CN112739661A - 氧化铝质陶瓷和陶瓷加热器 - Google Patents
氧化铝质陶瓷和陶瓷加热器 Download PDFInfo
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- CN112739661A CN112739661A CN201980062131.3A CN201980062131A CN112739661A CN 112739661 A CN112739661 A CN 112739661A CN 201980062131 A CN201980062131 A CN 201980062131A CN 112739661 A CN112739661 A CN 112739661A
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- zirconia
- alumina
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000000919 ceramic Substances 0.000 title claims description 43
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 206
- 239000002245 particle Substances 0.000 claims abstract description 147
- 239000013078 crystal Substances 0.000 claims abstract description 97
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 17
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 17
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 17
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000013001 point bending Methods 0.000 claims description 13
- 229910052788 barium Inorganic materials 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052712 strontium Inorganic materials 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 description 39
- 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 20
- 239000011777 magnesium Substances 0.000 description 18
- 239000000395 magnesium oxide Substances 0.000 description 18
- 239000010936 titanium Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 229910052593 corundum Inorganic materials 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000006104 solid solution Substances 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 239000001095 magnesium carbonate Substances 0.000 description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- -1 for example Chemical compound 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence 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
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
本发明的氧化铝质陶瓷含有氧化铝结晶粒子、氧化锆结晶粒子以及Ti、Mg和Si,关于Ti、Mg和Si的合计的含量,将Ti作为TiO2换算,Mg作为MgO换算,Si作为SiO2换算时,为1.4质量%以上,氧化锆结晶粒子中,将构成氧化锆结晶粒子的氧化锆表示为ZrO2时,相对于ZrO2的稀土元素的含量,以氧化物换算为2mol%以下,氧化锆结晶粒子中含有最大长度为1μm以上的单独粒子和最大长度为1μm以上的凝聚粒子中的至少一种,最大长度为1μm以上的所述单独粒子和最大长度为1μm以上的凝聚粒子的比率的合计,是氧化锆结晶粒子全体的50体积%以上。
Description
技术领域
本发明涉及氧化铝质陶瓷和陶瓷加热器。
背景技术
有半导体基板的加热用加热器、煤油热风加热器的汽化器的加热器、热水加热器、或与氧传感器等气敏元件一体化的加热用加热器。作为这些加热器利用有陶瓷加热器。陶瓷加热器形成为在使用了绝缘性陶瓷的绝缘层中埋设有金属发热体的结构。在绝缘性陶瓷中主要使用氧化铝。氧化铝的情况下,出于提高机械强度的目的,会使ZrO2的粒子分散在氧化铝的陶瓷中。
例如,专利文献1中公开有一种氧化铝烧结基板,其将固溶有2-6mol%的Y2O3的ZrO2添加到氧化铝中,使烧结温度降低。
另外,对于加热器有小型化的要求。为此,用于加热器的绝缘性陶瓷,为了在小型零件中也实现高耐久性,从而要求机械强度更高,并要求高温下的耐久性。
在专利文献2中公开有将粒径小的ZrO2添加到氧化铝从而提高机械强度。含有粒径小的ZrO2的氧化铝,作为ZrO2的亚稳相的正方晶的比率高。另外,在被施加应力时,ZrO2容易从正方晶相变成单斜晶。其结果是,能够得到机械强度高的氧化铝质陶瓷。
在先技术文献
专利文献
日本特开平03-223157号公报
日本特开2007-2695524号公报
发明内容
本发明的氧化铝质陶瓷包含氧化铝结晶粒子、氧化锆结晶粒子、及Ti、Mg和Si,所述Ti、所述Mg和所述Si的合计含量,在将所述Ti作为TiO2换算,将所述Mg作为MgO换算,将所述Si作为SiO2换算时,为1.4质量%以上,所述氧化锆结晶粒子中,将构成该氧化锆结晶粒子的氧化锆表示为ZrO2时,稀土元素相对于该ZrO2的含量以氧化物换算为2mol%以下,所述氧化锆结晶粒子中,含有最大长度为1μm以上的单独粒子和最大长度为1μm以上的凝聚粒子中的至少一种,最大长度为1μm以上的所述单独粒子和最大长度为1μm以上的所述凝聚粒子的比率的合计是所述氧化锆结晶粒子全体的50体积%以上。
本发明的陶瓷加热器,具备发热体、和被覆该发热体的绝缘性陶瓷,该绝缘性陶瓷是上述的氧化铝质陶瓷。
具体实施方式
本发明的氧化铝质陶瓷包含氧化铝结晶粒子、氧化锆结晶粒子、及Ti、Mg和Si。氧化锆结晶粒子中,稀土元素相对于氧化锆的含量以氧化物换算为2mol%以下。这种情况下,作为稀土元素,除了Y(钇)以外,还能够列举镧系元素(原子序数57~71)。所谓将稀土元素进行氧化物换算,就是以RE表示稀土元素时,作为RE2O3表示时的摩尔百分率。这种情况下,氧化锆使用表示为ZrO2时的分子量。
另外,该氧化铝质陶瓷中含有Ti、Mg和Si。Ti、Mg和Si的合计含量为,在将各个元素进行氧化物换算时的合计量为1.4质量%以上。这种情况下,Ti的含量是表示为TiO2时的质量。Mg的含量是表示为MgO时的质量。Si的含量是表示为SiO2时的质量。
还有,该氧化铝质陶瓷的情况下,氧化铝和氧化锆的合计量可以为93质量%以上。这时,氧化铝的含量是作为Al2O3时的质量。氧化锆的含量是表示为ZrO2时的质量。另外,氧化铝和氧化锆的比率,例如,将氧化铝换算为Al2O3,将氧化锆作为ZrO2换算时,以质量比计,也可以为Al2O3:ZrO2=95:5~80:20。这种情况下,被选择的氧化锆结晶粒子可以包含稀土元素。氧化锆结晶粒子中含有稀土元素的状态,能够使用具备元素分析仪的电子显微镜确认。
氧化锆结晶粒子,在氧化铝结晶粒子间可以作为单独粒子,即单独的氧化锆结晶粒子存在,也可以作为2个以上的氧化锆结晶粒子在至少一部分发生接触的状态的凝聚粒子存在。
另外,该氧化铝质陶瓷包含成为最大长度为1μm以上的单独粒子的氧化锆结晶粒子,和成为最大长度为1μm以上的凝聚粒子的氧化锆结晶粒子中的至少一种。这种情况下,在氧化铝质陶瓷所包含的氧化锆结晶粒子之中,最大长度为1μm以上的氧化锆的单独粒子和最大长度为1μm以上的氧化锆的凝聚粒子加在一起的合计比率,可以为50体积%以上。
氧化铝结晶粒子间的氧化锆结晶粒子可以包含含有亚稳定的正方晶的部分稳定化ZrO2结晶粒子。由此,即使氧化铝质陶瓷发生龟裂,也可以抑制该龟裂的进展。这种情况下,氧化锆结晶粒子之中可以存在从正方晶向单斜晶进行相转变的结晶粒子。若氧化锆结晶粒子从正方晶向单斜晶进行相转变,则氧化锆结晶粒子的体积变大。由于该氧化锆结晶粒子的体积变化,龟裂的前端的应力集中得到缓和。这样能够抑制发生于氧化铝质陶瓷的龟裂的进展。这种情况下,正方晶的氧化锆结晶粒子,随着稀土元素等的固溶量越多而稳定性越高。
但是,若正方晶的稳定性过度变高,则在龟裂的前端的应力集中部,向单斜晶的相转变难以发生。其结果是,可能无法提高机械强度。这种情况下,氧化锆结晶粒子中的稀土元素的固溶量,以氧化物换算可以为2mol%以下。另外,稀土元素可以根据氧化锆结晶粒子的粒径,选择能够使正方晶稳定化的范围的固溶量。
正方晶的氧化锆结晶粒子,其粒径越小,稳定性越高。因此,通过使氧化锆结晶粒子微粒化,能够使正方晶的比率增加。另外,在氧化铝质陶瓷中,氧化锆结晶粒子的分散性得到提高。还有,氧化锆结晶粒子是微粒时,会包含稀土元素等的固溶量少,或稀土元素等未固溶的亚稳定的正方晶的氧化锆结晶粒子。但是,如上述,若正方晶的稳定性过度变高,则在龟裂的前端的应力集中部,向单斜晶的相转变难以发生,会无法提高机械强度。
本发明的氧化铝质陶瓷所包含的氧化锆结晶粒子,含有最大长度为1μm以上的单独粒子,或最大长度为1μm以上的凝聚粒子。通过使氧化锆结晶粒子的最大长度为1μm以上,从而从正方晶向单斜晶的相转变容易发生,氧化铝质陶瓷更难以破坏。这样的效果,不仅在单独的氧化锆结晶粒子中,在2个以上的氧化锆结晶粒子至少一部分发生接触的凝聚粒子中也同样,从正方晶向单斜晶的相转变容易发生。另外,若上述的最大长度为1μm以上的单独粒子,或最大长度为1μm以上的凝聚粒子存在一定量以上,则高温下氧化铝与氧化锆的相界面的滑移难以发生,氧化铝质陶瓷的高温强度得到改善。
特别是在氧化铝质陶瓷中包含氧化锆结晶粒子时,能够使室温(25℃)下的弯曲强度达到800MPa以上。另外,能够使高温(800℃)下的弯曲强度达到600MPa以上。这里的氧化锆结晶粒子,可以按2mol%以下的比例含有稀土元素。另外,作为氧化锆结晶粒子,可以是最大长度为1μm以上的单独粒子和最大长度为1μm以上的凝聚粒子中的至少一种。这种情况下,包含最大长度为1μm以上的单独粒子和最大长度为1μm以上的凝聚粒子中的至少一种的比例,相对于含有稀土元素的氧化锆结晶粒子的全体,可以为50体积%以上。
氧化铝质陶瓷中的氧化锆结晶粒子的平均粒径,例如可以是0.5μm以上,且1.5μm以下。氧化锆结晶粒子的凝聚粒子实质上也可以视为一个粒子。凝聚粒子的平均粒径可以为0.5μm以上,且2.0μm以下,还有,凝聚粒子的最大长度可以为10μm以下。
氧化铝结晶粒子的平均粒径,例如可以为1.5μm以上,且5μm以下。
还有,作为氧化铝质陶瓷中包含的各种粒子的最大直径,适合为15μm。这是由于,如果各种粒子的最大直径为15μm以下,则难以成为破坏的起点。在此,所谓各种粒子,是氧化铝结晶粒子和氧化锆结晶粒子。氧化锆结晶粒子中包含上述的单独粒子和凝聚粒子。
氧化铝质陶瓷中,含有Ti、Mg和Si。Ti、Mg和Si的合计含量,在将Ti进行TiO2换算,Mg进行MgO换算,Si进行SiO2换算时,可以为1.4质量%以上。还有,若参考平衡相图,则这些氧化物,即TiO2、MgO和SiO2的共晶温度为1300℃以下。因此,对于作为加热器的发热体的金属,和含这些成分的氧化铝质陶瓷同时烧成时,作为氧化铝质陶瓷的构成成分的Al、Zr、Ti、Mg、Si和稀土元素中的至少一种成分,根据情况,会容易以金属氧化物的状态向发热体中扩散。如此能够提高氧化铝质陶瓷和发热体的结合强度。
另外,通过将Ti、Mg和Si分别作为氧化物含有,能够使氧化铝瓷中所含的氧化锆结晶粒子生长。例如,即使将平均粒径1μm以下的氧化锆粉末作为原料粉末使用,在氧化铝质陶瓷中,也容易形成最大长度为1μm以上的氧化锆的单独粒子,或最大长度为1μm以上的氧化锆的凝聚粒子。
Ti含量以氧化物(TiO2)换算,可以为0.5质量%以上且1.0质量%以下。Mg的含量以氧化物(MgO)换算,可以为0.2质量%以上且4.0质量%以下。Si的含量以氧化物(SiO2)换算,可以为0.7质量%以上且1.4质量%以下。Ti、Mg和Si的合计的含量,按照将Ti进行TiO2换算,Mg进行MgO换算,Si进行SiO2换算时的比例,可以为6.4质量%以下,特别为5.0质量%以下。通过使Ti、Mg和Si经上述换算的合计的含量为6.4质量%以下,能够抑制氧化锆结晶粒子的过剩的晶粒生成,成为具有高机械强度的氧化铝质陶瓷。
另外,氧化铝质陶瓷也可以具有1.0%以下的气孔率。若气孔率为1.0%以下,则能够减少成为机械性断裂起点的气孔。如此能够得到具有高机械强度的氧化铝质陶瓷。
氧化铝质陶瓷中,Ca、Ba、Sr、Zn、Mn和Ce的合计含量,在将Ca进行CaO换算,Ba进行BaO换算,Sr进行SrO换算,所述Mn进行MnO换算,所述Ce进行Ce2O3换算时,可以为300ppm以下。若这些元素在氧化物换算时的合计为300ppm以下,则能够进一步提高氧化铝质陶瓷的高温下的弯曲强度。还有,Ca、Ba、Sr、Zn、Mn和Ce的一部分,有作为部分稳定氧化锆的固溶元素使用的情况。另外,还有与作为主成分的氧化铝结晶粒子和/或与作为辅助剂成分的含Ti、Mg和Si的氧化物反应而形成晶界相的情况。将Ca、Ba、Sr、Zn、Mn和Ce分别作为金属氧化物含有的晶界相,在700℃以上软化。通过使Ca、Ba、Sr、Zn、Mn和Ce的合计含量以氧化物换算为300ppm以下,能够成为高温下的机械强度高的氧化铝质陶瓷。在此,ppm简言之表示1×10-6级的质量比。
氧化锆结晶粒子中包含的稀土元素可以是Y。Y在作为部分稳定氧化锆的固溶元素使用的稀土元素之中,特别是使正方晶稳定化的效果高。还有,所谓氧化锆结晶粒子中Y以Y2O3换算含有2mol%,意思是相对于ZrO2,包含Y2O3为2mol%。
氧化锆结晶粒子中包含的单斜晶的氧化锆结晶粒子的比率可以为25%以下。若单斜晶的氧化锆结晶粒子的比率为25%以下,则正方晶氧化锆结晶粒子的比率变高,从正方晶向单斜晶的相变带来的氧化铝质陶瓷的机械强度提高效果更大。
氧化铝质陶瓷,依据JIS R 1601:2008的室温(25℃)下的三点弯曲强度可以为800MPa以上。若室温下的三点弯曲强度为800MPa以上,则能够得到高机械强度,同时可靠性优异,并且抗振性高的陶瓷加热器。这种情况下,氧化铝陶瓷加热器中所占的氧化铝质陶瓷(绝缘性陶瓷)的体积可以为一半左右(40体积%以上且60体积%以下)。
氧化铝质陶瓷,依据JIS R1604:2008的高温下的三点弯曲强度可以为600MPa以上。这种情况下,作为试验温度,能够例示800℃以上的温度。例如,若800℃的温度下的三点弯曲强度为600MPa以上,则对于在高温下放置(保持)的试验或温度循环试验的耐性高。这种情况下,氧化铝陶瓷加热器中所占的氧化铝质陶瓷(绝缘性陶瓷)的体积也可以为一半(40体积%以上且60体积%以下)左右。
陶瓷加热器具备发热体、和被覆该发热体的绝缘性陶瓷。在此,发热体由金属材料形成。若作为绝缘性陶瓷而使用上述的氧化铝质陶瓷,则能够得到发热体与绝缘性陶瓷的密接性(换言之也可以称为粘接性或接合性。)高的陶瓷加热器。这种情况下,氧化铝陶瓷加热器中的氧化铝质陶瓷的体积比例也可以为一半左右(40体积%以上且60体积%以下)。如此得到的陶瓷加热器,对于振动和温度循环具有高耐久性。
陶瓷加热器,例如可以是用2片绝缘性陶瓷夹住金属发热体而成的平板状的陶瓷加热器。另外,也可以是在作为绝缘性陶瓷的内筒和外筒之间具有发热体的筒状或柱状的陶瓷加热器。另外,陶瓷加热器也可以在内部或外部具备各种气敏元件。
陶瓷加热器不限定为上述的形态。换言之,具备发热体和被覆该发热体的绝缘性陶瓷,但只要绝缘性陶瓷是上述的氧化铝质陶瓷,也可以具有别的形态。例如,也可以具备发热体和气敏元件以外的构成要素。
上述的氧化铝质陶瓷,例如可以由以下这样的方法制作。
例如,作为主原料粉末,准备平均粒径为0.1μm以上且0.3μm以下的氧化锆粉末,和平均粒径为0.6μm以上且3.0μm以下的氧化铝粉末。氧化锆粉末,可以是含有稀土元素1~2mol%的部分稳定氧化锆。氧化铝粉末与氧化锆粉末的配比,例如可以按质量比计,氧化铝粉末:氧化锆粉末=95:5~80:20。
此外作为烧结助剂,准备氧化钛粉末、氧化镁粉末(也可以用碳酸镁粉末、氢氧化镁粉末代替氧化镁粉末)和氧化硅粉末。氧化钛粉末、氧化镁粉末、碳酸镁粉末、氢氧化镁粉末和氧化硅粉末,纯度可以为99质量%以上,平均粒径可以为2μm以下。平均粒径可以为0.1μm以上且2μm以下。在此,上述主原料粉末和烧结助剂,为了方便,也可以分别以如下方式表示。氧化铝为Al2O3,氧化锆为ZrO2,氧化钛为TiO2,氧化镁为MgO,碳酸镁为MgCO3,氢氧化镁为Mg(OH)2,氧化硅为SiO2。以下,会使用后者的表述。
作为主原料粉末与烧结助剂的调合组成,例如,能够例示以下。将Al2O3粉末、ZrO2粉末和烧结助剂合计作为100质量%时,TiO2为0.5质量%以上且1.0质量%以下,MgO为0.2质量%以上且4.0质量%以下,SiO2为0.7质量%以上且1.4质量%以下。合计为1.4质量%以上。TiO2、MgO和SiO2的合计,可以为6.0质量%以下,特别在5.0质量%以下。
可以将按照规定的比率调合的Al2O3粉末、ZrO2粉末、TiO2粉末、MgO粉末和SiO2粉末,例如用球磨机进行湿式混合,干燥后使用冲压成形、流延成形、浇铸成形、注射成形等众所周知的成形法,制成成形体。也可以对于所得到的成形体,例如进行冷等静压(CIP)处理。
对于所得到的成形体进行脱脂,根据辅助剂的组成和量,例如在大气中,以1400℃以上且1600℃以下的温度进行烧成,能够得到氧化铝质陶瓷。
发热体,例如,可以使用规定量调合有钨(W)粉末和Al2O3粉末的导电膏形成。在作为氧化铝质陶瓷的成形体的表面印刷导电膏。根据需要,在设于成形体的导通孔中埋入导电膏。如此形成导体图案。之后,对于导体图案和成形体同时进行烧成。这时,烧成气氛可以是还原气氛。
如此通过使用微细的ZrO2粉末,与上述的烧结助剂一起烧成,从而氧化锆结晶粒子成长,能够形成最大长度为1μm以上的单独粒子或最大长度为1μm以上的凝聚粒子。根据这样的方法,相比成为粒径为1μm以下的氧化锆结晶粒子均匀分散的结晶组织来说,能够提高氧化铝质陶瓷在室温(25℃)和高温(800℃)下的弯曲强度(三点弯曲强度)。
另外,作为烧结助剂,使用TiO2、MgO和SiO2,则氧化铝质陶瓷的构成成分,即,Al2O3、ZrO2、TiO2、MgO、SiO2和稀土元素物中的至少一种成分的其一部分,容易扩散至发热体的金属侧。如此,能够使氧化铝质陶瓷与发热体坚固地密接。
实施例
准备平均粒径(D50)0.6μm,纯度99.8质量%的Al2O3粉末,和以规定量固溶有Y2O3的平均粒径(D50)0.1μm的ZrO2粉末。另外,作为烧结助剂,准备纯度均为99.8%以上的TiO2粉末、SiO2粉末和MgCO3粉末。还有,对于试料No.4,除了添加表1所述的原料以外,还添加SrCO3粉末。
将它们以规定量调合,作为粘合剂添加纤维素,以及作为溶剂添加甲苯,进行混合而调制浆料。表1中的ZrO2的组成,是将Al2O3粉末和ZrO2粉末合计作为100质量%时的比率。表1中的TiO2、MgO和SiO2的组成,是将Al2O3、含稀土元素(Y)的ZrO2、TiO2、MgO和SiO2的合计作为100质量%时的比率。
将所得到的浆料,以刮刀法进行片状成形,使之干燥,制作厚度0.4mm的生胚。接着,将所得到的生胚层叠15层,得到厚度6mm的成形体。
将所得到的成形体切割成规定的形状,在大气中,以500℃进行10小时的脱脂处理后,在大气中,以表1所示的最高温度烧成5小时,得到氧化铝质陶瓷。试料No.13将烧成的最高温度下的保持时间设定为2小时。
【表1】
所得到的氧化铝质陶瓷的组成,以X射线荧光(XRF)确认。Al2O3、ZrO2、TiO2、MgO和SiO2的组成,以与调合时的误差范围一致。另外,作为其他而显示的Ca、Ba、Sr、Zn、Mn和Ce的含量,以电感耦合高频等离子体发射光谱(ICP)确认。制作的试料(试料No.1~13)的Ca、Ba、Sr、Zn、Mn和Ce的含量,各试料均为400ppm以下。
氧化铝结晶粒子的粒径和氧化锆结晶粒子的粒径以如下方式确认。对于氧化铝质陶瓷的截面进行镜面研磨之后,以低于表1的烧成温度50℃~100℃的温度进行10分钟的热处理,对晶界进行腐蚀。用扫描型电子显微镜,以倍率3000倍,拍摄晶界经过了腐蚀的截面的照片。对于所得到的截面照片进行图像分析,通过对于氧化铝结晶粒子和氧化锆结晶粒子分别各50个进行圆换算,计算平均粒径。还有,在氧化锆结晶粒子中,将凝聚粒子也视为一个粒子而计算平均粒径。另外,使用截面照片测量氧化锆结晶粒子的最大长度,根据最大长度为1μm以上的单独粒子和最大长度为1μm以上的凝聚粒子的面积比率,计算其体积比率。还有,通过截面照片的图像分析,测量所得到的氧化铝质陶瓷的气孔率时,任意试料的气孔率均为1%以下。
氧化锆结晶粒子的单斜晶比率,通过分析氧化铝质陶瓷的X射线衍射(CuKα)图案计算得到。单斜晶使用2θ为28.3°附近的(11-1)面,31.5°附近的(111)面的衍射峰,正方晶使用2θ为30.2°附近的(111)面的衍射峰。将单斜晶的上述衍射强度在单斜晶与正方晶的上述衍射强度之和中所占的百分比,作为氧化锆中单斜晶的比率。
氧化铝质陶瓷的弯曲强度通过如下方式评价:由所得到的氧化铝质陶瓷,制作规定形状的机械强度测量用试料,依据JIS R 1601:2008和JIS R1604:2008,测量室温(25℃)和800℃下的三点弯曲强度。结果显示在表2中。
【表2】
试料No.1~5、7~10和12中,含有50体积%以上的固溶有稀土元素的最大长度为1μm以上的氧化锆的单独粒子或最大长度为1μm以上的氧化锆的凝聚粒子,室温(25℃)下的三点弯曲强度为800MPa以上。另外,试料No.1~3、5、7~10和12中,Ca、Ba、Sr、Zn、Mn和Ce的含量以氧化物换算合计为300ppm以下,高温(800℃)下的三点弯曲强度为600MPa以上。
还有,在同温度下,使保持时间为2小时,制作与试料No.3同组成的成形体,该试料的结果在表2中作为试料No.13表示。试料No.13的氧化铝质陶瓷中,不含最大长度为1μm以上的氧化锆的单独粒子和最大长度为1μm以上的氧化锆的凝聚粒子。试料No.13的氧化铝质陶瓷,室温(25℃)下的三点弯曲强度为620MPa,高温(800℃)下的三点弯曲强度为420MPa,比其他的试料(试料No.1~12)低。这被认为是由于,试料No.13的氧化铝质陶瓷,与其他的试料的氧化铝质陶瓷相比,氧化锆结晶粒子是微粒。并认为在室温下,因为正方晶的稳定性高,所以应力下的相变难以发生。另外认为,在高温下,氧化铝结晶粒子与氧化锆结晶粒子之间或氧化锆结晶粒子彼此之间容易发生晶界滑移。其结果认为,室温和高温(800℃)下的三点弯曲强度变低。
Claims (7)
1.一种氧化铝质陶瓷,其含有氧化铝结晶粒子、氧化锆结晶粒子、以及Ti、Mg和Si,
在将所述Ti作为TiO2换算,所述Mg作为MgO换算,所述Si作为SiO2换算时,所述Ti、所述Mg和所述Si的合计含量为1.4质量%以上,
所述氧化锆结晶粒子中,在将构成该氧化锆结晶粒子的氧化锆表示为ZrO2时,稀土元素相对于该ZrO2的含量以氧化物换算为2mol%以下,并且,所述氧化锆结晶粒子含有最大长度为1μm以上的单独粒子和最大长度为1μm以上的凝聚粒子中的至少一种,
最大长度为1μm以上的所述单独粒子和最大长度为1μm以上的所述凝聚粒子的比率的合计,是所述氧化锆结晶粒子全体的50体积%以上。
2.根据权利要求1所述的氧化铝质陶瓷,其中,Ca、Ba、Sr、Zn、Mn和Ce的合计含量,在将所述Ca作为CaO换算,所述Ba作为BaO换算,所述Sr作为SrO换算,所述Mn作为MnO换算,所述Ce作为Ce2O3换算时,为300ppm以下。
3.根据权利要求1或2所述的氧化铝质陶瓷,其中,所述稀土元素是Y。
4.根据权利要求1~3中任一项所述的氧化铝质陶瓷,其中,所述氧化锆结晶粒子中所包含的单斜晶的比率为25%以下。
5.根据权利要求1~4中任一项所述的氧化铝质陶瓷,其中,室温下的三点弯曲强度为800MPa以上。
6.根据权利要求1~5中任一项所述的氧化铝质陶瓷,其中,800℃下的三点弯曲强度为600MPa以上。
7.一种陶瓷加热器,其具备发热体、和被覆该发热体的绝缘性陶瓷,该绝缘性陶瓷是权利要求1~6中任一项所述的氧化铝质陶瓷。
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