CN101037297A - 氧化铝-钛氧化物-氧化锆熔融晶粒 - Google Patents
氧化铝-钛氧化物-氧化锆熔融晶粒 Download PDFInfo
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Abstract
一种总量为100%的氧化铝-钛氧化物-氧化锆熔融晶粒,其化学组成如下所示:Al2O3:大于10%且小于50%;TiO2:大于10%且小于40%;ZrO2:大于50%;以及杂质:小于2%;百分比是基于氧化物重量的重量百分比。本发明可以应用到钢的连续铸造的滑动门上。
Description
技术领域
本发明涉及一种氧化铝-钛氧化物-氧化锆熔融晶粒,还涉及一种制造这种晶粒的方法和含有这种晶粒的滑动门。
背景技术
滑动门是钢的连续铸造中的部件,用作在流体窜槽中经滑动喷嘴的钢锭模铸造铸桶的开关分配器或输出孔。因此滑动门必须具有良好的机械强度,尤其是抗热冲击性和抗剥落性,还要具有良好的耐化学性,尤其是抗腐蚀性。
通常,滑动门可以通过烧结氧化铝-氧化锆熔融晶粒和氧化锆-莫来石熔融晶粒的混合物得到。由于其微裂纹的增加,氧化铝-氧化锆/氧化锆-莫来石复合物具有优异的抗热冲击性。在加热时,氧化锆的同素异形转变伴随着大的体积变化。这种尺寸上的变化导致微裂缝的形成。由于氧化铝-氧化锆(α1000℃=9.6×10-6/℃)与氧化锆-莫来石(α1000℃=6.9×10-6/℃)的热膨胀的差异较大,这些微裂缝还出现在氧化锆-莫来石颗粒与氧化铝-氧化锆基质的界面处。这两个现象导致微裂缝部件,因此提高其在热冲击时吸收能量的能力。
然而,氧化锆-莫来石具有耐腐蚀性差的缺点,因此构成该复合物的缺陷。
因此在制造滑动门时,需要一种适于代替莫来石-氧化锆晶粒的新晶粒,其可以使所制造的滑动门的耐腐蚀性得到改善。本发明的目的就是满足这种需要。
发明内容
根据本发明,所述目的可以通过总量为100%、化学组成如下表示的氧化铝-钛氧化物-氧化锆熔融晶粒实现:
·Al2O3:大于10%,优选大于15%,且小于50%,优选小于35%;
·TiO2:大于10%,优选大于15%,且小于40%,优选小于30%,更优选小于25%;
·ZrO2:大于50%,且优选小于70%,或小于61%;
·杂质:小于2%;
所述百分比是基于氧化物重量的重量百分比,晶粒不具有TiO2相,且大于98wt%的氧化锆是单斜晶。
在本发明的一个优选实施方案中,晶粒的组成包括约60%ZrO2、约20%Al2O3和约18%-20%TiO2。
令人惊讶地,发明人发现利用本发明的晶粒替代莫来石-氧化锆晶粒能使其制造具有较佳抗腐蚀性的复合滑动门,同时,不会降低抗热冲击的能力。
另外,发明人发现缺少TiO2相可以改善耐腐蚀性,本发明的晶粒优选仅以下列相表示:
·含有Zr5Ti7O24的Al2O3和/或,
·含有钛酸铝Al2TiO5的(ZrTiO4或ZrO2)。
优选的晶粒含有Al2O3-Zr5Ti7O24相,最优选的晶粒含有ZrO2-Al2TiO5相。
最后,本发明的晶粒可以通过电融合熔融,因此可以有效地制造大量晶粒,性价比优异。
优选地,本发明的熔融晶粒进一步包括一种或多种以下任选的特征:
其化学组成进一步含有大于2%,优选大于5%,且/或小于10%的氧化锡(SnO2),其他成分的含量范围不变。对于总量为100%,该晶粒的化学组成如下所示,百分比是基于氧化物的重量:
·Al2O3:大于10%,优选大于15%,且小于50%,优选小于35%,或小于20%;
·TiO2:大于10%,优选大于15%,且小于40%,优选小于30%,更优选小于25%;
·ZrO2:大于50%,且优选小于76%,或小于70%;
·SnO2:大于2%,优选大于5%,且小于10%,或小于6%;
·杂质:小于2%;
·氧化锆可以与氧化锡结合;
·大于98%的氧化锆是单斜晶相。
无论实施方式如何,本发明的晶粒包括优选至少0.1%,优选至少0.5%和/或小于3%的MgO,百分比是基于氧化物重量的重量百分比,上述其它成分的含量范围不变。
对于总量为100%,该晶粒的化学组成如下所示,百分比是基于氧化物的重量:
·Al2O3:大于10%,优选大于15%,且小于50%,优选小于35%,或小于20%;
·TiO2:大于10%,优选大于15%,且小于40%,优选小于30%,更优选小于25%;
·ZrO2:大于50%,且优选小于76%,或小于70%;
·SnO2:为任选的;
·MgO:为任选的;
·杂质:小于2%;
当SnO2存在时,其浓度优选大于2%,更优选5%,和/或小于10%或6%;
当MgO存在时,其浓度优选大于0.1%,更优选0.5%,和/或小于3%或2.5%。
“杂质”包括除SnO2、TiO2、Al2O3、ZrO2、以及明确提及的MgO以外的成分,且尤其是形成包括氧化物、氮化物、氮氧化合物、碳化物、碳氧化物、碳氮化物和诸如钠和其他碱金属、铁、硅、钒和铬等金属的群组中的一部分的混合物。在氧化锆源中天然存在,其浓度小于2%的氧化铪不被视为杂质。残留碳,其表示为C,形成本发明晶体组合物中的部分杂质。
一般认为杂质含量小于2%不会消除由本发明取得的技术效果。
本发明还提供了一种制造本发明的氧化铝-钛氧化物-氧化锆熔融晶粒的方法,该方法包括以下连续步骤:
a)将原料混合以形成初始进料;
b)将初始进料熔融以得到熔融液;
c)冷却所述熔融液使熔融液在3分钟内,优选1分钟内,更优选15秒内完全固化,从而得到固体块;
d)任选地,研磨所述固体块而得到晶粒混合物。
根据本发明,在步骤a)中,选择原料使得在步骤d)中得到与本发明一致的晶粒。
优选地,将一种或几种选自Al2O3、TiO2、ZrO2、SnO2、MgO、其前体和其混合物的氧化物有意地,也就是说有系统地且有方法地,按量加入步骤a)中,保证在步骤c)中得到与本发明一致的晶粒。
只要初始进料的组成能使所得到的晶粒的组成与本发明的晶粒一致,任何制造氧化铝-钛氧化物-氧化锆熔融晶粒的常规方法都可以实行。
在步骤a)中,可以引入任何形式的钛,尤其是金属形式或氧化锆-钛氧化物合金、或钛酸铝的形式。
本领域的技术人员可以通过Al2O3-TiO2-ZrO2的三元相图,且更精确地沿Al2TiO5-ZrO2的伪二元相图,容易地确定能获得Zr5Ti7O24相和/或钛酸铝Al2TiO5相和/或ZrTiO4相并避免TiO2相的组合物。
初始进料中的各种原料的含量也应该确定以计算步骤b)中加热时SnO2的减少量。本领域技术人员熟知减少量是加热条件的函数。
在步骤b)中,优选使用电弧炉,然而任何已知的炉子都可以考虑,例如感应炉或等离子炉,只要它可以使初始进料完全熔融。加热优选在诸如氩气等惰性条件下进行,或在氧化条件下进行,优选在大气压下进行。
在步骤c)中,冷却是快速的,即,由此在3分钟内使熔融液完全固化。优选地,如美国专利3 993 119中所述在CS模中铸型或由淬火所导致。有利地,此快速冷却避免生成TiO2相。相反,缓慢冷却将导致相分离,并因此生成Al2O3+TiO2或ZrO2+TiO2。
在步骤d)中,使用常规方法研磨固体块。
最后,本发明提供一种由本发明的氧化铝-钛氧化物-氧化锆熔融晶粒表示的烧结复合材料所制成的滑动门,该烧结复合材料通过氧化铝-氧化锆基质而结合。
具体实施方式
以下通过实施例举例说明本发明,而不是限制本发明的范围。
参考1(ref.1)是供应商Treibacher Schleifmittel出售的ZrO2-莫来石产品。
参考2(ref.2)是已知为FAZ 40的产品。该产品是供应商Sowa Denko出售的氧化铝-氧化锆。
为制备实施例1、2、和3的样品,将粉末在Turbula混合器中混合2小时,然后在氩气气氛下于感应炉中的石墨坩埚中熔融。根据炉子的惯性冷却。产生的样品一般很小,需要后熔融氧化热处理。
对于其它实施例和参考组合物,在空气中利用电弧炉的氧化电操作将粉末混合物熔融。利用各种方法控制冷却(CS模可以使样品快速冷却,在自由空气或再热器中冷却锭)。
原料如下:由SEPR出售的CC10单斜氧化锆,自Pechiney的AR75氧化铝,自Keeling & Walker Ltd.的氧化锡,自CRB GmbH的TiO2金红石。
用常规方法测量以基于氧化物重量的百分比表示的化学组成:通过X射线荧光进行化学分析。
用X射线衍射测定在耐火材料组合物中的晶相。在表1中,“~”表示“痕量”。
在由具有相同粒度(中间粒径d<150微米(μm))的粉末制备的片上测量1000℃时的膨胀系数“a”,在20千牛顿(kN)的压力下压缩超过13毫米(mm),然后烧结(在空气中,1450℃下经受3小时(h))。
在1450℃下煅烧晶粒-熔渣混合物后,通过光学显微镜评定熔渣对晶粒的腐蚀。熔渣基本由SiO2(40%)、CaO(40%)、Na2O(10%)、和Al2O3(5%)组成。其碱度指标(CaO+MgO)/SiO2为1。虽然晶粒并不打算与熔渣接触,但熔渣的腐蚀造成特别严重的环境,使晶粒能够被测量到显著性的腐蚀。级数“R”代表耐腐蚀性,范围是0-4,良好的耐腐蚀性对应较高R值。
所测试的晶粒的同素异形转变温度“T”需要尽可能与参考2(氧化铝-氧化锆晶粒)的相近,如前面所述,由此使微裂缝有效于改善由这两种晶粒的混合物制成的复合材料在热冲击时吸收能量的能力。相反,由于同样的原因,测试材料在1000℃的膨胀系数“a”应该尽可能与参考2的不同。
“V”表示熔融液固化的速率:“H”和“D”分别表示“几小时”和“几天”。“<10s”表示“小于10秒”。
结果总结在下面的表1中。
表1
V | 化学组成 | 相 | 于1100℃经受10h后的相 | a | T | R | |||||
Al2O3 | TiO2 | MgO | ZrO2 | SnO2 | |||||||
Ref1 | 6.9.10-6℃-1 | 1050℃ | 1 | ||||||||
Ref2 | 9.6.10-6℃-1 | 1100℃ | 0 | ||||||||
3 | H | 40.4% | 31.0% | 28.6% | Zr5Ti7O24,Al2O3 ,TiO2 | 5.4.10-6℃-1 | 500℃ | 1 | |||
4 | <10s | 21.5% | 20.2% | 58.3% | mZrO2,Al2TiO5 | mZrO2,Al2TiO5,~TiO2 | 7.3.10-6℃-1 | 770℃ | 4 | ||
5 | H | 20.2% | 19.5% | 60.3% | mZrO2,Al2TiO5,~Zr5Ti7O24 | mZrO2,Al2O3,TiO2,~Al2TiO5 | 7.3.10-6℃-1 | 770℃ | 2 | ||
6 | D | 25.7% | 21.0% | 53.3% | mZrO2,Al2TiO5,~Al2O3,~Al2Ti7O15 | 2 | |||||
7 | <10s | 19.6% | 15.9% | 58.6% | 5.9% | mZrO2,Al2TiO5,~SnO2 | 8.2.10-6℃-1 | 960℃ | 3 | ||
8 | D | 18.8% | 14.5% | 62.4% | 4.3% | mZrO2,Al2O3,TiO2,~Al2TiO5,~Zr0.6Sn0.4TiO4 | 2 | ||||
9 | D | 12.4% | 10.0% | 75.3% | 2.3% | mZrO2,Al2O3,TiO2,~Al2TiO5,~Zr0.6Sn0.4TiO4 | 2 | ||||
10 | <10s | 18.3% | 22.2% | 2.0% | 57.4% | mZrO2,固溶体AlTiMgO | mZrO2,固溶体AlTiMgO | 4.9.10-6℃-1 | 842℃ | 4 | |
11 | H | 18.1% | 22.0% | 2.0% | 57.9% | mZrO2,固溶体AlTiMgO | mZrO2,固溶体AlTiMgO | 6.10-6℃-1 | 811℃ | 2 |
上述表1显示本发明晶粒具有足以与氧化铝-氧化锆晶粒(参考2)的膨胀系数区别的膨胀系数“a”,在由这两种晶粒制成的烧结复合材料中生成微裂缝。因此本发明的晶粒可以代替现有技术的用于制造复合材料滑动门的莫来石-氧化锆晶粒,本发明的氧化铝-钛氧化物-氧化锆熔融晶粒通过氧化铝-氧化锆基质结合在一起。
表1还显示在改善耐腐蚀性上,快速冷却的优点(实施例4和7),以及含有TiO2相(实施例3)的缺点。
其他测量结果还显示本发明的晶粒类似于氧化锆-莫来石晶粒的方式,具有作为温度的函数而改变的膨胀系数。特别是,氧化锆的同素异形转变导致膨胀系数突变。为了使突变在尽可能高的温度下发生,有利地是在基本上与氧化铝-氧化锆晶粒相同的温度,优选本发明晶粒中的氧化锆全部为单斜晶(大于98%)。
由于钛是氧化锆的稳定剂,优选其在初始进料中含量很小。因此优选初始进料中的TiO2含量小于40%,优选小于30%,更优选小于25%。
如实施例10和11所示,含有氧化镁会进一步改善本发明晶粒的性能。优选,本发明的晶粒包括至少0.1%,优选至少0.5%的MgO。实施例10和11显示浓度接近2%,尤其是包括1.5%至2.5%之间的晶粒具有非常好的结果。
特别是,在1100℃下经受10小时的加热处理(所使用的代表性加热条件),显示这些相使其晶粒的性质保持稳定。
另外,值得注意的是,根据本发明,MgO的存在避免有害的TiO2的形成。
然而,MgO的浓度优选小于3%,所述百分比是基于氧化物的重量。在这个限值以外,部分氧化镁稳定了氧化锆,且单斜晶氧化锆的百分比可能会小于98%。
实施例10和11被认为是最优选的,因为其给出了在不同性质间的最佳权衡。
因此,在本发明的一个优选的实施方案中,本发明的晶粒以如下重量浓度表示,所述百分比是基于氧化物的重量:
·Al2O3:大于16%和/或小于20%;
·TiO2:大于20%和/或小于24%;
·MgO:大于1%和/或小于3%;
·ZrO2:大于55%和/或小于60%;
无需严格遵照这个理论解释,发明人认为本发明的晶粒与莫来石-氧化锆晶粒的作用方式相同,使复合材料具有微裂缝,并因此使其具有更良好的抗热冲击能力。
与氧化锆-莫来石晶粒不同,本发明的晶粒不会导致产生耐腐蚀性低的含石英环境。因此,使用本发明的氧化铝-钛氧化物-氧化锆熔融晶粒代替现有技术的莫来石-氧化锆晶粒在保留有效的抗热冲击性的同时还改善了耐腐蚀性。
自然地,所说明的实施例仅是一些例子,且它们可以被改良,尤其是通过技术上的等同替换,并没有脱离本发明的范围。
Claims (19)
1.一种氧化铝-钛氧化物-氧化锆熔融晶粒,其化学组成如下所示:
·Al2O3:大于10%且小于50%;
·TiO2:大于10%且小于40%;
·ZrO2:大于50%;
所述百分比是基于氧化物重量的重量百分比,晶粒不含TiO2相,且大于98wt%的氧化锆是单斜晶。
2.根据前述权利要求所述的熔融晶粒,其中Al2O3、TiO2、ZrO2和杂质的总量为100%,杂质小于2%,所述百分比是基于氧化物重量的重量百分比。
3.根据权利要求1所述的熔融晶粒,其中Al2O3、TiO2、ZrO2、MgO、SnO2和杂质的总量为100%,杂质小于2%,MgO和SnO2是任选的,所述百分比是基于氧化物重量的重量百分比。
4.根据前述权利要求所述的熔融晶粒,其中,基于氧化物的重量:
·MgO:0-3%重量百分比,和/或,
·SnO2:0-10%重量百分比。
5.根据前述权利要求所述的氧化铝-钛氧化物-氧化锆熔融晶粒,其中,基于氧化物的重量:
·SnO2:大于2%重量百分比。
6.根据前述权利要求所述的熔融晶粒,其中,基于氧化物的重量,氧化锡(SnO2)的浓度大于5%重量百分比。
7.根据权利要求1所述的熔融晶粒,其化学组成以如下浓度表示:
·Al2O3:大于15%和/或小于35%;和/或
·TiO2:大于15%和/或小于30%;和/或
·ZrO2:小于70%;
所述百分比是基于氧化物重量的重量百分比。
8.根据权利要求1所述的熔融晶粒,基于氧化物的重量,具TiO2含量小于25%重量百分比。
9.根据权利要求1所述的熔融晶粒,其含有约60% ZrO2、约20% Al2O3和约18%-20% TiO2。
10.根据权利要求1所述的熔融晶粒,所述晶粒仅具有含有Zr5Ti7O24的Al2O3和/或含有钛酸铝Al2TiO5的ZrTiO4或ZrO2的相。
11.根据权利要求1所述的熔融晶粒,其中100%的氧化锆是单斜晶。
12.根据权利要求3所述的熔融晶粒,其中,基于氧化物的重量:
·MgO.大于0.1%重量百分比。
13.根据前述权利要求的熔融晶粒,基于氧化物的重量,含有至少0.5%重量百分比的MgO。
14.根据权利要求3所述的熔融晶粒,总量为100%,其化学组成如下,所述百分比是基于氧化物重量的重量百分比:
·Al2O3:大于16%和/或小于20%;
·TiO2:大于20%和/或小于24%;
·MgO:大于1%和/或小于3%;
·ZrO2:大于55%和/或小于60%。
15.根据权利要求13所述的熔融晶粒,其中,基于氧化物的重量:
·SnO2:大于2%重量百分比。
16.一种滑动门,由前述任一权利要求所述的以氧化铝-钛氧化物-氧化锆熔融晶粒表示的烧结复合材料所制成,该复合材料通过氧化铝-氧化锆基质而结合。
17.一种制造氧化铝-钛氧化物-氧化锆熔融晶粒的方法,所述方法包括以下连续步骤:
a)将原料混合形以形成初始进料;
b)将初始进料熔融以得到熔融液;
c)冷却所述熔融液使熔融液在3分钟之内完全固化从而得到固体块;以及
d)任选地,研磨所述固体块从而得到晶粒混合物;
其中在步骤a)中选择原料使得在步骤d)中得到的晶粒为权利要求1-15中任一权利要求所述的晶粒。
18.根据前述制造氧化铝-钛氧化物-氧化锆熔融晶粒的方法,其中在步骤c)中,熔融液在1分钟内完全固化。
19.根据前述制造氧化铝-钛氧化物-氧化锆熔融晶粒的方法,其中在步骤c)中,熔融液在15秒内完全固化。
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JP4589642B2 (ja) | 2003-08-28 | 2010-12-01 | 京セラ株式会社 | アルミナ・ジルコニア系セラミックス及びその製法 |
-
2006
- 2006-02-17 FR FR0601403A patent/FR2897612B1/fr not_active Expired - Fee Related
-
2007
- 2007-01-31 US US11/700,118 patent/US7405173B2/en not_active Expired - Fee Related
- 2007-02-02 EP EP07300768A patent/EP1820785B1/fr not_active Not-in-force
- 2007-02-02 PL PL07300768T patent/PL1820785T3/pl unknown
- 2007-02-02 CA CA2577050A patent/CA2577050C/fr not_active Expired - Fee Related
- 2007-02-06 RU RU2007104346/02A patent/RU2434963C2/ru not_active IP Right Cessation
- 2007-02-14 ZA ZA2007/01322A patent/ZA200701322B/en unknown
- 2007-02-16 KR KR1020070016572A patent/KR101322442B1/ko active IP Right Grant
- 2007-02-16 JP JP2007036465A patent/JP5270099B2/ja not_active Expired - Fee Related
- 2007-02-16 AU AU2007200671A patent/AU2007200671C1/en not_active Ceased
- 2007-02-16 BR BRPI0700449-4A patent/BRPI0700449B1/pt not_active IP Right Cessation
- 2007-02-16 CN CN2007100841238A patent/CN101037297B/zh not_active Expired - Fee Related
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102083765A (zh) * | 2008-07-04 | 2011-06-01 | 欧洲技术研究圣戈班中心 | 熔化成的包含Al、Ti、Mg和Zr的氧化物颗粒和包含这种颗粒的陶瓷产品 |
CN102083765B (zh) * | 2008-07-04 | 2013-11-06 | 欧洲技术研究圣戈班中心 | 熔化成的包含Al、Ti、Mg和Zr的氧化物颗粒和包含这种颗粒的陶瓷产品 |
CN103459349A (zh) * | 2011-03-31 | 2013-12-18 | 法商圣高拜欧洲实验及研究中心 | Atz熔凝颗粒 |
CN102358826A (zh) * | 2011-08-19 | 2012-02-22 | 永州皓志稀土材料有限公司 | 一种铝掺杂的氧化锆复合抛光粉的制备方法 |
CN105473533A (zh) * | 2013-06-18 | 2016-04-06 | 康宁股份有限公司 | 低热膨胀钛酸铝-钛酸锆锡陶瓷 |
CN105473533B (zh) * | 2013-06-18 | 2019-01-04 | 康宁股份有限公司 | 低热膨胀钛酸铝-钛酸锆锡陶瓷 |
CN106011584A (zh) * | 2016-07-04 | 2016-10-12 | 合肥正浩机械科技有限公司 | 一种金属陶瓷密封环及其制备方法 |
CN113912297A (zh) * | 2021-08-02 | 2022-01-11 | 北京科技大学 | 一种固化放射性废料的烧绿石基玻璃陶瓷及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CA2577050A1 (fr) | 2007-08-17 |
BRPI0700449A (pt) | 2007-11-06 |
AU2007200671B2 (en) | 2011-10-13 |
RU2434963C2 (ru) | 2011-11-27 |
FR2897612A1 (fr) | 2007-08-24 |
FR2897612B1 (fr) | 2008-05-16 |
JP5270099B2 (ja) | 2013-08-21 |
AU2007200671A1 (en) | 2007-09-06 |
US20070197369A1 (en) | 2007-08-23 |
ZA200701322B (en) | 2008-04-30 |
CA2577050C (fr) | 2016-07-12 |
JP2007223892A (ja) | 2007-09-06 |
US7405173B2 (en) | 2008-07-29 |
AU2007200671C1 (en) | 2012-04-19 |
EP1820785A1 (fr) | 2007-08-22 |
KR101322442B1 (ko) | 2013-10-25 |
PL1820785T3 (pl) | 2013-01-31 |
BRPI0700449B1 (pt) | 2015-08-18 |
RU2007104346A (ru) | 2008-08-20 |
EP1820785B1 (fr) | 2012-06-13 |
KR20070082893A (ko) | 2007-08-22 |
CN101037297B (zh) | 2011-12-21 |
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