CN102471161B - 熔凝的氧化铝-氧化锆磨粒 - Google Patents
熔凝的氧化铝-氧化锆磨粒 Download PDFInfo
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Abstract
本发明涉及一种熔凝磨粒,该磨粒具有以下化学成分,用重量百分比表示:ZrO2+HfO2:38.0~46.0%;Al2O3:余量至100%;SiO2:0.20~0.60%;Y2O3:0.45~0.70%;TiO2:1.00~2.00%;其他氧化物:<1%,Y2O3/SiO2的比为0.80~2.00,氧化锆的重量的60~90%为四方晶相氧化锆,其余为单斜晶型。
Description
技术领域
本发明涉及熔凝的陶瓷磨粒,尤其是作为研磨磨粒的应用。本发明还涉及一种所述磨粒的混合物和一种含有根据本发明的磨粒混合物的磨具。
背景技术
通常,根据下列磨料的陶瓷磨粒的形成方法将磨具分类:游离磨料(通过喷雾或以悬浮的方式使用,无支撑);涂覆磨料(具有织物或纸支撑物,其中磨粒被置于多个层上);以及固结磨料(以圆形砂轮、棍等形式)。就后者而言,研磨磨粒被有机粘合剂或玻璃粘合剂(在该情况下,粘合剂由氧化物组成,基本上为硅酸盐粘合剂)挤压。这些磨粒本身必须具有良好的机械研磨性能(尤其是韧性)并且提供与粘合剂良好的机械粘聚力(界面结合强度)。目前,有着各种类别的磨料,使得能够覆盖广泛的应用和性能:通过熔融合成的氧化物磨粒尤其提供优异的质量/制造成本折中。
根据所遇到的应用类型和研磨方式,传统上用于砂轮或砂带的制造的基于氧化铝的研磨磨粒包括三个主类:基于氧化铝的熔凝磨粒;基于氧化铝-氧化锆的熔凝磨粒以及基于通过溶胶-凝胶法所获取的氧化铝的磨粒。
在熔凝磨粒的范围内,US-A-3181939公开了基于氧化铝和氧化锆的材料。这些磨粒通常组成为10%~60%的氧化锆、0~10%的添加剂和余量的氧化铝。已知的添加剂包括氧化钇(根据US-A-4457767,添加多达2%的氧化钇)或者氧化钛(根据专利DE-C1-4306966,添加多达10%的氧化钛)。这些添加剂改进了氧化铝-氧化锆磨粒的研磨力。US-5525135还公开了基于氧化铝-氧化锆-氧化钛的熔凝磨粒。
最后,JP59227726公开了氧化铝-氧化锆-氧化钛-氧化钇的熔凝磨粒,基于氧化铝、氧化锆及氧化钛总量计,氧化钇的可能添加量为0.05%~7%,优选1%~5%。
在切削加工硬钢情况下,基于氧化铝的熔凝磨粒具有低韧性,这造成磨粒的过度碎裂。基于氧化铝-氧化锆的熔凝磨粒具有非常高的韧性以及较低的硬度。它们使高效切削加工硬钢成为可能,但易于逐渐变平。总的来说,这导致施加于研磨部件上施加的力增大,以及,根据操作条件,该部件甚至可以被热损伤。通过溶胶-凝胶法获取的基于氧化铝的磨粒构成良好的折中。这是因为,它们具有高硬度、适中的韧性,使它们再生切削刃,以及良好的微结构产生磨粒的微断裂,保证了在硬钢上的长的寿命。
为切削加工低硬度的韧性钢,例如不锈钢,基于氧化铝-氧化锆的熔凝磨粒是有效的。这是因为它们的高韧性限制了它们的断裂。总的来说,通过溶胶-凝胶法所获取的基于氧化铝的磨粒比基于氧化铝-氧化锆的熔凝磨粒效果差,这是因为前者韧性较低。基于氧化铝的熔凝磨粒效果最差,这是因为它们韧性低以致于过度碎裂。
通常测量和比较各种磨粒的研磨性能是根据切削钢的质量除以在所述切削加工期间所消耗的研磨磨粒的质量,这称为比率S。尽管该比率给出了磨粒的研磨性能的数量级,然而,其没有考虑在切削加工期间所涉及的所有机理。例如,由于快速磨损使得材料被大量移除的快速消耗的磨粒可导致高比率S。然而,该磨粒不足以持久用于切削加工大量的部件。还可导致被切削加工的部件的过度热损伤,这是由于过度发出的切削功率由部件的发蓝处理引起的,但该功率是必需的以维持切削状态。
因此,需要一种熔凝的氧化铝-氧化锆研磨磨粒,该磨粒具有高比率S用于低发出功率切削加工,同时具有长的寿命或耐用度。本发明目的是为了满足该需求。
发明内容
根据本发明,通过具有下列化学组成的熔凝磨粒实现该目的,以重量百分比计:
其他元素,以氧化物的形式表示:<1%,
Y2O3/SiO2的比在0.80和2.00之间,
四方晶相氧化锆占氧化锆质量的60%~90%,其余氧化锆为单斜晶型。
从下文描述中可以看出更多的细节,本发明人已经发现,用上述化学组成,以及尤其在氧化钇含量的非常窄的范围内,四方晶相的氧化锆的有限比例是有利的。此外,该教导与US 5525135或JP 59227726相反,US 5525135或JP59227726中建议,或者甚至推荐,用最大比例的四方晶氧化锆以增加切削加工的效率。
根据本发明的磨粒还可具有一个或一个以上的下述可选特征:
-优选地,Y2O3/SiO2质量比大于1.00,优选大于1.10,和/或小于1.80,优选小于1.50,优选小于1.40以及更优选小于1.30;
-优选地,四方晶氧化锆占氧化锆的质量的大于70%和/或小于85%;
-优选地,ZrO2含量大于40%;
-优选地,SiO2含量大于0.03%,优选大于0.35%;
-氧化钛TiO2质量含量大于1.30%和/或小于1.70%;
-优选地,以氧化物形式表示的其他元素小于0.50%,尤其:
MgO:<0.30%,优选<0.10%,优选<0.05%,和/或
CaO:<0.30%,优选<0.20%,优选<0.10%,和/或
Na2O:<0.10%,优选<0.05%;以及
-以氧化物形式表示的其它元素为杂质。
本发明还涉及磨粒混合物,其包含:以重量百分比计,大于80%,优选大于90%,优选大于95%,优选大于99%,以及优选基本上为100%的根据本发明的研磨磨粒颗粒。优选地,根据本发明的磨粒混合物满足根据下述标准所测的与那些混合物或磨粒一致的粒度分布:FEPA标准42-GB-1984,R1993以及FEPA标准43-GB-1984,R1993。
本发明还涉及磨具,尤其是砂轮或砂带形式,包括研磨磨粒混合物,该研磨磨粒混合物通过粘合剂结合到一起或作为层沉积在支撑上,尤其是柔性支撑,并通过粘合剂保持,该工具的特征在于磨粒是根据本发明的磨粒。
总的来说,本发明涉及根据发明的磨粒用于研磨的用途。
定义
-根据本发明的氧化物含量涉及每种对应的化学元素的总含量,根据工业的常用惯例,每种对应的化学元素的总含量以最稳定的氧化物形式表示;因此,包括低价氧化物以及可选的氮化物、氮氧化物、碳化物、碳氧化物、碳氮化物或者甚至是上述元素的金属类化合物;
-术语“杂质”理解为伴随原材料必然引入的不可避免的组分。尤其,形成钠和其它碱金属铁、钒、铬的金属化合物的氧化物、氮化物、氮氧化物、碳化物、碳氧化物、碳氮化物以及金属形式的组中的一部分的化合物为杂质。举例来说,上文提到的MgO、CaO或Na2O。残余的碳形成根据本发明的产品的组合物的杂质的部分。然而,铪氧化物不视为杂质;
-术语氧化物的“前体”理解为在根据本发明的磨粒混合物或磨粒的制备期间,能够提供所述氧化物的组分;
-在通过熔化获取的产品中,HfO2没有从ZrO2中化学分离出来。在这样的产品的化学组成中,ZrO2+HfO2由此表示这两种氧化物的总量。然而,根据本发明,HfO2不是有意地被加入原料中的。HfO2因此仅表示痕量的铪氧化物,该氧化物常常以一般低于2%的含量自然存在于氧化锆源中。为清楚起见,因此,在用ZrO2+HfO2或者用ZrO2或者通过“氧化锆含量”表示氧化锆和痕量铪氧化物的含量之间可以没有区别;
-术语“熔凝磨粒”或更通用的“熔凝产品”,理解为通过冷却熔料而固化获取的固态磨粒(或产品);
-“熔料”是液相,其可含有少量固态颗粒,但是固态颗粒的量不能够构成所述相。为维持该形态,熔料必须被容纳在容器中;
-在本文中,除非另外提及,,所有的磨粒的组成是用基于磨粒的氧化物总质量的重量百分比给出的。
根据本发明的熔凝磨粒可以通过制造氧化铝-氧化锆磨粒的任意传统工艺来制造。一个传统工艺通常包括以下步骤:混合原材料;在电弧炉中熔化;通过对熔化的液体淬火固化;碾磨并可选地,根据所需的粒度分类。
熔凝的氧化铝-氧化锆磨粒的混合物的性能取决于熔液的热经历,其自身取决于工艺参数还强烈地取决于熔炉的几何形状和其环境(烟道气的收集、材料等)。该工艺参数由此可以根据所采用的熔炉、所用的原料等确定,使得在这些步骤结束后获取根据本发明的磨粒混合物。例如,该参数可用下文例子中的工艺取值。
具体实施方式
实施例
下文给出了非限制性的例子,其目的是例证本发明。
作为例子给出的产品是由下述原材料制造的:
-Alcan(加拿大铝业集团)所售的名为AR75的氧化铝粉末,具有的苏打含量小于0.4%;
-氧化锆粉末,具有ZrO2+HfO2的平均含量大于85%,含有平均5%的二氧化硅,氧化铝含量小于10%以及其它元素的含量小于0.7%;
-Altichem所售的名为“Yttrium Oxide 99.99LY”的氧化钇粉末,Y2O3的含量大于99.99%以及具有的中间粒径为3~6μm;
-Europe Minerals(欧洲矿业公司)所售的名为“rutile sand”的氧化钛粉末,具有TiO2的含量大于95%以及中间粒径为125μm左右;以及
-Solutia Incorporated(美国首诺公司)所售的石油焦,具有的尺寸为1~4mm。
采用本领域的技术人员熟知的下述传统工艺制备磨粒:
a′)混合原料,根据熔炉的状态在原料中加入有至少0.5%(最多为3%)的石油焦;
b′)在具有石墨电极的Héroult型的单相电弧炉中熔化所述材料,所用的炉膛直径为0.8m,电压为105~150V,电流为1500~2500A以及所传送的特定电能为每公斤载荷2.1~2.8kWh;
c′)通过在薄金属板之间对熔料浇注的装置骤然冷却熔料,例如专利US-A-3993119所示出的装置,以便获取完全实心的板,构成固体。
d′)在步骤c′)中冷却的所述固体被碾磨以获取磨粒混合物;以及
e′)通过筛分选择在500~600μm之间的磨粒。
为评估磨粒混合物的性能和寿命,生产了直径为12.7cm的砂轮,包含1g的每个例子中的磨粒。
然后,采用这些砂轮在恒定的速度下往复运动,并维持恒定的12.7μm的切削深度以及3600rpm的砂轮旋转速度,对304不锈钢制成尺寸为20.3cm×7.6cm×5.1cm的板的表面切削加工。记录了切削加工期间的通过砂轮牵引的最大功率Pmax。
砂轮完全被磨坏后,切削加工的钢的质量“Ma”(通过磨削操作去除钢的质量)和消耗的砂轮的质量“Mm”被测量,比率S是Ma/Mm的比值。
通过测量切削加工期间的砂轮牵引的最大功率Pmax以及砂轮的寿命tmax确定切削效率,当砂轮的所有磨粒被消耗时,视为砂轮的寿命结束。
表1给出了测试的各种磨粒混合物的化学组成和四方晶相氧化锆的比例。表2给出了用这些混合物所获取的结果。
通过以下公式计算比率S增加的百分比:100×(相关例的产品的比率S-参考例的产品的比率S)/(参考例的产品的比率S),参考例为比较例1*或比较例2*。高的正值的比例S增加的百分比是理想的。
在测试中通过砂轮牵引的最大功率Pmax减少的百分比,由以下公式计算:100×(参考例的产品的Pmax-相关例的产品的Pmax)/(参考例的产品的Pmax),参考例为比较例1*或比较例2*。高的正值的在测试中通过砂轮牵引的最大功率Pmax减少的百分比是理想的。
砂轮的寿命tmax增加的百分比,由以下公式计算:100×(相关例的产品的tmax-参考例的产品的tmax)/(参考例的产品的tmax),参考例为比较例1*或比较例2*。高的正值的砂轮的寿命tmax增加的百分比是理想的。
在氧化锆中的四方晶相的氧化锆的质量百分比含量用下述方式确定:用树脂包覆所测试的磨粒以构成球。在含有超过600个磨粒的球的抛光面上,采用带有铜阳极的Bruker D5000衍射计,获取X射线衍射图样。该获取过程是在25°~37°之间的2θ角度范围内进行的,步长为0.02°和每步长时间为4秒。采用了0.6mm的接收槽,样品绕自身旋转以限制优选的定向效果。获取时间增加的因子为5,以更好地统计计算。
ρMono是单斜晶相的氧化锆的密度,为5.8g/cm3,以及ρStab是稳定的氧化锆的密度,为6.1g/cm3。
稳定的氧化锆的质量百分比含量由以下公式得出:
在根据本发明的测试的磨粒中,稳定的氧化锆全部以四方晶相的形态存在,其余的氧化锆是单斜晶型。
四方晶相氧化锆的百分比含量是相对于结晶氧化锆总量表示的。
下面的表1和表2归纳了得到的结果。
比较例1*中的磨粒的组成接近于JP5922772的例5,以及比较例2*是根据US4457767的磨粒。
本发明人认为,当:
-与参考例的产品对比,比率S增加至少10%;以及
-与参考例的产品对比,最大牵引功率Pmax减小至少5%;以及
-与参考例的产品对比,砂轮的寿命tmax增加至少6%;在比率S、在切削加工测试中通过砂轮牵引的最大功率Pmax和砂轮的寿命tmax之间有良好的折中。
优选地,比率S增加至少15%,优选至少20%,优选至少25%或甚至至少30%和/或最大牵引功率Pmax减小至少10%,优选至少15%,或甚至至少20%和/或砂轮的寿命tmax增加至少10%,优选至少15%,或甚至至少20%。
例10示出,四方晶相氧化锆的含量为氧化锆的质量的91%不能实现所期望的折中。
例12及例14示出,四方晶相氧化锆的含量分别为氧化锆的质量的57%和55%不足以实现所期望的折中。
例11示出,四方晶相氧化锆的含量为氧化锆的质量的64%不能实现所述折中。
例9示出,0.66%的二氧化硅含量太高,不能实现所述折中。例10示出,二氧化硅含量低于0.20%时,不能实现所述折中。
例13示出,尽管四方晶相氧化锆和二氧化硅的含量合适,如果氧化钇含量小于0.45%,以及如果TiO2含量大于2%,不能实现所述折中。
例10、12和14示出,Y2O3/SiO2的比小于0.80和大于2.00不能实现所述折中。
在所有例子中,优选例17。
现在特别明显的是,本发明提供了熔凝氧化铝-氧化锆研磨磨粒的混合物,该混合物具有优异的研磨性能、耐用度以及切削效率。
当然,然而,本发明不限于所描述和示出的实施方式,这些给出的实施方式作为非限制性的例证。
Claims (12)
2.如权利要求1所述的磨粒,其中,所述Y2O3 / SiO2的质量比大于1.00且小于1.80。
3.如权利要求1或2所述的磨粒,其中,所述ZrO2的含量大于40%。
4.如权利要求1所述的磨粒,其中,所述SiO2的含量大于0.35%。
5.如权利要求1所述的磨粒,其中,所述Y2O3 / SiO2的比大于1.10且小于1.30。
6.如权利要求1所述的磨粒,其中,钛氧化物TiO2的质量含量大于1.30%且小于1.70%。
7.如权利要求1所述的磨粒,其中,大于70 %但小于85%的质量的氧化锆为四方晶相。
8.如权利要求1所述的磨粒,其中,所述其它氧化物小于0.50%。
9.如权利要求1所述的磨粒,其中,
MgO:<0. 30%, 和/或
CaO: < 0.30%,和/或
Na2O: < 0.10%。
10.如权利要求9所述的磨粒,其中,
MgO:<0.10%,和/或
CaO:<0.20%,和/或
Na2O:<0.05%。
11.一种包含磨粒混合物的磨具,其中,所述磨粒混合物包括按重量百分比计大于80%的权利要求1至10中任一项所述的磨粒,所述磨粒通过粘合剂结合到一起或在柔性支撑上沉积为层,并通过粘合剂保持。
12.如权利要求11所述的磨具,其中,所述磨具为砂轮或砂带的形式。
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DE102013106372B4 (de) | 2013-06-19 | 2018-08-23 | Center For Abrasives And Refractories Research & Development C.A.R.R.D. Gmbh | Schleifkörner auf Basis von eutektischem Zirkonkorund |
RU2016121145A (ru) * | 2013-11-01 | 2017-12-06 | Баладжи Индастриал Продактс Лтд. | Износостойкий состав для изготовления износостойкого элемента, применяемого для изготовления измельчающего валка или футеровки размольного стола вертикальной валковой мельницы, и способы их изготовления |
CN108251056A (zh) | 2016-12-29 | 2018-07-06 | 圣戈本陶瓷及塑料股份有限公司 | 研磨颗粒、固定研磨制品以及形成该固定研磨制品的方法 |
DE102017207322A1 (de) * | 2017-05-02 | 2018-11-08 | Robert Bosch Gmbh | Geformtes keramisches Schleifkorn sowie Verfahren zur Herstellung eines geformten keramischen Schleifkorns |
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