CN1153749C - 由锆石和氧化锆制造的烧结材料及其制造方法 - Google Patents

由锆石和氧化锆制造的烧结材料及其制造方法 Download PDF

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CN1153749C
CN1153749C CNB991052420A CN99105242A CN1153749C CN 1153749 C CN1153749 C CN 1153749C CN B991052420 A CNB991052420 A CN B991052420A CN 99105242 A CN99105242 A CN 99105242A CN 1153749 C CN1153749 C CN 1153749C
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J��M��L�������˹
J·M·L·圭戈尼斯
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E·T·G·乔治
C·N·麦克盖芮
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Abstract

本发明涉及新烧结材料,其特征在于从含5至40%锆石的原料制造该材料,其化学分析结果%(重量)为ZrO2+HfO2:82-96,SiO2:1.7-14,TiO2:0.2-3,Y2O3:0.4-5,Al2O3:0.2-2.5,其它<1。

Description

由锆石和氧化锆制造的烧结材料及其制造方法
本发明涉及由锆石和氧化锆制造的新烧结材料。
最初,以锆石和氧化锆制造的烧结产品由于其抗腐蚀行为不足以直接用于与玻璃接触,则主要用于玻璃制造工艺炉底的底层。
该产品日益倾向于被用于与玻璃接触;其原因在于其抗腐蚀行为虽低于以氧化铬为主要成分的产品但却不会将玻璃染色。
出让给CORHART REFRACTORIES CORPORATION公司的专利US5124287描述由于抗热冲击得到改进致密的及更易于使用与玻璃接触的以锆石为主要成分的产品。该产品主要由锆石和少量氧化锆和二氧化钛的添加物构成。发明人指出加入到组合物中的氧化锆含量达5至25%。实施例显示对于含高于25%氧化锆的产品当进行大块整体焙烧时会观察到出现裂纹并且甚至对于一块低于10公斤的小块整体焙烧也是如此。该专利明确指出若存在其它的化合物,如果想要保持该产品抗腐蚀水平与主要由致密锆石构成的产品的抗腐蚀水平相同,其应优选为低于2%(重量)。发明人也指出氧化锆百分比过高会招致高成本以及结石的倾向。另外,需明确指出优选使用单斜晶的氧化锆并因此避免如氧化钇稳定剂的存在。
CORHART公司目前商品化了在上述专利中描述的产物并取名为ZS-1300;该产品正主要地用于底部多电极电炉底。
从锆石和氧化锆出发制造的其它产品在文献中有所描述。它们中大多数被指定用于与熔融金属接触。对于此类应用诸种制约因素与在玻璃厂遇到的不同。事实上,冶金工业中耐火材料块的使用温度与在玻璃厂遇到的温度不同。此外,在冶金工业中使用如氧化镁或氧化钙作为氧化锆的稳定剂无特别的问题。相反地,在玻璃厂当耐火材料块与由玻璃蒸发出的蒸气(如在玻璃流动管道场合中)相接触时该稳定剂是不适合的。因为,该蒸气损害耐火材料块并且形成裂纹。这样能导致产品风化并且因此在玻璃中结石,即缺陷的同义词。而在玻璃中出现的所有缺陷,更具体地说在用于增强玻璃纤维的玻璃中所有缺陷均可造成严重阻碍。
在玻璃厂目前需要一种抗腐蚀性更强的材料,具体地说适合于底部电极夹块和增强纤维用玻璃炉的给料器。除改进抗腐蚀能力外这些材料应符合其它标准。首先应能够保证其工业可行性。人们用“工业可行性”一词意指获得无裂纹大块的可能性。事实上,在玻璃炉建设中砌块体积很大;不过,块越大,限制越多并且因此在焙烧进行之后出现裂纹的可能性也越大。因此,选择生产重于10公斤并无裂纹块的可能性做为可行性标准。避免产生可能成为优先被腐蚀部位的裂纹确实是很重要。为了同样的原因该产品应具有尽可能小的孔隙率。此外,考虑到增强玻璃纤维用玻璃的粘度低,应确保在炉运转温度下诸块之间的接缝封闭完好。最后,应限制成本。
本发明的目的是满足此需要。
为探求获得满足以上列举的不同需要的产品,我们业已证实获得抗腐蚀性更强材料的可能性。与专利US5124287的教导相反,我们发现较高百分比氧化锆的存在并不招致具体地说结石的倾向并且发现加入不同添加剂能符合先前提及的不同需要。
更确切地说,本发明涉及新烧结材料,其特征在于从含5至40%锆石的原料出发制造并且呈现如下的化学分析结果%(重量):
              宽范围            优选范围
 ZrO2+HfO2  82-96              87-94
 SiO2        1.7-14             3-8
 TiO2        0.2-3              0.4-1.5
 Y2O3       0.4-5              0.8-3.0
 Al2O3      0.2-2.5            0.5-1.0
 其它         <1                <0.5
本发明同样涉及本发明的焙烧材料于构成玻璃炉的炉身和/或流动管道方面的应用。
本发明涉及还所述烧结材料成型体的制造方法,其中包括下列步骤:
a)制备含有5~40%重量锆以及以氧化物重量为基准计82~96%ZrO2+HfO2、1.7~14%SiO2、0.2~3%TiO2、0.4~5%Y2O3、0.2~2.5%Al2O3和<1%其它成分的可烧结配合料;
b)将该配合料成型为生坯;
c)所形成的生坯在约4100~1650℃被烧成足以将其烧结的时间。
优选地,烧成温度为1600℃,烧成时间为10~30小时。
可烧结配合料含有5~40%重量锆,其组成取值导致烧结后产生具有定义本发明新型烧结材料的化学组成的烧结材料。可烧结配合料还可以含有任意常用的有助于形成生坯但在烧成步骤中可挥发掉的添加剂如粘合剂和/或润滑剂。
本发明烧结材料优选呈至少10公斤重块的形式。
优选地,本发明烧结材料从含10至20%锆石的原料制造。
氧化锆原料总含有少量的氧化铪,其性质与氧化锆的性质特别相近,该两种氧化物按习惯作法不能彼此分开。
对于“其它”一词,总体上是指如Na2O、Fe2O3、P2O5之类氧化物,和来自所用原料的其它杂质,这些“其它”不是必要的成分,但仅仅是可容许的。
以下有关实施例的描述内容显示每一个组分的作用和所获得的新产品的益处。
实施例1-28
这些实施例中描述的产品从下述起始配料制备:
由TAM公司提供的锆石E-MZ,其平均化学分析结果(重量)如下:
ZrO2+HfO2:66%,SiO2:33%,Al2O3:0.3%,P2O5:0.3%,Y2O3:0.1%,TiO2:0.1%和低于0.2%如F2O3的其它化合物。平均粒径4.7微米。
由申请人以Zircone CC10品牌投放市场的氧化锆的颗粒平均大小为3.5微米并且其平均化学分析结果(重量)是:ZrO2+HfO2:99%,SiO2:0.5%,Na2O:0.2%,Al2O3:0.1%,TiO2:0.1%。
由申请人提供的含钇的氧化锆的平均化学分析结果(重量)如下:ZrO2+HfO2:94%,Y2O3:5%,Al2O3:0.6%,TiO2:0.1%和低于0.2%的其它化合物。颗粒具有平均直径10微米。
在最终烧结材料中存在的二氧化硅是由锆石分解带来的,但是,可以视具体情况而定在原料中加入额外的烟法二氧化硅。
氧化钇或是来自部分地用氧化钇稳定的氧化锆或是来自加到组合物中的氧化钇。
加到组合物中的氧化钇颗粒具有平均直径3至4微米。
颜料性质的二氧化钛含有约98%的二氧化钛,其颗粒平均大小为0.3微米。
氧化铝具有颗粒平均大小约为3微米。
本领域专业人员已知碳化物或金属化物与熔融玻璃接触会招致“起泡”,因此应予以避免。
出示的实例通过等压成型获得。也可使用诸如泥浆浇注或震动浇注等其它的技术。实施的块是直径200毫米和高度200毫米的圆柱体,重量在28至33公斤之间。采用通常的烧结条件即在约1600℃烧制20小时。对于某些组合物使用重达约200公斤的特大块(76厘米×25厘米×20厘米)。不同实施块的化学分析结果列入表1中。制成品的表观密度在4.7和5.2克/厘米3之间。
表1概括本发明(实施例9-25和27-28)或非本发明的(对比例1-8和26)各种产品块的原料和最终烧结材料的组成。表1同样表明所得块是否有裂纹以及所得烧结材料在测定时呈现的孔隙率。对于“裂纹”一词,这里意指宽度大于0.1毫米的裂缝。
对比例2至6表明对于由其中锆石不是主要原始组分的原料制造的产物而言,仅仅使用二氧化钛作为烧结剂不可能获得无裂纹的大块。
实施例7至28与对比例2至6相比较表明加入氧化钇可获得当焙烧时无裂纹出现的大块。
此外,实施例11和17,12和18或22和23相比较表明对于含有二氧化硅和二氧化钛以及氧化钇的产品而言,加入氧化铝会达到更优良的烧结水平。这表现为开口孔隙率减少并且对于加入少量的氧化铝的情形也是如此。因此我们优选含高于0.5%氧化铝的产品。
另一方面,我们发现为了能制造无裂纹大块,对于其中锆石不占多数的原料锆石/氧化锆而言,材料至少含0.4%氧化钇是必要的。另一方面,无须氧化钇比例超过5%重量,否则就会使材料的电阻过分地下降,这样作为用于炉底的材料会招致经过炉底中电极供给块中的电能发生严重的耗散。
对玻璃的腐蚀经由使试样(直径22毫米和高度100毫米)浸没于熔融玻璃浴中旋转试样予以评估。试样的旋转速度是每分钟6转,玻璃是一种于1450℃增强玻璃纤维用的玻璃并且试验历时72小时。试验周期结束后评价每个试样的腐蚀体积。将市售的参照产品试样(实施例1)的腐蚀体积选作为标准。该腐蚀体积与所有其它试样的腐蚀体积之比再乘以100给出试样相对于标准的评价值。因此,高于100的评价值表示其因腐蚀损失比所选择的标准要小。
本发明材料的抗玻璃腐蚀能力优于市场产品,其原因在于氧化锆比率升高,其值超过目前市售产品如CORHART公司的ZS-1300,其经化学分析包含65.9%氧化锆和32.1%二氧化硅(起始组成主要包含锆石和少量二氧化硅)。产品ZS-1300对应于实施例1。
腐蚀试验结果列于表2中,Ic表示先前定义的腐蚀指数。
可以确认本发明的材料的腐蚀指数明显地高于参照产品1。当腐蚀指数高于参照材料1的腐蚀指数20%时可以认为抗腐蚀能力明显得到改善。这样作的目的是从至多含40%锆石的原料出发获得了所制造的材料和使最终烧结材料中ZrO2+HfO2含量高于82%(重量)。此外,可以估计到原料至少应含有5%的锆石并且ZrO2+HfO2的含量不超过96%(重量),因为在这些限度之外所获得的材料依据抗腐蚀能力的观点不显现特别的优势,如在实施例24和对比例26之间进行比较所显示的那样。
另一方面,实施例14、15和24的比较显示为了改进抗腐蚀能力宁愿通过在较小组分的百分比上运作来减少孔隙率而不愿意多加入氧化锆或减少锆石。
诸例显示从高于40%锆石出发得到大块的可行性(对比例7和8),可是这些块均不满足所有标准的需要。事实上,这种块并未提供与参照材料1相比得到充分提高的抗腐蚀能力,因此并不显示特别的益处。
此外,二氧化硅及其产生的玻璃相对于大块的可行性起着重要的作用。因此,最少量的玻璃相对于获得无裂纹块是必需的。二氧化硅来自锆石ZrSiO4的分解并且视具体情况而定由外界加入其他物质(例如烟法二氧化硅)。出于不同组分均匀性的原因,具体地说考虑到粒度,人们优选这样的组成即其中二氧化硅基本上来自锆石。另外,使用锆石比使用氧化锆更经济。原料至少含5%锆石(重量),这相当于二氧化硅最低含量为1.7%(重量)。另一方面,锆石最高比例40%相当于在最终的烧结材料中二氧化硅最高含量为14%(重量)。
对于用于玻璃炉中耐火块的另一个重要标准是能否合适地封闭毗连两块之间的接缝。
为此目的,根据膨胀随着温度而变化的曲线,在块的膨胀最大值与在使用温度下该膨胀值之间的差值Δl应该是尽可能的小。对于在炉身中放置的块使用温度约1500℃,对于熔融玻璃循环管道(玻璃管道)块使用温度为1250至1350℃。
我们研究了实施例16至20和27中的Δl的变化。其结果汇集于表3。
比较实施例16、17和27显示当氧化铝的比率提高时接缝的封闭状况越来越差。
此外,本领域专业人员已知用于与增强玻璃纤维用玻璃相接触的高比率氧化铝的块会招致结石。另一方面,氧化铝含量高导致玻璃相过量并且因此导致对腐蚀更大的敏感度。因此,重要的是限制氧化铝的比率。由于所有这些原因,估计最高允许氧化铝含量为2.5%。另一方面,因为原料总是不纯的,在最终烧结材料中实际上不能将氧化铝降至0.2%(重量)之下。
对于氧化钇的影响,实施例18至20显示增加该组分的比例倾向于减小Δl并且经过氧化钇含量的最优化能够保证炉身块之间接缝的封闭或对于玻璃管道的接缝,这对于流动玻璃如增强玻璃纤维用玻璃特别重要。
必须指出氧化钇的主要作用并不是完全使氧化锆稳定。事实上,其加入量太小以致氧化锆无法以立方晶系形式被稳定。事实上,X-射线分析显示主要相由单斜晶系的氧化锆和正方晶系的氧化锆构成,但是立方晶系的氧化锆是不可觉察的。
进行电子探针研究可以设想氧化钇在参与玻璃相产物的可行性中起着重要作用。
再说,值得注意的是对于给定氧化锆比率加入氧化钇对抗腐蚀能力并无有害影响,如同实施例14和15示出的那样。
二氧化钛有促进锆石并且可能促进氧化锆焙烧的功能。因此,其有助于获得孔隙率得到降低的材料。二氧化钛至少应重0.2%。因为低于此值其作用就变得微不足道了。不过,烧结材料不应该含有高于3%的二氧化钛,因为块的可行性受到影响(出现裂纹)。
                                      表1
                               进料的重量组成
  序号   锆石(%)   氧化锆(%)  含5%氧化钇的氧化锆(%)    二氧化钛(%)    氧化铝(%)   氧化钇(%)
  1
  2   49.0   50.0     /     1.0     /     /
  3   38.0   61.0     /     1.0     /     /
  4   28.5   70.5     /     1.0     /     /
  5   16.5   83.0     /     0.5     /     /
  6   5.5   94.0     /     0.5     /     /
  7   70.0   15.0     14.0     1.0     /     /
  8   48.0   20.0     30.0     2.0     /     /
  9   38.0   30.5     30.5     1.0     /     /
  10   29.0   40.0     30.0     1.0     /     /
  11   16.5   73.0     10.0     0.5     /     /
  12   16.5   63.0     20.0     0.5     /     /
  13   16.5   53.0     30.0     0.5     /     /
  14   16.0   81.7     /     0.7     0.6     1.0
  15   15.0   81.9     /     0.5     0.6     2.0
  16   16.6   81.8     /     0.5     0.6     0.5
  17   16.2   81.8     /     0.5     1.0     0.5
  18   16.2   81.8     /     0.5     0.5     1.0
  19   15.2   81.8     /     0.5     0.5     2.0
  20   14.2   81.8     /     0.5     0.5     3.0
  21   16.5   50.0     30.0     0.5     /     2.7
  22   10.0   59.6     30.0     0.4     /     /
  23   10.0   59.0     30.0     0.4     0.6     /
  24   5.0   64.8     30.0     0.2     /     /
  25   5.0   62.0     30.0     0.2     /     2.7
  26   /   69.0     30.0     1.0     /     /
  27   15.6   81.8     /     0.5     1.6     0.5
  28   5.0   89.4     /     0.5     0.6     4.5
                    表1(续)
                             材料的重量化学分析结果
  序号   ZrO2+HfO2(%)   SiO2(%)   TiO2(%)   Al2O3(%)   Y2O3(%)   其它   裂纹(%)   孔隙率(%)
  1     65.9   32.1   1.2   0.3   /   0.5   无   0.5
  2     81.8   16.4   1.1   0.2   /   0.5   有   ND
  3     85.5   12.8   1.1   0.2   /   0.4   有   ND
  4     88.6   9.8   1.1   0.2   /   0.2   有   ND
  5     93.1   5.9   0.6   0.1   /   0.3   有   14.7
  6     96.7   2.3   0.6   0.1   /   0.3   有   ND
  7     74.2   23.2   1.1   0.3   0.8   0.4   无   ND
  8     79.7   15.9   2.1   0.3   1.5   0.5   无   8.7
  9     83.9   12.7   1.1   0.3   1.6   0.4   无   ND
  10     86.9   9.8   1.1   0.3   1.5   0.4   无   11.2
  11     92.6   5.8   0.6   0.2   0.5   0.3   无   11
  12     92.1   5.8   0.6   0.2   1.0   0.3   无   8.8
  13     91.6   5.7   0.6   0.3   1.5   0.3   无   4.4
  14     91.4   5.7   0.8   0.7   1.0   0.4   无   0.9
  15     91.0   5.4   0.6   0.7   2.0   0.3   无   0.2
  16     91.9   5.9   0.6   0.7   0.5   0.4   无   1.5
  17     91.7   5.8   0.6   1.1   0.5   0.3   无   3.4
  18     91.7   5.8   0.6   0.6   1.0   0.3   无   0.4
  19     91.0   5.4   0.6   0.6   2.0   0.4   无   0.2
  20     90.4   5.1   0.6   0.6   3.0   0.3   无   0.2
  21     88.6   5.7   0.6   0.3   4.2   0.6   无   6.2
  22     93.8   3.6   0.5   0.3   1.5   0.3   无   6.4
  23     93.2   3.6   0.5   0.9   1.5   0.3   无   0.7
  24     95.7   2.0   0.3   0.3   1.5   0.2   无   10.5
  25     92.9   2.0   0.3   0.3   4.2   0.3   无   9.0
  26     96.5   0.3   1.1   0.2   1.5   0.4   无   8.5
  27     91.3   5.6   0.6   1.7   0.5   0.3   无   ND
  28     91.8   2.1   0.6   0.7   4.5   0.3   无   ND
 ND=未测定
                                   表2
                                    进料的重量组成
  序号   锆石(%)     氧化锆CC10(%)   含5%氧化钇的氧化锆(%)    二氧化钛(%)   氧化铝(%)   氧化钇(%)
  1
  7   70.0     15.0     14.0     1.0     /     /
  8   48.0     20.0     30.0     2.0     /     /
  9   38.0     30.5     30.5     1.0     /     /
  10   29.0     40.0     30.0     1.0     /     /
  13   16.5     53.0     30.0     0.5     /     /
  14   16.0     81.7     /     0.7     0.6     1.0
  15   15.0     81.9     /     0.5     0.6     2.0
  22   10.0     59.6     30.0     0.4     /     /
  24   5.0     64.8     30.0     0.2     /     /
  26   /     69.0     30.0     1.0     /     /
                               表2(续)
                           材料的重量化学分析结果
  序号   ZrO2+HfO2(%)   SiO2(%)   TiO2(%)   Al2O3(%)   Y2O3(%)   其它   Ic
  1     65.9   32.1   1.2   0.3   /   0.5   100
  7     74.2   23.2   1.1   0.3   0.8   111
  8     79.7   15.9   2.1   0.3   1.5   0.5   119
  9     83.9   12.7   1.1   0.3   1.6   0.4   122
  10     86.9   9.8   1.1   0.3   1.5   0.4   131
  13     91.6   5.7   0.6   0.3   1.5   0.3   150
  14     91.4   5.7   0.8   0.7   1.0   0.4   179
  15     91.0   5.4   0.6   0.7   2.0   0.3   178
  22     93.8   3.6   0.5   0.3   1.5   0.3   158
  24     95.7   2.0   0.3   0.3   1.5   0.2   162
  26     96.5   0.3   1.1   0.2   1.5   0.4   163
                                  表3
  序号   ZrO2+HfO2(%)   SiO2(%)   TiO2(%)   Al2O3(%)   Y2O3(%)     Δl(1500℃)     Δl(1350℃)
  16     91.9   5.9   0.6   0.7   0.5   +0.43     /
  17     91.7   5.8   0.6   1.1   0.5   +0.6     /
  18     91.7   5.8   0.6   0.6   1.0   +0.28   -0.36
  19     91.0   5.4   0.6   0.6   2.0   +0.07   -0.17
  20     90.4   5.1   0.6   0.6   3.0   -0.07     0
  27     91.3   5.6   0.6   1.7   0.5   +0.9     /
实施例29和30
当从细小粒度粉末出发制备实施例1至28时,实施例29-30则阐明从较粗的粉末出发制造烧结块的可能性。同样阐明本发明的块作为氧化锆来源循环使用的可能性。
本发明烧结块具有如下的重量组成:ZrO2+HfO2:91%,SiO2:5.9%,TiO2:0.75%,Y2O3:1.1%,Al2O3:0.8%,其它:0.45%,将其研碎和过筛以获得三种粒度的颗粒,即2-5毫米,0.5-2毫米和<0.5毫米。这些颗粒用于实施例30中。
同样研碎和过筛CORHART公司的ZS-1300以获得两种颗粒度的颗粒,即0.5-2毫米和<0.5毫米。这些颗粒用于实施例29中。
被用作其它原料组分的还有:
—申请人提供的具有如下平均化学分析结果的烟法二氧化硅:SiO2:93.5%,ZrO2:2.4%,Al2O3:3.5%,其它0.6%,其平均粒径0.5微米,
—锆石砂,平均直径140微米并且其组成如下:ZrO2+HfO2:65%,Al2O3:0.5%,SiO2:34%,其它:0.5%。
—ALCOA公司的铝水泥CA25,其化学分析组成是:CaO:19%,Al2O3:79%,SiO2:0.3%,其它:1.7%。
—如实施例1-28使用的锆石,氧化锆CC10和氧化钇。
从这些原料出发制备了两种烧结块29和30,原料和所获得材
料的重量组成如下:
原料重量组成,%            实施例29             实施例30
颗粒,2-5毫米                  -                   10
颗粒,0.5-2毫米                12                  25
颗粒,<0.5毫米                10                  30
氧化锆CC10                     73.5                8
锆石砂                         -                   12.4
锆石                           -                   10
氧化钇                         0.5                 0.6
二氧化硅(烟法)                 2                   2
铝水泥CA25                     2                   2
烧结材料重量
化学分析结果,%
ZrO2+HfO2                    87.3                81.7
SiO2                          9.5                 13.4
Al2O3                        1.7                 2.2
TiO2                          0.3                 0.5
Y2O3                         0.5                 1.3
实施例29和30的块没有裂纹,其孔隙率分别是3.1和12%。

Claims (9)

1.新烧结材料,其特征在于从含5至40%锆石的原料制成的该材料呈现如下以wt%表示的化学分析结果:
     ZrO2+HfO2            82-96
     SiO2                  1.7-14
     TiO2                  0.2-3
     Y2O3                 0.4-5
     Al2O3                0.2-2.5
     其它                   <1
2.根据权利要求1的烧结材料,其特征在于该烧结材料呈现如下以wt%表示的化学分析结果:
     ZrO2+HfO2            87-94
     SiO2                  3-8
     TiO2                  0.4-1.5
     Y2O3                 0.8-3.0
     Al2O3                0.5-1.0
     其它                   <0.5
3.根据权利要求1的烧结材料,其特征在于该烧结材料是至少重达10公斤的块。
4.根据权利要求1的烧结材料,其特征在于烧结材料从含有作为氧化锆来源的循环材料的原料制造。
5.根据权利要求1的烧结材料,其特征在于烧结材料从含有10至20%锆石的原料制造。
6.权利要求1-5中任一项的烧结材料于玻璃炉中在构成炉身方面的用途。
7.权利要求1-5中任一项的烧结材料于玻璃炉中在构成玻璃流动管道方面的用途。
8.烧结材料成型体的制造方法,其中包括下列步骤:
a)制备含有5~40%重量锆以及以氧化物重量为基准计82~96%ZrO2+HfO2、1.7~14%SiO2、0.2~3%TiO2、0.4~5%Y2O3、0.2~2.5%Al2O3和<1%其它成分的可烧结配合料;
b)将该配合料成型为生坯;
c)所形成的生坯在约1400~1650℃被烧成足以将其烧结的时间。
9.权利要求8的方法,其中烧成温度为1500~1600℃,烧成时间为10~30小时。
CNB991052420A 1998-04-22 1999-04-22 由锆石和氧化锆制造的烧结材料及其制造方法 Expired - Lifetime CN1153749C (zh)

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