CN1656041A - 锆石/氧化锆混合料作耐高温涂料和耐高温印剂 - Google Patents
锆石/氧化锆混合料作耐高温涂料和耐高温印剂 Download PDFInfo
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- CN1656041A CN1656041A CNA038116553A CN03811655A CN1656041A CN 1656041 A CN1656041 A CN 1656041A CN A038116553 A CNA038116553 A CN A038116553A CN 03811655 A CN03811655 A CN 03811655A CN 1656041 A CN1656041 A CN 1656041A
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000576 coating method Methods 0.000 title claims abstract description 58
- 229910052845 zircon Inorganic materials 0.000 title claims abstract description 37
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000000976 ink Substances 0.000 title 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000000919 ceramic Substances 0.000 claims abstract description 61
- 239000000758 substrate Substances 0.000 claims abstract description 54
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 37
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 24
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 23
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims description 67
- 239000011248 coating agent Substances 0.000 claims description 50
- 239000008199 coating composition Substances 0.000 claims description 46
- 229960001866 silicon dioxide Drugs 0.000 claims description 32
- 235000012239 silicon dioxide Nutrition 0.000 claims description 32
- 230000000087 stabilizing effect Effects 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 18
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 13
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 9
- 239000012764 mineral filler Substances 0.000 claims description 7
- 239000003086 colorant Substances 0.000 claims 2
- 239000007921 spray Substances 0.000 claims 1
- HDSBZMRLPLPFLQ-UHFFFAOYSA-N Propylene glycol alginate Chemical compound OC1C(O)C(OC)OC(C(O)=O)C1OC1C(O)C(O)C(C)C(C(=O)OCC(C)O)O1 HDSBZMRLPLPFLQ-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 229910021487 silica fume Inorganic materials 0.000 description 5
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910017083 AlN Inorganic materials 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- DYAHQFWOVKZOOW-UHFFFAOYSA-N Sarin Chemical compound CC(C)OP(C)(F)=O DYAHQFWOVKZOOW-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006501 ZrSiO Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011214 refractory ceramic Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000009736 wetting Methods 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
- -1 zirconium white compound Chemical class 0.000 description 1
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- C04B35/481—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 zirconium or hafnium oxides, zirconates, zircon or hafnates containing silicon, e.g. zircon
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Abstract
这里揭示了包含未稳定氧化锆、二氧化硅以及可用的锆石和/或富铝红柱石的耐高温涂层。未稳定氧化锆、二氧化硅以及可用的锆石和/或富铝红柱石作为浆料涂覆在如碳化硅或氮化硅一类的陶瓷基片上。涂敷到基片上的本发明耐高温涂层经受超过1100的温度后,能保持良好的边缘清晰度和颜色。。
Description
本发明涉及耐高温材料上的涂层,具体涉及陶瓷基片上的锆石/氧化锆涂层。
陶瓷,诸如碳化硅(SiC)、氮化硅(Si3N4)等用的高温涂层在高温氧化性气氛下由于与不断增厚的二氧化硅(SiO2)玻璃层相互作用而导致失效。最稳定的涂料候选物发现为氧化铝(Al2O)、富铝红柱石(3Al2O3·2SiO2)以及氧化锆(ZrO2)-等为基的组合物,这是由于它们耐高温的体性、相似的热膨胀系数以及与碳化硅、氮化硅与二氧化硅接触时的化学稳定性所致。
在高于1,200℃温度情况下,多孔氧化铝涂层会溶于不断增厚的二氧化硅层中。生成的铝硅酸盐玻璃填充了氧化铝涂层的孔隙产生不透气膜。这层膜阻挡了如二氧化碳一类氧化反应的气态副产物。被填充的孔隙聚结一起引起局部隆起或剥落。致密氧化铝涂层由于较高的热膨胀系数而常导致开裂或微细裂方。当氧化铝涂料作印刷用的涂料时,所述氧化铝涂层的溶解渗入玻璃,导致沿边缘白色涂料微外泄。对于薄的涂层而言,这特别成问题,因为它们要末完全溶解于玻璃层,要末看不见。
类似地,碳化硅/氮化硅陶瓷上的富铝红柱石涂层容易隆起或剥落,而且当存在容量玻璃层时,会成为半透明。稳定化的氧化锆涂层已知是化学稳定的,且在玻璃中的溶解度有限。然而,钙稳定化或氧化钇稳定化的氧化锆被发现在1,100℃附近经一、两次高温循环后会从碳化硅部件上剥落。
本领域现有技术有一些耐火材料基片上用的涂层。两个Matsui等人的专利US.Pat.No.4,804,589与4,921,721揭示了金属基片与碳化硅基片上用的涂层,它基本上由用氧化钇、氧化镁或氧化钙部分稳定化或全稳定化的氧化锆组成。这种涂层故意很薄用以减少剥离或裂方。在氧化锆层与基片之间可以加一层兼容层。Matsui等人还要求对碳化硅基片表面进行表面预处理,使表面粗糙或提高表面反应活性。采用现今涂料组合物涂覆耐火材料基片的实用性因需要表面预处理而下降。另外,较厚的涂层容易剥离且产生裂纹。
Sarin的专利US Pat.No.4,950,558揭示了硅基基片用的多层涂层。所述涂层包含多层:一层或多层氮化铝,氧氮化铝材料的中间层,以及一个铝、锆或钇的氧化物外层。采用化学气相沉积法,用气体混合物以连续沉积工艺形成这种涂层,其中反应物气体逐渐改变来提供多层涂层。理想的是提供这种涂层时不产生与化学气相沉积有关的环境问题。
Moh等人的美国专利6,165,594,6,214,250和6,251,212揭示了金属基片与陶瓷基片上用的标记。所述标记包括陶瓷体作基层,它含有能润湿基片的玻璃相和带有浅色或暗色颗粒的高熔点相;含有带色差对比颗粒的玻璃相与高熔点相的顶层。顶层与陶瓷体之间的色差可以形成看得见的标记图案。然而,在将标记附着在基片之前必须先形成并烧结这睦标记。
尽管现有技术领域现状如此,但还需要提供耐高温陶瓷基片用的涂料组合物,所提供的组合物要使用方便,附着力强,并且在氧化性气氛下稳定。
本发明第一方面,涉及用来涂敷高温基片用的耐高温涂料组合物,所述组合物包含:未稳定化氧化锆以及二氧化硅。组合物最好含50-90%未稳定氧化锆,含10-50%二氧化硅。所述组合物还可以包含锆石,其含量可高达100%。所述组合物还可以包含如富铝红柱石等无机填料,其含量可高达50%。在本发明第一方面较佳实施方式的组合物中,未稳定氧化锆与二氧化硅的重量之比约9∶1-1∶1。所述组合物用来在高于1,100的温度涂覆基片。
本发明第二方面涉及耐高温涂料组合物,它包含15-75%未稳定氧化锆,5-25%二氧化硅,以及高达100%的锆石。所述组合物可以以浆料或釉料形式涂在基片上。组合物被涂成的薄膜厚度最好在20-500μm之间。
本发明第三方面涉及陶瓷灼烧部件。它包括陶瓷体;陶瓷体表面上形成的耐高温涂层,所述耐高温涂层包含:未稳定氧化锆、二氧化硅以及锆石。所述耐高温涂层在温度超过1,100℃时仍然稳定。所述陶瓷体最好是碳化硅或氮化硅。
本发明第三方面涉及制造陶瓷烧结体的方法,包括如下步骤:
提供陶瓷基片;提供包含未稳定氧化锆、二氧化硅以及锆石的耐高温涂料组合物;将耐高温涂料组合物涂覆在陶瓷基片上;将被涂陶瓷基片进行烧结部件,此时陶瓷基片上的耐高温涂层在高于1,200℃温度下仍能维持其稳定性。所述陶瓷基片最好是碳化硅或氮化硅。耐高温涂料组合物可涂在陶瓷基片的一部分上。所述耐高温涂料组合物与所述陶瓷基片可以有不同色彩,且将此组合物涂覆在陶瓷基片的一个部分上作为一个标记。所述耐高温涂料组合物最好涂抹、喷涂、海绵揩拭、刷涂、筛网印刷到陶瓷基片上。
本发明涉及涂覆高温基片的耐高温涂料组合物,它包含未稳定氧化锆,二氧化硅以及可用的锆石。意想不到的是本发明的涂料组合物在温度达1,100℃,较佳1,200℃,且更佳超过1,400℃时对耐高温基片仍保持良好的附着力。这些涂料组合物特别可于在耐高温基片上作标记用的涂料。如果用作耐高温基片上的印刷涂料,则此涂料组合物显示出清晰线条,这些线条不会渗入基片,且与基片保持良好的色对比度,甚至在多次重复加热循环之后仍是如此。这里所说的锆石是指ZrSiO4和/或它的分解产物SiO2与ZrO2。
本发明的耐高温涂料组合物的组成可以用百分重量数表示,优选的组合物可以含有0-100%锆石。如果锆石的量小于100%,则组合物中剩余成份可以包含50-90%,较佳15-75%,未稳定氧化锆;且包含10-50%,较佳5-25%未稳定氧化锆。未稳定氧化锆与二氧化硅重量之比较佳为9∶1-1∶1,更佳为4∶1-2∶1,且最佳为3∶1。
可以假定,耐高温涂层经受极端高温时,未稳定氧化锆当与二氧化硅生成锆英石,该锆石在二氧化硅层中具有低溶解度,且与二氧化硅接触时物理上呈稳定性。
用于本发明涂料组合物的未稳定氧化锆,优选是高纯的单斜晶系氧化锆。单斜晶秒氧化锆是氧化锆三种晶型结构之一,它在低于1,150℃温度之下时呈稳定状态,在高于1,150℃温度时,氧化锆是正方晶系结构,当此正方晶秒氧化锆为未稳定化时,它会发生马氏体转变,又变回成为单斜晶系结构,伴随3-6%的体积膨胀。单斜晶系氧化锆的平均粒径为0.1-200μm,较佳为0.5-2.0μm,更佳为1.0-10μm,且最佳为45μm。特别理想的未稳定氧化锆,市场上有售的商品名为ZIRCOA A-325,Saint-Gobain/Norton Industrial CeramicsCorporation,Worcester,Massachusetts生产。有色氧化锆可以替代或连同单斜晶系氧化锆一起使用,产生有色涂料,包括有色印刷用的涂料。
部分稳定化或全稳化氧化锆如果与足量锆石或二氧化硅一起,可以制成耐高温涂料组合物,这也属本发明范围。部分稳定化或全稳定化氧化锆与二氧化硅会反应生成更稳定锆石。或者,如果存在足量锆石,稳定化氧化锆不易溶于增厚的二氧化硅层。
适用于本发明涂料组合物的二氧化硅是无定形二氧化硅。所述无定形二氧化硅的平均粒径较佳为0.1-1.0μm,更佳为0.5μm,是球形初生颗粒以及其聚集物。比表面积较佳为15-30m2/g。特别理想的市售二氧化硅为挪威ElkemMaterials生产的MICROSILICA。可用于耐高温涂料的二氧化硅的级别有级别983,级别971,级别965,与级别940,其中级别971为最佳。较好使用致密化的微细二氧化硅,它含有松散结合的次生团聚物,将堆积密度提高到500-650kg/m3,且改善了材料的运送特性。
用于本发明涂料组合物的锆石的平均粒径在10-20μm,较佳为12.8μm。表面积为0.8-2.0m2/g,较佳约为1.2m2/g。特别理想的市售锆石是Saint-Gobain/Norton Industrial Ceramics Corporation,Worcester,Massachusetts生产的,商品名为ZIRCON G。有色锆石也可以替代或连同锆石一起产生有色涂料,包括印刷用涂料。
所述组合物也可以包含不与二氧化硅反应,且能承受极端高温即不会烧失的无机填料。这类无机填料例如包括富铝红柱石。这里所说的富铝红柱石是指3Al2O3·2SiO2。富铝红柱石的用量较佳占组合物的总量高达50%。也可以用这代替锆石。因此本发明一个实施方式可以包含高达50%的富铝红柱石,组合物的其余部份可以包含25-90%,较佳45-50%的未稳定氧化锆以及5-50%,更佳10-25%的二氧化硅。还有,非稳定氧化铝与二氧化硅的重量比约9∶1-1∶1,更佳为4∶1-2∶1,最佳为3∶1。
特别适用的市售富铝红柱石可购自Washington Mills Electro MineralsCompany,Niagra Falls,New York,商品名为DURAMULTM。富铝红柱石中过量的氧化铝可以确保所有二氧化硅都包含在富铝相内,而不会出现在玻璃相内。富铝红柱石的平均粒径为0.2-250μm,较佳为1.0-100μm,更佳为2.0-45μm。很合用的富铝红柱石为DURAMULTM 325/F。
未稳定氧化锆、二氧化硅以及可用的锆石与富铝红柱石最好以在合适介质中的浆料形式涂在基片表面上。浆料介质可以是无机的或有机的。水是是本发明耐高温涂料各组分的浆料介质。未稳定氧化锆、二氧化硅以及可用的锆石与富铝红柱石,通过采用一种或多种诸如增稠剂、触变剂或其它流变改性剂一类的稳定剂,可保持悬浮状态而提供合适粘度的涂料包括印刷用的涂料。对含水浆料较佳的稳定剂为Monsanto Company,St.Louis,Missouri生产的KELCOLOID LVF。所述稳定剂的用量较佳为0.1-2.0重量%,更佳约为1.2重量%。因此,一种示例性的浆料介质可以由98.8重量%的去离子水与1.2重量%的KELCOLOID LVF组成。将涂料组合物组分保持悬浮在含水浆料的另一种方法,包括用酸或碱调节获得稳定或半稳定的静电分散液。稳定剂也可加入所述静电分散液,确保涂料组分悬浮在液相中。
未稳定氧化锆、二氧化硅以及可用的锆石与富铝红柱石加入到浆料介质中,搅拌足够长时间得到均匀的悬浮液。一般说来,搅拌时间至少10-15分钟,但是搅拌时间长达一个小时也是有的,因为较长搅拌时间对涂料包括印刷用的涂料所用的组合物并无损害。浆料包含40-60重量%的固体。
浆料的稠度应使其容易涂到基片上,取决于涂覆方法。将浆料涂到基片上的方法包括涂抹、涂搽、刷涂、喷涂、海绵揩拭、丝网印刷等。取决于涂覆方法,所述涂料组合物涂覆厚度为20-500μm。例如,涂釉料时,采用325目丝网印刷技术,涂覆厚度可达50μm。本领域技术人员会明白什么时候以及如何采用不同技术涂覆涂料组合物,以及其厚度为多少,无需经过生活繁重的试验。合适的话,也可以涂覆多层涂层。涂料组合物涂覆好之后,将基片加热驱除浆料介质,再进行烧结。
实施例
下面一些实施例叙述本发明耐高温涂料组合物的制备与使用。这些实施例仅作为进一步说明与解释本发明之用,并不用来限制本发明的范围。
将100g样品的(其中各组分含量以重量百分数计)悬浮在1.0重量%KELCOLOID LVF水溶液中。将涂料组合物的组分加入到水封混料缸中的KELCOLOID LVF溶液中,用惰性磨介质研磨混合物约一个小时,确保充分混合与悬浮。涂料组合物含有40重量%固体。每次加热循环约为72小时,平均升温速率为75℃/小时,达到约为1,420℃的最高温度,随后控制冷却到窒温。
实施例1(比较):
此比较例涂料组合物的制备是将50.0重量份的A-15氧化铝(从Alcoa Inc.Pittsburgh,Pennsylvania购得)和50重量份,氧化钇稳定化的氧化锆用KELCOLOID LVF溶液调成浆液。用绘画刷将所述组合物刷涂到与氮化硅结合的碳化硅瓷片表面上,涂层厚度约为100μm,然后将样品进行干燥,去除浆料中的水分。五次加热循环之后,约有25%组合物在第一次加热循环后即剥落。剩下的组合物在瓷片上留有细小的棕色气泡。
实施例2(比较):
此比较例的涂料组合物的是由100重量份20F筛目的用氧化钇稳定的氧化锆配制而成的。所述稳定化的氧化锆涂料组合物在KELCOLOID LVF溶液中配成浆料。除了大约10%的样品外,所有样品上的涂层都有剥落。剩余部分仍保持良好清晰的边缘,尽管有些晶粒太粗,没有提供平滑表面。
实施例3
本发明涂料组合物由100重量份ZIRCON G在KELCOLOID LVF溶液中调浆配制而成。用绘画刷将所述组合物刷涂到与氮化硅结合的碳化硅瓷片表面上,涂层厚度约为100μm。三次加热循环之后,所述组合物仍保持良好清晰的边缘,与瓷片有良好的色对比度。
实施例4
本发明组合物是将56.25重量份未稳定化氧化锆、18.75重量份致密化MICROSILICA级别971(购自Elkem Materials)以及25.0重量份ZIRCON G在KELCOLOID LVF溶液中调浆配制而成。将所述组合物刷涂到与氮化硅结合的碳化硅瓷片表面上。三次加热循环之后,所述组合物仍保持良好清晰的边缘,与瓷片有良好的色对比度。
实施例5
本发明组合物是将37.5重量份非稳定化氧化锆、12.5重量份致密化MICROSILICA级别971(购自Elkem Materials)以及50.0重量份ZIRCON G在KELCOLOID LVF溶液中调浆配制而成。将所述组合物刷涂到与氮化硅结合的碳化硅瓷片表面上。三次加热循环之后,所述组合物仍保持良好清晰的边缘,与瓷片有良好的色对比度。
实施例6
本发明组合物是将18.75重量份未稳定化氧化锆、6.25重量份致密人MICROSILICA级别971(购自Elkem Materials)以及75.0重量份ZIRCON G在KELCOLOID LVF溶液中调浆配制而成。将所述组合物刷涂到与氮化硅结合的碳化硅瓷片表面上。三次加热循环之后,所述组合物仍保持良好清晰的边缘,与瓷片有良好的色对比度。
实施例7
本发明组合物是将37.5重量份中稳定人氧化锆、12.5重量份致密人MICROSILICA级别971(购自Elkem Materials)以及50.0重量份DURAMULTM富铝红柱石(购自Washingtom Mills Electro Minerals Company)在KELCOLOIDLVF溶液中调浆配制而成。将所述组合物刷涂到与氮化硅结合的碳化硅瓷片表面上。三次加热循环之后,所述组合物仍保持良好清晰的边缘,与瓷片有良好的色对比度。
本发明提供的耐高温涂料组合物涂到耐高温基片上,能提高粘着接力并显示良好的边缘清晰度。其优点在于,所述涂料组合物在经历超过1,100℃极端高温的多次热循环后不会剥落,也不会溶解于在氧化气氛下不断增厚的二氧化硅层中。
虽然结合一些特定较佳实施方式具体叙述了本发明,对本领域技术人员来说,有关前面叙述的内容显然可以有许多变换、修改与改变。因此,所附权利要求将包括所有这些符合本发明范围和精神的变换、修改与改变。
Claims (37)
1.用于涂覆高温基片的耐高温涂料组合物,所述组合物包含:
未稳定氧化锆;
二氧化硅。
2.如权利要求1所述的组合物,其特征在于,所述未稳定氧化锆用量占所述组合物的50-90%。
3.如权利要求1所述的组合物,其特征在于,所述未稳定氧化锆用量占所述组合物的10-50%。
4.权利要求1所述的组合物,还包含锆石。
5.如权利要求4所述的组合物,其特征在于,所述锆石的用量占所述组合物高达100%。
6.权利要求1所述的组合物,还包含无机填料。
7.如权利要求6所述的组合物,其特征在于,所述无机填料为富铝红柱石。
8.如权利要求7所述的组合物,其特征在于,所述富铝红柱石的用量占所述组合物高达50%。
9.如权利要求1所述的组合物,其特征在于,所述未稳定氧化锆与二氧化硅的重量之比为9∶1-1∶1。
10.如权利要求1所述的组合物,其特征在于,涂覆基片时,所述组合物的温度高于1100℃。
11.耐高温涂料组合物,所述组合物包含:
15-75%的未稳定氧化锆;
5-25%的二氧化硅;以及
至多100%的锆石。
12.权利要求11所述的组合物,还包含无机填料。
13.如权利要求12所述的组合物,其特征在于,所述无机填料为富铝红柱石。
14.如权利要求13所述的组合物,其特征在于,所述富铝红柱石的用量占所述组合物高达50%。
15.如权利要求11所述的组合物,其特征在于,所述组合物涂覆到陶瓷基片上。
16.如权利要求11所述的组合物,其特征在于,所述组合物以浆料形式进行涂覆。
17.如权利要求11所述的组合物,其特征在于,所述组合物以釉料形式涂覆到基片上。
18.如权利要求11所述的组合物,其特征在于,以厚度为20-500μm的薄膜形式涂覆所述组合物。
19.陶瓷烧结部件,包括:
陶瓷体;
所述陶瓷体表面上形成的耐高温涂层,所述耐高温涂层包含:
未稳定氧化锆;
二氧化硅;
锆石,
其中,所述耐高温涂层在超过1100℃温度仍能保持稳定。
20.如权利要求19所述的陶瓷烧结部件,其特征在于,所述耐高温涂层还包含富铝红柱石。
21.如权利要求19所述的陶瓷烧结部件,其特征在于,所述陶瓷体表面上形成的耐高温涂层的厚度为20-500μm。
22.如权利要求19所述的陶瓷烧结部件,其特征在于,所述耐高温涂层还会富铝红柱石。
23.如权利要求19所述的陶瓷烧结部件,其特征在于,所述陶瓷体包含碳化硅或氮化硅。
24.如权利要求19所述的陶瓷烧结部件,其特征在于,所述陶瓷体或耐高温涂层具有不同颜色,使得所述耐高温涂层在所述陶瓷体上形成标记。
25.制造烧结陶瓷体的方法,包括;
提供陶瓷基片;
提供耐高温涂料组合物,该组合物包含;
未稳定氧化锆;
二氧化硅;
锆石;
将所述耐高温涂料组合物涂到所述陶瓷基片上;
对被涂的陶瓷基片进行烧结;
其中陶瓷基片上所述耐高温涂层在超过1100℃温度时仍能保持稳定。
26.如权利要求25所述的方法,其特征在于,所述陶瓷基片包含碳化硅或氮化硅。
27.如权利要求25所述的方法,其特征在于,所述涂料组合物还包含富铝红柱石。
28.如权利要求27所述的方法,其特征在于,所述富铝红柱石的用量高达50%。
29.如权利要求25所述的方法,其特征在于,所述涂料组合物包含50-90%的未稳定氧化锆,10-50%的二氧化硅;以及高达100%的锆石。
30.如权利要求25所述的方法,其特征在于,耐高温涂料组合物涂层的厚度为20-500μm。
31.如权利要求25所述的方法,其特征在于,耐高温涂料组合物涂在部分陶瓷基片的一部分上。
32.如权利要求25所述的方法,其特征在于,耐高温涂料组合物和陶瓷基片具有不同颜色,因此将组合物涂在陶瓷基片部分上可作为标记。
33.如权利要求25所述的方法,其特征在于,耐高温涂料组合物涂到陶瓷基片上。
34.如权利要求25所述的方法,其特征在于,耐高温涂料组合物喷涂到陶瓷基片上。
35.如权利要求25所述的方法,其特征在于,耐高温涂料组合物用海绵揩拭到陶瓷基片上。
36.如权利要求25所述的方法,其特征在于,耐高温涂料组合物刷涂到陶瓷基片上。
37.如权利要求25所述的方法,其特征在于,耐高温涂料组合物丝网印刷到陶瓷基片上。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US10/154,134 | 2002-05-23 | ||
US10/154,134 US6753089B2 (en) | 2002-05-23 | 2002-05-23 | Zircon/zirconia mix for refractory coatings and inks |
Publications (2)
Publication Number | Publication Date |
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CN1656041A true CN1656041A (zh) | 2005-08-17 |
CN100352787C CN100352787C (zh) | 2007-12-05 |
Family
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CNB038116553A Expired - Lifetime CN100352787C (zh) | 2002-05-23 | 2003-05-13 | 锆石/氧化锆混合料作耐高温涂料和耐高温印剂 |
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US (3) | US6753089B2 (zh) |
EP (1) | EP1506145B1 (zh) |
JP (3) | JP2005530670A (zh) |
CN (1) | CN100352787C (zh) |
AT (1) | ATE459583T1 (zh) |
AU (1) | AU2003229077A1 (zh) |
BR (1) | BR0311218B1 (zh) |
DE (1) | DE60331538D1 (zh) |
WO (1) | WO2003099739A1 (zh) |
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TWI411593B (zh) * | 2006-02-24 | 2013-10-11 | Saint Gobain Gentre De Rech S Et D Etudes Europ | 具有高氧化鋯含量之高電阻耐火物質 |
CN112299883A (zh) * | 2019-07-26 | 2021-02-02 | 维沃泰克仪器(扬州)有限公司 | 一种碳化硅加热元件的耐高温保护涂层及其制备方法 |
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- 2003-05-13 CN CNB038116553A patent/CN100352787C/zh not_active Expired - Lifetime
- 2003-05-13 JP JP2004507401A patent/JP2005530670A/ja active Pending
- 2003-05-13 WO PCT/US2003/015160 patent/WO2003099739A1/en active Application Filing
- 2003-05-13 EP EP03726859A patent/EP1506145B1/en not_active Expired - Lifetime
- 2003-05-13 AT AT03726859T patent/ATE459583T1/de not_active IP Right Cessation
- 2003-05-13 DE DE60331538T patent/DE60331538D1/de not_active Expired - Lifetime
- 2003-05-13 BR BRPI0311218-7A patent/BR0311218B1/pt active IP Right Grant
- 2003-05-13 AU AU2003229077A patent/AU2003229077A1/en not_active Abandoned
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2004
- 2004-04-01 US US10/815,917 patent/US7026039B2/en not_active Ceased
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2006
- 2006-11-21 US US11/603,354 patent/USRE40301E1/en not_active Expired - Lifetime
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TWI411593B (zh) * | 2006-02-24 | 2013-10-11 | Saint Gobain Gentre De Rech S Et D Etudes Europ | 具有高氧化鋯含量之高電阻耐火物質 |
CN101679126B (zh) * | 2007-05-07 | 2013-02-27 | 康宁股份有限公司 | 应变减小的耐火陶瓷复合物及其制造方法 |
CN112299883A (zh) * | 2019-07-26 | 2021-02-02 | 维沃泰克仪器(扬州)有限公司 | 一种碳化硅加热元件的耐高温保护涂层及其制备方法 |
CN112299883B (zh) * | 2019-07-26 | 2022-06-07 | 维沃泰克仪器(扬州)有限公司 | 一种碳化硅加热元件的耐高温保护涂层及其制备方法 |
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EP1506145A1 (en) | 2005-02-16 |
US20040192536A1 (en) | 2004-09-30 |
BR0311218B1 (pt) | 2012-10-02 |
USRE40301E1 (en) | 2008-05-06 |
US6753089B2 (en) | 2004-06-22 |
WO2003099739A1 (en) | 2003-12-04 |
JP2009234911A (ja) | 2009-10-15 |
EP1506145B1 (en) | 2010-03-03 |
ATE459583T1 (de) | 2010-03-15 |
JP2005530670A (ja) | 2005-10-13 |
US7026039B2 (en) | 2006-04-11 |
US20040018395A1 (en) | 2004-01-29 |
JP2013212983A (ja) | 2013-10-17 |
AU2003229077A1 (en) | 2003-12-12 |
DE60331538D1 (de) | 2010-04-15 |
EP1506145A4 (en) | 2007-11-28 |
CN100352787C (zh) | 2007-12-05 |
BR0311218A (pt) | 2005-03-01 |
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