CN1882501A - 双相硬质材料及其制备方法和应用 - Google Patents

双相硬质材料及其制备方法和应用 Download PDF

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CN1882501A
CN1882501A CNA2004800341693A CN200480034169A CN1882501A CN 1882501 A CN1882501 A CN 1882501A CN A2004800341693 A CNA2004800341693 A CN A2004800341693A CN 200480034169 A CN200480034169 A CN 200480034169A CN 1882501 A CN1882501 A CN 1882501A
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C·格尔克
K·-D·维尔尼克
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Sun Tech Surface Technology And Ceramic Powder Ltd By Share Ltd
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Abstract

本发明涉及一种由粉末颗粒组成的碳化钨粉末，该颗粒具有由碳化钨熔体制成的芯体和由一碳化钨制成的壳，本发明还涉及通过在有碳源存在下加热到1300－2000℃而制备该粉末的方法，本发明还涉及该粉末在受磨损的构件的表面层中的应用和在制备钻头中的应用。

Description

双相硬质材料及其制备方法和应用
本发明涉及一种由粉末颗粒组成的碳化钨粉末，所述粉末颗粒具有由碳化钨熔体构成的芯体和由一碳化钨构成的壳，本发明还涉及所述碳化钨粉末的制备及其用于受磨损构件或其涂层中和用途。
硬质材料，特别是碳化钨由于其硬度和耐受性具有广泛应用。例如可在工具如挖掘机铲斗上涂覆含该硬质材料的层，以使该工具对磨擦和冲击具有高的耐磨性和韧性。
从碳化钨族中，在工业上使用一碳化钨(WC)和所谓的碳化钨熔体(WSC)。WSC是由WC和碳化二钨(W2C)组成的低共熔混合物，其中平均碳质量比通常为3.8-4.2重量％。这相应于73-80重量％的W2C和20-27重量％的WC的相分布。WSC具有非常细粒的晶体结构，该结构常被形容为羽状结构，并通过碳化物熔体的快速淬火而获得。
从US-A 4834963已知所谓微晶WC(mWC)的制备。它是经铝热法制备的，其特征特别在于非常少的杂质含量。通过将金属铁加到原料混合物中，该制备过程在所需温度范围内进行。mWC由于其粒度而在许多领域代替WSC使用。但与WSC相比，mWC具有明显较低的硬度和韧性。
已知各种制备WSC的方法，这些方法的主要差别在于加热和散热的类型。DE 3626031 A1描述了在电弧中制备WSC。得到碳含量为3.5-4.2重量％和具有细针形结构的WSC。硬度HV0.4为2100-2400。该WSC经受经典加工技术如破碎和过筛处理，以得到经破碎并分级的WSC。
从EP 238425 B1、DE 19945318 A1和EP 687650 A1中已知各种制备WSC的方法，该WSC的特征是球形颗粒形态。球形的WSC(sWSC)除具有超过3000HV0.1的特高硬度外，还由于其形态而相对于破碎的WSC具有优点，例如在避免负荷下的应力峰方面。
为制备磨损保护层或构件而加工WSC时，该WSC通常与基于Fe、Ni或Co的粉末状金属合金混合，并在热作用下加工。在制备钻头时，基质金属如Cu也可通过渗入加入。但在任何情况下均需热处理。通过基质金属的熔融和再凝固，硬质材料均匀分布在延展性金属基质中并牢固嵌入。
WSC的主要缺点在于，在嵌入基质金属时所需的金属热处理过程中该WSC会部分溶解(B.Z.Li等人：Acta.Met.，Vol 12，No.4，566-572(1999)，F.Schreiber：Ziegelindustrie International，55(6)，12-17(2002)，I.Aydin等人：DVS-Bericht 175137-142(1996))。因比，部分可用的硬质材料和作为基质材料使用的金属合金会通过钨和碳的浓集呈不可逆改变。该硬质材料在待加工的硬质材料-基质金属混合物中的含量的简单增加在加工方面明显设置了限制。由于该混合物的流动特性，该硬质材料在含基质金属的混合物中的含量在焊接应用时不超过60重量％。
另一复杂因素是，溶解的WSC的量随处理温度和热作用的时间的增加而增加。为阐明这种效应，作为例子可提及磨损保护层的手工焊接。所得层的局部质量与用于焊接的设备的操作人员的能力、稳定性和耐性直接有关，因为该操作人员影响了热处理的强度和时间。在机焊或类似标准化的工艺中该WSC的溶解也产生负作用。例如用于热处理的温度和焊接速度仅可在窄的范围内选定，以避免WSC太多溶解或甚至完全溶解。
WSC的溶解可明显改变基质材料。通过碳和钨在金属中的溶解会导致例如脆性碳化物相的不可控沉淀，该碳化物相降低了基质的延展性并促使裂纹形成。对含较少量附加的碳化物形成剂的基质合金，WSC的溶解也是有缺点的，因为在任何情况下均会降低硬质材料的可用含量。在应用Fe基合金时，碳的浓集会引起奥氏体的沉淀，与所需的铁素体相相比，该奥氏体具有较差的磨损性。
大量的技术研发是间接针对在制备磨损保护层时抑制所用硬质材料的溶解。如应用低熔点的基质合金、含少量碳化物形成剂的基质合金或具有与温度相关的高工艺稳定性的加热方法(等离子体转换弧(PTA)，激光)。但并未由此消除WSC在许多基质金属中的高溶性的主要问题。
因此，本发明的目的在于提供一种碳化钨，其特征在于高的化学稳定性，特别是在金属熔体中的稳定性，并同时具有高硬度和韧性。
该目的是通过一种碳化钨粉末实现的，该粉末具有WSC芯体及包围该芯体的WC致密壳。
因此本发明涉及碳化钨粉末，其中粉末颗粒具有由碳化钨熔体形成的芯体和由一碳化钨形成的壳。
在下面简称为“cWSC”的本发明硬质材料可通过渗碳到所需深度而将WSC转变成WC来制得，并例如可用于制备磨损保护层和耐磨构件。
本发明的cWSC的特征尤其在于，当以通常方法加工，即与液态基质材料接触时仍可保持在WC/WSC复合体的芯体中的WSC的优异韧性和硬度。
本发明的碳化钨粉末的结合碳含量优选为4-6重量％，特别优选为4.5-5.5重量％，更特别优选4.3-4.8重量％。游离碳的含量应不超过0.1重量％。
如果结合碳含量小于4重量％，则无足够致密的WC壳形成，由此得不到比WSC提高的化学稳定性。当该结合碳含量接近纯WC的6.13重量％的限值时，则该WSC芯体会如此小，以致不再达到比纯WC提高的硬度。
当具有少量WC颗粒，即并非所有粉末颗粒均由WSC芯体和WC壳构成时，本发明的碳化钨粉末的有利特性仍可保持。因此这种碳化钨粉末也属本发明。但优选是至少90％的粉末颗粒具有WSC芯体和WC壳，特别优选是至少95％，更特别优选至少99％的粉末颗粒具有WSC芯体和WC壳。
平均粒度可在宽范围内变化，特别是取决于cWSC的预计应用。按ASTM B 214借助于RoTap筛所测定的粒度例如可达3000μm。如果cWSC用于以PTA法制备磨损保护层，则该按ASTM B 214借助于RoTap筛所测定的粒度级分为40-160μm是有利的。平均粒度的调节例如可通过选定具有确定的平均粒度的WSC粉末作为制备cWSC的原料而实现。但例如也可由已制备的cWSC例如通过筛分或分选而混合或分离特定的颗粒级分。
在本发明的碳化钨粉末中，WSC芯体由致密的一碳化钨壳所包围。用光学显微镜对蚀刻的材料所测定的该壳的厚度优选为0.05-0.4倍、特别优选0.05-0.15倍于按ASTM B 214借助于RoTap筛所测定的平均粒度。
cWSC具有优异的硬度。维氏硬度优选为＞2000HV0.1，特别优选＞2500HV0.1。
颗粒形态的调节例如可通过应用合适的WSC粉末实现。
因此，本发明的碳化钨粉末可具有各种形态，例如锐边破碎形或球形。球形形态在耐磨方面具有大的优点，但其制备比具有无规则形态的粉末更为耗费。
本发明的目的还在于提供一种制备本发明的碳化钨(cWSC)的方法，其中将碳化钨熔体粉末在有碳源存在的条件下加热到1300-2000℃，优选1400-1700℃。
本发明的方法可在有惰性气体存在下、在反应性气体存在下或在真空中进行。优选在有氢存在下进行。
特别适于作为反应性气体的是气态碳源，例如一氧化碳、CO/CO2混合物、烃或烃混合物，如天然气。
气态和固态的碳源可作为碳源。作为固态碳源可例如使用炭黑或石墨。当然也可使用各种气态和/或固态碳源的混合物。
通过在有碳源存在下对WSC进行热处理，可在表面上引起W2C向WC的转变。即在WSC周围形成致密的WC层。
温度、转化时间和加入的碳源量的选择要使以所需厚度形成WC壳。这时要注意，在颗粒内部仍保持WSC。该遵循的条件主要由所用WSC粉末的粒度和颗粒形状来确定，并可用简单系列试验来确定。如果使用太高的碳含量，则会不必要地增加用于转变所需的时间和温度，并减少羽状结构即WSC的含量。
有利的是，加入的碳源量应使反应混合物中的总碳含量即WSC的碳含量和碳源之和为4-6重量％，优选为4.3-5.5重量％。
在WSC与宽粒度变化的粉末颗粒反应时，细颗粒级分在颗粒直径上比粗颗粒的渗碳更强。这主要是针对具有高含量的＜45μm的特细颗粒的粉末而言，并且可通过预先分离掉细粒级分和使各种粉末级分单独进行反应来加以防止。
转化时间例如可为1-10小时，优选1.5-7小时。
为制备本发明的碳化钨，例如可从破碎的或球形WSC开始，将其筛分到所需粒度。接着使该材料与所需量的碳源如炭黑进行强烈混合，并经受热处理，这时在表面渗碳。适用于热处理的是例如常规推进式炉或相当的装置，这些装置例如可在1550-1900℃的温度范围内于氢气气氛或保护气气氮下运行。将WSC和炭黑的混合物装入例如石墨小舟中。在转化时碳与WSC中存在的W2C反应，并使W2C转变成WC，该WC与已存在的WC不再有区别。由此所形成的WC表面层形成了碳的天然扩散屏障，以致可通过参数即时间和温度控制所需的渗碳深度。
本发明的cWSC可以通常的方式通过烧结、喷涂、焊接、渗入、旋涂或其它适于制备致密复合材料的方法进行加工。特别适于制备受磨损的构件的表面层。为此通常将cWSC与基质金属如基于Fe、Ni或Co的合金混合，并接着用所述方法特别是通过焊接施加到要保护的表面上。
因此，本发明的目的还在于本发明的碳化钨粉末在受磨损构件的表面层和制备钻头中的应用。
下面的实施例用于详述本发明，该实施例应有助于理解本发明的原理，不对本发明构成限制。
实施例
总碳含量通过在氧流中燃烧样品和导热性检测测定，游离碳含量通过酸浸(HF/HNO3/H3PO4)和接着的在氧流中燃烧后的非色散红外吸收测定。结合碳的含量相应于总碳量和游离碳量的差。
实施例1
含约3.94重量％的结合碳和0.035重量％的游离碳的粒度为-150+45μm的WSC与炭黑(BET比表面积为10m2/g)相混合。加入的炭黑量的选择要使总碳量C总＝5.7重量％。将该混合物装入石墨小舟中，并在1550℃的推式炉中于氢气下灼烧2小时。将所得cWSC制成截面磨片，蚀刻以用于显示相组成，并在反射光显微镜下进行研究。显微镜照片(放大1000倍)示于图1。
经渗碳后该粗颗粒具有由WC组成的约15μm厚的表面层，其在图1中呈亮的表面层。具有大的长宽比(纵横比)的颗粒即长形颗粒有部分完全渗碳。最终产物的结合碳含量为5.26重量％，游离碳含量为0.41重量％。高含量的游离碳表明，在所选的渗碳条件下所提供的碳未被完全吸收。与原料相比，150-45μm的筛分粒级的比例通过处理未经改变。
在6kg的所得的碳化钨中加入4kg的作为基质金属的粒度为-150+53μm的Ni-3B-3Si合金，并借助于等离子体输送弧(PTA)焊接以手持焊抢在70-80A/约30V下将其以一层和两层焊在钢板上。该材料易形成不平稳的熔体以及形成溅沫，这可归因于高的游离碳含量。该样品以截面磨片在反射显微镜下研究。显微照片示于图2(放大50倍)和图3(放大500倍)。
在焊接时所形成的结构几乎无碳化物沉淀。基质金属和硬质材料保持其原始组成。特别是朝向大气的经受强热应力的表面区与热影响区的中心范围和下面范围相比显示出未经改变的高含量的完好硬质材料，其中明显量的颗粒甚至突出于朝向大气的表面之外。
为进行比较，对用于制备本发明碳化钨所用的WSC在相同条件下进行焊接。该WSC在外表面范围直到200-500μm深处几乎完全溶解。这产生细碳化物的沉淀。该样品以截面磨片在反射显微镜下研究。显微照片示于图4(放大50倍)和图5(放大500倍)。可明显看出细碳化物颗粒。
定量图象分析表明，在相同量的所使用的硬质材料下，在复合材料中所淀积的硬质材料颗粒数比在相同条件下所焊接的未经渗碳的对比材料(WSC)高约30％。
实施例2
类似实施例1，使粒度为-150+45μm的WSC与炭黑反应。但处理时间为6小时。得到结合碳含量为5.48重量％和游离碳含量为0.06重量％的cWSC。粒度分布不受反应时间延长的影响。如所预料的，与实施例1相比游离碳和结合碳的比可通过延长热处理而降低。类似实施例1，将6kg的cWSC与4kg的Ni-3B-3Si合金相混合，并用PTA手提焊抢焊接。与实施例1相比，该较少的游离碳含量在焊接特性上产生有利的效果。在焊层的显微镜研究中表明，未溶解的碳化钨颗粒数与未经渗碳的比较样品(WSC)相比再提高10％，即总共高40％。
实施例3
类似实施例1，使粒度为-150+45μm的WSC与炭黑反应。但应用较少量的炭黑，以使该混合物的总碳含量为4.3重量％。得到结合碳含量为4.3重量％和游离碳含量为0.01重量％的cWSC。由于加入的碳源量少，仅形成非常薄的WC壳。类似实施例1，将6kg如此所得的碳化钨与4kg的Ni-3B-3Si合金相混合，并用PTA手提焊抢焊接。该混合物的焊接特性与未经渗碳的对比样品(WSC)难以区分。在焊层的显微镜研究中表明，尽管是非常薄的WC壳，仍可明显抑制碳化钨的溶解。但与实施例1和2相比，形成明显较高含量的在冷却时在金属基质中从熔体中沉淀出的碳化物。与未经渗碳的对比材料(WSC)相比，在焊接层中保留的碳化钨颗粒数增加为约18％。
图6示出焊接后该碳化钨的以截面磨片的显微镜照片(放大50倍)。可看出少量的游离的碳化物颗粒。
实施例4(对比)
为比较，类似实施例1，将4kg的Ni-3B-3Si合金加到6kg的粒度为-150+45μm的含6.1重量％的结合碳的微晶WC中，并在实施例1的条件下焊接。如所预料的，该微晶WC在焊接时未溶解。在焊接层中的硬质材料颗粒的含量比应用实施例1中的WSC原料约高48％。在焊接层中的微晶WC的硬度约为1500HV0.1，因此明显低于本发明实施例1-3中的cWSC的硬度(该硬度可为2200-2500HV0.1)。焊接后的基质金属的平均硬度约为700HV0.1。

Claims (11)

1.一种碳化钨粉末，其特征在于，该粉末颗粒具有由碳化钨熔体构成的芯体和由一碳化钨构成的壳。
2.权利要求1的碳化钨粉末，其特征在于，结合碳的含量为4-6重量％，优选4.3-5.5重量％。
3.权利要求1或2的碳化钨粉末，其特征在于，按ASTM B 214借助于RoTap筛分析所测定的粒度达3000μm。
4.权利要求1-3中至少一项的碳化钨粉末，其特征在于，由一碳化钨构成的壳的厚度为所述平均粒度的0.05-0.4倍。
5.权利要求1-4中至少一项的碳化钨粉末，其特征在于，其硬度大于2000 HV 0.1。
6.权利要求1-5中至少一项的碳化钨粉末，其特征在于，该粉末颗粒具有锐边破碎形态。
7.一种制备权利要求中1-6之一的碳化钨粉末的方法，其特征在于，将碳化钨熔体粉末在有碳源存在的条件下加热到1300-2000℃，优选1400-1700℃。
8.权利要求7的方法，其特征在于，所述碳源是炭黑、石墨和/或烃。
9.权利要求7或8的方法，其特征在于，所述碳源的加入量要使在反应混合物中的总碳量为4-6重量％。
10.权利要求1-6之一的碳化钨粉末在受磨损的构件的表面层中的应用。
11.权利要求1-6之一的碳化钨粉末在制备钻头中的应用。
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CN103930578A (zh) * 2011-10-27 2014-07-16 H.C.施塔克股份有限公司 硬质金属组合物
CN109562947A (zh) * 2016-07-21 2019-04-02 霍加纳斯股份有限公司 一碳化钨(wc)球形粉末的制造

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CN100441505C (zh) 2008-12-10
IL175668A (en) 2010-11-30
US7541090B2 (en) 2009-06-02
JP2007516918A (ja) 2007-06-28
US20090263646A1 (en) 2009-10-22
US20070079905A1 (en) 2007-04-12
IL175668A0 (en) 2006-09-05
KR101083940B1 (ko) 2011-11-15
ATE359233T1 (de) 2007-05-15
WO2005049490A1 (de) 2005-06-02
US7810587B2 (en) 2010-10-12
CA2546617A1 (en) 2005-06-02
EP1687239B1 (de) 2007-04-11
DE502004003500D1 (de) 2007-05-24
JP4773362B2 (ja) 2011-09-14
PL1687239T3 (pl) 2007-09-28
EP1687239A1 (de) 2006-08-09

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