a polyurethane foam plastic template into the ceramic slurry, extruding the polyurethane foam plastic template through a roller press to remove redundant immersion slurry to prepare a biscuit, and then removing an ethanol solvent in a ventilation chamber at the temperature of 40-50 ℃ to dry the biscuit;
(3) and (3) putting the dried 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 magnesia-based foamed ceramic filter.
3. The method for preparing an MA-MF composite spinel reinforced magnesia-based ceramic foam filter according to claim 2, wherein: the solid content of the nano aluminum sol is 20-25%, and the PH value of the nano aluminum sol is more than or equal to 4.
4. The method for preparing an MA-MF composite spinel reinforced magnesia-based ceramic foam filter according to claim 2, wherein: the nano ferric oxide accounts for 1-2% of the mass of the ceramic powder.
5. The method for preparing an MA-MF composite spinel reinforced magnesia-based ceramic foam filter according to claim 2, wherein: the particle size of the nano ferric oxide is 30-60 nm.
6. The method for preparing an MA-MF composite spinel reinforced magnesia-based ceramic foam filter according to claim 2, wherein: the particle size of the light-burned magnesium oxide is 250-500 meshes.
7. The method for preparing an MA-MF composite spinel reinforced magnesia-based ceramic foam filter according to claim 2, wherein: the specification of the polyurethane foam plastic template is 10 PPI-20 PPI, the polyurethane foam plastic template is obtained by soaking the template in 15% -20% NaOH aqueous solution at 40-50 ℃ before use, etching the surface for 40-60 min, washing the template with clear water, naturally drying the template, then soaking the template in 2% -4% dodecylbenzene sulfonic acid wetting agent aqueous solution, and taking out and drying the template.
8. The method for preparing an MA-MF composite spinel reinforced magnesia-based ceramic foam filter according to claim 2, wherein in the step (3), the sintering process is: heating to 550 ℃ at a heating rate of 30 ℃/h to decompose and gasify organic matters in the biscuit of the foam ceramic filter and discharge the organic matters, then heating to 1100 ℃ at a heating rate of 200 ℃/h, finally heating to 1350-1550 ℃ at a heating rate of 50 ℃/h and preserving heat at the temperature for 2-3 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810307627.XA CN108546094B (en) | 2018-04-08 | 2018-04-08 | MA-MF composite spinel reinforced magnesium oxide base foamed ceramic filter and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810307627.XA CN108546094B (en) | 2018-04-08 | 2018-04-08 | MA-MF composite spinel reinforced magnesium oxide base foamed ceramic filter and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108546094A CN108546094A (en) | 2018-09-18 |
| CN108546094B true CN108546094B (en) | 2020-05-01 |
Family
ID=63514269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810307627.XA Active CN108546094B (en) | 2018-04-08 | 2018-04-08 | MA-MF composite spinel reinforced magnesium oxide base foamed ceramic filter and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108546094B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6855076B2 (en) * | 2019-06-17 | 2021-04-07 | 東和耐火工業株式会社 | Amorphous refractory and its manufacturing method |
| CN110981539B (en) * | 2019-12-30 | 2021-11-16 | 武汉科技大学 | Magnesium oxide based filter containing functional coating multi-pore structure and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030146151A1 (en) * | 2002-01-23 | 2003-08-07 | Feng Chi | Sintered magnesium oxide filter |
-
2018
- 2018-04-08 CN CN201810307627.XA patent/CN108546094B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108546094A (en) | 2018-09-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108516803B (en) | Magnesium aluminate spinel reinforced magnesium oxide base foamed ceramic filter and preparation method thereof | |
| CN108503378B (en) | Spinel reinforced magnesium oxide base foamed ceramic filter 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 | |
| CN108424124B (en) | Spinel reinforced magnesium oxide base crucible synthesized in situ by magnesium oxide whisker and preparation method thereof | |
| CN103819219B (en) | Acid and alkali corrosion-resistant silicon carbide porous support | |
| WO2018006885A1 (en) | Ceramic powder composition, straight hole ceramic filter and preparation method therefor | |
| CN108546093B (en) | Alumina short fiber reinforced magnesium oxide base crucible and preparation method thereof | |
| CN108546094B (en) | MA-MF composite spinel reinforced magnesium oxide base foamed ceramic filter and preparation method thereof | |
| CN108439957B (en) | MA-M2T-spinel solid solution reinforced magnesium oxide base foamed ceramic filter 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 | |
| CN112125686A (en) | Method for preparing silicon carbide coated graphite by molten salt isolation | |
| CN108484181B (en) | Alumina short fiber reinforced magnesium oxide based foamed ceramic filter and preparation method thereof | |
| CN108484128B (en) | Mg (Al, Cr)2O4Composite spinel reinforced magnesium oxide base foamed ceramic filter and preparation method thereof | |
| CN104072142A (en) | Preparation method of oxide combined SiC porous ceramic | |
| CN112759418B (en) | Silicon nitride whisker reinforced corundum porous ceramic filter and preparation method thereof | |
| CN109180205B (en) | Chromite refractory 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 | |
| US6814903B1 (en) | Low-firing temperature method for producing AL2O3 bodies having enhanced chemical resistance | |
| CN107686338B (en) | Y-PSZ reinforced refractory material and preparation process thereof | |
| CN116003156B (en) | MgAlON ceramic filter with multiple pore structures for magnesium alloy and preparation method thereof | |
| CN115448700B (en) | Magnesium ramming material for refining furnace bottom and preparation process thereof | |
| CN117923944A (en) | Preparation method and product of composite ceramic filter | |
| CN118125842A (en) | MgO-Y for super vacuum smelting Ni-TiAl alloy2O3Base crucible and preparation method thereof | |
| CN111087252A (en) | High-strength porous ceramic filter 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 |