CN102741196B - 无机纤维质耐火成形体、无机纤维质耐火成形体的制造方法以及无机纤维质不定形耐火组合物 - Google Patents
无机纤维质耐火成形体、无机纤维质耐火成形体的制造方法以及无机纤维质不定形耐火组合物 Download PDFInfo
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Abstract
本发明提供一种即使不含硅酸铝纤维等的陶瓷纤维或氧化铝粉末、二氧化硅粉末也可以表现所希望的耐热性,并且降低制造成本和产品价格,生物可溶性高的无机纤维质耐火成形体。本发明的无机纤维质耐火成形体,其特征在于,由含有在40℃下溶解于生理盐水的溶解率为1质量%以上的生物可溶性无机纤维2~95质量%、具有针状结晶结构的无机粉末2~95质量%和粘结剂3~32质量%的材料构成。特别优选具有针状结晶结构的无机粉末的平均长度为1~3000μm,并且长宽比为1~1000的无机纤维质耐火成形体。
Description
技术领域
本发明涉及无机纤维质耐火成形体、无机纤维质耐火成形体的制造方法以及无机纤维质不定形耐火组合物。
背景技术
以前在工业炉、烧成炉或者热处理装置等中,作为加热室内部的天井或壁等的内衬材料或者隔热材料,使用砖等比较重质的耐火物,近些年来则开始使用以无机纤维为主要成分的无机纤维质耐火成形体(例如,参照专利文献1(特开2001-192278号公报))。
无机纤维质成形体由含有无机纤维、和使无机纤维之间结合的粘结剂、以及根据必要添加的无机填料的材料构成,作为上述无机纤维,使用以提高成形体的耐热性并降低密度为目的的硅酸铝纤维等的陶瓷纤维,作为上述无机填料,使用以提高耐热性为目的的氧化铝粉末或者二氧化硅粉末。
然而,在上述无机纤维质成形体中,由于作为原料使用的氧化铝粉末或二氧化硅粉末等无机填料价格高,因此存在增大无机纤维质成形体的制造成本和产品价格的技术问题。
另外,在上述无机纤维质成形体中,由于所使用的陶瓷纤维、二氧化硅粉末对体液的耐化学性高,因此在通过呼吸侵入到肺中的情况下,有被指出对健康方面造成影响的可能性。
进一步,在铝或镁等的铸造装置中,将多个上述无机纤维质耐火成形体连结起来,在作为排水管、熔融材料保持炉、铁水包等与金属熔融材料接触的部件的内衬材料而使用的情况下,会在接缝处使用糊状的无机纤维质不定形耐火组合物,该糊状的无机纤维质不定形耐火组合物也是在与无机纤维质耐火成形体同样的材料中加入液体溶剂而形成的物质,因此,也和无机纤维质耐火成形体同样地存在制造成本以及产品价格增大的技术问题。
现有技术文献
专利文献
专利文献1:特开2001-192278号公报
发明内容
发明所要解决的技术课题
在这种情况下,本发明的目的在于提供即使不使用氧化铝粉末或二氧化硅粉末作为无机填料,也可以发挥高的耐热性,降低制造成本和产品价格,生物可溶性高的无机纤维质耐火成形体,并且提供能够简单制造该无机纤维质耐火成形体的方法。进一步,本发明的目的在于提供即使不使用陶瓷纤维作为无机纤维,不使用氧化铝粉末或二氧化硅粉末作为无机填料,也可以发挥高的耐热性,降低制造成本和产品价格的无机纤维质不定形耐火组合物。
解决技术课题的方法
为了达到上述目的,本发明者们进行了专门探讨,结果发现通过使用含有在40℃下溶解于生理盐水的溶解率为1质量%以上的生物可溶性无机纤维2~95质量%、具有针状结晶结构的无机粉末2~95质量%和粘结剂3~32质量%的材料来制作无机纤维质耐火成形体或者无机纤维质不定形组合物,可以达成上述目的,从而基于本发现而完成本发明。
即,本发明提供:
(1)一种无机纤维质耐火成形体,其特征在于,由含有在40℃下溶解于生理盐水的溶解率为1质量%以上的生物可溶性无机纤维2~95质量%、具有针状结晶结构的无机粉末2~95质量%和粘结剂3~32质量%的材料构成;
(2)如上述(1)所述的无机纤维质耐火成形体,其中,上述具有针状结晶结构的无机粉末的平均长度为1~3000μm,并且长宽比为1~1000;
(3)一种无机纤维质耐火材料成形体的制造方法,其中,将浆料进行脱水成形,所述浆料按固形物换算时含有在40℃下溶解于生理盐水的溶解率为1质量%以上的生物可溶性无机纤维2~95质量%、具有针状结晶结构的无机粉末2~95质量%和粘结剂3~32质量%。
(4)一种无机纤维质不定形耐火组合物,其特征在于,由按固形物换算时含有在40℃下溶解于生理盐水的溶解率为1质量%以上的生物可溶性无机纤维2~95质量%、具有针状结晶结构的无机粉末2~95质量%和粘结剂3~32质量%的材料构成。
发明的效果
根据本发明,通过含有特定量的生物可溶性无机纤维并且含有特定量的具有针状结晶结构的无机粉末,从而能够提供即使不含氧化铝粉末、二氧化硅粉末也可以具有所希望的耐热性,并且降低制造成本和产品价格,生物可溶性高的无机纤维质耐火成形体。另外,根据本发明,可以提供能够简单制造上述无机纤维质耐火成形体的方法。进一步,根据本发明,可以提供降低制造成本和产品价格的无机纤维质不定形耐火组合物。
具体实施方式
(无机纤维质耐火成形体)
首先,针对本发明的无机纤维质耐火成形体进行说明。
本发明的无机纤维质耐火成形体,其特征在于,由含有在40℃下溶解于生理盐水的溶解率为1%以上的生物可溶性无机纤维2~95质量%、具有针状结晶结构的无机粉末2~95质量%和粘结剂3~32质量%的材料构成。
本发明的无机纤维质耐火成形体的构成材料含有在40℃下溶解于生理盐水的溶解率为1%以上的生物可溶性无机纤维。作为这样的生物可溶性无机纤维,例如可以列举在空气气氛下在800℃下加热处理24小时时的长度方向的收缩率([(加热前的长度-加热后的长度)/加热前的长度])×100)为1%以下,在1100℃下加热处理24小时时的长度方向的收缩率为5%以下。
作为上述生物可溶性无机纤维,例如,可以列举CaO和MgO的合计含量为20~40重量%,并且含有60~80重量%的SiO2的碱土金属类硅酸盐纤维。具体来说,可以列举选自在特开2000-220037号公报、特开2002-68777号公报、特开2003-73926号公报或者特开2003-212596号公报中记载的无机纤维,即,SiO2和CaO的合计含量为85质量%以上,并含有0.5~3.0质量%的MgO以及2.0~8.0质量%的P2O5,且根据德国危险物质规则的致癌性指数(KI值)为40以上的无机纤维;或以SiO2、MgO以及TiO2作为必要成分的无机纤维;或以SiO2、MgO以及氧化锰作为必要成分的无机纤维;或含有SiO252~72质量%、Al2O3小于3质量%、MgO 0~7质量%、CaO 7.2~95质量%、B2O30~12质量%、BaO 0~4质量%、SrO 0~3.5质量%、Na2O 10~20.5质量%、K2O 0.5~4.0质量%、以及P2O50~5质量%的无机纤维;或含有SiO275~80质量%、CaO+MgO 19~25质量%、Al2O31~3质量%的无机纤维中的一种以上的物质。
通过在40℃下溶解于生理盐水的溶解率为1质量%以上,使生物可溶性无机纤维变得容易在体内溶解。另一方面,如果在40℃下溶解于生理盐水的溶解率小于1质量%,生物可溶性无机纤维变得难以在生物体内溶解。
如果以考虑硅、镁、钙以及铝作为构成生物可溶性无机纤维的金属元素的情况为例进行说明,生物可溶性无机纤维溶解于生理盐水的溶解率的测定方法如下所述。
将生物可溶性无机纤维粉碎至200目以下的样品1g以及生理盐水150mL装入三角烧瓶(300mL)中,设置于40℃的培养箱中,以每分钟120的转数持续水平振荡50小时。振荡结束之后,过滤经过振荡的液体,通过ICP发光分析对所得到的滤液中含有的硅、镁、钙以及铝测定各元素的浓度(mg/L)。
这样,从上述滤液中各元素的浓度以及溶解前的生物可溶性无机纤维中的各元素的含量(质量%),通过下述式(1)算出在40℃下溶解于生理盐水中的溶解率C(%),另外,将由ICP发光分析得到的滤液中的各元素的浓度作为:硅元素的浓度:a1(mg/L)、镁元素的浓度:a2(mg/L)、钙元素的浓度:a3(mg/L)以及铝元素的浓度:a4(mg/L),溶解前的无机纤维中的各元素含量作为:硅元素的含量:b1(质量%)、镁元素的含量:b2(质量%)、钙元素的含量:b3(质量%)以及铝元素的含量:b4(质量%)。
C(%)={滤液量(L)×(a1+a2+a3+a4)×100}/{溶解前的无机纤维的量(mg)×(b1+b2+b3+b4)/100} (1)
在本发明的无机纤维质耐火成形体中,生物可溶性无机纤维发挥作为骨料的功能。
生物可溶性无机纤维的平均纤维直径优选为1~50μm,更加优选为1~10μm,更进一步优选为1~6μm。如果平均纤维直径小于1μm,耐水性变得容易降低,因此得到的耐火成形体的强度容易变低,另外,如果超过50μm,耐火成形体的密度变低,因此得到的耐火成形体的强度也容易变低。另外,无机纤维的平均纤维长度优选为1~200mm,进一步优选为1~100mm,更进一步优选为1~50mm。通过将平均纤维长度设置在上述范围内,容易形成具有适当密度的耐火成形体。
另外,在本申请文件中,平均纤维直径、平均纤维长度是指用光学显微镜测定300~500根测试样品的纤维直径和纤维长度时的各自的平均值。
本发明的无机纤维质耐火成形体的构成材料优选含有在40℃下溶解于生理盐水的溶解率为1%以上的生物可溶性无机纤维2~95质量%。上述构成材料中生物可溶性无机纤维的含量优选为18~72质量%,进一步优选为27~63质量%。
本发明的无机纤维质耐火成形体因为由含有生物可溶性无机纤维2~95质量%的材料构成,因此,发挥和具有针状结晶结构的无机粉末的相互作用,从而能够发挥所希望的耐热性,并且发挥高的生物可溶性。
本发明的无机纤维质耐火成形体的构成材料含有具有针状结晶结构的无机粉末。
作为具有针状结晶结构的无机粉末,存在着天然矿物以及合成物,具体来说,可以列举选自硅灰石粉末、海泡石粉末、凹凸(attapulgite)棒石粉末等中的一种以上的无机粉末。
硅灰石(Wollastonite)是用CaSiO3(CaO·SiO2)表示,具有用钙离子连结的无限的硅-氧链(SiO3)结构,且结晶结构为针状的无机物质。作为天然矿物产出的硅灰石,是作为硅灰石而从石灰岩地带产出的,可以含有微量(例如,小于0.5重量%)的Al2O3或Fe2O3作为杂质。
另外,海泡石(sepiolite)是粘土状的含水镁硅酸盐矿物,并且是具有以Mg4Si6O15(OH)2·6H2O为代表的组成式,且结晶结构为针状的无机物质,凹凸棒石粉末(attapulgite)是粘土状的含水硅酸铝·镁化合物,并且是具有以Si8O20Mg5(OH)2·Al(OH2)4·4H2O为代表的组成式,且结晶结构为针状的无机物质。
在本发明的无机纤维质耐火成形体中,作为具有针状结晶结构的无机粉末,优选平均纤维长度为1~3000μm,进一步优选为2~2000μm,进一步优选为3~1000μm。另外,平均直径优选为1~100μm,进一步优选为1~90μm,更加优选为1~80μm。
另外,作为具有针状结晶结构的无机粉末,长宽比优选为1~1000,进一步优选为2~100,更加优选为3~50。
具有针状结晶结构的无机粉末的平均长度和平均直径是指用光学显微镜测定成为测试样品的300~500个无机粉末的长度和直径时的各自的平均值。
于是,具有针状结晶结构的无机粉末的长宽比可以通过上述无机粉末的平均长度/无机粉末的平均直径求得。
本发明的无机纤维质耐火成形体的构成材料含有具有针状结晶结构的无机粉末2~95质量%,优选含有18~72质量%,更加优选含有27~63质量%。
本发明的无机纤维质耐火成形体因为由含有2~95质量%的具有针状结晶结构的无机粉末的材料构成,因此,发挥和生物可溶性无机纤维的相互作用而能够发挥所希望的耐热性,并且可以降低制造成本或产品成本,并发挥优异的生物可溶性。
在构成本发明的无机纤维质耐火成形体的材料中,作为具有针状结晶结构的无机粉末,例如可以采用熔点为1500℃的硅灰石或熔点为1550℃的海泡石等,这些等的无机粉末与氧化铝(α-氧化铝熔点为2053℃)或二氧化硅(熔点为1650℃)相比熔点低,因此一直以来认为其不适合作为耐火成形体的构成材料。
然而,本发明者们经过专门探讨结果发现,通过使用含有特定量的熔点低原本不期待其具有耐热性提高效果的硅灰石等具有针状结晶结构的无机粉末,并且含有规定量的生物可溶性无机纤维的构成材料,可以具有针状结晶结构的无机粉末和生物可溶性无机纤维发挥相互作用而显示优异的耐热性,至此完成本发明。
硅灰石等具有针状结晶结构的无机粉末与氧化铝粉末等相比价格便宜,容易获得,另外,硅灰石等也是其自身显示生物可溶性的物质,因此,可以降低无机纤维质耐火成形体的制造成本或产品成本,并且可以提高无机纤维质耐火成形体的生物可溶性。
本发明的无机纤维质耐火成形体的构成材料含有粘结剂3~32质量%,进一步优选含有5.5~22质量%,更加优选含有7~18质量%。
在本发明的无机纤维质耐火成形体中,作为粘结剂,可以列举选自无机粘结剂以及有机粘结剂中的一种以上的粘结剂,在使用多种粘结剂的情况下,上述粘结剂的含量是指所使用的粘结剂的总量。
作为无机粘结剂,可以列举选自阴离子性的胶体二氧化硅、阳离子性的胶体二氧化硅等的胶体二氧化硅、锻制二氧化硅、氧化铝溶胶、氧化锆溶胶、二氧化钛溶胶等中的一种以上的粘结剂。
如后面所述,通过在耐火成形体的制造时或者使用时在高温下进行烧成处理,上述无机粘结剂采用二氧化硅或氧化铝等氧化物形态,在本申请处理中,上述烧成处理前后的任意形态均称为无机粘结剂。另外,在本申请文件中,无机粘结剂的含有比例是指按氧化物换算的值。
构成本发明的无机纤维质耐火成形体的材料按氧化物换算优选含有无机粘结剂3~20质量%,进一步优选含有3.5~15质量%,更加优选含有4~12质量%。
在构成本发明的无机纤维质耐火成形体的材料中,如果无机粘结剂的含有比例小于3质量%,难以得到在高温的使用环境下提高强度的效果,如果无机粘结剂的含有比例超过20质量%,在后述的耐火成形体的制造时在脱水成形工序中滤水性降低,从而制造效率降低。
如后面所述,胶体二氧化硅等的无机粘结剂在与生物可溶性无机纤维的共存下,通过在600~1000℃左右的温度下烧成,可以使生物可溶性纤维之间牢固地结合,将原料脱水成形得到的预成形物干燥处理之后,通过烧成处理或者在工业炉内等与被处理物一起烧成,可以发挥作为粘结剂的高能力。
作为有机粘结剂,可以列举淀粉、丙烯酸树酯、聚丙烯酰胺等。
构成本发明的无机纤维质耐火成形体的材料优选含有有机粘结剂0.1~12质量%,进一步优选含有2~7质量%,更加优选含有3~6质量%。
在本发明的无机纤维质耐火成形体中,如果有机粘结剂的含有比例小于0.1质量%,在后述的耐火成形体的制造时干燥处理预成形体的时候,难以赋予干燥处理物以足够的强度,如果超过12质量%,会有烧成干燥处理物的时候增加燃烧气体的排出量,或者保存时吸收水分,从而降低无机纤维质耐火成形体的性能的情况。
构成本发明的无机纤维质耐火成形体的材料通过含有有机粘结剂,从而如后面所述,可以在无机纤维质耐火成形体的制造时,对于将原料脱水成形、干燥处理得到的耐火成形体赋予足够的保形性和强度。
构成本发明的无机纤维质耐火成形体的材料优选含有上述生物可溶性无机纤维、具有针状结晶结构的无机粉末和粘结剂合计为50质量%以上,进一步优选含有70质量%以上,更加优选含有90质量%以上。
本发明的无机纤维质耐火成形体通过由含有生物可溶性无机纤维、具有针状结晶结构的无机粉末以及粘结剂合计为50质量%以上的材料构成,从而可以更有效地提高耐热性或生物可溶性等。
本发明的构成无机纤维质耐火成形体的材料,可以根据必要含有粉末状的填料或骨料,由此可以提高无机纤维质耐火成形体的机械强度。
作为填料或骨料,可以列举熟耐火粘土(chamotte)、气球陶瓷(ceramic balloon)这样的轻质骨料;或氧化铝、二氧化硅、堇青石、硅藻土、锆石、氧化锆、氧化镁、氧化钙这样的无机粉末;或高岭石这样的粘土矿物等。
构成本发明的无机纤维质耐火成形体的材料可以根据必要含有适量的六偏磷酸钠、三聚磷酸钠、超聚磷酸钠等分散剂;硫酸铝、聚丙烯酰胺等凝聚剂等。
构成本发明的无机纤维质耐火成形体的材料可以根据必要含有填料或骨料1~30质量%,含有分散剂0.5~10质量%,含有凝聚剂0.5~10质量%。
本发明的无机纤维质耐火成形体中,通过含有特定量的生物可溶性无机纤维,并且含有特定量的具有针状结晶结构的无机粉末,从而即使不含硅酸铝纤维等陶瓷纤维或氧化铝粉末、二氧化硅粉末,也可以表现所希望的耐热性,并且降低制造成本和产品价格,提高生物可溶性。
本发明的无机纤维质耐火成形体优选例如在空气气氛下,在1100℃下加热处理24小时时的长度方向的收缩率([(加热前的长度-加热后的长度)/加热前的长度])×100)为5%以下,进一步优选为3.0%以下,更加优选为1.0%以下。
本发明的无机纤维质耐火成形体由于是由含有特定量的生物可溶性无机纤维和具有针状结晶结构的无机粉末的材料构成,因此可以表现优异的耐热性。
本发明的无机纤维质耐火成形体例如体密度为0.1~1.0g/cm3,优选为0.15~0.7g/cm3,进一步优选为0.17~0.35g/cm3。
另外,本发明的无机纤维质耐火成形体例如弯曲强度为0.1~2.0MPa,优选为0.2~1.5MPa。
作为本发明的无机纤维质耐火成形体的形状,例如可以列举圆筒状、有底筒状、平板形状或块状等。
本发明的无机纤维质耐火成形体可以在后述的无机纤维质耐火成形体的制造方法中,通过对原料脱水成形而制作,在本申请中,无机纤维质耐火成形体中除了将脱水成形得到的预成形物干燥处理之外,还包括进一步进行烧成处理。即使是在脱水成形之后不进行烧成处理的无机纤维质耐火成形体,也可以将其作为耐火材料配置于所希望的位置,在使用时与被处理物同时加热而形成烧成物。
本发明的无机纤维质耐火成形体在例如工业炉、烧成炉或者热处理装置等中,可以优选作为加热室内部的天井或者壁等的内衬材料或者隔热材料使用。
(无机纤维质耐火成形体的制造方法)
以下,对本发明的无机纤维质耐火成形体的制造方法进行说明。
本发明的无机纤维质耐火成形体的制造方法是制造本发明的无机纤维质耐火成形体的方法,其特征在于,将按固形物换算时含有在40℃下溶解于生理盐水的溶解率为1质量%以上的生物可溶性无机纤维2~95质量%、具有针状结晶结构的无机粉末2~95质量%和粘结剂3~32质量%的浆料进行脱水成形。
在本发明的无机纤维质耐火成形体的制造方法中,生物可溶性无机纤维发挥作为所得到的耐火成形体的骨料的功能,可以列举和上述物质同样的物质。
在本发明的无机纤维质耐火成形体的制造方法中,生物可溶性无机纤维在浆料中,按固形物换算时含有2~95质量%,优选含有18~72质量%,更加优选含有27~63质量%。
在本发明的无机纤维质耐火成形体的制造方法中,具有针状结晶结构的无机粉末是在所得到的无机纤维质耐火成形体中,发挥和生物可溶性无机纤维的相互作用而提高耐火成形体的耐热性的物质,作为具有针状结晶结构的无机粉末,可以列举和上述物质同样的物质。
在本发明的无机纤维质耐火成形体的制造方法中,具有针状结晶结构的无机粉末在浆料中按固形物换算时含有2~95质量%,优选含有18~72质量%,进一步优选为含有27~63质量%。
在本发明的无机纤维质耐火成形体的制造方法中,粘结剂在浆料中按固形物换算时含有3~32质量%,优选含有5.5~22质量%,更加优选含有7~18质量%。
在本发明的无机纤维质耐火材料成形体的制造方法中,作为粘结剂可以列举上述无机粘结剂或有机粘结剂。
在本发明的无机纤维质耐火成形体的制造方法中,无机粘结剂优选在构成浆料的固形物中,按氧化物换算时含有3~20质量%,进一步优选含有3.5~15质量%,更加优选含有4~11质量%。
在构成浆料的固形物中无机粘结剂的含有比例如果按氧化物换算小于3质量%,难以在耐火成形体表面迅速形成氧化膜,另外,如果超过20质量%,水分量变多,从而脱水成形时的操作性降低。
另外,在本发明的无机纤维质耐火成形体的制造方法中,有机粘结剂在构成浆料的固形物中优选含有0.1~12质量%,更加优选含有2~7质量%,更加优选含有3~6质量%。
如果有机粘结剂的含有比例小于0.1质量%,难以对脱水成形之后干燥处理时得到的干燥处理物赋予足够的强度,如果超过12质量%,会出现烧成干燥处理物时燃烧气体的排出量增加,或者保存时吸收水分,从而降低所得到的耐火成形体的性能的情况。
在本发明的无机纤维质耐火材料成形体的制造方法中,在浆料中按固形物换算,生物可溶性无机纤维、具有针状结晶结构的无机粉末和粘结剂合计含有50质量%以上,更加优选含有70质量%以上,更加优选含有90质量%以上。
在本发明的无机纤维质耐火材料成形体的制造方法中,通过在浆料中按固形物换算,生物可溶性无机纤维、具有针状结晶结构的无机粉末和粘结剂合计含有50质量%以上,从而可以更有效提高所得到的耐火成形体的耐热性或生物可溶性。
在本发明的无机纤维质耐火成形体的制造方法中,在浆料中可以根据必要含有粉末状的填料或骨料、分散剂、凝聚剂,由此可以提高所得到的无机纤维质耐火成形体的机械强度。
填料或骨料、分散剂、凝聚剂的具体例子或配合量与在本发明的无机纤维质耐火成形体的说明中所述的内容相同,这些成分的配合量按固形物换算量优选为与上述本发明的无机纤维质耐火成形体的说明中所述的内容相同的配合量。
在本发明的无机纤维质耐火成形体的制造方法中,作为形成浆料的液体介质,不特别限定,可以列举水和极性有机溶剂,作为极性有机溶剂,可以列举乙醇、丙醇等一元醇类;乙二醇等二元醇类。在这些等的液体介质中,如果考虑操作环境和环境负担,优选水。另外,作为水不特别限定,可以列举蒸馏水、离子交换水、自来水、地下水、工业用水等。
浆料中的固形物浓度优选为0.1~10质量%,进一步优选为0.3~8质量%,更加优选为0.5~3质量%。如果上述浆料浓度小于0.1质量%,在脱水成形工序中除去的水的量变得过多而导致没有效率,另外,如果超过10质量%,固形物难以均匀分散于浆料中。
在本发明的无机纤维质耐火成形体的制造方法中,在浆料形成时在液体介质中混合生物可溶性无机纤维、具有针状结晶结构的无机粉末、粘结剂等的原料的顺序不特别限定,可以将这些等依次或者同时在液体介质中混合。
在本发明的无机纤维质耐火成形体的制造方法中,上述浆料经过脱水成形处理而除去液体介质。
在本发明的耐火成形体的制造方法中,也有浆料含有水以外的介质作为液体介质的情况,在本申请的文件中将除去水以外的液体介质的情况也称为脱水成形。
脱水成形例如可以通过向底部设有网的成形模具中注入该浆料,吸收上述水等液体介质的吸收脱水成形法、或加压脱水成形法进行。
在本发明的无机纤维质耐火成形体的制造方法中,在将浆料搬送至成形模具等中的时候,可以使用泵等,也可以通过在含有上述浆料的槽的下部配置成形模具等,利用浆料的自重来搬送。
脱水成形物优选具有和要得到的耐火成形体相似的形状,作为脱水成形物的形状,例如可以列举圆筒状、有底筒状、平板状、块状。
得到的脱水成形物优选使用干燥机等进行干燥。干燥温度优选为40~180℃,进一步优选为60~150℃,更加优选为80~120℃。另外,干燥时间优选为6~48小时,进一步优选为8~40小时,更进一步优选为10~36小时。另外,干燥时的气氛可以列举空气气氛、氧气氛、氮气氛等。
在本发明的耐火成形体的制造方法中,将上述脱水成形物进行干燥处理之后,可以进一步进行烧成处理。
烧成温度优选为600~1200℃,进一步优选为700~1150℃,更进一部优选为800~1100℃。另外,烧成时的气氛不特别限定,优选为空气气氛、氧气氛或者氮气氛。烧成时间优选为0.5~36小时,进一步优选为1~30小时,更加优选为3~24小时。
通过施加烧成处理,预先使成形体中的有机粘结剂消失,这样可以抑制成形体的收缩,降低在加热炉等中施工之后的CO2等的气体的产生量,抑制成形体之间的接缝开口或成形体本身的破裂、破损的产生等。
得到的耐火成形体的详细内容如本发明的耐火成形体的说明中所述。
根据本发明的耐火成形体的制造方法,可以简单制造即使不含硅酸铝纤维等陶瓷纤维或氧化铝粉末、二氧化硅粉末也可以显示所希望的耐热性,并且降低制造成本和产品价格,生物可溶性高的无机纤维质耐火成形体。
(无机纤维质不定形耐火组合物)
以下,对本发明的无机纤维质不定形耐火组合物进行说明。
本发明的无机纤维质不定形耐火组合物,其特征在于,由按固形物换算时含有在40℃下溶解于生理盐水的溶解率为1质量%以上的生物可溶性无机纤维2~95质量%、具有针状结晶结构的无机粉末2~95质量%和粘结剂3~32质量%的材料构成。
在本发明的无机纤维质不定形耐火组合物中,作为生物可溶性无机纤维,可以列举在本发明的无机纤维质耐火成形体的说明中所举的同样的物质,具有针状结晶结构的无机粉末或粘结剂也可以举本发明无机纤维质耐火成形体的说明中所举的同样的物质。
构成本发明的无机纤维质不定形耐火物的材料在固形物中含有生物可溶性无机纤维2~95质量%,优选含有10~90质量%,更加优选含有20~80质量%。
通过使生物可溶性无机纤维的含有比例在固形物中为2~95质量%,可以提供能够赋予施工物(耐火物)必要的最低限度的强度和耐腐蚀性,并且能够赋予保温性(绝热性)和轻质性的无机纤维质不定形耐火组合物。
构成本发明的无机纤维质不定形耐火组合物的材料在固形物中含有具有针状结晶结构的无机粉末2~95质量%,优选含有10~90质量%,更加优选含有20~80质量%。
通过使具有针状结晶结构的无机粉末的含有比例为2~95质量%,可以在施工后发挥和具有针状结晶结构的无机粉末的相互作用从而发挥所希望的耐热性,并且降低制造成本和产品成本。
构成本发明的无机纤维质不定形耐火组合物的材料在固形物中含有粘结剂3~32质量%,进一步优选为含有3.5~22质量%,更加优选含有4~18质量%。
在本发明的无机纤维质不定形耐火组合物中,作为粘结剂,可以列举选自无机粘结剂以及有机粘结剂中的一种以上,在使用多种粘结剂的情况下,上述粘结剂的含量是指所使用的粘结剂的总量。
构成本发明的无机纤维质不定形耐火组合物的材料优选在固形物中按氧化物换算含有无机粘结剂3~20质量%,进一步优选含有3~15质量%,更加优选含有3~12质量%。另外,优选含有有机粘结剂0.1~12质量%,进一步优选含有0.5~7质量%,更进一步优选含有1.0~6质量%。
在本发明的无机纤维质不定形耐火组合物中,在固形物中优选含有生物可溶性无机纤维、具有针状结晶结构的无机粉末以及粘结剂合计为50质量%以上,进一步优选含有70质量%以上,更加优选含有90质量%以上。
通过使构成本发明的无机纤维质不定形耐火组合物的材料在固形物中含有生物可溶性无机纤维、具有针状结晶结构的无机粉末和粘结剂的合计为50质量%以上,可以对所得到的施工物(耐火物)有效地赋予所希望的耐热性。
构成本发明的无机纤维质不定形耐火组合物的材料,作为任意成分,可以根据必要含有粉末状的填料或骨料,由此可以提高无机纤维质耐火成形体的机械强度。
作为填料或骨料的具体例子,与本发明的耐火成形体的说明中所述的内容相同,填料或骨料的按固形物换算的配合量和本发明的耐火成形体的说明中所述的内容相同。
另外,本发明的不定形耐火组合物可以含有pH调节剂、增粘剂、分散剂、防腐剂等添加物。
作为pH调节剂,可以列举作为pH4标准溶液的邻苯二甲酸盐标准溶液(Sorensen缓冲液)、作为pH7标准溶液的中性磷酸盐标准溶液等的缓冲溶液,作为酸,可以举醋酸、苹果酸、柠檬酸等的果酸等。
缓冲溶液或酸的含量优选为使不定形耐火组合物的pH为3~11的量。
作为增粘材料,可以列举羟乙基纤维素、丙烯酸钠聚合物等,作为分散剂,可以列举羧酸类、多元醇、胺类等,作为防腐剂,可以列举具有氮原子或者硫原子的无机化合物或者有机化合物。
在本发明的无机纤维质不定形耐火组合物中,作为不定形状,可以列举在固形物中混合液体溶剂形成的糊状。
作为形成糊状物的液体溶剂,不特别限定,可以列举水以及极性有机溶剂,作为极性有机溶剂,可以列举乙醇、丙醇等一元醇类;乙二醇等二元醇类。在这些等液体介质中,如果考虑操作环境和环境负担,优选水。另外,作为水不特别限定,可以列举蒸馏水、离子交换水、自来水、地下水、工业用水等。
糊状物的粘度,即,溶剂中固形物浓度可以考虑使用目的或操作性等适当决定。例如,溶剂的含量相对于本发明的无机纤维质不定形耐火组合物的固形物100质量%,优选为20~800质量%,进一步优选为30~500质量%,更进一步优选为40~300质量%。如果上述溶剂含量小于20质量%,由于无机纤维质不定形耐火组合物的流动性降低而导致施工性变差,并且,施工物的机械强度特别是弯曲强度降低。
另外,如果上述溶剂含量超过800质量%,由于无机纤维质不定形耐火组合物的稠度变高,因此施工时糊状的组合物滴落,另外,由于干燥造成接缝等的施工物的收缩变大。
本发明的无机纤维质不定形耐火组合物通过在例如非铁金属铸造装置中,作为排水管、熔融材料保持炉、铁水包等与熔融材料接触的部件的内衬材料中使用的耐火成形体的接缝来使用,通过干燥或者烧成处理可以制成具有任意形状的施工物。该施工物除了在不定形耐火组合物的施工时采用任意的形状施工这点之外,构成材料的组成或物性可以和本发明的耐火成形体视为相同,可以在接缝等的施工物表面上迅速形成金属氧化膜。
本发明的无机纤维质不定形耐火组合物优选在例如铝或镁等非铁金属的铸造装置中,作为构筑排水管、熔融材料保持炉、铁水包等与熔融材料接触的部件的内衬材料的接缝而优选使用。
接下来,对制造本发明的无机纤维质不定形耐火组合物的方法进行说明。
作为本发明的制造不定形耐火组合物的方法,可以列举通过将上述在40℃下溶解于生理盐水的溶解率为1质量%以上的生物可溶性无机纤维、具有针状结晶结构的无机粉末、粘结剂等构成材料与液体溶剂混合来制造的方法。
无机纤维质不定形耐火组合物的构成材料或溶剂的配合量如上面所述。
作为本发明的无机纤维质不定形耐火组合物的优选制造方法,优选向液体溶剂中加入生物可溶性无机纤维、具有针状结晶结构的无机粉末、粘结剂,进一步根据希望添加增粘材料、防腐剂等其它的配合成分的方法。
作为上述构成材料和溶剂的混合方法,可以列举用捏合机或加压捏合机等的混炼装置进行混炼的方法。混炼时间优选为0.1~1.0小时,混炼温度优选为5~40℃。
本发明的无机纤维质不定形耐火组合物即使不含硅酸铝纤维等陶瓷纤维或氧化铝粉末、二氧化硅粉末,也可以在得到的施工物(耐火物)中表现所希望的耐热性,并且降低制造成本以及产品价格。
接下来,列举实施例,进一步具体说明本发明,这些只是示例,并不限定本发明。
(实施例1)
1.浆料的形成工序
如表1所示,相对于由生物可溶性无机纤维(Nichias Corporation制造的“Fine Flex-E”,在40℃下的溶解于生理盐水的溶解率为1质量%以上)81质量%、硅灰石(Hayashi Kasei Co.,Ltd.制造的“NYAD G”,平均长度为660μm,平均粒径为40μm,长宽比为16.5)9质量%、胶体二氧化硅(日产化学株式会社制造的“ST-30”)按二氧化硅换算为5质量%、淀粉4.5质量%、凝聚剂(荒川化学工业株式会社制造的“Polystron 117”)0.5质量%构成的原料100质量份,加入水5000质量份,通过搅拌形成浆料。
2.成形工序
向在底部设置网的成形模具中注入上述浆料,通过吸收浆料中的水进行脱水成形,得到块状的脱水成形物。
接下来,在大气气氛下,通过在105℃的温度下干燥24小时,得到长为900cm、宽为600cm、高为5cm的块状干燥处理物(无机纤维质耐火成形体)。
制作多个上述无机纤维质耐火成形体,在空气气氛下,分别求得分别在800℃下烧成24小时、在1100℃下烧成24小时时的长度方向的收缩率。将上述长度方向的收缩率和所得到的耐火成形体的组成一起示于表1。
(实施例2~实施例5、比较例1)
除了将要得到的耐火成形体的组成按照表1所示进行变换之外,其它都和实施例1同样制作无机纤维质耐火成形体,和实施例1同样求得所得到的耐火成形体的长度方向的收缩率。
另外,对于实施例3及比较例1中得到的无机纤维质耐火成形体,还求得在空气气氛下,在1200℃下烧成24小时时的长度方向的收缩率。
将上述长度方向的收缩率测定结果和得到的无机纤维质耐火成形体的组成一起示于表1中。
[表1]
从表1可知,实施例1~实施例5中得到的无机纤维质耐火成形体在800℃下烧成24小时时的长度方向的收缩率为0~0.36%,并且在1100℃下烧成24小时时的长度方向的收缩率为0.40~1.68%,进一步在实施例3中得到的无机纤维质耐火成形体,在1200℃下烧成24小时时的长度方向的收缩率为0.81%。
相对于此,在比较例1中得到的无机纤维质耐火成形体在800℃下烧成24小时时的长度方向的收缩率为0.53%,并且在1100℃下烧成24小时时的长度方向的收缩率为2.71%,在1200℃下烧成24小时时的长度方向的收缩率为3.42%。
由此结果可知,在实施例1~实施例5中得到的无机纤维质耐火成形体由于含有规定量的生物可溶性无机纤维和硅灰石粉末,因而发挥优异的耐热性。
另外还可知,在实施例1~实施例5中得到的无机纤维质耐火成形体即使不使用高价的氧化铝粉末、二氧化硅粉末也可以发挥优异的耐热性,因此,可以降低制造成本和产品价格。
进一步,在实施例1~实施例5中得到的无机纤维质耐火成形体因为是由含有生物可溶性无机纤维和显示生物可溶性的硅灰石粉末所构成的,因此可知其在生物可溶性方面优异。
产业上的利用可能性
根据本发明,可以提供即使不含氧化铝粉末、二氧化硅粉末也可以表现所希望的耐热性,并且降低制造成本和产品价格,生物可溶性高的无机纤维质耐火成形体。另外,根据本发明,可以提供能够简单制造上述无机纤维质耐火成形体的方法。进一步,根据本发明,可以提供降低制造成本和产品价格的无机纤维质不定形耐火组合物。
Claims (4)
1.一种无机纤维质耐火成形体,其特征在于,
由含有在40℃下溶解于生理盐水的溶解率为1质量%以上的生物可溶性无机纤维27~63质量%、选自硅灰石粉末、海泡石粉末、凹凸棒石粉末中的一种以上的具有针状结晶结构的无机粉末27~63质量%和粘结剂3~18质量%的材料构成,
不使用氧化铝粉末或二氧化硅粉末,
所述生物可溶性无机纤维、所述具有针状结晶结构的无机粉末和所述粘结剂合计含有90质量%以上。
2.如权利要求1所述的无机纤维质耐火成形体,其特征在于,
所述具有针状结晶结构的无机粉末的平均长度为1~3000μm,并且长宽比为2~1000。
3.一种无机纤维质耐火成形体的制造方法,其特征在于,
将浆料进行脱水成形,
所述浆料按固形物换算时含有在40℃下溶解于生理盐水的溶解率为1质量%以上的生物可溶性无机纤维27~63质量%、选自硅灰石粉末、海泡石粉末、凹凸棒石粉末中的一种以上的具有针状结晶结构的无机粉末27~63质量%和粘结剂3~18质量%,
不使用氧化铝粉末或二氧化硅粉末,
所述生物可溶性无机纤维、所述具有针状结晶结构的无机粉末和所述粘结剂合计含有90质量%以上。
4.一种无机纤维质不定形耐火组合物,其特征在于,
由按固形物换算时含有在40℃下溶解于生理盐水的溶解率为1质量%以上的生物可溶性无机纤维27~63质量%、选自硅灰石粉末、海泡石粉末、凹凸棒石粉末中的一种以上的具有针状结晶结构的无机粉末27~63质量%和粘结剂3~18质量%的材料构成,
不使用氧化铝粉末或二氧化硅粉末,
所述生物可溶性无机纤维、所述具有针状结晶结构的无机粉末和所述粘结剂合计含有90质量%以上。
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- 2010-12-24 AU AU2010340533A patent/AU2010340533B2/en not_active Ceased
- 2010-12-24 WO PCT/JP2010/073273 patent/WO2011083696A1/ja active Application Filing
- 2010-12-24 EP EP10842209.8A patent/EP2522646A4/en not_active Withdrawn
- 2010-12-24 CN CN201080060882.0A patent/CN102741196B/zh active Active
- 2010-12-24 US US13/520,938 patent/US9067832B2/en active Active
- 2010-12-24 KR KR1020127017598A patent/KR101429373B1/ko active IP Right Grant
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2014
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CN102741196A (zh) | 2012-10-17 |
US20130225391A1 (en) | 2013-08-29 |
JP2015127295A (ja) | 2015-07-09 |
EP2522646A1 (en) | 2012-11-14 |
KR20120113750A (ko) | 2012-10-15 |
JP5973729B2 (ja) | 2016-08-23 |
EP2522646A4 (en) | 2013-11-13 |
KR101429373B1 (ko) | 2014-08-11 |
AU2010340533B2 (en) | 2014-04-10 |
AU2014203785A1 (en) | 2014-07-31 |
AU2010340533A1 (en) | 2012-07-12 |
US9067832B2 (en) | 2015-06-30 |
JPWO2011083696A1 (ja) | 2013-05-13 |
WO2011083696A1 (ja) | 2011-07-14 |
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