CN1880490A - 制备成团烧结碳化物粉末混合物的方法 - Google Patents
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Abstract
本发明涉及通过湿磨粉末混合物并喷雾干燥所述的浆料来制备成团粉末混合物的方法,该粉末混合物含有基于Ti、Zr、Hf、V、Nb、Ta、Cr、Mo和/或W的碳化物的硬质成分粉末、大于15wt-%的Co和/或Ni的粘结相粉末、以及压合剂。通过在研磨前向所述的粉末混合物中另外添加0.05-0.50wt-%的复合成形添加剂和/或升高/降低pH的添加剂如三乙醇胺、氢氧化物或酸,以及0.01-0.10wt-%量的增稠剂,得到具有优良流动性的颗粒团。
Description
本发明涉及制备具有高粘结相(binder phase)含量的成团(agglomerated)烧结碳化物粉末混合物的方法。
烧结碳化物合金是由粘结相中基于碳化物的硬质成分制成的,该粘结相基于Co和/或Ni。在用于金属机械加工和凿岩以及许多耐磨部件的工具中,粘结相含量通常为5-15wt-%。低粘结相含量的合金具有高耐磨性和低韧性,但是高粘结相含量的合金具有高韧性和低耐磨性。在需要非常高耐磨性的场合,可以采用低于5wt-%的粘结相含量。对具有如此低的粘结相含量的部件必须在预应力条件下予以固定(mounted)。例子如密封圈,在这种情况下其中低粘结相含量的另一优点是耐腐蚀性提高。另一方面,在高韧性必不可少但同时也需要好耐磨性的场合,采用20-30wt-%的粘结相含量。典型的例子为用于热轧的辊。在这些辊中高粘结相含量的另一优点是磨损后可以容易地对它们重新研磨。
烧结碳化物刀体是通过粉末冶金方法制造的,该方法包括湿磨粉末混合物,把经研磨的混合物干燥形成具有良好流动性的粉末,将经干燥的粉末压制成所需形状的刀体并最终烧结,所述的粉末混合物含有形成硬质成分的粉末、粘结相、压合剂(pressing agent)、以及通常是专属(proprietary)性能的其它添加剂。
使用烧结碳化物研磨体(milling body)在不同规格的研磨机中进行高强度研磨操作。为在磨碎的混合物中得到均匀分布的粘结相,研磨被认为是必要的。研磨时间为数小时乃至数天。研磨操作产生的浆料适于随后的喷雾干燥。成功的喷雾干燥非常取决于浆料的性质。必须优化浆料的粘度,避免剪切变稠并且使沉降减至最少。沉降将使经喷雾干燥的粉末性能变差并可能造成严重的流动性问题。目前的超时高强度研磨技术产生非常细粒的粉末悬浮液,其中很少或没有沉降发生。由于该喷雾干燥过程,得到了通过压合剂结合在一起的直径约0.1mm的球形颗粒团(agglomerate)。对于中等至低粘结相含量的烧结碳化物组合物是如此。但是,对于粘结相含量为20-30wt-%的情况,由于目前未知的某些原因,所形成的颗粒团的性能差,得到了不能用于自动化生产的流动性非常差的易压制(ready to press)粉末。因此不得不使更多使用手工方法以确保得到满意的烧结产品。
本发明的一个目的是提供制备具有高粘结相含量的烧结碳化物组合物的改进方法。
本发明的另一个目的是提供易压制的具有高粘结相含量的烧结碳化物粉末,其基本由粒度分布窄的球形颗粒团组成。
图1以50X的放大率显示了根据本发明制备的烧结碳化物颗粒团。
图2以50X的放大率显示了根据现有技术制备的烧结碳化物颗粒团。
现在出人意料地发现可以制得经喷雾干燥的具有高粘结相含量并且具有成形良好的颗粒团的烧结碳化物粉末,该成形良好的颗粒团为圆形且粒度分布窄。
本发明的一个方面提供了优选在研磨用液体中通过湿磨粉末混合物并喷雾干燥所述的浆料来制备成团粉末混合物的方法,所述的研磨用液体包括水和/或醇或水与丙酮的混合物,所述的粉末混合物含有基于Ti、Zr、Hf、V、Nb、Ta、Cr、Mo和/或W的碳化物的硬质成分粉末、大于15wt-%的Co和/或Ni的粘结相粉末、以及压合剂。根据本发明,在研磨前向所述的粉末混合物中另外添加0.05-0.50wt-%的复合成形(complex forming)添加剂和/或升高/降低pH的添加剂如三乙醇胺、氢氧化物或酸,以及0.01-0.10wt-%量的增稠剂。适合的增稠剂包括单独使用或联合使用的交联(cross-bonded)丙烯酸乳液、疏水改性的羟乙基纤维素(HM-HEC)、疏水改性的环氧乙烷聚氨酯(HEUR)、苯乙烯-马来酸酐共聚物、黄原胶多糖以及乙基羟乙基纤维素(EHEC)。在一个优选的实施方案中,所述的浆料含有20-30wt-%的粘结相粉末。在另一优选的实施方案中,所述的硬质成分包括WC。
本发明的另一方面提供了一种浆料,其含有基于Ti、Zr、Hf、V、Nb、Ta、Cr、Mo和/或W的碳化物的硬质成分粉末、大于15wt-%的Co和/或Ni的粘结相粉末、以及压合剂,还含有0.05-0.50wt-%的复合成形添加剂和/或升高/降低pH的添加剂如三乙醇胺、氢氧化物或酸,以及0.01-0.10wt-%量的增稠剂。适合的增稠剂包括单独使用或联合使用的交联丙烯酸乳液、疏水改性的羟乙基纤维素(HM-HEC)、疏水改性的环氧乙烷聚氨酯(HEUR)、苯乙烯-马来酸酐共聚物、黄原胶多糖以及乙基羟乙基纤维素(EHEC)。
在一个优选的实施方案中,所述的浆料含有20-30wt-%的粘结相粉末。在另一优选的实施方案中,所述的硬质成分包括WC。
本发明的另一方面提供了成团粉末,其含有基于Ti、Zr、Hf、V、Nb、Ta、Cr、Mo和/或W的碳化物的硬质成分粉末、大于15wt-%的Co和/或Ni的粘结相粉末、以及压合剂,该成团粉末的颗粒团粒度分布的跨度(span)S=d97/d03<1.2,其中
d97=颗粒团的累计粒度分布数达到97%时所对应的粒径,即小于该粒径的颗粒团占97%,以及
d03=颗粒团的累计粒度分布数达到3%时所对应的粒径,即小于该粒径的颗粒团占3%。
在一个优选的实施方案中,所述的浆料含有20-30wt-%的粘结相粉末。在另一优选的实施方案中,所述的硬质成分包括WC。
实施例1
通过在水和醇的混合物中将适量的Co粉、Ni粉和WC粉与2wt-%PEG、0.125wt-%三乙醇胺以及0.025wt-%Bermocoll EBS 451 FQ一起研磨9小时来制备用于生产热轧辊的易压制的烧结碳化物粉末,该烧结碳化物粉末具有粘结相且平均晶粒粒度为18μm,该粘结相由15wt-%Ni、13wt-%Co以及余量的WC组成。所得浆料的沉降倾向低。根据标准操作在喷雾干燥器中干燥所述的浆料。从而得到如图1所示具有窄的粒度分布的成团的粉末混合物。
实施例2
重复实施例1但不添加三乙醇胺和Bermocoll。即使在该条件下也得到了具有低沉降倾向的浆料。如图2所示,所得的“成团”粉末具有宽的粒度分布,并且其中部分原先的粉末根本没有形成颗粒团。
实施例3
对由实施例1和实施例2得到的粉末进行测试,根据ISO 4490测试流动时间,根据ISO 3953测试表观密度,结果如下。也对颗粒团的粒度分布进行了测试并以跨度S=d97/d03进行表征,其中
d97=颗粒团的累计粒度分布数达到97%时所对应的粒径,即小于该粒径的颗粒团占97%,以及
d03=颗粒团的累计粒度分布数达到3%时所对应的粒径,即小于该粒径的颗粒团占3%。
流动时间s | 表观密度g/cm3 | 跨度 | |
实施例1 | 36 | 3.02 | 1.1 |
实施例2 | 42 | 2.85 | 1.5 |
Claims (10)
1.通过湿磨粉末混合物并喷雾干燥所述的浆料来制备成团粉末混合物的方法,该粉末混合物含有基于Ti、Zr、Hf、V、Nb、Ta、Cr、Mo和/或W的碳化物的硬质成分粉末、大于15wt-%的Co和/或Ni的粘结相粉末、以及压合剂,其特征在于在研磨前向所述的粉末混合物中另外添加0.05-0.50wt-%的复合成形添加剂和/或升高/降低pH的添加剂如三乙醇胺、氢氧化物或酸,以及0.01-0.10wt-%量的增稠剂。
2.根据权利要求1所述的方法,其特征在于所述的增稠剂为交联丙烯酸乳液、疏水改性的羟乙基纤维素(HM-HEC)、疏水改性的环氧乙烷聚氨酯(HEUR)、苯乙烯-马来酸酐共聚物、黄原胶多糖以及乙基羟乙基纤维素(EHEC)中的一种或多种,其能单独使用或联合使用。
3.根据前面任一权利要求所述的方法,其特征在于所述的浆料含有20-30wt-%的粘结相粉末。
4.根据前面任一权利要求所述的方法,其特征在于所述的硬质成分包括WC。
5.一种浆料,其含有基于Ti、Zr、Hf、V、Nb、Ta、Cr、Mo和/或W的碳化物的硬质成分粉末、大于15wt-%的Co和/或Ni的粘结相粉末、以及压合剂,其特征在于其还含有0.05-0.50wt-%的复合成形添加剂和/或升高/降低pH的添加剂如三乙醇胺、氢氧化物或酸,以及0.01-0.10wt-%量的增稠剂。
6.根据权利要求5所述的浆料,其特征在于所述的增稠剂为交联丙烯酸乳液、疏水改性的羟乙基纤维素(HM-HEC)、疏水改性的环氧乙烷聚氨酯(HEUR)、苯乙烯-马来酸酐共聚物、黄原胶多糖以及乙基羟乙基纤维素(EHEC)中的一种或多种,其能单独使用或联合使用。
7.根据权利要求5或6中任意一项所述的浆料,其特征在于所述的浆料还含有20-30wt-%的粘结相粉末。
8.根据权利要求5、6或7中任意一项所述的浆料,其特征在于所述的硬质成分包括WC。
9.一种成团粉末,其含有基于Ti、Zr、Hf、V、Nb、Ta、Cr、Mo和/或W的碳化物的硬质成分粉末、大于15wt-%的Co和/或Ni的粘结相粉末、以及压合剂,其特征在于颗粒团的粒度分布的跨度S=d97/d03<1.2,其中
d97=颗粒团的累计粒度分布数达到97%时所对应的粒径,即小于该粒径的颗粒团占97%,以及,
d03=颗粒团的累计粒度分布数达到3%时所对应的粒径,即小于该粒径的颗粒团占3%。
10.根据权利要求9所述的成团的粉末,其特征在于含有20-30wt-%的粘结相粉末并且所述的硬质成分包括WC。
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SE0501103A SE529202C2 (sv) | 2005-05-17 | 2005-05-17 | Sätt att tillverka en agglomererad pulverblandning av en slurry och agglomererat pulver |
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EP (1) | EP1724363B1 (zh) |
JP (1) | JP2006322073A (zh) |
KR (1) | KR100778266B1 (zh) |
CN (1) | CN100519793C (zh) |
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SE533912C2 (sv) * | 2009-02-19 | 2011-03-01 | Seco Tools Ab | Finkornig hårdmetallpulverblandning med låg sintringskrympning och sätt att tillverka densamma |
JP2013514258A (ja) | 2009-12-18 | 2013-04-25 | インビスタ テクノロジーズ エス エイ アール エル | 塩基性炭酸ニッケルから生じさせたニッケル金属組成物およびニッケル錯体 |
CN103080120B (zh) | 2010-09-07 | 2016-06-01 | 因温斯特技术公司 | 制备镍磷配体配合物 |
CN103732323B (zh) | 2011-06-10 | 2016-09-14 | 因温斯特技术公司 | 用于催化镍-配体配合物的制备的镍形式 |
US9475945B2 (en) | 2013-10-03 | 2016-10-25 | Kennametal Inc. | Aqueous slurry for making a powder of hard material |
IN2013CH04500A (zh) | 2013-10-04 | 2015-04-10 | Kennametal India Ltd | |
EP2955241B1 (en) | 2014-06-12 | 2024-01-24 | Maschinenfabrik Gustav Eirich GmbH & Co. KG | Method for manufacturing a cemented carbide or cermet body |
CN108188387A (zh) * | 2017-12-28 | 2018-06-22 | 苏州新锐合金工具股份有限公司 | 一种采用替代成型剂的硬质合金混粉工艺 |
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US4397889A (en) * | 1982-04-05 | 1983-08-09 | Gte Products Corporation | Process for producing refractory powder |
CA2041668C (en) * | 1989-09-14 | 1999-08-03 | Nobuyuki Kitagawa | Method of preparing cemented carbide or cermet alloy |
KR0163992B1 (ko) * | 1995-06-01 | 1999-01-15 | 서상기 | 초미립 WC-Co 합금 분말의 제조방법 |
WO1998000256A1 (en) * | 1996-06-28 | 1998-01-08 | Sandvik Ab (Publ) | Method of spray drying powder mixtures |
SE9702154L (sv) * | 1996-06-28 | 1997-12-29 | Sandvik Ab | Metod att tillverka en pulverblandning |
SE518810C2 (sv) * | 1996-07-19 | 2002-11-26 | Sandvik Ab | Hårdmetallkropp med förbättrade högtemperatur- och termomekaniska egenskaper |
SE9603936D0 (sv) * | 1996-10-25 | 1996-10-25 | Sandvik Ab | Method of making cemented carbide by metal injection molding |
SE510749C2 (sv) | 1997-12-22 | 1999-06-21 | Sandvik Ab | Sätt att framställa ett metallkompositmaterial innehållande hårda partiklar och bindemetall |
US6245288B1 (en) * | 1999-03-26 | 2001-06-12 | Omg Americas, Inc. | Method of preparing pressable powders of a transition metal carbide, iron group metal of mixtures thereof |
SE516324C2 (sv) * | 2000-05-09 | 2001-12-17 | Sandvik Ab | Framställning av väldispergerade suspensioner lämpliga för spraytorkning |
SE0203559L (sv) * | 2002-12-02 | 2004-02-10 | Seco Tools Ab | Slurry och metod att framställa denna för framställning av hårdmetall och ett pulver |
EP1440956A1 (en) * | 2003-01-24 | 2004-07-28 | Seco Tools Ab | Method of making tungsten carbide based hard materials |
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KR20060119790A (ko) | 2006-11-24 |
JP2006322073A (ja) | 2006-11-30 |
US7537637B2 (en) | 2009-05-26 |
IL175616A0 (en) | 2006-09-05 |
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