CN101573307A - 熔融陶瓷材料的颗粒 - Google Patents
熔融陶瓷材料的颗粒 Download PDFInfo
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Abstract
本发明涉及熔融陶瓷颗粒,其特征在于具有以下化学组成,以基于氧化物的重量%表示,总计100%:55%<ZrO2+HfO2<70%;20%<SiO2<30%;6.5%<MgO<9.5%;Al2O3的量使得MgO/Al2O3质量比率为2.4-6.6;及低于0.6%的其它氧化物。
Description
技术领域
本发明涉及由熔结(fused)陶瓷制成的新型颗粒,特别是珠粒形式的颗粒,并涉及制备这些珠粒的方法,还涉及这些颗粒作为研磨剂、在湿介质中的分散剂或用于表面处理的用途。
背景技术
矿物工业使用珠粒来精细研磨已使用常规方法在干状态下预研磨的材料,特别是碳酸钙、氧化钛、石膏、高岭土和铁矿石。
涂料、油墨、染料、磁性釉和农用化学化合物工业使用这样的珠粒用于分散和均化各种液体和固体组分。
最后,表面处理工业使用这些颗粒或珠粒,特别是在用于以下操作中:清洗金属模具(例如用于制造瓶子)、对部件去毛刺、去除氧化皮、调制有待对其涂覆的载体、喷丸处理、喷丸形成等。
常规地,颗粒近似为球形,并具有0.1-4mm的尺寸以适用于所有上述市场。所以,所述颗粒可用于那三种应用中,它们必须特别具有以下性质:
-相对于处理的产品具有化学和颜色惰性;
-机械冲击强度;
-磨损抵抗性;
-对设备特别是搅拌器部件和槽罐或者喷涂部件具有低磨损性;
及
-低的开放孔隙率以方便清洗。
在市场上尤其在微研磨领域中发现各种颗粒特别是珠粒:
■具有圆形粒的砂子例如渥太华(Ottawa)砂是天然且廉价的产品,但不适合于现代的、加压的和高生产量的磨机。这是因为所述砂子并不很坚固,具有低密度,品质可变,并且对于设备具有磨损性;
■玻璃珠粒,其得到广泛使用,具有较好的强度、较低磨损性,并且在较宽直径范围内可获得;及
■金属珠粒特别是由钢制造的珠粒,相对于处理的产品具有不足的惰性,特别是导致矿物填料的污染和涂料的变灰,且具有太高的密度,需要特殊的磨机,这特别导致设备的高机械应力、高的能量消耗和大量的加热。
还已知由陶瓷材料制成的珠粒。这些珠粒比玻璃珠粒具有更好的强度、较高的密度和优异的化学惰性。以下性质可能是突出的:
■烧结的陶瓷珠粒,其通过冷成形陶瓷粉末然后通过在高温下烧制固结获得;及
■所谓的“熔结”陶瓷珠粒,通常通过熔化陶瓷成分,从熔融(molten)材料形成球形微滴,然后凝固所述微滴而获得。
大多数的熔结珠粒具有氧化锆/氧化硅(ZrO2/SiO2)型组成,其中氧化锆以单斜形式结晶和/或部分稳定化(通过合适的添加物),而氧化硅以及一些任选的添加剂形成粘结氧化锆晶体的玻璃相。熔结陶瓷珠粒为研磨提供了最优的性质,即相对于研磨设备的低磨损性、良好机械强度、高密度和化学惰性。
例如,FR 2320276和EP 0662461描述了基于氧化锆的熔结陶瓷珠粒及其在研磨和分散中的用途。这些文献描述了SiO2、Al2O3、MgO、CaO、Y2O3、CeO2和Na2O对于主要性质特别对于抗压强度和耐磨性的影响。
尽管现有技术的熔结陶瓷珠粒具有优良的品质,然而工业上始终需要具有更优品质的产品。这是因为对研磨条件的要求越来越高,而且为降低制备成本需要提高所使用的机器的生产率。特别地,期望降低这些机器的停机时间。
发明内容
本发明旨在通过提供熔结陶瓷颗粒满足这些需求,所述熔结陶瓷颗粒除了上述的所需品质以外还具有改善的破裂抵抗性。
更具体地,本发明涉及新型熔结陶瓷颗粒,优选是珠粒形式,具有以下化学组成,以基于氧化物的重量百分比计,且总量为100%:
55%<ZrO2+HfO2<70%;
20%<SiO2<30%;
6.5%<MgO<9.5%;
Al2O3的量使得MgO/Al2O3重量比率为2.4-6.6;及
低于0.6%的其它氧化物。
本发明人意外发现,使得MgO/Al2O3重量比率为2.4-6.6的氧化铝(Al2O3)和氧化镁(MgO)的存在量显著改善了熔结陶瓷颗粒的性质,特别是与以不同比率含有这两种氧化物的颗粒(如FR2320276所述)对比时。特别地,获得了在使用期间具有更好的破裂抵抗性的颗粒。
因此,根据本发明的颗粒特别适于湿介质中分散、微研磨和表面处理的应用。在研磨应用中,根据本发明的颗粒在开始时和使用期间具有改善的破裂抵抗性。
除非另外指出,则所有的百分比均为以相对于氧化物总重量的百分比表示的重量百分比。
优选地,根据本发明的颗粒具有至少一种且优选若干种以下的任选特性:
■根据本发明的颗粒的氧化物含量占所述颗粒总重量的大于99.5%,优选大于99.9%,且更优选约100%;
■根据本发明的熔结陶瓷颗粒包含的ZrO2量大于或等于58.9%,优选大于或等于60%,优选大于或等于60.7%,和/或小于或等于69.5%,优选小于或等于68%,优选小于或等于65%,更优选小于或等于62%,优选小于或等于61.2%,以重量计。更优选地,该量约等于60.8%;
■根据本发明的熔结陶瓷颗粒包含的SiO2量大于或等于22%,优选大于或等于25%,更优选大于或等于27%,更优选大于或等于28%,和/或小于或等于29%,优选小于或等于28.5%,以重量计。更优选地,该量约等于28.3%;
■根据本发明的熔结陶瓷颗粒包含的MgO量大于或等于8%,优选大于或等于8.3%,和/或小于或等于9%,优选小于或等于8.8%,以重量计。更优选地,该量约等于8.6%;
■根据本发明的熔结陶瓷颗粒包含的Al2O3量大于或等于1.2%,优选大于或等于1.4%,和/或小于或等于3.2%,优选小于或等于2.5%,优选小于或等于2%,以重量计。更优选地,该量约等于1.9%;
■根据本发明的熔结陶瓷颗粒的MgO/Al2O3重量比率大于3,优选大于3.7,优选大于4.2,和/或小于或等于6,优选小于或等于5.5,优选小于5。优选地,MgO/Al2O3的重量比率约为4.6;
■“其它氧化物”仅以杂质形式存在。认为“其它氧化物”的总含量小于0.6%并不显著改变所获结果。然而,优选地,它们占根据本发明的熔结陶瓷颗粒的氧化物总重量的小于0.5%,优选小于0.45%。
■根据本发明的熔结陶瓷颗粒具有小于4mm和/或大于0.1mm的尺寸;
■根据本发明的优选颗粒具有以下化学组成,以基于氧化物的重量百分比计,且总量为100%:
60%<ZrO2+HfO2<62%;
27%<SiO2<29%;
8%<MgO<9%;
Al2O3的量使得MgO/Al2O3重量比率为4.2-5;及
低于0.5%的其它氧化物;及
■根据本发明的颗粒优选是珠粒形式。
本发明还涉及这样的颗粒组:其包含大于90%,优选大于95%,优选约100%的本发明的颗粒,以重量百分比计。
术语“珠粒”理解为意指具有球形度的颗粒(即其最小直径与其最大直径的比率)小于或等于0.6,而不论获得该球形度的方式。优选地,根据本发明的珠粒具有大于或等于0.7的球形度。
表述“熔结珠粒”或更常用的“熔结颗粒”理解为意指通过凝固液态的组合物获得的固体珠粒(或颗粒)。
珠粒(或颗粒)的“尺寸”是指其最大尺度dM与其最小尺度dm之间的平均值:(dM+dm)/2。
术语“杂质”理解为意指随原材料必然引入的不可避免的组分。特别地,构成氧化物、氮化物、氧氮化物、碳化物、氧碳化物、碳氮化物中一部分的化合物以及钠和其它碱金属、铁、硅、钒和铬的金属态物质是杂质。作为例子,可提及CaO、Fe2O3或Na2O。残余碳构成了根据本发明的颗粒组成中的部分杂质。另一方面,不认为氧化铪为杂质。优选地,Y2O3和CeO2是杂质。特别地,优选Y2O3<0.2%且CeO2<0.6%。Y2O3含量甚至可小于0.1%,或甚至小于0.05%,且CeO2含量甚至可以小于0.5%,以基于氧化物的重量百分比计。
当提及ZrO2时,应理解为(ZrO2+HfO2)。这是因为少量HfO2总是以小于2%的含量天然存在于氧化锆源中,HfO2不能从ZrO2化学分离并且其具有相似的性质。
本发明还涉及用于制备根据本发明的熔结颗粒的方法,特别是熔结珠粒,包含以下连续步骤:
a)混合原材料以形成起始进料;
b)熔化起始进料直到获得熔融液体;和
c)以液滴的形式分散熔融液体并以固体颗粒(特别是珠粒)的形式凝固这些液滴。
根据本发明,在步骤a)中选择原材料以便在步骤c)中获得的颗粒符合本发明。
在步骤a)中,从所述氧化物或其前体形成起始进料。优选地,使用含有约66%的ZrO2和33%的SiO2以及杂质的天然锆砂(ZrSiO4)。通过锆石提供ZrO2确实比添加ZrO2更加经济。
可以通过添加纯的氧化物或氧化物的混合物特别是ZrO2、SiO2、MgO和Al2O3来进行对组成的调整。
根据本发明,本领域技术人员调节起始进料的组成以便在步骤c)结束时获得根据本发明的颗粒。本发明熔结陶瓷颗粒的化学分析通常与起始进料的化学分析几乎相同。此外,适当时,例如当在还原条件下进行熔化时,为了考虑挥发性氧化物的存在或为了考虑SiO2的损失,本领域技术人员知晓如何相应地调节起始进料的组成。
优选地,不将除ZrO2+HfO2、SiO2、MgO和Al2O3之外的氧化物有意地引入起始进料中,存在的其它氧化物是杂质。
优选地,Y2O3和CeO2是杂质。
在步骤b)中熔化起始进料,优选在电弧炉中进行。这是因为电熔融允许以有利的产率制备大量颗粒(优选是珠粒形式)。然而,可以考虑所有已知的炉,如感应炉或等离子炉,只要它们能够使起始进料完全熔化。
在步骤c)中,将熔融液流分散成小的液滴,大多数这些液滴因表面张力而呈现近似球形。本领域技术人员知晓,可以通过喷吹,特别是采用空气和/或水蒸气或通过用于喷涂熔融材料的任何其它方法来进行这种分散。可以由此制备具有0.1-4mm尺寸的熔结陶瓷颗粒。
由分散引起的冷却导致液滴的凝固。因而,获得了根据本发明的固体颗粒,特别是珠粒。
可以使用制备熔结颗粒特别是熔结珠粒的任何常规方法,只要起始进料的组成使得能够获得具有如下组成的颗粒:该组成符合本发明的颗粒的组成。
根据本发明,“珠粒”之外的形状也是可行的,但优选近似球形。在本说明书的其它部分中特别提及珠粒,但这并非限制性的。
根据本发明的熔结珠粒具有很高的破裂抵抗性和很高的磨损抵抗性。
不受一定理论限制,发明人说明通过以所述量添加MgO和Al2O3而导致具有玻璃相(氧化硅玻璃)的氧化锆晶体的内聚力改善而获得该抵抗性。
根据本发明的熔结陶瓷珠粒特别适于作为研磨剂和用于在湿介质中的分散剂以及用于表面处理。因此,本发明还涉及根据本发明的许多颗粒特别是珠粒、或者依照本发明方法制备的珠粒的用途:作为研磨剂、作为湿介质中的分散剂、或用于表面处理。
然而应注意,所述珠粒的性质特别是其抵抗性、其密度及其制备的容易性能够使其适于其它应用,特别是作用用于负载、用于热交换和用于干研磨的试剂。
具体实施方式
出于说明本发明的目的提供以下非限制性实施例。
以下方法用于确定熔结陶瓷珠粒的各种混合物的某些性质。这些方法能够在操作中、在研磨应用中优异地模拟实际行为。
为了测试珠粒的磨损抵抗性,在具有1.2升容量的卧式加压磨机中填充1升(表观容积)的待测试珠粒,即填充水平为83.3%。从相对于旋转轴偏心的金属圆盘形成搅拌器部件,并以2750rpm旋转,即圆盘周边速度为10m/s。
待研磨的悬浮液是在水中浓度为60%的氧化锆粉末的悬浮液,即每4kg水中6kg粉末。通过蠕动泵使该悬浮液以6 l/h的流动速率穿过磨机。测试的持续时间为1.5小时。一旦测试完成,从磨机中取出珠粒,清洗并干燥。
在每次测试后,通过称重确定珠粒的重量损失。珠粒的磨损表示为每小时测试的百分比(%/h),其等于相对于珠粒起始重量的珠粒重量损失,总量除以测试的持续时间。
为了测试珠粒的破裂抵抗性,建议将它们置于极端条件下,这在常规操作的磨机中可导致开裂现象。
卧式加压磨机在转子上装配有指状物,在腔室内部装配有反指状物。在容积为1.2升的该磨机中填充50体积%的具有预定颗粒尺寸(表观体积)的珠粒,其对应于珠粒的起始质量mi。
在磨机开始旋转之前,且在测试的整个持续期间,将腔室充有流动速率为6 l/h的水。旋转速度设定为7.3m/s,持续30分钟。
一旦测试完成,将珠粒从腔室中取出,干燥然后过筛。人工分选所有的珠粒,以除去破碎珠粒,然后称重破碎珠粒。破碎珠粒的重量等于mbb。破碎珠粒的百分比等于100×mbb/mi。
在实施例中,对于起始进料,使用了基于锆石的组合物,并添加了氧化镁和氧化铝。更具体地,将由锆砂组成的粉状组合物引入Héroult型电弧炉中。进行几个熔化/浇铸循环同时逐渐调整组合物中的氧化镁和氧化铝。然后,通过喷吹压缩空气将熔融产物分散成珠粒并通过浇铸分离。
该技术使得能够具有不同组成的很多珠粒,其特征可在于符合本领域技术人员公知的方法。
由于最可能在使用中破碎的珠粒是尺寸大于1.6mm的珠粒,因此对颗粒尺寸为1.6-2.5mm的部分进行上述测试。
下表1中总结了所获得的结果。
表1
实施例 | ZrO2+HfO2(%) | SiO2(%) | MgO(%) | Al2O3(%) | MgO/Al2O3 | 其它氧化物(%) | mi(g) | mbb(g) | %破碎的珠粒 | %相对于对照物在破碎方面的改善 | 磨损(%/h) |
对照(*) | 67,9 | 30 | 0,01 | 1,86 | 0,01 | 0,23 | 1367,6 | 10,83 | 0,79 | - | 2,94 |
1 | 60,6 | 26,3 | 9,12 | 3,65 | 2,5 | 0,33 | 1352,6 | 11,9 | 0,88 | 11,39 | n.d. |
2 | 60,8 | 27 | 8,72 | 3,11 | 2,80 | 0,37 | 1355,3 | 9,08 | 0,67 | 15,19 | 1,80 |
3 | 61 | 28,2 | 7,93 | 2,42 | 3,28 | 0,45 | 1357,2 | 8,55 | 0,63 | 20,25 | 1,70 |
4 | 60,8 | 28,3 | 8,64 | 1,86 | 4,65 | 0,4 | 1348,7 | 3,53 | 0,26 | 67,09 | 1,60 |
5 | 61,2 | 28,5 | 8,58 | 1,44 | 5,96 | 0,28 | 1357,2 | 7,62 | 0,56 | 29,11 | n.d. |
6 | 61,7 | 28,2 | 8,41 | 1,29 | 6,52 | 0,4 | 1353,2 | 9,01 | 0,67 | 15,19 | 1,61 |
7 | 67,5 | 22,2 | 8,36 | 1,52 | 5,5 | 0,42 | 1351,7 | 6,35 | 0,47 | 40,5 | 1,80 |
8(*) | 62,4 | 28,4 | 7,81 | 1,03 | 7,58 | 0,36 | 1345,7 | 14,6 | 1,08 | -36,7 | n.d. |
n.d.:数据未获得;
(*)本发明之外的实施例。
本发明之外的对照珠粒是在研磨应用中常用的珠粒。
当珠粒具有以下性质时认为结果是特别令人满意的:
-相对于对照物,破裂抵抗性的改善至少为10%;和
-至少与对照物的磨损抵抗性相同。
实施例出人意料地显示,相对于对照珠粒,2.4-6.6的MgO/Al2O3比值在破裂抵抗性方面提供了明显的改善,还在磨损抵抗性方面提供了显著的改善。在该范围之外(对照物,珠粒8),破裂抵抗性比根据本发明的珠粒的破裂抵抗性明显更差。
来自实施例4的珠粒的组成是所有组成中的优选组成。对于来自实施例4的珠粒,上述测得的磨损为1.60%/h,而对于对照珠粒为2.94%/h。
当然,本发明不局限于所述的实施方案,仅以说明性和非限制性实施例的方式提供所述实施方案。
Claims (10)
1.熔结陶瓷颗粒,具有以下化学组成,以基于氧化物的重量百分比计,且总量为100%:
55%<ZrO2+HfO2<70%;
20%<SiO2<30%;
6.5%<MgO<9.5%;
Al2O3的量使得MgO/Al2O3重量比率为2.4-6.6;及
低于0.6%的其它氧化物。
2.根据权利要求1的颗粒,其中ZrO2含量大于或等于60%和/或小于或等于62%,以基于氧化物的重量百分比计。
3.根据权利要求1和2之一的颗粒,其中SiO2含量大于或等于27%和/或小于或等于29%,以基于氧化物的重量百分比计。
4.根据任一在前权利要求的颗粒,其中MgO含量大于或等于8%和/或小于或等于9%,以基于氧化物的重量百分比计。
5.根据任一在前权利要求的颗粒,其中MgO/Al2O3重量比率大于或等于4.2和/或小于或等于5。
6.根据任一在前权利要求的颗粒,其中“其它氧化物”的含量小于或等于0.5%,以基于氧化物的重量百分比计。
7.根据任一在前权利要求的颗粒,其中氧化物的含量占所述颗粒总重量的大于99.5%。
8.根据任一在前权利要求的颗粒,具有以下化学组成,以基于氧化物的重量百分比计,且总量为100%:
60%<ZrO2+HfO2<62%;
27%<SiO2<29%;
8%<MgO<9%;
Al2O3的量使得MgO/Al2O3重量比率为4.2-5;及
低于0.5%的其它氧化物。
9.根据任一在前权利要求的颗粒,具有大于或等于0.6的球形度。
10.多个根据权利要求1-9中任一项的颗粒的用途,用作研磨剂、在湿介质中的分散剂、或用于表面处理。
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FR2929940B1 (fr) | 2008-04-11 | 2010-05-21 | Saint Gobain Ct Recherches | Particule en matiere ceramique fondue. |
CN102348535B (zh) * | 2009-03-11 | 2015-01-14 | 圣戈班磨料磨具有限公司 | 包含具有改进形状的熔凝的氧化锆氧化铝颗粒的磨料物品 |
US20160163005A1 (en) * | 2014-06-06 | 2016-06-09 | The Energy Cooperative Association of Pennsylvania | Renewable Natural Gas Rights System and Method |
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