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CN100509699C - 氮化硅结合SiC耐火材料及其制造方法 - Google Patents

氮化硅结合SiC耐火材料及其制造方法 Download PDF

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Publication number
CN100509699C
CN100509699C CNB2004800258361A CN200480025836A CN100509699C CN 100509699 C CN100509699 C CN 100509699C CN B2004800258361 A CNB2004800258361 A CN B2004800258361A CN 200480025836 A CN200480025836 A CN 200480025836A CN 100509699 C CN100509699 C CN 100509699C
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sic
silicon nitride
nitride bonded
quality
refractory
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CN1849276A (zh
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木下寿治
古宫山常夫
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NGK Insulators Ltd
NGK Adrec Co Ltd
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NGK Insulators Ltd
NGK Adrec Co Ltd
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Abstract

本发明是一种氮化硅结合SiC耐火材料，其特征在于，以SiC作为主相并含有Si3N4和/或Si2N2O作为副相，其抗弯强度是150～300MPa，松比重是2.6～2.9。本发明还提供了氮化硅结合SiC耐火材料的制造方法，其特征在于，具有下述工序，即，在作为骨料的30～70质量%的30～300μm的SiC粉末、10～50质量%的0.05～30μm的SiC粉末和10～30质量%的0.05～30μm的Si粉末中，按氧化物换算混合0.1～3质量%的选自Al、Ca、Fe、Ti、Zr、Mg中的至少1种。采用该氮化硅结合SiC耐火材料及其制造方法，可以得到具有耐热性、抗热冲击性及耐氧化性并且强度高而且抗蠕变性、热传导性好的耐火材料。

Description

氮化硅结合SiC耐火材料及其制造方法
技术领域
本发明涉及氮化硅结合SiC耐火材料及其制造方法。
背景技术
碳化硅(SiC)耐火材料因其优良的耐热性及耐火性而在工业上占有重要的位置，例如多用于瓷砖、陶瓷器、蜂窝状物等的烧成用搁板、其它烧成用夹具、烧盆等。
通常，在烧成瓷砖、陶瓷器、蜂窝状物等被烧成物(陶瓷制品)的场合，例如，在搁板角部的多处位置载置为均匀烧成被烧成物而形成作为必要的空间的块状的支柱，使搁板和支柱相互地堆积成多层，同时将被烧成物放置在多层搁板组合的搁板上，进行烧成。
以往，这样的搁板组大多采用手工操作，但是近年来，即使在陶瓷制品的烧成、制造的生产线中，也在谋求自动化、省力化，对于搁板和制品的输送正在进行自动化。
作为构成上述搁板组的搁板及支柱的基体材料，以往主要使用可以在高温(例如1200～1600℃)下使用的莫来石、氧化铝及氧化锆，但是由于其强度(抗弯强度及杨氏模量)不足，所以根据用途使用强度更高的氧化物结合SiC耐火材料、氮化物结合SiC耐火材料。
但是，使用氧化物结合SiC耐火材料、氮化物结合SiC耐火材料的搁板组，为了得到能够承受搁板组的使用、组装、拆卸时产生的外部应力的强度，必须将搁板及支柱的壁厚加厚，这样不仅重量增加、操作性降低，而且热容量也增大，因此，不仅与近年的节能策略难以充分对应，而且因热传导性太差而难以实现被烧成体均热。
另外，为了确保作为上述耐火材料必要的抗氧化性和强度，其松比重必须在2.6或其以上，通常，作为氧化物要添加3～10质量％的氧化铝和氧化铁。
在这样添加3～10质量％的氧化铝和氧化铁的场合，存在结合部的玻璃相增加、作为耐火材料必要的抗蠕变性降低、寿命缩短等问题。另外，由于氧化铝和氧化铁起到原料配合时的原料分散效果和烧结辅助材料的作用，所以在以往的方法中将氧化铝和氧化铁减量至3％或其以下的场合，松比重降低，存在不能得到必要的强度的问题。
为了消除以上问题，人们使用高强度且耐热性、耐氧化性及热传导性优良的、含有Si作为金属Si相(多孔质或者致密质)的含Si材料(例如，含有Si和SiC作为主相的金属硅—碳化硅复合材料“Si浸渗SiC耐火材料”)的搁板组。
使用了Si浸渗SiC耐火材料的搁板组，可以使搁板及支柱薄壁化及轻量化，因此不仅可以提高操作性和对节约能源作出贡献，而且因寿命长，还可以提高搁板的重复利用率。
但是，使用了Si浸渗SiC的搁板组，作为基体材料的Si浸渗SiC的使用上限温度低于1400℃，因而难以例如在1400～1600℃的高温下使用。
本发明是鉴于上述现有技术的问题而完成的，本发明的目的在于，提供具有耐热性、耐热冲击性及耐氧化性，同时强度高而且抗蠕变性、热传导性优良的氮化硅结合SiC耐火材料及其制造方法。
发明内容
即，按照本发明，提供了氮化硅结合SiC耐火材料，该耐火材料以SiC作为主相并含有Si3N4和/或Si2N2O作为副相，同时，其抗弯强度是150～300MPa，而且松比重是2.6～2.9。
此时，在本发明中优选的是，在构成主相的SiC骨料的周边均匀地分散0.1～1μm的SiC超微粉。
另外，在本发明中优选的是满足(1)～(5)条件中的任一个或其以上。
(1)杨氏模量是100～500GPa。
(2)热传导率是20～80W/(m·K)。
(3)按氧化物换算含有0.1～3质量％的选自Al、Ca、Fe、Ti、Zr和Mg中的至少1种。
(4)构成主相的SiC骨料的最大粒径是50～300μm。
(5)含有60～90质量％的SiC、10～40质量％的Si3N4和/或Si2N2O。
另外，按照本发明，提供了氮化硅结合SiC耐火材料的制造方法，其特征在于，该方法具有下述工序，即，在30～70质量％的作为骨料的30～300μm的SiC粉末、10～50质量％的0.05～30μm的SiC粉末和10～30质量％的0.05～30μm的Si粉末中，按氧化物换算混合0.1～3质量％的选自Al、Ca、Fe、Ti、Zr和Mg中的至少1种。
此时，在本发明的制造方法中优选的是，以浇注成形的方式进行成形工序。
另外，在本发明的制造方法中优选的是，基本上在氮气氛中、1350～1500℃下进行热处理。此时，优选的是，在1350～1500℃下进行热处理时的氮气气氛中的氧浓度是0.01～2.00％。
另外，在本发明的制造方法中优选的是，在氮气气氛中热处理后，再在空气气氛中、于1300～1500℃进行热处理。
附图说明
图1表示抗蠕变性的评价试验的结果，是将蠕变量(mm)相对于经过时间(小时)进行绘图的曲线图。
具体实施方式
本发明的氮化硅结合SiC耐火材料，是以SiC作为主相，含有Si3N4和/或Si2N2O作为副相，同时，其抗弯强度是150MPa或其以上，而且松比重是2.6或其以上。此时，抗弯强度是150～300Mpa时，例如可以很好地适用于构成搁板组的搁板及支柱的场合，因此优先加以选用。另外，优选松比重是2.6～2.9。这是由于，松比重为低值的场合，耐火材料内的气孔增多，气孔的内表面积增大，在使用中的高温下与氧的接触面积增加，容易发生氧化。
此时，在本发明中优选的是，在构成主相的SiC骨料的周边均匀地分散1μm或其以下、更优选均匀地分散0.1～1μm的SiC超微粉。这是由于，在填充SiC颗粒时的颗粒的间隙部分中常常残留空隙，通过均匀地分散1μm或其以下的SiC超微粉，即使在1μm或其以下的空隙部分中也被SiC填充，可以接近于最密填充而提高密度。另外，由于这里成为问题的微细气孔的存在量对基体材料内部的开口气孔的内表面积(比表面积)影响很大，所以对耐氧化性也有很大的影响。在SiC骨料的周边均匀地分散1μm或其以下的SiC超微粉时，用SiC填充微细气孔，因而可以提高耐氧化性。
另外，本发明的耐火材料优选的是，杨氏模量在100GPa或其以上，更优选是100～500GPa。这是因为，例如在用于构成搁板组的搁板及支柱的场合，特别是在搁板组的组装及将被烧成物载置在搁板上时，由于搁板及支柱相对于外部应力无大的变形，所以搁板组的稳定性提高，同时由于搁板的变形小，所以可以提高陶瓷制品的质量。
另外，本发明的耐火材料的热传导率是20W/(m·K)或其以上，更优选是20～80W/(m·K)，这是因为，在高温下被加热时，如果热传导高，可以实现被烧成物的均热化，提高被烧成物的品质。
这里，本发明的耐火材料，按氧化物换算含有0.1～3质量％的选自Al、Ca、Fe、Ti、Zr和Mg中的至少1种，这是从耐氧化特性及抗热冲击性、控制方英石的生成量和控制玻璃相量的角度考虑而优选的。特别优选的是，本发明的耐火材料通过荧光X射线分析进行组成分析的原料组成中的氧化铝(Al2O3)的含量(按氧化物换算)是0.05～1.5质量％，氧化铝+氧化铁[Al2O3+Fe2O3]的含量(按氧化物换算)是0.5～2.0质量％。
另外，优选本发明的耐火材料优选的是，构成主相的SiC骨料的最大粒径是50～300μm。这是因为，SiC骨料的最大粒径低于50μm的场合，热应力增加时微裂纹扩展，若组织内存在50μm或其以上的SiC粒子，该粒子显示出阻止裂纹扩展的作用。与此相反，在低于50μm的SiC粒子的场合，由于裂纹容易沿晶界扩展并激烈地进行，所以抗热冲击性降低。另一方面还因为，在SiC骨料的最大粒径超过300μm的场合，不容易得到充分的抗热冲击性及强度(抗弯强度和杨氏模量)。
另外，本发明的耐火材料优选的是，含有60～90质量％的SiC及10～40质量％的Si3N4和/或Si2N2O。这是因为，本发明的耐火材料作为骨料具有SiC，在结合部中存在Si3N4和/或Si2N2O作为副相。主相的SiC的量在上述范围以下时，难以得到足够的抗热冲击性和强度(抗弯强度及杨氏模量)，在多数场合下因构成结合部的副相少而不能显现足够的强度。另外，Si3N4和/或Si2N2O的作用在于，作为副相将主相结合而显现强度，其含量过多时，与主相的平衡被破坏，难以得到充分的抗热冲击性及强度(抗弯强度和杨氏模量)，其含量过少时，不能显现充分的强度。
由以上可知，本发明的耐火材料具有耐热性、抗热冲击性及耐氧化性，同时，强度高且抗蠕变性优良。更具体地说，本发明的耐火材料具有相当于氧化物结合SiC耐火材料、氮化物结合SiC耐火材料的使用温度(1600℃左右)和相当于Si浸渗SiC的强度(225～250MPa左右)，是兼具以往耐火材料的优点的耐火材料。
以下说明本发明的氮化硅结合SiC耐火材料的制造方法。通常，本发明的耐火材料经过[1]原料配合、[2]混合、[3]浇注成形、[4]脱模、[5]干燥、[6]烧成(氮气气氛烧成([6]-1)、氧化烧成([6]-2))和[7]检查的工序而制造。这里，本发明的耐火材料的制造方法的主要特征在于，具有下面所述的工序，即，在作为骨料材料的30～70质量％的30～300μm的SiC粉末、10～50质量％的0.05～30μm的SiC粉末和10～30质量％的0.05～30μm的Si粉末中，混合0.1～3质量％(按氧化物换算)的选自Al、Ca、Fe、Ti、Zr、Mg中的至少1种的工序([1]+[2])。如果无机氧化物较多，使用时晶界中生成的玻璃相的量增加，作为耐火材料必要的抗蠕变性降低，寿命缩短。
此时，在本发明的耐火材料的制造方法中，如果在原料配合([1])时添加Si粉，可以使Si均匀地分散在SiC骨料的周边，因而是优选的。另外，在本发明的耐火材料的制造方法中，优选在无机氧化物(Al、Ca、Fe、Ti、Zr和Mg)中，至少Al2O3是0.05～2.0质量％、Fe2O3是0.05～1.0质量％、Na2O低于0.1质量％。另外，在本发明的耐火材料的制造方法中，通过添加10～30质量％的1μm或其以下的粒径的SiC超微粉，可以提高所得到的耐火材料的密度(致密度)。按照以往的配合，无机氧化物成为3质量％或其以下时，密度降低，但是添加SiC超微粉时，即使无机氧化物的量少，也可以得到2.6或其以上的松比重。
另外，本发明的耐火材料的制造方法优选的是，采用浇注成形([3])的方式进行成形工序。这样，采用本发明的耐火材料的制造方法时，可以提高所得到的成形品的致密性，因而可以提高烧成后的耐火材料的强度(抗弯强度和杨氏模量)。
另外，本发明的耐火材料的制造方法优选的是，实质上在氮气气氛中、于1350～1500℃下进行烧成，烧成时间是1～30小时([6]-1)。这样，本发明的耐火材料的制造方法可以使成形体中的Si和气氛中的氮发生反应，在SiC粒子的晶界上生成氮化硅和由微量氧形成的氧氮化合物，使SiC骨料结合在一起。另外，更优选的是，在1350～1500℃下热处理时的氮气气氛中的氧浓度是0.01～2.00％。这是因为，在微量氧存在的条件下可以形成氧氮化合物，使SiC晶界更坚固地与结合。另外，氮气气氛中的氮含有比例低于90容量％的场合，热处理时氮化速度减慢或者发生一部分氧未氮化的现象，致使原料氧化，因而不可取。
另外，本发明的耐火材料的制造方法优选的是，在氮气气氛中烧成([6]-1)后，再在空气气氛中于1300～1500℃下进行热处理([6]-2)。这是因为，通过使所得到的耐火材料的表面上形成坚固的氧化覆膜，即使是高温下长时间使用的场合，也可以抑制氧化劣化，因而几乎没有变形和膨胀，也不发生裂纹等，可以显现极好的抗热冲击性。
此时，若氧化处理温度低于1300℃，不能充分形成氧化皮膜，有可能不能发挥抗氧化性。另一方面，若氧化处理温度超过1500℃，氧化皮膜形成时的氧化十分剧烈，因氧化而产生的气泡会卷入氧化皮膜中，形成有孔的氧化皮膜，因而有可能不能发挥耐氧化性。
另外，本发明的耐火材料在1300℃或其以上温度下使用的场合，也可以不进行热处理，但在低于1300℃下使用的场合，还是进行热处理比较好。
下面，根据实施例更详细地说明本发明，但是本发明不限于这些实施例。
实施例1
按照表1所示的配比(质量％)将表1中所示的SiC粉末、Si粉末、Fe2O3、Al2O3、分散材料和离子交换水进行原料配合(原料配合([1])。
[表1]
 
成分    (粒径) 配比(质量％)
SiC     100μm3μm1μm1μm>     47.0010.0024.501.00 
Si 17.00
Fe<sub>2</sub>O<sub>3</sub> 0.50
Al<sub>2</sub>O<sub>3</sub> 0.50
分散材料 0.15
水 13.00
将得到的原料投入滚筒筛内进行混合，以达到原料的均匀混合，粉碎泥浆内的原料粒子的二次粒子和一次粒子(混合[2])。此时，滚筒筛混合按照100kg/批进行20小时左右。
将经过上述滚筒筛混合得到的泥浆注入石膏型内，泥浆内的水分被石膏型吸收，通过壁厚达到规定的厚度，得到成形体(成形(浇注成形)[3])。
将得到的成形体从石膏型中取出，干燥除去成形体内的水分(脱模[4]和干燥[5])。
将得到的干燥成形体在氮气气氛中、1450℃下烧成10小时(氮气气氛烧成([6]-1))。然后，将得到的烧成体在空气气氛中、1450℃下氧化烧成10小时(氧化烧成([6]-2))。
最后，对于经过尺寸及外观热裂检查(检查[7])的耐火材料，进行抗弯强度、杨氏模量、松比重、气孔率、热传导率及磨削抗力的测定，同时进行加工性的评价，其结果示于表2中。
比较例1
对于以往公知的Si浸渗SiC耐火材料(日本ガイシ(株)制NEWSIC)进行抗弯强度、杨氏模量、松比重、气孔率、热传导率、最高使用温度的测定，同时进行烧成变形及加工性的评价。其结果示于表2中。
[表2]
 
实施例1 比较例1
抗弯强度(MPa) 200 250
杨氏模量(GPa) 240 350
松比重(g/cc) 2.80 3.00
气孔率(％) 10.0 0.0
热传导率(W/mk) 30 180
最高使用温度(℃) 1500 1350
烧成变形 小 有
磨削加工(N) 60 60
加工性 稍难 难
考察：实施例1、比较例1
根据表2的结果，实施例1与比较例1相比，其强度(抗弯强度及杨氏模量)和热传导率稍差，但是作为构成搁板组的搁板及支柱的基体材料能够充分满足需要。另外，实施例1与比较例1相比，其最高使用温度提高了，因此可以适用于更高温度烧成用的搁板组。另外，由于实施例1在制造工序中的烧成变形小，因而几乎不必进行磨削加工。另一方面，比较例1不仅在制造过程中具有烧成变形，而且难以加工，因此修正变形要花费许多工夫，有成本升高的可能性。
实施例2、比较例2
准备2种具有表3所示的根据化学分析结果的氧化物换算比例的氮化硅结合SiC耐火材料，分别通过荧光X射线分析进行组成分析，通过XRD进行结晶相的定性分析及抗蠕变性的评价试验。其结果示于表3及图1中。
其中，一种是采用与实施例1同样的制造方法得到的氮化硅结合SiC耐火材料(实施例2)，而另一种是以往公知的氮化硅结合SiC耐火材料(比较例2)。
[表3]
Figure C200480025836D00121
另外，抗蠕变性的评价试验按照以下条件进行。
·试验温度：1400℃×200小时
·试件形状：10mm×2mm×120mml
·应力：1MPa
·测定部位：试件的端部及中央部
考察：实施例2、比较例2
对于实施例2及比较例2进行抗蠕变性评价的结果可以判明，如由图1的结果表明的那样，实施例2的抗蠕变性与比较例2相比非常优。
另外，可以确认，在实施例2中，如表3所示，其组成分析的氧化铝(Al2O3)的含量与比较例2相比非常少。另外，在实施例2中，如表3所示，根据XRD得到的结晶相定性分析的结果可以确认，不含有比较例2中存在的β—Si5AlON7(β—硅铝纶)及Al2O3(刚玉)的结晶相，相反，其α—Si3N4的结晶相比比较例2要多，具有比较例2中不存在的β—Si3N4及Si2N2O结晶相。由以上所述可以推测，由于实施例2在原料配合阶段将氧化铝(Al2O3)量控制为必要的最小限度，结晶相的界面上的玻璃相没有增加，因而可以大幅度地抑制抗蠕变性的降低。
本发明的氮化硅结合SiC耐火材料及其制造方法，例如适合作为构成瓷砖、陶瓷器、蜂窝状物等被烧成物(陶瓷制品)的烧成时所用的搁板组的搁板及支柱。

Claims (10)

1.氮化硅结合SiC耐火材料，其特征在于，含有SiC作为主相，并含有Si3N4和/或Si2N2O作为副相，其抗弯强度是150～300MPa，松比重是2.6～2.9，在构成该主相的SiC骨料的周围均匀地分散有尺寸为0.1～1μm的SiC超微粉。
2.根据权利要求1所述的氮化硅结合SiC耐火材料，其特征在于，其杨氏模量是100～500GPa。
3.根据权利要求1所述的氮化硅结合SiC耐火材料，其特征在于，其热传导率是20～80W/(m·K)。
4.根据权利要求1所述的氮化硅结合SiC耐火材料，其特征在于，按氧化物换算含有0.1～3质量％的选自Al、Ca、Fe、Ti、Zr和Mg中的至少1种。
5.根据权利要求1所述的氮化硅结合SiC耐火材料，其特征在于，构成主相的SiC骨料的最大粒径是50～300μm。
6.根据权利要求1所述的氮化硅结合SiC耐火材料，其特征在于，含有60～90质量％的SiC以及10～40质量％的Si3N4和/或Si2N2O。
7.权利要求1所述的氮化硅结合SiC耐火材料的制造方法，包括原料配合、混合、浇注成形、脱模、干燥、烧成和检查的工序，其特征在于，包括将下述物料混合的工序：
30～70质量％的作为骨料的30～300μm的SiC粉末；
10～50质量％的0.05～30μm的SiC粉末；
10～30质量％的0.05～30μm的Si粉末；以及
按氧化物换算0.1～3质量％的选自Al、Ca、Fe、Ti、Zr和Mg中的至少1种。
8.根据权利要求7所述的氮化硅结合SiC耐火材料的制造方法，其特征在于，所述烧成是：实质上在氮气气氛中、于1350～1500℃进行热处理。
9.根据权利要求7所述的氮化硅结合SiC耐火材料的制造方法，其特征在于，所述烧成是：在含氧0.01～2.00％的氮气氛中、于1350～1500℃进行热处理。
10.根据权利要求8或9所述的氮化硅结合SiC耐火材料的制造方法，其特征在于，在氮气氛中进行热处理后，在空气中、于1300～1500℃进行热处理。
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CN111548164A (zh) * 2020-05-19 2020-08-18 中钢集团洛阳耐火材料研究院有限公司 一种持续自增韧氮化物结合碳化硅耐火材料

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US7494949B2 (en) 2009-02-24
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