CN103524139B - Low-creep zircon overflowing brick and preparation method thereof - Google Patents
Low-creep zircon overflowing brick and preparation method thereof Download PDFInfo
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- CN103524139B CN103524139B CN201310539068.2A CN201310539068A CN103524139B CN 103524139 B CN103524139 B CN 103524139B CN 201310539068 A CN201310539068 A CN 201310539068A CN 103524139 B CN103524139 B CN 103524139B
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- zircon
- powder
- staple fibre
- overflow brick
- zirconium white
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- 229910052845 zircon Inorganic materials 0.000 title claims abstract description 104
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000011449 brick Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 49
- 239000000835 fiber Substances 0.000 claims abstract description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000654 additive Substances 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 238000010304 firing Methods 0.000 claims abstract description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 50
- 239000004575 stone Substances 0.000 claims description 24
- 230000000996 additive effect Effects 0.000 claims description 23
- 238000005452 bending Methods 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- 238000000462 isostatic pressing Methods 0.000 claims description 5
- 239000003595 mist Substances 0.000 claims description 4
- 238000001238 wet grinding Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 5
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 3
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 abstract 3
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 239000000523 sample Substances 0.000 description 13
- 238000005245 sintering Methods 0.000 description 12
- 239000011521 glass Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000011819 refractory material Substances 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- -1 VO 2 Inorganic materials 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000011863 silicon-based powder Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000013003 hot bending Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000011194 food seasoning agent Nutrition 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910006501 ZrSiO Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003280 down draw process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical group [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 description 1
- UXBZSSBXGPYSIL-UHFFFAOYSA-K yttrium(iii) phosphate Chemical compound [Y+3].[O-]P([O-])([O-])=O UXBZSSBXGPYSIL-UHFFFAOYSA-K 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 1
- ATYZRBBOXUWECY-UHFFFAOYSA-N zirconium;hydrate Chemical compound O.[Zr] ATYZRBBOXUWECY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to a low-creep zircon overflowing brick and a preparation method thereof. The low-creep zircon overflowing brick comprises, by mass, 100% of zircon powder, wherein zircon oxide short fibers account for, by mass, 0.0-4.0% of the zircon powder, silicon oxide powder accounts for, by mass, 0.1-2.0% of the zircon powder, and composite additives account for, by mass, 0.1-0.8% of the zircon powder. The composite additives can be La2O3, or CeO2, or combination of La2O3 and Y2O3, or combination of CeO2 and Y2O3, or combination of La2O3, CeO2 and Y2O3. According to the low-creep zircon overflowing brick and the preparation method thereof, strength of green bodies is improved, firing shrinkage of the green bodies is reduced, manufacturing yield of products is improved, bonding strength of crystal boundaries of zircon is enhanced, the high-temperature bend-creep rate of products is effectively lowered, and the service life of super-large-size overflowing bricks is prolonged.
Description
Technical field
The present invention relates to a kind of low creep zircon stone overflow brick and preparation method thereof, belong to technical field of refractory materials.
Technical background
Along with the development of overflow downdraw production technology manufacturing liquid-crystalline glasses, external liquid-crystalline glasses generally define with 8.5 generation crystal liquid substrate take the market orientation of product as the leading factor.Glass tube down-drawing is produced 8.5 generation liquid-crystalline glasses overflow brick length used and is reached more than 3100mm, in use procedure, overflow brick is at 1000-1200 DEG C, bear the weight of self and glass metal, and the pulling force be delivered to by melten glass in drawn glass process on overflow brick, although the zircon material of routine has lower creep speed, and glass manufacturer applies certain pressure to resist flexural deformation from the supported on both sides position of brick, but the creep that still can bend under these conditions.Be in particular in below the height reduction of overflow brick middle portion to support end height, cause finally cannot being shaped the uniform glass substrate of thickness.In order to solve the bending creep problem in overflow brick use procedure, prior art provides multiple solution.
Publication number is that the Chinese patent of CN1657499A discloses a kind of creep resistant zircon refractory material used in glass making system, has the composition comprising following component, ZrSiO
4: 98.85-99.68wt%; ZrO
2: 0.01-0.15wt%; TiO
2: 0.23-0.50wt%; Fe
2o
3: this patent of 0.08-0.60wt%. mainly improves the creep resistance of overflow brick by controlled oxidization titanium and ferric oxide, wherein Fe
2o
3although to promoting that the densification of base substrate has remarkable effect, also there is the shortcoming causing glass coloring and foaming tendency to increase.
Chinese patent application 200980119562.5(CN102036934A) disclose and a kind ofly adopt the zircon particle of multimodal size distribution curve, the TiO of at least 0.1% weight
2the Y of 10% weight at the most
2o
3mixing, isostatic pressing form green compact, at least at 1500 DEG C, sintering obtains the method for fine and close zircon material, have employed multi-stage particle grating to improve the tap density of goods and to reduce porosity as far as possible, to reduce grain boundary concentration, and improve the bonding strength between zircon particle crystal boundary.But consider that the granularity of zircon raw material is relevant to the smooth finish of final overflow brick goods, thus increase granularity and raising tap density improve the effect of the bending creep performance of overflow brick is finally limited.
Chinese patent application 200880114001.1(CN101842325A) disclose a kind of matrix material, in zircon, add the Ith, II, III class additive and their combination, its content is that the Ith class additive accounts for 0.0-0.1 % by weight, is selected from Fe
2o
3, SnO
2, oxide glass and their mixture and combination; IIth class additive accounts for 0.1-0.8 % by weight, is selected from TiO
2, SiO
2, VO
2, CoO, NiO, NbO and their mixture and combination; IIIth class additive accounts for 0.1-0.8 % by weight, is selected from Y
2o
3, ZrO
2, CaO, MgO, Cr
2o
3, Al
2o
3and their mixture and combination; Wherein the amount of agglutinant is with oxide basis, based on the per-cent of the gross weight of composition.The mean particle size of described zircon particle is at least 1um, is at least 3um, 5um, 7um, 10um in some embodiments, and mean particle size is not higher than 15um.By adding the IIth, III class sinter additives, obtained matrix material at high temperature has low creep speed and good intensity.But CaO, MgO, Al
2o
3the decomposition of zircon can be caused under high temperature, cause the firing property of material to worsen.
Chinese patent application 200880123970.3(CN101910090A) disclose one zircon is contacted with sintering aid, wherein said sintering aid is liquid, solation or and their composition.Described sintering aid comprises at least one in titanium compound, iron containing compounds or its composition, carrys out the effect of intensified-sintered auxiliary agent by sintering aid being uniformly coated on zircon powder surface.
Chinese patent application 200880009665.1(CN101641171B) disclose the zircon composition with multimodal granularity.Described multimodal zircon composition comprises the thin zircon component that the thick zircon component that the median particle being greater than 40% weight part is greater than 3 microns to 25 microns and the median particle being less than 60% weight part are less than or equal to 3 microns.Described composition also comprises the oxide compound that yttrium phosphate and at least one comprise at least one in titanium, iron, calcium, yttrium, niobium, neodymium, or their combination.Described goods are less than 1 × 10 the creep speed of 1180 DEG C
-4inch per hour, but need to fire under helium-atmosphere or vacuum atmosphere, industrialization manufactures large-sized base substrate certain difficulty.
Chinese patent application 200780043916.3(CN101558023A) disclose use zircon precursor, silica precursors, Sol-gel forming agents contact with preformed zircon, fires the method for refractory of densification, creep resistance.It is characterized in that adopting zircon precursor to the hole of filling between preformed zircon and the crystal boundary reduced in structure, thus reduce the creep properties of zircon material.But the zirconium oxide precursor of various ways, as nitric hydrate zirconium, zirconium dichloride, hydration zirconium or its combination, with silica precursors, as silica gel, tetraethoxysilane, hydration silicon, silicon tetrachloride, amorphous silicon or their combination and Sol-gel forming agents comprise at least one or their combination in ammonia, ammonium hydroxide, Neutral ammonium fluoride, relate to the chemical reagent of multiple scent of or the strict protection of needs in manufacturing processed, need to add extra waste gas cleaning system in refractory materials manufacturing process.
The present inventor applies for and the patent of having the right (application number 200710013446.8) discloses a kind of preparation method of large compact zircon overflow brick, disclose to adopt and vacuumize the method that large-scale zircon overflow brick is slowly burnt till in rear isostatic pressing, heating and cooling, solve the problem that large-scale overflow brick very easily ftractures in process of production, wherein fully disclose the process for making of overflow brick, but and the problem of not mentioned reduction overflow brick bending creep speed.
In the manufacture and use procedure of reality, along with the increase of base substrate length and weight, be necessary the method taking other simple and easy to do on the one hand, the hot bending creep speed of further reduction overflow brick material, the intensity being also necessary on the other hand to improve green is to reduce base substrate fracture or seminess in shaping, loading of kiln process, when reducing to burn till, the contraction of base substrate, burns till cracking and problem on deformation to solve simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of low creep zircon stone overflow brick and preparation method thereof, utilize the intensity of the raising green compact of zirconium white staple fibre; Add composite additive to improve the bonding strength between crystal boundary, promote that in sintering process, zirconium white and silicon oxide form zircon generation volumetric expansion, that reduces base substrate burns till contraction; The hot bending creep speed of effective reduction zircon goods.
One of the present invention low creep zircon stone overflow brick, the content of raw material is as follows:
Zircon opaque amount is 100%, and zirconium white staple fibre accounts for zircon opaque amount 0.0-4.0%, and silica powder accounts for zircon opaque amount 0.1-2.0%, and composite additive accounts for zircon opaque amount 0.1-0.8%; Wherein composite additive is La
2o
3or CeO
2or La
2o
3with Y
2o
3combination or CeO
2with Y
2o
3combination or La
2o
3with CeO
2with Y
2o
3combination.
When composite additive compound is added, preferred Y
2o
3add-on be La
2o
3or CeO
2the 1-2 of quality doubly.The present invention adds composite additive to be had accelerating oxidation zirconium staple fibre and partly or entirely changes into zircon, increases consistency between raw material zircon and the zircon particle newly formed, thus the effect of reduction hot bending creep speed.
When the present invention does not add zirconium white staple fibre: add Y separately
2o
3sample after burning till, high temperature break resistant intensity is lower, creep speed is higher; Independent interpolation La
2o
3or CeO
2sample after burning till, high temperature break resistant intensity, creep speed are slightly improved.When adding zirconium white staple fibre, add La separately
2o
3or CeO
2burn till rear sample, high temperature break resistant intensity, creep speed have further improvement; Work as La
2o
3with Y
2o
3or CeO
2with Y
2o
3compound is added, and Y
2o
3add-on be La
2o
3or CeO
21-2 times time, volume density, the high temperature break resistant intensity of sample significantly improve, and 1200 DEG C of bending creep speed obviously reduce, and reach 1/10th of conventional zircon stone material, even one of 20.
Zircon powder, zirconium white staple fibre, silica powder and composite additive are all selected containing Al
2o
3, Fe
2o
3, CaO, MgO, K
2o, Na
2the raw material that O content is low.
The preferred Al of zircon powder
2o
3≤ 0.2%, Fe
2o
3≤ 0.05%, CaO+MgO≤0.05%, K
2o+Na
2o≤0.03%.Due to Al
2o
3, Fe
2o
3, CaO, MgO, K
2o, Na
2o finally forms glassy phase in the sintering process of brick, and 1200 DEG C time, glassy phase is softening can bring disadvantageous effect to creep speed.
The diameter of zirconium white staple fibre is 1-7um, and length is less than 3mm, wherein ZrO
2+ Y
2o
3quality>=99%; The diameter of preferential oxidation zirconium staple fibre is 1-5um, and length is less than 2mm; Most preferably the diameter of zirconium white staple fibre is 1-3um, and length is less than 1mm.
The preferred silicon powder of silica powder, silicon powder meso-position radius≤1um, SiO
2content>=99.5%, wherein contained Al
2o
3, Fe
2o
3, CaO, MgO, K
2o, Na
2total mass content≤0.3% of O, preferred total mass content≤0.1%.
La
2o
3preferred meso-position radius≤the 3um of powder, further preferred meso-position radius≤2um, most preferably meso-position radius≤1um, wherein La
2o
3quality>=99%, loss on ignition≤0.5%.
CeO
2preferred meso-position radius≤the 3um of powder, further preferred meso-position radius≤2um, most preferably meso-position radius≤1um, wherein CeO
2quality>=99%, loss on ignition≤0.5%.
Y
2o
3preferred meso-position radius≤the 3um of powder, further preferred meso-position radius≤2um, most preferably meso-position radius≤0.7um, wherein Y
2o
3quality>=99%, loss on ignition≤0.5%.
The zircon stone overflow brick of low creep of the present invention is less than 3.0 × 10 the bending creep speed of 1200 DEG C
-7hour
-1, bending creep speed is preferably less than 1.0 × 10
-7hour
-1.Length is 3100-6000mm, and thickness is 100-900mm, width is 1000-1700mm.
The preparation method of low creep zircon stone overflow brick of the present invention, be after 5-10um by zircon powder wet grinding to meso-position radius, add zirconium white staple fibre dispersion liquid, silica powder and composite additive again, after co-ground, mist projection granulating, dress rubber cast, isostatic pressing obtain green compact, high temperature burns till to obtain base substrate, and base substrate precision work obtains the zircon stone overflow brick of low creep.
The content of raw material is as follows:
Zircon opaque amount is 100%, and zirconium white staple fibre accounts for zircon opaque amount 0.0-4.0%, silica powder accounts for zircon opaque amount 0.1-2.0%, and composite additive accounts for zircon opaque amount 0.1-0.8%; Wherein composite additive is La
2o
3or CeO
2or La
2o
3with Y
2o
3combination or CeO
2with Y
2o
3combination or La
2o
3with CeO
2with Y
2o
3combination.
In green compact, the mass percentage content scope of impurity is Al
2o
3≤ 0.2%, Fe
2o
3≤ 0.05%, CaO+MgO≤0.05% and K
2o+Na
2o≤0.03%.
The preparation method of zirconium white staple fibre dispersion liquid is: in zirconium white staple fibre, add dispersion agent, then the zircon powder co-ground adding silica powder or add 1-4% becomes zirconium white staple fibre dispersion liquid.
Dispersion agent is Sodium dodecylbenzene sulfonate.
Zirconium white staple fibre adds Sodium dodecylbenzene sulfonate, becomes zirconium white staple fibre dispersion liquid to use with silica powder or zircon powder raw material co-ground.
In order to dispensing zirconia staple fibre fully, it is made to be in monofilament state, with play the effect increasing blank strength after all the other raw material blendings, zirconium white staple fibre adds Sodium dodecylbenzene sulfonate dispersion agent, with silica powder raw material co-ground or with part zircon powder raw material co-ground, until evenly spread in water.The object of co-ground is accelerating oxidation silica flour and the mixing of zirconium white staple fibre, and is conducive to zirconium white staple fibre and changes into zircon, or increase the consistency between raw material zircon and the zircon particle newly formed.In order to reduce the impurity that dispersion agent is introduced, Sodium dodecylbenzene sulfonate can play dissemination, and Sodium dodecylbenzene sulfonate consumption is be less than zirconium white staple fibre quality 0.1%, and preferably 0.06% or 0.04%.
Add the short agglutinant accounting for zircon opaque amount 0.3-0.5% in raw material, wherein, short agglutinant is TiO
2powder.TiO
2powder, preferred meso-position radius≤5um, further preferred meso-position radius≤3um, most preferably meso-position radius≤1um, wherein TiO
2tiO in powder
2quality>=99%, loss on ignition≤0.5%.TiO
2powder promotes zircon blank Densification.
The ethanol or the Virahol that account for zircon opaque amount 2-5% is added in co-ground process.
Co-ground for by zircon powder in zirconia ball: zirconium English powder: water is after the ratio of 2-3:2:1 adds and grinds in ball milling, then by zirconium white staple fibre dispersion liquid, the TiO being less than 1um
2powder, composite additive add in ball mill in proportion, then add the ethanol or the Virahol that account for zircon opaque amount 2-5%, grind and obtain slip in 10-15 minute.The slip mist projection granulating mixed, pelletizing loads in mould, and isostatic pressing is large-sized green compact.
Wherein, controlling zircon powder footpath is 5-10um, presents normal particle diameter normal distribution curve.Do not add separately particle diameter to be less than 3um or to be greater than the zircon powder of 10um, size distribution curve only has a peak.The Main Function of co-ground is the particle diameter of adjustment zircon particle, and composite additive is uniformly distributed between zircon particle.Interpolation ethanol or Virahol can reduce phosphoric acid and fully make Granular composite≤1um.
Work as TiO
2, La
2o
3, CeO
2or Y
2o
3meso-position radius when being greater than 1um, adopt conventional wet grinding manner, use zirconia ball to be ground to meso-position radius to be in advance less than 1um, spraying dry or adopt other modes to be fully dried to moisture content lower than for subsequent use after 0.3%.
Dry employing seasoning or the drying of the equipment of use.When selecting seasoning, need the time of several days, the natural drying condition of preferred 1-3 days is advisable.
Sintering temperature is 1530-1600 DEG C, and preferred sintering temperature is 1550 ± 20 DEG C.The soaking time 30-100 hour burnt till, preferred 40-100 hour be, more preferably 40-72 hour.
The heat-up rate burnt till, at 1 DEG C/h-10 DEG C/h, is preferably 1 DEG C/h-5 DEG C/h.Because base substrate is huge, the warming and cooling rate relaxed very much therefore should be adopted in sintering process.Cooling adopts naturally cooling, or cools by certain cooling rate, preferably uses and cools by certain cooling rate.
Preferred firing temperature and heating-cooling speed as follows:
After base substrate cool to room temperature, the feature transmitted with heat when burning till according to the rule of pressure transmission during isostatic pressed, bears the pressure minimum position minimum with temperature when burning till when suppressing in test brick body.From the physics center of gravity of brick, namely length, thickness, width are all the position of half, cut sample, the bending creep speed at the volume density of working sample, void content, cold crushing strength, 1200 DEG C of high temperature break resistant intensities and 1200 DEG C.
Compared with prior art, the present invention has following beneficial effect:
The present invention with the addition of zirconium white staple fibre and silica powder in zircon powder, changes the interpolation state of zircon stone initial feed on the one hand, improves the intensity of super zircon green compact, easy loading of kiln and movement; Facilitate volumetric expansion when zirconium white and silicon oxide in sintering process change zircon into, what decrease base substrate burns till contraction simultaneously, reduces cracking and the distortion tendency of base substrate, improves the manufacture qualification rate of super overflow brick goods; Use composite additive on the other hand, impel zirconium fiber in sintering process, define the zircon particle of needle-like or column, significantly reduce the bending creep speed of overflow brick, improve the work-ing life of super overflow brick and the quality of glasswork.Obtained zircon stone overflow brick has extremely low bending creep speed, for making super overflow brick.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
In the present invention, volume density and void content adopt the fine and close shaping refractory product volume density of GB/T2997-2000, apparent porosity and true porosity determination of test method; Cold crushing strength adopts GB/T5073-2008 refractory materials cold crushing strength determination of test method; High temperature break resistant intensity adopts GB/T3002-2004 refractory materials high temperature break resistant intensity determination of test method.Bending creep speed adopts JIS R1612-2010 fine ceramics bending creep test method to measure.JIS R1612-2010 adopts four-point bending device, and specimen size is 50mm × 4mm × 2mm, and length of support is 30mm ± 0.5mm, and loading dot spacing is 10mm ± 0.5mm, and probe temperature is 1200 DEG C and keeps 100 hours, and the pressure of applying is 2Mpa.
In the present invention, particle diameter all measures with laser particle analyzer, particle diameter corresponding when meso-position radius refers to that the cumulative particle sizes percentile of sample reaches 50%.Its physical significance is that the particle that particle diameter is greater than it accounts for 50%, and the particle being less than it also accounts for 50%, but does not relate to the length-to-diameter ratio of particle.
Embodiment 1
The preparation method of low creep zircon stone overflow brick:
In zircon powder, the mass percent of each component and component thereof is Al
2o
3be 0.12%, Fe
2o
3be 0.03%, CaO be 0.02%, MgO is 0.01%, K
2o is 0.01%, ZrO
2be 66.4%, SiO
2be 33.1%, its surplus is TiO
2and P
2o
5.
In silicon powder, the mass percent of each component and component thereof is Al
2o
3be 0.07%, Fe
2o
3be 0.01%, CaO be 0.01%, MgO is 0.00%, K
2o is 0.00%, and its surplus is SiO
2.
In the present embodiment, the content of each raw material is in table 1.
The preparation process of zirconium white staple fibre dispersion liquid: be 6um by the diameter accounting for zircon powder total mass 1%, length is less than 3mm, ZrO
2+ Y
2o
3water put into by the zirconium white staple fibre of>=99%, adds the Sodium dodecylbenzene sulfonate dispersion agent accounting for zirconium white staple fibre quality 0.06%, then add the zircon powder with zirconium white staple fibre equivalent weight, and co-ground makes zirconium white staple fibre dispersion liquid after 60 minutes.Wherein, zirconium white staple fibre dispersion liquid in use stirs, and prevents sedimentation.
The preparation process of low creep zircon stone overflow brick:
In zirconia ball: remaining zircon powder: water is that the ratio of 2:2:1 adds in ball milling, it is the slip of 6um that zircon powder meso-position radius is made in grinding, adds zirconium white staple fibre dispersion liquid, grinds after 3 minutes, then by TiO
2powder, La
2o
3powder and silicon powder add in ball mill in proportion, then add ethanol, and co-ground is after 10 minutes, and mist projection granulating obtains pelletizing.
Pelletizing loads in mould, and after vacuumizing, under 180Mpa, isostatic pressed makes length is 5000mm, and thickness is 500mm, width is the green compact of 1300mm.Burn till at 1570 DEG C, be incubated 60 hours.Physics center of gravity from brick after cooling cuts sample, and the bending creep speed at the volume density of working sample, void content, cold crushing strength, 1200 DEG C of high temperature break resistant intensities and 1200 DEG C, detects the detected result of data in table 3 embodiment.
Wherein, firing temperature and heating-cooling speed as follows:
Embodiment 2-13
In embodiment 2-13, the preparation method of zircon stone overflow brick is all identical with embodiment 1, and the parameter in the raw materials used mass ratio of embodiment 2-8, preparation process is in table 1; Parameter in the raw materials used ratio of embodiment 9-13, preparation process is in table 2.Detection method is identical with embodiment 1, and embodiment 2-8 detects the detected result of data in table 3; Embodiment 9-13 detects the detected result of data in table 4.
Wherein in the zircon powder that uses of embodiment 9, each component and constituent mass per-cent thereof are Al
2o
3be 0.35%, Fe
2o
3be 0.06%, CaO be 0.05%, K
2o is 0.02%, Na
2o is 0.02%, ZrO
2be 66.1%, SiO
2be 33.0%, the TiO of its surplus
2and P
2o
5.
Comparative example 1-2
In comparative example 1-2, the preparation method of zircon stone overflow brick is all identical with embodiment, and the parameter in raw materials used mass ratio and preparation process is in table 2.Detection method is identical with embodiment 1, detects the detected result of data in table 4.
Embodiment 1 with the addition of zirconium white staple fibre and La
2o
3, the bending creep speed of sample at 1200 DEG C is 30% of comparative example 1, and embodiment 3 with the addition of zirconium white staple fibre and CeO
2, the bending creep speed of sample at 1200 DEG C is 50% of comparative example 1, although embodiment 2 does not add zirconium white staple fibre, its bending creep speed is also only 50% of comparative example 1.
Embodiment 4-8 adds La
2o
3with Y
2o
3composite additive; Embodiment 9-12 with the addition of CeO
2with Y
2o
3composite additive; Embodiment 13 adds La
2o
3, Y
2o
3and CeO
2three kinds of composite additives.Wherein adopt La
2o
3with Y
2o
3composite additive or CeO
2with Y
2o
3composite additive, Y
2o
3add-on be La
2o
3or CeO
2doubly, and when the mass ratio of silica powder and zirconium white staple fibre is 0.50, the bending creep speed of embodiment 4 and 11 is only 1/20th of comparative example 1 for the 1-2 of quality; Add La simultaneously
2o
3, Y
2o
3and CeO
2the embodiment 13 of three kinds of composite additives or add La separately
2o
3or CeO
21200 DEG C of bending creep speed of embodiment 1,2 be 3-5 × 10
-7hour
-1, also have than the bending creep speed of comparative example 1 and significantly improve.The bending creep speed of embodiment 9 is also up to 7.86 × 10
-7hour
-1, slightly high relevant with foreign matter content in base substrate.
Use diameter to be 3um in addition, the sample bent creep speed that length is less than the zirconium white staple fibre of 1mm is slightly better than using diameter to be 6um, and length is less than 3mm zirconium white staple fibre.
Above embodiment is only used to disclose implementation process of the present invention and beneficial effect, does not directly limit scope of the present invention.
Parameter (one) in the mass ratio of table 1 embodiment 1-8 Raw and preparation process
Parameter (two) in the ratio of table 2 embodiment 9-13 and comparative example 1-2 Raw and preparation process
Table 3 embodiment 1
-the detected result (one) of 8
The detected result (two) of table 4 embodiment 9-13 and comparative example 1-2
Claims (8)
1. a low creep zircon stone overflow brick, it is characterized in that, the content of raw material is as follows:
Zircon opaque amount is 100%, and zirconium white staple fibre accounts for zircon opaque amount 0.3-4.0%, and silica powder accounts for zircon opaque amount 0.1-2.0%, and composite additive accounts for zircon opaque amount 0.1-0.8%; Wherein composite additive is La
2o
3or CeO
2or La
2o
3with Y
2o
3combination or CeO
2with Y
2o
3combination or La
2o
3with CeO
2with Y
2o
3combination.
2. low creep zircon stone overflow brick according to claim 1, it is characterized in that, the diameter of zirconium white staple fibre is 1-7 μm, and length is less than 3mm, ZrO in zirconium white staple fibre
2+ Y
2o
3>=99%.
3. low creep zircon stone overflow brick according to claim 1, is characterized in that, the zircon stone overflow brick of described low creep is less than 3.0 × 10 1200 DEG C of bending creep speed
-7hour
-1, length is 3100-6000mm, and thickness is 100-900mm, width is 1000-1700mm.
4. the preparation method of a low creep zircon stone overflow brick according to claim 1, it is characterized in that, after zircon powder wet grinding to meso-position radius is 5-10 μm, add zirconium white staple fibre dispersion liquid, silica powder, composite additive again, after co-ground, mist projection granulating, dress rubber cast, isostatic pressing obtain green compact, and high temperature burns till base substrate, and base substrate precision work obtains the zircon stone overflow brick of low creep;
The preparation method of zirconium white staple fibre dispersion liquid is: in zirconium white staple fibre, add dispersion agent, the more common wet grinding of zircon powder adding silica powder or add 1-4% becomes zirconium white staple fibre dispersion liquid.
5. the preparation method of low creep zircon stone overflow brick according to claim 4, it is characterized in that, in green compact, the mass percentage content scope of impurity is Al
2o
3≤ 0.2%, Fe
2o
3≤ 0.05%, CaO+MgO≤0.05% and K
2o+Na
2o≤0.03%.
6. the preparation method of low creep zircon stone overflow brick according to claim 4, it is characterized in that, dispersion agent is Sodium dodecylbenzene sulfonate.
7. the preparation method of low creep zircon stone overflow brick according to claim 4, is characterized in that, add the short agglutinant accounting for zircon opaque amount 0.3-0.5% in raw material, and wherein, short agglutinant is TiO
2powder.
8. the preparation method of low creep zircon stone overflow brick according to claim 4, it is characterized in that, firing temperature is 1530-1600 DEG C, insulation 30-100 hour.
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| CN105060902B (en) * | 2015-07-24 | 2017-05-31 | 淄博工陶耐火材料有限公司 | Modified zircon stone sintered article and preparation method thereof |
| CN105218121B (en) * | 2015-10-30 | 2017-05-31 | 淄博工陶耐火材料有限公司 | Low creep, the Undec overflow brick of zircon and preparation method thereof |
| CN105272187B (en) * | 2015-11-10 | 2018-01-09 | 浙江大学 | The preparation method of zircon ceramics |
| CN107117963B (en) * | 2017-04-25 | 2020-09-18 | 山东君道高温材料有限公司 | Manufacturing process of large-size and large-span zircon refractory material |
| CN107935608B (en) * | 2017-11-17 | 2020-10-09 | 淄博工陶新材料集团有限公司 | Method for preparing zircon brick by using compact zircon aggregate |
| CN115650739B (en) * | 2022-09-13 | 2024-07-09 | 上海利尔耐火材料有限公司 | Long-service-life zirconia metering nozzle and preparation method thereof |
| CN116026278A (en) * | 2022-12-21 | 2023-04-28 | 湖南特种玻璃研究院有限公司 | A Method for Life Prediction of Overflow Bricks |
| CN116573935A (en) * | 2023-05-23 | 2023-08-11 | 广东新岭南科技有限公司 | Ceramic materials and their preparation methods and applications |
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