氧(yang)化锆(gao)制品(zirconia products)
以纯度大于99%的(de)氧化锆(ZrO2)为原料(liao),用高温陶瓷(ci)工艺方(fang)法或其他特殊工艺方(fang)法制(zhi)成的氧(yang)化物(wu)耐火(huo)材料(liao)。
性能氧化(hua)锆熔点2700℃,莫氏硬度7,有两种变体,1000℃以下为单斜(xie)晶系(密度5.68g/cm3),1000℃时生成(cheng)四方晶系(密(mi)度6.10g/cm3),此晶型转(zhuan)变为可(ke)逆转(zhuan)变,冷却过程中(zhong)晶型转(zhuan)化时(shi)伴有7%的体积膨胀,可(ke)导致制品(pin)开(kai)裂。加入(ru)稳(wen)定剂与Zr02生成立(li)方晶系(xi)固溶(rong)体,可消除由上述晶型(xing)转化(hua)带来的(de)体积膨胀(zhang)。氧(yang)化(hua)锆热(re)导率低(1000℃,2.09W/(m•K)),线膨(peng)胀系数大(25~1500℃ 9.4×10-6/℃),高温(wen)结构强度高,1000℃时(shi)(shi)耐(nai)压(ya)强度可达1200~1400MPa。导电性好,具有(you)负(fu)的电阻温(wen)度系数,电阻率1000℃时(shi)(shi)104Ω•cm,1700℃时6~7Ω•cm。化学稳定性好,2000℃以下对多种(zhong)熔融金(jin)属、硅(gui)酸盐、玻璃等不起作(zuo)用(yong)。苛性碱、碳酸盐和各种(zhong)酸(浓硫酸和氢氟酸除外)的溶液与氧化锆(gao)不起作(zuo)用(yong)。
工(gong)艺氧(yang)化(hua)锆制品生产工(gong)艺包(bao)括:原料预(yu)处理、制粉、成型、烧结等工(gong)序。(1)原料预处理。氧化锆(gao)原料必(bi)须进行稳定(ding)化预处理,通常采用的(de)方法(fa)为固相合成法(fa),即(ji)将氧化锆(gao)原料加入一定(ding)比例的(de)稳定(ding)剂(如(ru)CaO、MgO、Y203、Ce02等),在(zai)(zai)(zai)(zai)(zai)球(qiu)磨(mo)(mo)机中(zhong)湿(shi)磨(mo)(mo)到小于(yu)2um的(de)细(xi)粉(fen),经干燥、打粉(fen),制(zhi)成(cheng)(cheng)团块,在(zai)(zai)(zai)(zai)(zai)1700℃下煅烧(shao)(shao),使(shi)之形成(cheng)(cheng)稳(wen)定型(xing)(xing)或半稳(wen)定型(xing)(xing)氧(yang)化锆。预处(chu)理的(de)方(fang)法(fa)(fa)(fa)还有(you)常温(wen)或高温(wen)水解法(fa)(fa)(fa)、金属有(you)机化合物(wu)水解法(fa)(fa)(fa)、喷雾热(re)分(fen)解法(fa)(fa)(fa)和溶(rong)胶、凝胶法(fa)(fa)(fa)等(deng)。(2)制(zhi)粉(fen)。将(jiang)(jiang)稳(wen)定化处(chu)理后(hou)的(de)原(yuan)料(liao)(liao)破(po)碎、细(xi)磨(mo)(mo)至(zhi)90%以上颗(ke)粒小于(yu)5um,其中(zhong)60%~70%小于(yu)2um。(3)成(cheng)(cheng)型(xing)(xing)。成(cheng)(cheng)型(xing)(xing)方(fang)法(fa)(fa)(fa)可(ke)采用(yong)(yong)(yong)(yong)泥浆(jiang)浇(jiao)(jiao)注(zhu)法(fa)(fa)(fa)、机压(ya)(ya)法(fa)(fa)(fa)、热(re)压(ya)(ya)注(zhu)法(fa)(fa)(fa)或热(re)等(deng)静(jing)压(ya)(ya)法(fa)(fa)(fa)。泥浆(jiang)浇(jiao)(jiao)注(zhu)法(fa)(fa)(fa)是(shi)将(jiang)(jiang)细(xi)磨(mo)(mo)后(hou)的(de)原(yuan)料(liao)(liao)用(yong)(yong)(yong)(yong)浓度为(wei)10%的(de)盐(yan)酸(suan)处(chu)理48h后(hou),用(yong)(yong)(yong)(yong)蒸馏水清(qing)洗(xi)至(zhi)pH=6~7,再(zai)经脱水、干燥,配成(cheng)(cheng)中(zhong)性(xing)泥浆(jiang)浇(jiao)(jiao)注(zhu)料(liao)(liao),在(zai)(zai)(zai)(zai)(zai)石(shi)膏模(mo)(mo)中(zhong)浇(jiao)(jiao)注(zhu)成(cheng)(cheng)型(xing)(xing);也可(ke)采用(yong)(yong)(yong)(yong)pH值为(wei)2的(de)酸(suan)性(xing)泥浆(jiang)浇(jiao)(jiao)注(zhu)。机压(ya)(ya)法(fa)(fa)(fa)是(shi)将(jiang)(jiang)一(yi)(yi)定比(bi)例(li)的(de)颗(ke)粒料(liao)(liao)和细(xi)磨(mo)(mo)料(liao)(liao)(一(yi)(yi)般(ban)颗(ke)粒料(liao)(liao)与细(xi)磨(mo)(mo)料(liao)(liao)比(bi)例(li)为(wei)60%~70%比(bi)40%~30%)混合,加入结(jie)合剂(ji)(如磷酸(suan)、糊精、羧(suo)甲基纤维素等(deng)),制(zhi)成(cheng)(cheng)坯(pi)料(liao)(liao),在(zai)(zai)(zai)(zai)(zai)金属模(mo)(mo)具内用(yong)(yong)(yong)(yong)压(ya)(ya)力(li)机成(cheng)(cheng)型(xing)(xing),压(ya)(ya)力(li)一(yi)(yi)般(ban)为(wei)80~100MPa,或在(zai)(zai)(zai)(zai)(zai)弹性(xing)模(mo)(mo)套内用(yong)(yong)(yong)(yong)等(deng)静(jing)压(ya)(ya)机成(cheng)(cheng)型(xing)(xing),压(ya)(ya)力(li)一(yi)(yi)般(ban)为(wei)100~250MPa。热(re)压(ya)(ya)注(zhu)法(fa)(fa)(fa)是(shi)将(jiang)(jiang)细(xi)粉(fen)与热(re)塑剂(ji)(石(shi)蜡(la)和油酸(suan))充分(fen)搅拌均匀后(hou),在(zai)(zai)(zai)(zai)(zai)热(re)压(ya)(ya)注(zhu)机上成(cheng)(cheng)型(xing)(xing),成(cheng)(cheng)型(xing)(xing)后(hou)的(de)坯(pi)体需(xu)在(zai)(zai)(zai)(zai)(zai)高温(wen)(1100℃左右)脱去石(shi)蜡(la)等(deng)有(you)机物(wu)。热(re)压(ya)(ya)法(fa)(fa)(fa)是(shi)将(jiang)(jiang)细(xi)粉(fen)装入石(shi)墨模(mo)(mo)具内,在(zai)(zai)(zai)(zai)(zai)热(re)压(ya)(ya)机上同时加热(re)加压(ya)(ya),一(yi)(yi)般(ban)压(ya)(ya)力(li)为(wei)20~50MPa,最(zui)终温(wen)度1400~1800℃。(4)烧(shao)(shao)结(jie)。干燥后(hou)的(de)坯(pi)体可(ke)在(zai)(zai)(zai)(zai)(zai)中(zhong)性(xing)或氧(yang)化气(qi)氛下烧(shao)(shao)结(jie),烧(shao)(shao)结(jie)温(wen)度一(yi)(yi)般(ban)为(wei)1800~1950℃。
用(yong)途氧化锆坩埚用(yong)于(yu)熔炼(lian)铂、铑、铱等(deng)贵重金属及合金。氧化锆砖用(yong)于(yu)2000℃以上(shang)的(de)高(gao)温(wen)炉衬。氧(yang)(yang)(yang)化(hua)(hua)锆(gao)(gao)棒(bang)体可(ke)作为(wei)发热元件,用(yong)于氧(yang)(yang)(yang)化(hua)(hua)气氛下(xia)2000~2200℃的(de)高(gao)温(wen)炉。氧(yang)(yang)(yang)化(hua)(hua)锆(gao)(gao)固体电(dian)解质(zhi)可(ke)作为(wei)快速测(ce)定钢液、铜液及(ji)炉气中氧(yang)(yang)(yang)含(han)量(liang)的(de)测(ce)氧(yang)(yang)(yang)探头及(ji)高(gao)温(wen)燃(ran)料(liao)电(dian)池的(de)隔膜等(deng)。利用(yong)氧(yang)(yang)(yang)化(hua)(hua)锆(gao)(gao)的(de)马(ma)氏(shi)体相(xiang)变,将氧(yang)(yang)(yang)化(hua)(hua)锆(gao)(gao)引入氧(yang)(yang)(yang)化(hua)(hua)物和(he)非氧(yang)(yang)(yang)化(hua)(hua)物陶瓷中,可(ke)作为(wei)增韧剂,以改(gai)善陶瓷的(de)脆(cui)性,如氧(yang)(yang)(yang)化(hua)(hua)锆(gao)(gao)增韧氧(yang)(yang)(yang)化(hua)(hua)铝、氮化(hua)(hua)硅(gui)等(deng)。
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