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CN105859256B - 基于包含矿物学相的氧化铝的烧结成型磨粒及其制备方法 - Google Patents

基于包含矿物学相的氧化铝的烧结成型磨粒及其制备方法 Download PDF

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CN105859256B
CN105859256B CN201610104524.4A CN201610104524A CN105859256B CN 105859256 B CN105859256 B CN 105859256B CN 201610104524 A CN201610104524 A CN 201610104524A CN 105859256 B CN105859256 B CN 105859256B
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让-安德烈·阿拉里
亚历山大·赫尔施
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Abstract

本发明涉及基于包含矿物学相的氧化铝的烧结成型磨粒以及使用氧化铝、钛铁矿和锆砂作为原料制备其的方法，该矿物学相由莫来石、铝钛氧化物和/或阿姆阿尔柯尔矿石、和斜锆石和/或斯里兰卡石构成。

Description

基于包含矿物学相的氧化铝的烧结成型磨粒及其制备方法
本发明涉及基于包含矿物学相的氧化铝的烧结成型磨粒及其制备方法，该矿物学相由莫来石、铝钛氧化物(tialite)和/或阿姆阿尔柯尔矿石(armalcolite)、和斜锆石和/或斯里兰卡石(srilankite)构成，其中将氧化铝、钛铁矿和锆砂用作原料。本发明还涉及这样的烧结成型磨粒的用途，特别是在黏合磨料中的用途。
因为其高硬度、高断裂韧性、化学稳定性、和高温度耐受性，在工业中大量使用基于氧化铝的磨粒用于生产磨料制品。除了在电弧炉中以成本有效方式生产的熔凝氧化铝(其基于数量代表着用于生产磨料制品的磨粒的最大百分比)之外，通过陶瓷或化学工艺生产的烧结磨粒也常用于特殊用途。用于特殊研磨操作的烧结磨粒的优势来源于其微晶结构和/或其几何学特定形状。
通常，磨粒或研磨制品的研磨性能由所谓的g-比率决定，该g-比率计算为切削量(stock removal)与磨料磨损之比。磨粒的高硬度引起高的切削速率，因此引起高的g-比率。同时，磨粒的高断裂韧性产生低的磨料磨损以及高的g-比率。因此，在理想情形中，为了获得高的g-比率，磨粒的硬度和断裂韧性应当尽可能高。
然而，由于要处理的多种材料(例如木、钢、不锈钢、塑料、石头、陶瓷等)的不同物理性能，磨粒必须在其硬度和断裂韧性方面分别满足不同的要求，在硬度与断裂韧性的比率方面满足不同的要求。
该比率可例如受到化学组成改变的影响。然而，磨粒的研磨性能的特征不仅在于其化学组成，还在于其结晶结构、其密度，以及尤其是其几何学形状。此外，磨粒是否用于特定研磨操作的决定不仅受到其潜在研磨性能的影响，在很多情形中还受到磨粒生产成本的影响，该生产成本基本取决于原料成本，而且工艺条件也起到重要作用。
在US－A－3 387 957中记载了一种烧结杆状磨粒，该磨粒通过挤压精细研磨的铝土矿、水和粘合剂的混合物而制成。这样获得的狭长挤压生坯具有均匀的圆形横截面，随后将其切割成规定长度的粒子，然后在1300－1600℃的温度范围对所述粒子进行烧结。优选地，将这样的杆状烧结磨粒用于重载研磨操作的树脂黏合研磨轮，例如不锈钢和高合金钢的钢坯的粗磨。
由于氧化铝之外所使用的原料，所得的磨粒包含氧化硅、氧化铁、氧化钛以及少量的其他氧化物，例如氧化钙和氧化镁。这些氧化物中的一些与氧化铝组合形成单独的矿物学相，例如莫来石(3Al2O3*2SiO2)或铝钛氧化物(Al2TiO5)，所述相具有比氧化铝(刚玉)低的硬度，导致相应的磨粒也不那么硬，然而，由于不同相的偏析或夹杂，所述磨粒通常显示出较高的断裂韧性，其对于特定研磨应用可能是有利的。在该情形中，对应磨粒用途的可能领域得到额外延展，因为铝土矿用作低价原料。然而，由化学组成的可能变化引起使用天然存在的铝土矿的有害影响，这可能对产品品质具有不利影响。
在US－A－4 252 544中公开了一种烧结磨粒，其具有大于3.75g/cm3的密度、大于1.900kg/mm2的Knoop硬度、大于98重量％的氧化铝含量以及由粗和细晶体颗粒的混合物配置成的晶粒结构，其中粗晶体具有在3－10微米范围内的平均颗粒尺寸，而小晶体颗粒具有小于2微米的平均颗粒尺寸。通过如下方式制备磨粒：在水和粘合剂的存在下，混合颗粒尺寸为3－10微米的粗电熔凝或高温烧结的氧化铝粉末和颗粒尺寸小于1微米的细粉末；挤压该混合物；干燥该挤压的材料，同时将其切割成确定的长度；和在1550－1650℃的温度下烧结该切割和干燥的片。这样获得的磨粒与基于铝土矿的磨粒相比具有较高的硬度，较高的切削速率，而磨料制品的磨损同时增加。增加的原料成本具有有害的影响，且使生产更加昂贵。
US－A—2 360 841记载了烧结磨粒，其由氧化铝晶体构成，该氧化铝晶体含有固溶体形式的氧化钛和氧化铁。记载的一个实施方案包括额外的氧化锆作为晶体生长抑制剂。
在US－A－3 454 385中记载了用于重载研磨或粗磨操作的烧结磨粒，其包含30－70重量％氧化铝，15－60重量％氧化锆和5－15重量％的一种或多种氧化物，所述氧化物选自氧化铁、氧化钛、氧化锰和氧化硅。
US－A－3 481 723的主题是柱形磨粒，其基本由选自氧化铝、氧化锆、硅酸锆、碳化硅、氧化钛、氧化锰、膨润土、硅及其混合物的磨料构成。
EP 2 636 655 A1记载了基于氧化铝烧结压块的磨粒，其具有高硬度和高断裂韧性。为了生产磨粒，将氧化铝粉末和钛铁矿粉末添加到含有粘合剂的水性介质中。随后，将该混合物均匀化，成型以具有所需形式，并烧结以获得具有高硬度和优异断裂韧性的烧结成型磨粒。通过在氧化铝晶体的晶界中形成FeTiAlO5晶体提高磨粒的断裂韧性。
所述上述成型磨粒都用于重载研磨操作，其中尽可能快和尽可能多的除去材料。在铸造厂和制钢工业中钢坯和板坯的粗磨或初磨是这样的应用的例子，其中例如使用高度致密的近无孔热压树脂黏合轮。如上所述，用作磨粒的压缩固体的适应性基本取决于其硬度和其断裂韧性。然而，其他参数也起到作用，例如将磨粒保持在研磨轮的结合基体中的黏合力，以及在研磨过程中外部作用于磨粒的力(压力)。考虑到磨粒的磨损机制，磨粒首先自我磨掉并钝化，直到部分磨粒破坏且因外部压力形成新的切削刃。在磨粒的很高断裂韧性的情形中，存在相反效应的可能性，其中整个磨粒脱离黏合且因此为研磨过程而丧失。因此，在不同的情形中处理不同的材料；所以，有必要首先使磨粒适应待加工的材料以及适应研磨条件和可能发生的研磨力，且其次特别就硬度和断裂韧性之间的相互作用优化磨粒。
因此，本发明的任务是提供一种用于特定用途的磨粒，其特征是具有最高可能的硬度和断裂韧性。本发明的另一任务是根据可接受的成本/性能比提供一种这样的优化的磨粒的生产方式。
根据本工作已经确立，基于氧化铝的烧结磨粒具有优化的硬度和断裂韧性，其包含85－95重量％Al2O3、0.5－5.0重量％Ti化合物(表示为TiO2)、0.3－4.0重量％硅化合物(表示为SiO2)；0.4－9.0重量％铁化合物(表示为Fe2O3)、1.0－9.0重量％锆化合物(表示为ZrO2)、和小于2重量％的原料基杂质；由此，获得在特定研磨操作中提供相对于现有技术的优势的磨粒。
为了生产烧结的磨粒，将85－95重量％α氧化铝、0.5－8.0重量％钛铁矿和1.0－10.0％锆砂用作原料，首先由其制备均匀的原料干混合物。原料基杂质小于2重量％。由于烧结体的晶态结构应该在组织上尽可能细，因此如果必要，预先粉碎所述原料。其次，与一种或多种添加剂一起添加至少一种粘合剂和至少一种溶剂用于获得可挤压的物质，所述添加剂选自分散剂、润滑剂和增塑剂。再次，挤压该物质并制成成型磨粒前体(生坯)，随后在1450－1650℃的温度范围中烧结。其中，钛铁矿与锆砂的重量比为1：6至6：1。
在烧结后，烧结的磨粒的矿物学成分包含刚玉(Al2O3)、莫来石(3Al2O3*2SiO2)、铝钛氧化物和/或阿姆阿尔柯尔矿石(Al2TiO5/AlFeTiO5)、和斜锆石和/或斯里兰卡石(ZrO2/Ti0.75Zr0.25O2)，其中莫来石与铝钛氧化物和/或斯里兰卡石的重量百分比比率优选为6：1至1：6。
优选地且根据本发明，烧结的磨粒具有≥3.6g/cm3的密度和14－18GPa的硬度HV。此外，烧结磨粒具有≤2.0％，更优选≤1.2％的MKZ值。
有利地，烧结的磨粒是具有0.5－5mm直径和1－10mm长度的杆状体，其中直径与长度之比为0.2：1.0－1.0：1.0。
为了评价磨粒的品质，有必要进行研磨试验。研磨试验是相对延续和时间密集的。由此，在磨料工业中，通常预先通过机械特征评价磨粒品质，可以更容易地得到该机械特征，且机械特征可以在研磨试验充当后者行为的指示。在本工作的上下文中，除了磨粒的硬度鉴定，还通过在球磨机中球磨通过微粒分解(MKZ)确定磨粒的磨粒韧性。
微粒分解(MKZ)
为了测量磨粒分解，将10g规定磨料粒度的磨粒(例如基于刚玉；优选磨料粒度24或36)在填充有12个钢球(直径19mm，重330－332g)的球磨机(高10.5cm，直径6.8cm)中以185转/分钟球磨150秒的时间段。随后在Rotap筛分机(Haver
Figure GDA0000970493850000052
EHL 200)中通过对应的细筛(优选250微米)将球磨的磨粒进行筛分五分钟，所述细筛比对于对应的磨粒粒度确定的底筛细2级，随后，平衡掉细的部分。MKZ值遵从如下：
Figure GDA0000970493850000051
微粒分解不仅与磨粒的断裂韧性有关，而且同时还是磨粒的研磨性能的重要指示。因而，对于特定的研磨操作，可基于MKZ值进行研磨性能的相对可靠的预测，如果对于对应的研磨操作给出了硬度和断裂韧性之间的必要的相互作用。
如之前所述，对于铸造厂和制钢工业中的板坯和钢坯的粗磨或初磨优选使用杆状磨粒，其中使用高度压缩的几乎无孔的树脂黏合的研磨轮。在典型的试验中，例如用树脂黏合的研磨轮在恒定机械参数下处理由厚220mm、宽400mm和长1540mm的碳钢制成的工件，或由厚140mm、宽500mm和长2080mm的不锈钢制成的工件，其中该轮具有616mm的横截面直径(dimension)和76mm的宽度。在这些试验中，通常发现，对于本发明的磨粒的使用，g-比率(材料去除与轮磨损之比)随着下降的MKZ值而升高。因此，可以由MKZ值对于磨粒的性能得出结论。然而，这仅适用于磨粒的硬度也在对于特定研磨操作所需的范围内的情形，该范围对于本发明的磨粒为14－18GPa硬度HV。
磨粒的硬度和MKZ值的相互作用可以分别受到锆砂添加或者锆砂与钛铁矿之比的影响。烧结磨粒最终还将此反映在矿物学成分莫来石与铝钛氧化物和/或阿姆阿尔柯尔矿石之比上。对于原料，锆砂与钛铁矿的重量之比应当为1：6至6：1以便确保高性能的磨粒。然而，已经得出，用其中以5：1至1：1的重量之比使用锆砂与钛铁矿的磨粒获得了优异的结果。烧结的磨粒具有的莫来石与铝钛氧化物和/或阿姆阿尔柯尔矿石之比为6：1至1：6。
下表1提供了一些所选杆状烧结磨粒的化学组成、所用原料、物理性能和矿物学相的概述。
Figure GDA0000970493850000061
对于根据本发明的实施例A、B和C，在每一情形中使用90重量％的氧化铝作为原料，而锆砂和钛铁矿的比率是变动的。具有3：1的锆砂与钛铁矿之比的样品A显示了最低的MKZ值，且具有最高的磨粒断裂强度。可能是在成品中莫来石相的高分数(8％)由此起到作用，这将会成为进一步研究的主题。分别具有1：1和1：3的锆砂与钛铁矿之比的样品B和C显示出略高的MKZ值，由此可期待较低的研磨性能。
对于实施例D和E保持3：1的锆砂与钛铁矿之比，而氧化铝的百分比增加。发现在此情形中MKZ值随着增加的氧化铝含量而变差，同时具有较低氧化铝含量也具有3：1的锆砂与钛铁矿之比的实施例F显示出1.0％的优异MKZ值和16.6GPa的硬度，这也是添加剂钛铁矿和锆砂的优势的另一指示。
对比例G、H和I基于作为原料的铝土矿，其中对于对比例I使用高品质铝土矿。都基于不同类型铝土矿作为原料的样品G和H之间的区别主要在于产品中莫来石相的不同百分比。在此情形中，还必须更详细地研究莫来石相对于产品品质的影响。
此外，将实施例J，基于纯氧化铝的烧结刚玉杆用于对比。对比例J显示出18.6GPa的高硬度和1.0％的低MKZ值，且落在根据本发明的实施例B、C和F的相同范围内。样品A的MKZ值显著更好。初步的常规研磨试验对于本样品指示出g-比率(材料去除与轮磨损之比)直接与MKZ值相关，所以，对于根据本发明的磨粒，可以以成本有效的方式生产的产品是可获得的，且其对于特殊研磨操作提供与基于纯氧化铝的烧结杆相比相同或甚至更好的研磨结果。
图1还对于本发明的样品A、B和C的实施例图示地显示了这些相关性。可以看出，具有3：1的锆砂与钛铁矿之比的样品A的特征是相对高的硬度(HV 15.1GPa)和同时很低的MKZ值(0.8％)；因此，它提供了这些性能，由其可预期很好的研磨性能。实际上，在初步研磨试验中，这样的烧结磨粒与基于铝土矿的烧结杆(样品G和H)相比提供了改善的g-比率(高达75％)。具有1：1的锆砂与钛铁矿之比的样品B和具有1：3的锆砂与钛铁矿之比的样品C的特征是其机械性能仅具有极小的区别。然而，小于15GPa的硬度HV和约1.0％的微粒分解MKZ导致在烧结的氧化铝杆范围内的g-比率，而生产成本是更有利的，这归因于低价原料基础。为了变得更好，矿物学相引起提高的磨粒断裂强度(较低MKZ)连同不显著降低的硬度，使得根据本发明的磨粒对于机加工特殊类型的非常坚韧的钢是注定的。

Claims (7)

1.一种用于生产烧结磨粒的方法，包括步骤：
－制备85－95重量％氧化铝、1.0－10重量％锆砂和0.5－8.0重量％钛铁矿的均匀干混合物，其中原料基杂质小于2重量％；
－与一种或多种添加剂一起添加至少一种粘合剂和至少一种溶剂用于获得可挤压的物质，所述添加剂选自分散剂、润滑剂和增塑剂；
－挤压该物质；
－将挤压产物切割成成型的磨粒前体；和
－在1450－1650℃的温度范围中烧结该成型的磨粒前体用于获得烧结磨粒，
其中烧结磨粒是具有0.5－5mm直径和1－10mm长度的杆状体，其中直径与长度之比为0.2：1.0－1.0：1.0，
其中该烧结磨粒的矿物学成分包含：
刚玉、
莫来石、
铝钛氧化物或AlFeTiO5、和
斜锆石或斯里兰卡石。
2.根据权利要求1的方法，
其中锆砂与钛铁矿的重量百分比的比率为1：6至6：1。
3.根据权利要求1或2的方法生产的烧结磨粒，包括如下重量含量：
－85－95重量％Al2O3；
－0.5－5.0重量％Ti化合物，表示为TiO2；
－0.3－4.0重量％的硅化合物，表示为SiO2；
－0.4－9.0重量％铁化合物，表示为Fe2O3；
－1.0－9.0重量％锆化合物，表示为ZrO2；
－和小于2重量％的原料基杂质，
其中烧结磨粒基于氧化铝。
4.根据权利要求1的烧结磨粒，
其中莫来石与铝钛氧化物和/或斯里兰卡石的重量百分比的比率为6：1至1：6。
5.根据权利要求3的烧结磨粒，其具有≥3.6g/cm3的密度和14－18GPa的硬度HV。
6.根据权利要求3的烧结磨粒，其具有≤2.0％的MKZ值，其中为了测量磨粒分解，将10g规定磨料粒度的磨粒在填充有12个钢球的球磨机中以185转/分钟球磨150秒的时间段，随后在Rotap筛分机中通过对应的细筛将球磨的磨粒进行筛分五分钟，所述细筛比对于对应的磨粒粒度确定的底筛细2级，随后，平衡掉细的部分，MKZ值遵从如下：
Figure FDA0002709702230000021
7.根据权利要求6的烧结磨粒，其具有≤1.2％的MKZ值。
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