CN107417279A - 烧结陶瓷体及其应用 - Google Patents
烧结陶瓷体及其应用 Download PDFInfo
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Abstract
本发明公开了烧结陶瓷体及其应用。在一个方面,本文描述了烧结陶瓷体,在一些实施例中,所述烧结陶瓷体展现出改善的耐磨性和增强的切削寿命。例如,烧结陶瓷体包含40‑95重量%的量的碳化钨(WC)、5‑30重量%的量的氧化铝以及至少1重量%的量的碳化二钨(W2C)。
Description
技术领域
本发明涉及烧结陶瓷体,并且具体地讲,涉及具有用于金属切削应用的组成和特性的烧结陶瓷体。
背景技术
硬质碳化物(Cemented carbide)通常用作加工各种金属和合金的切削工具主体。硬质碳化物对于金属切削应用是有吸引力的材料,因为碳化物特性可针对切削环境的特定要求进行调整。例如,具有小晶粒大小和低粘结剂含量的硬质碳化物适用于要求高硬度和耐磨性的应用。或者,具有较高粘结剂含量的硬质碳化物表现出所需的耐热冲击性,并且一般用于断续切削应用。
然而,硬质碳化物不适用于所有金属加工应用。在一些应用中,硬质碳化物可能与正在加工的金属或合金发生化学反应。此外,硬质碳化物可能不适用于因高进料速率和更大切削深度而要求高热硬度和优异热散逸的应用。对于这些应用,烧结陶瓷组合物用作切削工具主体。烧结陶瓷体可表现出化学惰性、高耐磨性、高热硬度以及对于热耗散优异的热特性。目前使用的烧结陶瓷体在很大程度上基于氧化铝(Al2O3)和/或氮化硅(Si3N4)。此类材料提供相对于硬质碳化物而言增强的高温特性,从而能够缩短制成成品的操作时间。然而,烧结陶瓷基材的改善必需满足金属加工应用的发展需求,并且当对烧结陶瓷体做出组成变化以便向切削工具提供改善的性能时,需要竞争特性之间的仔细平衡。
发明内容
在一个方面,本文描述了烧结陶瓷体,其展现出改善的耐磨性和增强的切削寿命。例如,在一些实施例中,烧结陶瓷体包含40-95重量%的量的碳化钨(WC)、5-30重量%的量的氧化铝以及至少1重量%的量的碳化二钨(W2C)。在一些实施例中,W2C以1-25重量%的量存在。
或者,烧结陶瓷体包含40-95重量%的量的WC、1-50重量%的量的氧化铝以及一种或多种含钛和钼(Ti,Mo)的化合物。在一些实施例中,含(Ti,Mo)的化合物以0.1至20重量%的总量存在于烧结陶瓷体中。在一些实施例中,W2C还以至少0.1重量%的量存在。
在另外的实施例中,烧结陶瓷体包含40-95重量%的量的WC以及氮氧化铝(AlON)。
如本文进一步所述,烧结陶瓷体可用于金属切削应用。因此,烧结陶瓷体可具有金属切削工具的形状。例如,本文所述组成的烧结陶瓷体可包括前刀面以及与前刀面相交形成刀刃的后刀面。
这些和其他实施例在下文的具体实施方式中更详细地描述。
附图说明
图1为根据本文所述的一个实施例的包含WC和AlON的烧结陶瓷体的X射线衍射图(XRD)。
图2为根据本文所述的一个实施例的烧结陶瓷体的XRD。
图3为根据本文所述的一个实施例的烧结陶瓷体的XRD。
图4示出了本文所述的烧结陶瓷体相对于对比烧结陶瓷体的金属切削结果。
图5示出了本文所述的烧结陶瓷体相对于对比烧结陶瓷体的金属切削结果。
图6为根据本文所述的一个实施例的烧结陶瓷体的XRD。
图7示出了本文所述的烧结陶瓷体相对于对比烧结陶瓷体的金属切削结果。
具体实施方式
参考以下具体实施方式和实例以及前述和下述内容可更容易地理解本文所述的实施例。然而,本文所述的元素、设备和方法并不限于具体实施方式和实例中所述的具体实施例。应当认识到,这些实施例仅示例性地说明本发明的原理。在不脱离本发明精神和范围的情况下,多种修改和变更对于本领域技术人员而言将是显而易见的。
I.WC-W2C-Al2O3烧结陶瓷体
本文描述了具有对于金属切削应用所需的特性的烧结陶瓷体。在一个方面,烧结陶瓷体包含40-95重量%的量的WC、5-30重量%的量的氧化铝以及至少1重量%的量的W2C。在一些实施例中,W2C以选自表I的量存在于烧结陶瓷体中。
表I-W2C含量(重量%)
1-25 |
1.5-25 |
2-25 |
5-20 |
10-20 |
12-18 |
3-15 |
此外,氧化铝可以选自表II的量存在于烧结陶瓷体中。
表II-Al2O3含量
10-25 |
15-30 |
20-30 |
10-20 |
5-15 |
在一些实施例中,烧结陶瓷体的氧化铝仅仅为α-氧化铝。或者,烧结陶瓷体的氧化铝可包括多晶型物的混合物,诸如α+κ。可根据X射线衍射(XRD)分析技术确定氧化铝晶相或晶体结构。
在一些实施例中,烧结陶瓷体还包含含一种或多种稀土元素的氧化物组分。例如,氧化物组分可包含选自镱、镧、钐、镝和铒的一种或多种稀土元素。当制造烧结陶瓷体时,氧化物组分可以稀土氧化物粉末的形式提供,诸如Yb2O3、La2O3、Dy2O3、Sm2O3、Er2O3或它们的混合物。当用其他形成主体的粉末组分(例如,WC、W2C和Al2O3)烧结时,氧化物组分可形成混合的氧化物。在一些实施例中,例如,在烧结过程中形成包含一种或多种稀土元素和铝的混合氧化物。此类混合氧化物可包括由化学式RE3Al15012表示的那些,其中RE为一种或多种稀土元素。也可形成由其他化学式表示的混合氧化物。在一些实施例中,氧化物组分还可包括诸如Y2O3和/或MgO之类的氧化物。
含一种或多种稀土元素的氧化物组分一般可以0.1-20重量%范围内的量存在于烧结陶瓷组合物中。在一些实施例中,氧化物组分以1-15重量%的量存在。另外,一种或多种稀土元素以0.05-3重量%的总量存在于烧结陶瓷体中。可根据若干熟知的技术(包括X射线荧光(XRF)或电子能谱术)实施烧结陶瓷体的元素分析。
烧结陶瓷体还可包含氧化锆。在一些实施例中,氧化锆包含稳定剂,诸如氧化钇、氧化铈、氧化镁和/或氧化钙。在此类实施例中,氧化锆可表现出四方晶体结构或者四方和单斜晶体结构的混合物。与氧化铝一样,可用XRD技术阐明氧化锆的晶体结构。氧化锆一般可以0.1-10重量%的量存在于烧结陶瓷体中。在一些实施例中,氧化锆以0.1-5重量%的量存在。此外,锆(Zr)可以0.05-5重量%的量存在于烧结陶瓷组合物中。
如本文进一步所述,烧结陶瓷体还可包含一种或多种Ti化合物、Mo化合物或(Ti,Mo)化合物或它们的混合物。此类化合物可为碳化物、氮化物、碳氮化物、氧碳氮化物或氧化物或它们的混合物。Ti化合物、Mo化合物和/或(Ti,Mo)化合物一般以0.1-20重量%的总量存在于烧结陶瓷体中。当制造烧结陶瓷体时,可在烧结之前将各种含Ti的和/或含Mo的粉末掺入到主体中。合适的粉末包括但不限于TiC、TiN、TiCN、MoC、MoO3和Mo金属。在一些实施例中,Mo以0.05-5重量%的量存在于烧结陶瓷体中。与烧结陶瓷体中的其他元素一样,可根据XRF或电子能谱技术确定Mo含量。
在一些实施例中,烧结陶瓷体还可包含添加剂组分。添加剂组分可包括一种或多种VB族金属碳化物,诸如碳化钒(VC)、碳化钽(TaC)、碳化铌(NbC)和/或NbZrC。在一些实施例中,添加剂组分包括作为VB族金属碳化物的补充或与其分开的碳化铬。烧结陶瓷体中包含的碳化铬可由化学式Cr2C3或其他化学式表示。在一些实施例中,添加剂组分以0.1-15重量%的量存在于烧结陶瓷体中。添加剂组分的单独物质可以选自表III的量存在。
表III-添加剂组分的物质(重量%)
物质 | 量 |
VC | 0.05-1 |
Cr2C3 | 0.05-1 |
TaC | 0.05-5 |
NbC | 0.5-5 |
ZrNbC | 0.5-5 |
烧结陶瓷体还可包含AlON。在一些实施例中,AlON以0.1至20重量%的量存在。在存在AlON的实施例中,可在生坯形成期间将氮化铝(AlN)加入到粉末混合物中。在粉末混合物的烧结期间,AlN部分或完全转化为AlON。可在氮气气氛中实施烧结,以有利于AlON相的形成。当部分转化为AlON时,AlN可仍为烧结陶瓷体的组分。在一些实施例中,例如,AlN以0.05-5重量%的量存在于烧结陶瓷体中。或者,可在生坯形成期间将AlON粉末以所需的量加入到粉末混合物中。
如本文所述,烧结陶瓷体可包含多种组分。表IV总结了该第I部分中涉及的烧结陶瓷体的必需组分和任选组分。上文提供了必需组分和任选组分的特定量。
表IV-必需组分和任选组分
必需 | 任选 |
WC | 含稀土金属的氧化物组分 |
W2C | 氧化锆 |
Al2O3 | Ti化合物、Mo化合物和/或(Ti,Mo)化合物 |
添加剂组分-VB族碳化物、碳化铬 | |
AlON |
具有不同必需组分和任选组分的烧结陶瓷体在本文的以下部分中描述。
II.WC-Al2O3-(Ti,Mo)化合物烧结陶瓷体
在另一个方面,本文描述了烧结陶瓷体,其包含WC、氧化铝及一种或多种含Ti和Mo(Ti,Mo)的化合物。在一些实施例中,烧结陶瓷体包含40-95重量%WC、1-50重量%氧化铝以及总量为0.1-20重量%的一种或多种含(Ti,Mo)的化合物。烧结陶瓷体的氧化铝含量还可选自本文的表II。如第I部分中所述,可在生坯形成期间将各种含Ti的和/或含Mo的粉末掺入到主体中。合适的粉末包括但不限于TiC、TiN、TiCN、MoC、MoO3和Mo金属。当烧结时,可形成含(Ti,Mo)的碳化物、氮化物、碳氮化物、氧碳氮化物和/或氧化物。烧结体中的(Ti,Mo)化合物的特定成分物质取决于生坯中采用的粉末。在一些实施例中,例如,TiC、TiN和/或TiCN可以一般在0.5-5重量%范围内的量提供于生坯中,并且Mo、MoC和/或MoO3可以0.5-20重量%的量提供于生坯中。在一些实施例中,Mo以0.05-5重量%的量存在于烧结陶瓷体中。
除了WC、氧化铝和含Ti,Mo的化合物之外,烧结陶瓷体还可包含W2C。在一些实施例中,W2C以至少0.1重量%的量或以选自本文表I的量存在于烧结陶瓷体中。烧结陶瓷体的附加任选组分包括氧化锆(诸如YSZ)、AlON、含一种或多种稀土元素的氧化物组分、和/或含一种或多种VB族金属碳化物和/或碳化铬的添加剂组分。烧结陶瓷体中的这些任选组分的特定量描述于本文的第I部分中。表V总结了该第II部分中涉及的烧结陶瓷体的必需组分和任选组分。
表V-必需组分和任选组分
必需 | 任选 |
WC | 含稀土金属的氧化物组分 |
Al2O3 | 氧化锆 |
W2C | |
含(Ti,Mo)的化合物 | AlON |
添加剂组分-VB族碳化物、碳化铬 |
III.WC-AlON烧结陶瓷体
在另一个方面,本文描述了烧结陶瓷体,其包含AlON和40-99.9重量%的量的WC。在一些实施例中,AlON以0.1至50重量%的量存在于烧结陶瓷体中。烧结陶瓷体中的AlON含量还可选自表VI。
表VI-AlON含量(重量%)
0.5-25 |
1-15 |
2-10 |
10-25 |
1-40 |
1-30 |
如本文所述,可在生坯形成期间将AlN添加到粉末混合物中。在粉末混合物的烧结期间,AlN部分或完全转化为AlON。可在氮气气氛中实施烧结,以有利于AlON相的形成。此外,氧可由粉末混合物的一种或多种组分提供。例如,氧可源自粉末混合物中的氧化铝和/或其他氧化物。当部分转化为AlON时,AlN可仍为烧结陶瓷体的组分。在一些实施例中,AlN以0.05-5重量%的量存在于烧结陶瓷体中。或者,可在生坯形成期间将AlON粉末以所需的量加入到粉末混合物中。
除了WC和AlON之外,烧结陶瓷体还可包含W2C。在一些实施例中,W2C以至少0.1重量%的量或以选自本文表I的量存在于烧结陶瓷体中。烧结陶瓷体的附加任选组分包括氧化铝、氧化锆(诸如YSZ)、含(Ti,Mo)的化合物、含一种或多种稀土元素的氧化物组分、和/或含一种或多种VB族金属碳化物和/或碳化铬的添加剂组分。烧结陶瓷体中的这些任选组分的特定量描述于本文的第I部分中。表VII总结了该第III部分中涉及的烧结陶瓷体的必需组分和任选组分。
表VII-必需组分和任选组分
图1为根据本文所述的一个实施例的包含WC和AlON的烧结陶瓷体的XRD。
本文第I-III部分中所述的烧结陶瓷体可表现出对于金属切削应用所需的特性,包括高硬度、弹性模量和合适的断裂韧度。在一些实施例中,例如,烧结陶瓷体具有至少18GPa的硬度。烧结陶瓷体还可具有18-25GPa或19-23GPa范围内的硬度。
根据ASTM C1327-15,使用Armstrongs维氏硬度测试仪在18.5kg的载荷下进行维氏压痕测试,由此确定本文所述的硬度值。此外,本文所述组成的烧结陶瓷体可具有430-500GPa的弹性模量(E)。在一些实施例中,烧结陶瓷体具有450-500GPa的弹性模量。
除了硬度和弹性模量之外,第I-III部分中所述的烧结陶瓷体可具有至少4.0MPam0.5的断裂韧度(K1c)。在一些实施例中,烧结陶瓷体具有4-6MPam0.5的K1c。烧结陶瓷体的断裂韧度使用直接压痕裂纹方法确定,并根据Anstis方程计算[参见G.R.Anstis,P.Chantikul,B.R.Lawn,D.B.Marshall,A Critical Evaluation of IndentationTechniques for Measuring Fracture Toughness:I,Direct Crack Measurements,Journal of the American Chemical Society,Vol.64,No.9,pp.533-538(1981)(G.R.Anstis、P.Chantikul、B.R.Lawn、D.B.Marshall,用于测量断裂韧度的压痕技术的关键评价:I,直接裂纹测量,《美国化学会志》,第64卷,第9期,第533-538页,1981年)]。
烧结陶瓷体可具有细小平均晶粒大小,一般在0.5μm至5μm的范围内。在一些实施例中,烧结陶瓷体具有0.5μm至1.5μm的平均晶粒大小。此外,烧结陶瓷体可为完全致密的或基本上完全致密的。
本文所述的烧结陶瓷体一般可通过以下方式制造:以所需的量称取组分粉末,并通过研磨来紧密混合这些粉末。将紧密混合的粉末组合物提供给模具以进行热压烧结。该模具可具有任何所需的形状。由于本文所述的烧结陶瓷体适用于金属切削应用,该模具可具有切削工具(诸如切削刀片)的形状。本文所述的烧结陶瓷体可具有任何ANSI或ISO切削刀片几何形状。在另外的实施例中,烧结陶瓷体还可为旋转切削工具,诸如端铣刀或钻头。
一般在1600℃-1800℃的温度和20-50MPa的压力下实施热压烧结45-120分钟的时间段。烧结气氛可为氩气和/或其他惰性气体。或者,如本文所述,可在烧结气氛中包括氮气以有利于AlON形成。热压陶瓷可任选在1600℃-1800℃的温度范围内以100-300MPa的压力进一步热等静压,从而消除或减少残余孔隙度。
在以下非限制性实例中对这些和其他实施例进行进一步说明。
实例1-烧结陶瓷体
具有本文所述组成的烧结陶瓷体1和2通过以下方式制备:以所需的量称取组分粉末,并通过研磨来紧密混合这些粉末。将紧密混合的粉末组合物各自提供给模具,并热压烧结成ANSI几何形状RNG45E的切削刀片,其磨刃半径在60-100μm的范围内。在1750℃和25MPa压力下在氩气氛中进行热压烧结,持续60分钟的时间段,并在1700℃和200MPa压力下进行进一步热等静压。烧结陶瓷体1和2的组成参数提供于表VIII中。样品1和2的XRD分别提供于图2和图3中。
表VIII-烧结陶瓷体组成参数(重量%)
样品 | WC | W2C | Al2O3 | AlON | AlN | 氧化锆* | Yb3Al15O12 | TiCN+Mo |
1 | 70 | - | 25 | - | - | 4.2 | - | 0.6 |
2 | 56 | 14 | 24 | - | - | 3 | 3 | - |
*氧化钇稳定的氧化锆(YSZ)
样品1和2的元素组成提供于表IX中。通过XRF进行元素分析,其中余量为碳和氧。
表IX-元素组成(重量%)
在以下条件下对样品1和2进行金属切削测试:
工件-ME16
切削速度-700sfm
进料速度-0.007ipr
切削深度-0.070英寸
还对可从肯纳金属公司(Kennametal Inc.)商购获得的对比烧结陶瓷等级KYS30和KY4300进行金属切削测试。金属切削测试的结果提供于图4中。如图4所示,与先前等级KYS30和KY4300相比,具有本文所述组成和特性的样品1和样品2的烧结陶瓷体展现出切削寿命的显著延长。
实例2-金属切削测试
根据实例1制备具有样品1和2的组成和几何形状的切削刀片。在以下条件下对样品1和2进行金属切削测试:
工件-ME16
切削速度-600sfm
进料速度-0.010ipr
切削深度-0.070英寸
还对可从肯纳金属公司商购获得的对比烧结陶瓷等级KY4300进行金属切削测试。金属切削测试的结果提供于图5中。如图5所示,与KY4300相比,样品1和2表现出切削寿命的显著延长。
实例3-烧结陶瓷体
具有本文所述组成的烧结陶瓷体3通过以下方式制备:以所需的量称取组分粉末,并通过研磨来紧密混合这些粉末。将紧密混合的粉末组合物提供给模具,并热压烧结成切削刀片ANSI几何形状RNG45E,其磨刃半径在60-100μm的范围内。在1750℃和25MPa压力下在氩气氛中进行热压烧结,持续60分钟的时间段,并在1700℃和200MPa压力下进行进一步热等静压。烧结陶瓷体3的组成参数提供于表X中。样品3的XRD提供于图6中。
表X-烧结陶瓷体组成参数(重量%)
样品 | WC | W2C | Al2O3 | AlON | AlN | 氧化锆* | Yb3Al15O12 | TiCN+Mo |
3 | 71.1 | 1.0 | 24.2 | - | - | 2.4 | - | 1.3 |
*氧化钇稳定的氧化锆(YSZ)
样品3的元素组成提供于表XI中。通过XRF进行元素分析,其中余量为碳和氧。
表XI-元素组成(重量%)
元素 | 样品3 |
铝 | 14.49 |
钛 | 0.32 |
钒 | 0.21 |
铬 | 0.014 |
钇 | 0.17 |
锆 | 2.61 |
钼 | 0.16 |
钨 | 70.54 |
钴 | - |
镱 | - |
在以下条件下对样品3进行金属切削测试:
工件-ME16
切削速度-600sfm
进料速度-0.010ipr
切削深度-0.070英寸
还对可从肯纳金属公司商购获得的对比烧结陶瓷等级KYS30进行金属切削测试。金属切削测试的结果提供于图7中。如图7所示,与先前等级KYS30相比,具有本文所述组成和特性的样品3的烧结陶瓷体展现出切削寿命的显著延长。
针对实现本发明多个目的,现已描述了本发明的多个实施例。应当认识到,这些实施例仅示例性地说明本发明的原理。在不脱离本发明精神和范围的情况下,其多种修改和变更对于本领域技术人员而言将是显而易见的。
Claims (27)
1.一种烧结陶瓷体,包含:
40-95重量%的量的碳化钨(WC)、5-30重量%的量的氧化铝(Al2O3)以及至少1重量%的量的碳化二钨(W2C)。
2.根据权利要求1所述的烧结陶瓷体,其中W2C以最高至25重量%的量存在。
3.根据权利要求1所述的烧结陶瓷体,其中W2C以5-20重量%的量存在。
4.根据权利要求1所述的烧结陶瓷体,其中W2C以12-18重量%的量存在。
5.根据权利要求1所述的烧结陶瓷体,还包含0.1-10重量%的量的氧化锆。
6.根据权利要求1所述的烧结陶瓷体,还包含一种或多种钛(Ti)化合物、钼(Mo)化合物或(Ti,Mo)化合物。
7.根据权利要求6所述的烧结陶瓷体,其中所述一种或多种Ti化合物、Mo化合物或(Ti,Mo)化合物或它们的混合物以0.1-20重量%的总量存在。
8.根据权利要求1所述的烧结陶瓷体,还包含含一种或多种稀土元素的氧化物组分。
9.根据权利要求8所述的烧结陶瓷体,其中所述氧化物组分以0.1至15重量%的量存在。
10.根据权利要求8所述的烧结陶瓷体,其中所述氧化物组分包含镱。
11.根据权利要求1所述的烧结陶瓷体,还包含氮氧化铝(AlON)。
12.根据权利要求11所述的烧结陶瓷体,其中所述AlON以0.1至20重量%的量存在。
13.根据权利要求1所述的烧结陶瓷体,还包含添加剂组分,所述添加剂组分包含一种或多种VB族金属碳化物、碳化铬、ZrNbC或它们的混合物。
14.一种烧结陶瓷体,包含:
40-95重量%的量的碳化钨(WC)、1-40重量%的量的氧化铝(Al2O3)以及一种或多种含钛(Ti)和(Mo)的化合物。
15.根据权利要求14所述的烧结陶瓷体,其中所述一种或多种含(Ti,Mo)的化合物以0.1-20重量%的总量存在。
16.根据权利要求14所述的烧结硬质碳化物组合物,还包含至少1重量%的量的碳化二钨(W2C)。
17.根据权利要求14所述的烧结陶瓷体,还包含0.1-10重量%的量的氧化锆。
18.根据权利要求14所述的烧结陶瓷体,其中钼以0.05至1重量%的量存在。
19.根据权利要求14所述的烧结陶瓷体,还包含含一种或多种稀土元素的氧化物组分。
20.根据权利要求14所述的烧结陶瓷体,还包含添加剂组分,所述添加剂组分包含一种或多种VB族金属碳化物、碳化铬、ZrNbC或它们的混合物。
21.一种烧结陶瓷体,包含:
40-95重量%的量的碳化钨(WC)及AlON。
22.根据权利要求21所述的烧结陶瓷体,其中所述AlON以0.1至40重量%的量存在。
23.根据权利要求21所述的烧结陶瓷体,还包含碳化二钨(W2C)。
24.根据权利要求23所述的烧结陶瓷体,其中所述W2C以0.1-25重量%的量存在。
25.根据权利要求21所述的烧结陶瓷体,还包含0.1-10重量%的量的氧化锆。
26.根据权利要求21所述的烧结陶瓷体,还包含氧化铝、氮化铝或它们的组合。
27.根据权利要求21所述的烧结陶瓷体,还包含添加剂组分,所述添加剂组分包含一种或多种VB族金属碳化物、碳化铬、ZrNbC或它们的混合物。
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CN111848168B (zh) * | 2020-07-29 | 2022-03-18 | 台州学院 | 一种原位反应热压烧结制备wc-y2o3无粘结相硬质合金的方法 |
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