CN102910904A - 一种含氮化物的复合材料及应用该材料的浸入式水口 - Google Patents
一种含氮化物的复合材料及应用该材料的浸入式水口 Download PDFInfo
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Abstract
本发明提供一种含氮化物的复合材料,包括以下组分:电熔稳定氧化锆、氮化物、石墨、硅或碳化硅。本发明还提出应用所述复合材料制备的浸入式水口。本发明采用电熔稳定氧化锆、石墨为主要原料,以及塞隆、阿隆、镁阿隆、氮化硅、氮化硅铁、氮化硼等氮化物中的一种或数种,以树脂为结合剂制备的复合浸入式水口,具有极佳的抗侵蚀性和抗热震稳定性。电熔稳定氧化锆自身就具有优良的抗保护渣侵蚀性能,再引入含氮化合物,利用含氮化合物热膨胀系数低、导热率高、强度高、对钢水和保护渣不润湿等优良特性,大大提高了浸入式水口的抗侵蚀性和抗热震稳定性。
Description
技术领域
本发明属于复合材料领域,具体涉及一种含氧化物、氮化物的复合材料。
背景技术
浸入式水口是钢液从中间包到结晶器的通道,用来保护钢水不与外界空气接触,防止钢水氧化,促进非金属杂质上浮,防止钢水夹带保护渣以及防止结晶器中钢水分流等功能。浸入式水口在使用过程中,由于长时间承受高温钢液的机械冲刷作用,水口壁径的温度梯度产生的热应力作用以及保护渣的化学侵蚀作用,使用条件极为恶劣。浸入式水口在高速连铸生产中起到分流、防止二次氧化、稳定结晶器内钢水流场、提高铸坯质量、防止卷渣及漏钢等多重作用。但是,浸入式水口的使用寿命是影响连铸机作业率的关键环节之一。虽然在渣线部位添加了ZrO2复合材料,但是其耐侵蚀性能还未达到连铸生产的要求标准。
浸入式水口在使用过程中由于长时间的受到钢水的侵蚀和冲刷,很容易产生扩径,特别是渣线部分,外面是保护渣的化学侵蚀,里面是钢水的侵蚀和冲刷,常常会侵蚀断,而影响连铸作业,给钢厂造成很大的影响。浸入式水口的渣线部位采用的材质一般为锆碳材料,即以稳定氧化锆、石墨为主要原料,再加入少量抗氧化剂,为了提高抗侵蚀性,一般采用增加氧化锆含量、降低石墨含量,这虽然能提高抗侵蚀性,但由于降低了石墨含量,抗热震性又存在问题,往往容易炸裂。
发明内容
针对现有技术的不足之处,本发明的目的是提出一种用于浸入式水口渣线的含氮化物的复合材料,能够耐化学腐蚀、钢水的侵蚀,具有抗热震性。
本发明的另一目的是提出所述复合材料的应用。
本发明的第三个目的是提出应用所述复合材料的浸入式水口,以及该浸入式水口的制备方法。
实现本发明上述目的的具体技术方案为:
一种含氮化物的复合材料,包括以下重量份的组分:
其中,所述电熔稳定氧化锆中氧化锆质量含量为92-97%;所述电熔稳定氧化锆中立方氧化锆相占70-85%。
所述石墨为鳞片石墨。其主要应用于复合材料、陶瓷色料、陶瓷制品、磨料及金属锆等领域。鳞片石墨:天然晶质石墨,其形似鱼磷状,属六方晶系,呈层状结构,具有良好的耐高温、导电、导热、润滑、可塑及耐酸碱等性能。本发明所述的石墨的含碳量为98-99%。
所述硅为金属硅粉。金属硅粉就是粉末状的单质硅,是将硅块研磨成粉末。按严格的化学元素分类,硅其实不是金属,是非金属。但硅有很多性质接近金属,硅块在外观上也有金属的光泽,很象金属。所以工业上常常称为金属硅。
其中,所述氮化物为塞隆(Si-Al-O-N)、阿隆(Al-O-N,氧氮化铝)、镁阿隆(MgAlON,化学式为Al23O27N5)、氮化硅、氮化硅铁、氮化硼中的一种或多种。塞隆是Si、Al、O、N四种元素的合成词,是Si3N4中Si、N原子被Al和O原子置换所形成的固溶体。
所述复合材料通过以下方法制备:将电熔稳定氧化锆、含氮化合物、石墨、硅或碳化硅按比例混合,加入重量份8-14份的结合剂,造粒混炼而得。所述造粒混炼是在造粒设备中,加热控制被处理物料的温度,造粒时按照低速(80-100r/min)5-10分钟,中速(400-600r/min)3-7分钟,高速(800-1000r/min)5-15分钟造粒,造粒设备中的物料温度控制在40-65℃之间。
其中,所述结合剂为酚醛树脂或环氧树脂。
应用本发明所述的复合材料制备的浸入式水口。
本发明所述的浸入式水口,包括本体和渣线,所述渣线为所述含氮化物的复合材料制备。
其中,所述本体为铝碳材料制备。铝碳材料为本领域常规耐高温材料,其是以刚玉、石墨、锆莫来石、熔融石英以及硅粉、碳化硅粉为原料,以酚醛树脂为结合剂经过造粒混炼而成的复合材料。
制备所述的浸入式水口的方法,其是将电熔稳定氧化锆、氮化物、石墨、硅或碳化硅、结合剂按比例混合,造粒混炼、干燥后,与本体复合,成型,在900-1100℃下焙烧。焙烧的时间为20-30h。
所述成型是等静压成型。等静压成型是将待压试样置于高压容器中,利用液体介质不可压缩的性质和均匀传递压力的性质从各个方向对试样进行均匀加压,当液体介质通过压力泵注入压力容器时,根据流体力学原理,其压强大小不变且均匀地传递到各个方向。此时高压容器中的粉料在各个方向上受到的压力是均匀的和大小一致的。通过上述方法使瘠性粉料成型为致密坯体的方法称为等静压法。本发明的方法中,等静压成型压力为80-125MPa。
其中,所述焙烧是在非氧化气氛中焙烧。非氧化气氛可以通过通入惰性气体的方法得到,也可以通过密闭焙烧,消耗尽密闭空间的氧气的方法得到。
本发明的有益效果在于:
本发明采用电熔稳定氧化锆、石墨为主要原料,以及塞隆、阿隆、镁阿隆、氮化硅、氮化硅铁、氮化硼含氮化物中的一种或数种,树脂为结合剂制备的整体复合浸入式水口,具有极佳的抗侵蚀性和抗热震稳定性。电熔稳定氧化锆自身就具有优良的抗保护渣侵蚀性能,再引入含氮化合物,利用含氮化合物热膨胀系数低、导热率高、强度高、对钢水和保护渣不润湿等优良特性,大大提高了浸入式水口的抗侵蚀性和抗热震稳定性。
具体实施方式
现以以下最佳实施例来说明本发明,但不用来限制本发明的范围。实施例中,如无特殊说明,所使用的设备和方法均为所属领域常规的设备和方法。
本发明的实施例中,塞隆购自唐山六方碳化硅有限公司,粒度0.074mm;阿隆购自武汉科技大学,AlON的摩尔分数为35.7%,粒度0.074mm;石墨购自青岛天盛石墨有限公司,599#、899#。电熔稳定氧化锆购自振中电熔锆业有限公司。
实施例1
渣线材料:电熔稳定氧化锆80%(振中电熔锆业有限公司,其中氧化锆质量含量为92-97%,该含量范围内的电熔稳定氧化锆均能得到同样技术效果的复合材料),石墨5%,塞隆12%(购自唐山六方碳化硅有限公司,其中N为14-30%质量比例,该含量范围内的塞隆均可达到同样技术效果),金属硅粉3%,外加酚醛树脂10%(均为质量比)。石墨为含碳量99%的鳞片石墨。
造粒混炼的过程在造粒机中进行,控制造粒时按照80r/min低速8分钟,500r/min中速5分钟,800r/min高速10分钟造粒,造粒设备中的物料温度控制为55℃。经造粒混炼、干燥后与铝碳材料的本体用模具复合成型,用等静压成型后(成型压力85MPa),密闭,于900℃的温度下20h烧成,制成浸入式水口。该浸入式水口在某钢厂使用15炉,使用10小时,没有出现炸裂、扩径、蚀断等现象,满足了客户使用要求。
实施例2
渣线材料:电熔稳定氧化锆65%,石墨12%,塞隆20%,金属硅粉3%,外加酚醛树脂10%。石墨为含碳量98%的鳞片石墨。
造粒混炼的过程在造粒机中进行,控制造粒时按照100r/min低速8分钟,550r/min中速5分钟,800r/min高速12分钟造粒,造粒设备中的物料温度控制在40℃。经造粒混炼、干燥后与铝碳质本体复合,用等静压成型后(成型压力100MPa),密闭,在非氧化气氛下于1100℃的温度下经过25h烧成,制成的浸入式水口在某钢厂使用16炉,使用12小时,没有出现炸裂、扩径、蚀断等现象,满足客户使用要求。
实施例3
渣线材料:电熔稳定氧化锆70%,石墨20%,塞隆5%,阿隆3%,碳化硅粉2%,外加酚醛树脂14%。石墨为含碳量99.5%的鳞片石墨。
造粒混炼的过程在造粒机中进行,控制造粒时按照80r/min低速8分钟,600r/min中速5分钟,1000r/min高速15分钟造粒,造粒设备中的物料温度控制在65℃。经造粒混炼、干燥后与铝碳质本体复合,用等静压成型后(成型压力80MPa),密闭,在非氧化气氛下于1000℃的温度下经过30h烧成,制成的浸入式水口在某钢厂使用20炉,使用8小时,没有出现炸裂、扩径、蚀断等现象,满足客户使用要求。
实施例4
渣线材料:电熔稳定氧化锆75%,石墨10%,氮化硅+塞隆13%其中氮化硅5%、塞隆8%,金属硅粉1%,碳化硅粉1%,外加酚醛树脂12%。石墨为含碳量99%的鳞片石墨。造粒混炼方法同实施例1。经造粒混炼、干燥后与铝碳质本体复合,用等静压成型(成型压力125MPa)后,密闭,在非氧化气氛下于900℃的温度下28h烧成,制成的浸入式水口在某钢厂使用20炉,使用8小时,没有出现炸裂、扩径、蚀断等现象,满足了客户使用要求。
实施例5
渣线材料:电熔稳定氧化锆78%,石墨10%,氮化硼10%,金属硅粉2%,外加酚醛树脂10%。造粒混炼方法同实施例2。经造粒混炼、干燥后与铝碳材料的本体复合,用等静压成型后(成型压力90MPa),在非氧化气氛下于1050℃的温度下烧成,制成的浸入式水口在某钢厂使用10炉,使用9小时,没有出现炸裂、扩径、蚀断等现象,满足客户使用要求。
实施例6
渣线材料:电熔稳定氧化锆75%,石墨8%,氮化硅铁+阿隆15%其中氮化硅铁8%、阿隆7%,金属硅粉2%,外加酚醛树脂8%。造粒混炼方法同实施例3。经造粒混炼、干燥后与铝碳质本体复合,用等静压成型(成型压力85MPa)后,在非氧化气氛下于1000℃的温度下烧成,制成的浸入式水口在某钢厂使用35炉,使用12小时,没有出现炸裂、扩径、蚀断等现象,满足了客户使用要求。
以上的实施例仅仅是对本发明的优选实施方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通工程技术人员对本发明的技术方案作出的各种变型和改进,均应落入本发明的权利要求书确定的保护范围内。
Claims (10)
2.如权利要求1所述的复合材料,其特征在于,所述电熔稳定氧化锆中氧化锆质量含量为92-97%;所述石墨为鳞片石墨,所述硅为金属硅粉。
3.如权利要求1所述的复合材料,其特征在于,所述氮化物为塞隆、阿隆、镁阿隆、氮化硅、氮化硅铁、氮化硼中的一种或多种。
4.如权利要求1-3任一所述的复合材料,其特征在于,所述复合材料是通过以下方法制备:将电熔稳定氧化锆、氮化物、石墨、硅或碳化硅按比例混合,加入8-14份结合剂,经过造粒混炼而得。
5.如权利要求4所述的复合材料,其特征在于,所述结合剂为酚醛树脂或环氧树脂。
6.应用权利要求1-5任一所述的复合材料的浸入式水口。
7.如权利要求6所述的浸入式水口,包括本体和渣线,其特征在于,所述渣线为所述含氮化物的复合材料制备。
8.如权利要求4所述的浸入式水口,其特征在于,所述本体为铝碳材料制备。
9.权利要求6-8任一所述的浸入式水口的制备方法,其特征在于,是将电熔氧化锆、含氮化合物、石墨、硅或碳化硅按比例混合,加入结合剂,造粒混炼,干燥后,与本体复合,成型,在900-1100℃下焙烧。
10.如权利要求9所述的制备方法,其特征在于,所述成型是等静压成型,所述焙烧是在非氧化气氛中焙烧,焙烧的时间为20-30h。
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