CN101952220B - 难熔炉渣带 - Google Patents

难熔炉渣带 Download PDF

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CN101952220B
CN101952220B CN2009801055579A CN200980105557A CN101952220B CN 101952220 B CN101952220 B CN 101952220B CN 2009801055579 A CN2009801055579 A CN 2009801055579A CN 200980105557 A CN200980105557 A CN 200980105557A CN 101952220 B CN101952220 B CN 101952220B
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诺尔曼·爱德华·罗杰斯
大卫·肯尼迪
大卫·米勒德
杨时标
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Abstract

本发明在于用作冷启动炉渣带的难熔化合物。该化合物包括部分稳定氧化锆和/或全稳定氧化锆和单斜晶氧化锆的混合物,特征在于,以重量计,单斜晶相对于总氧化锆含量所占的比例至少为40%。本发明还在于由该化合物形成的炉渣带、结合该炉渣带的浸入式水口和形成这种浸入式水口的方法。

Description

难熔炉渣带
技术领域
本发明涉及用在金属浇铸工艺中的难熔带(refractory band),特别地涉及用于应用于在制造钢铁的连续铸造工艺中接触炉渣的耐火材料体(refractory body)的难熔带(通常称为“炉渣带”)。
背景技术
在连续铸造炼钢工艺中,钢水从钢包经由钢包长水口注入熟知为中间包的大容器中。中间包具有一个或多个出口,钢水通过所述出口从中间包流入一个或多个对应的铸模中。钢水冷却,在铸模中形成固体表层,并最终形成金属人连续固体连铸流。浸入式水口或铸口位于中间包和每个铸模之间,以控制从中间包流向铸模的钢水的流动特性,并防止空气进入。流入每个铸模中的钢水的速率通常由塞铁芯控制,塞铁芯位于中间包中,并且可以通过提升装置垂直移入和移出浸入式水口的入口。
诸如钢包长水口、浸入式水口和塞铁芯的多种耐火材料体具有与在熔融金属顶部沉淀的炉渣层频繁接触的区域。炉渣是高度腐蚀性的,因此所有的上述装置在浸入或部分浸入熔融金属中相对短的时间周期之后都处于受腐蚀的危险,除非以一些方式保护免受炉渣腐蚀特性的影响。
该问题的常用解决方案是在耐火材料体在使用中可能接触炉渣的区域中提供“炉渣带”,即耐磨材料区。一种这种材料是碳结合氧化锆-石墨。然而,它的使用受阻于下述事实,即氧化锆为多晶,在室温中以单斜晶形存在,在1170℃改变为四面体结构,在约2300℃改变为立方型。单斜晶到四面体的改变伴随约5%的可逆体积变化(收缩)(参见图1),这导致晶粒破裂,因此导致难熔体出现故障。通过添加受控量的各种立方氧化物,如氧化钙、氧化镁和氧化钇,已经在一定程度上减轻了这种不期望的体积变化。这些稳定氧化物形成具有氧化锆的固溶体,并产生作为立方体和单斜晶氧化锆混合物的结构,即“部分稳定氧化锆”(PSZ)。PSZ用在炉渣带中,因为认为它展现出了热膨胀和抗热震性的最佳均衡。
与用于炉渣带的PSZ的使用相关的缺点是,该材料的高热膨胀系数(10×10-6/℃)使得在难熔体可以用于液态钢流之前预热该难熔体成为必要。预热温度通常在900℃至1400℃的范围内,预热时间通常在1至8小时之间。这明显是不希望的,因为它增加了工艺成本,并且如果由于任何原因必须停止铸造工艺,则引起长时间的停工期。钢铁制造商对浸入式水口/长水口要求来自炉渣带的冷启动能力,特别是在诸如当连铸流由于启动失败而漏失的紧急情况中。为了在这种情况中维持钢铁的铸造,在保持备用的连铸流上使用非预热管。这些冷启动管可以设置有炉渣带,该炉渣带制造为用碳化硅代替约10%的氧化锆,并且该管被脱碳。然而,虽然碳化硅的低热膨胀性使冷启动具有足够的抗热震性,但碳化硅在铸模炉渣中是可溶的。因此,这种使用仅仅用作临时措施,因为严重损害了该管的耐腐蚀性。
发明内容
本发明的目标是提供一种改善的难熔带,特别是冷启动炉渣带,其克服了或至少减轻了前述问题。
因此,本发明的第一方面提供了一种用作冷启动炉渣带的难熔化合物,包括部分稳定氧化锆和/或全稳定氧化锆和单斜晶氧化锆的混合物,其中以重量计,单斜晶相对于总氧化锆含量所占的比例至少为40%。
本发明的第二方面提供了一种难熔冷启动炉渣带,包括部分稳定氧化锆和/或全稳定氧化锆和单斜晶氧化锆的混合物,其中以重量计,单斜晶相对于总氧化锆含量所占的比例至少为40%。
发明人意外发现,将部分稳定氧化锆(PSZ)或全稳定氧化锆(FSZ)与单斜晶氧化锆混合产生了比仅采用PSZ或FSZ实现的热膨胀低很多的总热膨胀,因此使得难熔带能够从冷启动开始使用,同时保持耐久性。虽然发明人不希望束缚于理论,但相信,各种类型的氧化锆在带加热期间在PSZ/FSZ的热膨胀和单斜晶氧化锆的收缩之间产生了平衡效应。
以重量计,单斜晶氧化锆可以包括至少50%或约57%的总氧化锆含量。在其它实施方式中,以重量计,单斜晶氧化锆可以包括至少70%的总氧化锆含量。
在一些实施方式中,以重量计,单斜晶氧化锆相对于总氧化锆含量的最大量可以为80%(特别是在剩余的氧化锆为FSZ时)。在其它实施方式中,以重量计,相对于总氧化锆含量的单斜晶氧化锆含量可以在65%至90%的范围内(特别是在剩余的氧化锆为FSZ时)。
在其它实施方式中,特别是在剩余的氧化锆为PSZ时,以重量计,单斜晶氧化锆的量可以在65%至80%的范围内。
在该混合物中可以提供任何合适粒径的PSZ/FSZ和单斜晶氧化锆,PSZ/FSZ的粒径可以与单斜晶的粒径相同或不同。然而,在一些实施方式中,单斜晶的最大粒径等于或小于1mm,并且在其它实施方式中为从0.25至0.5mm。
用在本发明中的PSZ和FSZ可以通过熔化具有受控量的各种氧化物(如氧化钙、氧化镁和氧化钇,更优选为氧化钙)的氧化锆而形成。将会理解,对应给定的掺杂剂,如氧化钙,无论PSZ或FSZ都根据添加的掺杂剂的水平简单地形成。
除了氧化锆之外,其它合适的成本可以包括在该化合物或炉渣带中,更特别地为石墨。在一些实施方式中,以重量计,该化合物或炉渣带的至少50%包括PSZ/FSZ和单斜晶氧化锆的混合物,并且在一些实施方式中至少为75%。
氧化锆混合物可以由碳基结合料粘合。该结合料可以包括该化合物重量的至少2%,或至少3%。在一些实施方式中,以重量计,该结合料可以包括不大于10%或不大于6%的总化合物。在其它实施方式中,该结合料可以包括该化合物重量的4%。
根据第三方面,本发明在于结合第二方面的冷启动炉渣带的难熔物件。
难熔带可以与难熔物件一体地形成,难熔物件要求与炉渣隔离。该物件例如可以为钢包长水口、塞铁芯或浸入式水口/长水口,且优选为浸入式水口。在一些实施方式中,该带与耐火材料体共同压制,该耐火材料体由任何合适的惰性耐热材料组成,如陶瓷材料。可替换地,该带可以与难熔物件分开形成,并且随后连接到难熔物件上。例如,该带可以为环形套筒形式,用于围绕在使用中接触炉渣的区域中的物件连接。在一些实施方式中,套筒的内部尺寸对应于耐火材料体的外部尺寸,套筒围绕该耐火材料体放置,以形成防护障,延长物件的寿命。
该带应当足够厚,以在难熔物件使用寿命期间防护难熔物件免受炉渣的腐蚀效应影响。将会认识到,难熔带的宽度将取决于难熔物件与炉渣接触的长度。典型地,难熔带具有约20cm的宽度。在一些实施方式中,过渡层设置在难熔带和难熔物件之间,该过渡层由抑制热膨胀的材料组成,以解决带和物件之间的热膨胀差异问题。
根据本发明的第四方面,提供了一种形成浸入式水口的方法,包括用难熔材料共同均衡地挤压根据本发明的第一方面的难熔化合物,以形成结合冷启动炉渣带的浸入式水口。
附图说明
为了更好地理解本发明,并且为了更清楚地示出如何可以实现它,将仅以举例的方式参照附图,在附图中:
图1为图示各种形式的氧化锆的热膨胀的图示;
图2为用于结合根据本发明的多种耐火材料体的熔融金属的连续铸造的设备的示意图;
图3为试样的横截面图;
图4图示了热膨胀,用于阐述本发明;以及
图5为根据本发明的浸入式水口的横截面图。
具体实施方式
附图中的图2示意性地图示了用于钢水的连续铸造的设备的零件。钢铁在熔炉(未示出)中熔化,并输送至钢包2。钢水S从钢包浇铸进入通称为中间包的大容器4中。大致管状的钢包长水口6在顶端连接至钢包的出口,并在其底端延伸到中间包(处于稳态铸造条件)中的金属表面之下。中间包4具有至少一个出口8,其经由浸入式水口12将钢水从中间包4传递至水冷铸模10。可往复移动的塞铁芯14设置在中间包4中,用于调整熔融金属流出中间包4进入浸入式水口12的流量。
一旦传递至铸模10,则钢铁的邻近铸模表面的表面开始固化,连铸流经由一系列轧辊14弯曲,以形成为水平钢锭。固态钢随后由气焊焊炬15切割成段。为了简化,已经从示意图中省略了钢铁铸造领域中标准的其它部件,如闸式阀、中间包设备和水冷喷射器。
从图2明显可以看出的是,钢包长水口6、塞铁芯14和浸入式水口12都与熔融金属接触。这些耐火材料体的大多处于危险的区域是与形成在熔融金属顶部的高腐蚀性炉渣20层接触的区域。除非由阻挡层进行合适地防护,耐火材料体将在接触炉渣20的区域中快速腐蚀,由此降低它们的工作寿命,因此难熔炉渣带30围绕在位于与炉渣20接触的区域中的每个耐火材料体6、12、14设置。
图2示出了接触钢水的耐火材料体6、12、14中的每一个上的难熔带30,但将会理解的是,根据本发明,这不是需要的情况,或者至少每个难熔带30没有必要是这种情况。而且,设想的是本发明的难熔带可以用来防护其它物体免受炉渣腐蚀效应的影响。
实施例
以下述方式由下面的表1中列出的配方制备试样。熔融耐火氧化物,即部分稳定氧化锆(16mol%氧化钙掺杂剂)或全稳定氧化锆和单斜晶氧化锆在Eirich混合器中与石墨片干混和3分钟,之后添加液态酚醛树脂。这种混合继续进行15分钟,之后混合的材料冷却至室温,并以振动方式填充到铸模中,之后将它均衡地压至一定的形状。
适合热冲击试验的形状在图3中示出。基本上试样40为由具有向外扩展的上端44的管状导管42构成的简化喷嘴。共同压入试样的下部区域中是炉渣带46。试样以通常方式由标准氧化铝配方(而不是炉渣带本身)制备。
压制的试样首先固化至约200℃,随后在还原空气中干燥至900℃。各种配方的测试包括将每种配方的10个试样经受下述条件。试样悬挂在砂箱中,它们的底端突出。随后用涂覆有酚醛树脂的砂子填充砂箱,以在室温中硬化。当砂子已经充分硬化到支撑试样时,试样的突出端浸入1550℃的液态钢中(至炉渣带的近似中点)10分钟。随后视觉地检查试样,检查氧化锆-石墨炉渣带中出现的任何热冲击破裂。
表1
Figure BPA00001205365000061
1以wt%给出定量
2粒度<0.50mm
在10个被测试的试样中,具有实施例2的配方的所有试样都通过了,且未展现出由于热冲击引起的破裂。通过对比,根据比较例1配制的试样中的7个由于热冲击而破裂了,因此测试失败。
图4示出了根据实施例2配制的样品的热膨胀与温度(温度上升)的曲线。热膨胀采用膨胀计(Model DIL402PC,Netzsch Geratebau GmbH)测量。如可以看到的那样,与由单斜晶氧化锆展现的大的收缩或由PSZ和FSZ展现的连续的相对大的膨胀(图1)形成对比,实施例2的配方在高达约900℃温度仍展现出稳定的膨胀,之后基本上观察不到进一步的膨胀。
图5示出了结合根据实施例2配制的炉渣带的浸入式水口(SEN)。SEN50类似于试样40,为大致管状导管52,在其上端具有凸缘54。SEN在其底端56封闭,但设置有两个径向端口58。炉渣带60通常位于SEN 50的两端之间。在使用中,SEN 50经由凸缘54例如夹紧至中间包的内水口,不需要预热。钢水流过导管52,并经由两个径向端口58引出到铸模中。

Claims (4)

1.一种难熔冷启动炉渣带,包括部分稳定氧化锆和/或全稳定氧化锆、单斜晶氧化锆和石墨的混合物,特征在于,以重量计,单斜晶氧化锆相对于总氧化锆含量所占的比例至少为50%,炉渣带重量的至少50%包括PSZ/FSZ和单斜晶氧化锆的混合物。
2.根据权利要求1所述的难熔冷启动炉渣带,其中,炉渣带包括FSZ,以重量计,相对于总氧化锆含量的单斜晶氧化锆含量不大于85%。
3.根据前述权利要求中任一项所述的难熔冷启动炉渣带,其中,炉渣带包括PSZ,以重量计,相对于总氧化锆含量的单斜晶氧化锆含量不大于65%。
4.根据前述权利要求中任一项所述的难熔冷启动炉渣带,其中,单斜晶氧化锆的粒径为从0.25mm至0.5mm。
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