CN1827279A - 陶瓷组件的低形变扩散焊方法 - Google Patents

陶瓷组件的低形变扩散焊方法 Download PDF

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CN1827279A
CN1827279A CNA200510099285XA CN200510099285A CN1827279A CN 1827279 A CN1827279 A CN 1827279A CN A200510099285X A CNA200510099285X A CN A200510099285XA CN 200510099285 A CN200510099285 A CN 200510099285A CN 1827279 A CN1827279 A CN 1827279A
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弗兰克·梅施克
乌尔苏拉·凯泽
安德烈亚斯·伦托尔
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3M Innovative Properties Co
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Abstract

本发明涉及陶瓷组件的连接方法,其中,被连接的组件包括烧结的非氧化物陶瓷,并且采用扩散焊方法在保护气体气氛存在下将组件彼此接触,并且在至少1600℃的温度下,优选超过1800℃,尤其优选超过2000℃下,以及在任选存在的负载下几乎无形变地进行连接,形成一个整体,被连接的组件在施加压力的方向的塑性形变低于5%,优选低于1%。

Description

陶瓷组件的低形变扩散焊方法
                    技术领域
本发明涉及陶瓷组件的低形变扩散焊方法,和由此方法制得的整体块及其应用。
                    背景技术
陶瓷组件通常用于加工厂和机械工程,其中会涉及到磨损,腐蚀和高热负载。陶瓷的硬度、化学稳定性和高温稳定性远比钢铁相应的功能优越。而且碳化硅作为工业陶瓷的代表具有极优异的热传导性(是钢铁的4倍多)。这种优点不仅使该材料可用于喷嘴、阀门、轴面密封和滑动接触磨损中而且可用于反应器如管束热交换器或柴油微粒过滤器。在许多此类的应用中,基于设计的原因,陶瓷组件必须具有非常复杂的形状。但该设计通常与已有的陶瓷成形工艺不一致,从而使得需要连接单独的构件。文献中已公开了涉及连接陶瓷的多种方法,包括许多涉及连接SiC陶瓷的方法。根据不同的工艺过程,文献中使用“扩散焊”,“反应粘合”或“软钎焊”。软钎焊和反应粘合在连接部件的界面处留下焊缝,而扩散焊可用于连接部件形成无缝组件。该类型的无缝组件也被称为整体块。
关于扩散焊烧结的SiC组件的基本原理早在20世纪80年代已被Thomas Moore公开。他在论文“Feasibility Study of the Welding of SiC”J.Am.Ceram.Soc.68[6]C151-C153(1985)中介绍了只有当温度和压力足够高时利用扩散焊才可获得在抛光的a-SiC平面盘之间的稳定、粘性连接,并且需允许连接组件在加压方向有约25%的塑性形变。上述论文得出的结论是不可能制得没有塑性形变的无缝焊接连接的烧结SiC。即使在1950℃和13.8MPa压力(时间2h)的热压下,在被连接的且形变大的盘之间也存在焊缝。温度的降低不可能获得更好的无缝连接的结果。在扩散焊中,在热均压力作用下加压至138MPa,根据相关报道也不会获得成功的连接。在组件中观察到的不够的粘合连接归因于SiC不够的烧结活性。
US专利4,925,608(1990)描述了为了获得粘接的无缝SiC粘合,基于热均压力的轻微预烧结的SiC组件的扩散焊过程。在此,尤其侧重于SiC的β-改性和组件更高的烧结活性,所述组件具有不高于85%的孔隙率。优选温度大于1700℃和压力大于150MPa。由于在连接中仍存在多孔组件的增浓,因而会发生高度的塑性形变。
为使塑性形变的总体水平降低且还实现高质量的连接,在文献中公开的大量工作侧重于在极低温度下的“软钎焊”和“反应粘合”的连接过程。目前,本领域的发展状况是在室温下使用粘合剂连接陶瓷组件、使用金属和玻璃焊剂在约1000℃范围内连接组件、或者在约1400℃通过反应粘合组合成组件。在此背景下,尤其应该提及Si-渗透的SiC(Si-SiC)的反应粘合,在过去用于制备更复杂组件如盘形热交换器的过程。然而,连接缝仍然是该组件的弱点。在高温的、腐蚀的、或磨损的负载下,初期就会出现Si的分解,软化或释放,从而导致失败。即使是在现在,无缝地连接烧结SiC(SSiC)且几乎不发生形变被认为是不可能实现的。
                    发明内容
因此,本发明的一个目的是提供使得由非氧化烧结的陶瓷制得的组件彼此连接的方法,从而形成无缝的整体块和在连接中保持塑性形变在低的水平以使整体块的形状对应于所期望组件的形状。从而节省后期的工作。
根据本发明,该目的是基于以下事实实现的,采用扩散焊方法将被连接的组件在保护性气体气氛下彼此接触,并且几乎没有形变地连接,所用温度至少为1600℃,并且在任选存在的负载下形成整体块,被连接的组件在施加压力的方向的塑性形变低于5%,优选低于1%。
                    附图说明
图1是显示SiC材料蠕变速率随温度变化的图。
图2是显示用于以错流方式引导气体的由粗粒SSiC制得的没有密封和焊缝的整体微反应器(45°部分)。
图3是显示由6个SSiC组件在2150℃无缝连接的整体块,其中使用3种类型的烧结的SiC材料,尺寸为初始平均粒径。
图4是显示无缝焊SSiC组件。
图5是显示由6个SSiC组件在1800℃无缝连接的整体块,其中使用3种类型的烧结的SiC材料,尺寸为初始平均粒径。
图6是显示由2个组件扩散焊制得的B4C部件的连接处的抛光基面部分。
图7是显示由2个组件扩散焊制得的B4C部件的连接处的蚀刻的基面部分。
                  具体实施方式
本发明中所采用的扩散焊优选为热压过程。
在材料学中,在高温范围内的耐塑性形变被称为高温抗蠕变力。蠕变速率被用来测量抗蠕变力。出人意料的是,已发现被连接的材料的蠕变速率可用作在无缝连接烧结陶瓷组件的连接过程中最小化塑性形变的主要参数。
多数可商购获得的烧结SiC材料(SSiC)具有相似的具有单峰颗粒大小分布和颗粒大小约5μm的微结构。因此它们在上述大于1700℃的连接温度下具有足够高的烧结活性。然而,它们也具有相应的太低的抗蠕变力而不能低形变地连接。于是,目前,在成功的扩散焊过程中也经常观察到高度的塑性形变。由于SSiC材料的抗蠕变力通常不会有太多的不同,因此目前蠕变速率不被认为是可用于连接SSiC的变量参数。
已发现通过改变微结构的形成可以在大范围内改变SSiC的蠕变速率。低形变地连接SSiC材料仅可通过使用某特定类型实现。
陶瓷材料的抗蠕变力通常可以通过下述两种方法大大增加:
-使微结构粗糙。如果使微结构粗糙,在蠕变过程中发生的质量传递所需的扩散通道大大变长,因此显著减慢了蠕变速率。文献中描述了蠕变速率与颗粒大小的3次方成倒数关系。该关系已广泛由如氧化铝和氮化硅等材料证明。
-纳米颗粒。纳米技术可用于获得陶瓷纳米颗粒,当用于陶瓷颗粒边界时,在高温下和任选的负载下大大减慢了陶瓷的蠕变速率。例如,作为氧化物陶瓷的代表例,被称为氧化铝的形变速率的蠕变速率[单位l/s]通过掺杂纳米SiC颗粒可以降低两个数量级。对于氮化硅材料可以实现类似的效果,且可以应用于所有的非氧化物陶瓷。
上述两种方法均等地适用于制备具有烧结活性和使得由此制备的组件低形变地连接的抗蠕变材料。
优选至少一种被连接的组件包括在连接过程中蠕变速率一直低于2.10-4l/s的材料,优选一直低于8.10-5l/s,尤其优选一直低于2.10-5l/s。
所述陶瓷材料优选选自二硼化钛,碳化硼,氮化硅,碳化硅,和它们的混合物。
优选至少一种被连接的组件是具有双峰颗粒大小分布和平均颗粒大小大于5μm的烧结的碳化硅(SSiC),其中所述材料可以包含其它的材料成分,其体积含量不高于35体积%,优选低于15体积%,尤其优选低于5体积%,例如石墨,碳化硼或其它陶瓷颗粒,优选纳米颗粒。
尤其适合于本发明过程的具有双峰颗粒大小分布的烧结的SiC是具有平均颗粒大小大于5μm的SSiC,优选大于20μm,尤其优选大于50μm。因此,该材料的平均颗粒大小比传统烧结的具有平均颗粒大小仅约为5μm细颗粒SiC高10-100倍。由此原因,粗颗粒的烧结碳化硅(SSiC)具有比细颗粒SSiC高得多的抗蠕变力。文献中未给出关于此类SiC材料的蠕变速率。图1例举了在不同温度下粗颗粒SSiC(平均颗粒大小约为200μm)的较低的蠕变速率,并在相同负载条件下将其与细颗粒SSiC(平均颗粒大小为5μm,市售的如E KasicF由ESK Ceramus GmbH&Co.KG生产)进行比较。
本发明的过程优选在温度大于1600℃下进行,尤其优选大于1800℃,更优选大于2000℃。该过程优选在压力大于10kPa下进行,优选大于1MPa,尤其优选大于10MPa。温度维持时间优选至少为10min,尤其优选至少为30min。
本发明的方法可用来制备复杂形状的陶瓷组件以形成具有极高热稳定性、耐腐蚀性或耐磨损的用于加工厂和机械工程的接近网状(net shape)的组件。其中在密封处和焊缝处形成弱点的反应器现在可以以无缝整体被制得。
接着,本方法可用来由烧结SiC陶瓷制备的盘形热交换器,其具有极高的热稳定性和耐腐蚀性,盘形热交换器已由Si渗透的SiC陶瓷(Si-SiC)通过反应粘合制得。然而不是普遍都具有的耐腐蚀性对于在可能的应用中造成了极大限制。
过滤器和尤其是陶瓷微反应器现在可同样由烧结SiC陶瓷作为整体块产品制备。尤其是具有交错流通道的微反应器现在可形成SSiC整体块。
另外,本应用还可包括由电传导的SSiC陶瓷制成的加热元件,例如炉和反应器。
衬里,规整的保护装置或用于熔合反应器的第一壁组件是可以被制得的。其它用于高温技术的复杂形状的高抗蠕变组件,例如炉辊,炉支撑装置和燃烧器组件也可被形成。或多或少的复杂结构组件如形变工具,盘,管,法兰,或气密封接容器可采用这种方法由绝缘或导电非氧化物陶瓷连接。
由于本方法首次可以提供具有无缝连接的相应组件,本发明还涉及具有至少一处无缝连接的由非氧化物陶瓷制得的组件。
优选组件在无缝连接处具有采用4点法(4-point method)测得的大于150MPa的弯曲断裂强度,优选大于250MPa。
本发明的组件的弯曲断裂强度优选与在组件基质材料中的无缝连接区域处的一样高。
所述组件优选是结构组件或功能组件,优选为容器,管,反应器,衬里,阀,热交换器,加热元件,镀层,耐磨组件如滑动接触轴承或轴面密封件,闸,离合器,喷嘴或形变工具。
本发明还涉及由本发明方法制备的组件作为结构组件和功能组件的用途,所述组件包括容器,反应器,衬里,阀,热交换器,形变工具,喷嘴,镀层。
尤其有利的是如果所述组件包括粗粒的SSiC陶瓷(平均颗粒大小大于50μm)。结果不仅使低变形连接更简单而且大大提高了组件的耐腐蚀性。
                     实施例
以下实施例用来进一步解释本发明。
实施例1扩散焊粗粒SSiC组件
将由烧结的粗粒SiC(平均颗粒尺寸约200μm)制得的尺寸为50×35×5mm的抛光盘在热压下以一个置于另一个的上部的形式形成堆叠。在氮气气氛,温度为2150℃,负载11.4MPa和维持时间45min下进行连接操作,在引入力的方向实现小于1%的塑性形变。连接的组件为无缝整体块。该SSiC材料的蠕变速率在2150℃低于2·10-5l/s。
可以采用连接操作制备如图2所示的微反应器作为整体块。与通道方向成45°的基面部分显示整体块均匀地包括粗粒SSiC,通道处没有形变且没有缝隙。
实施例2扩散焊由不同类型的SSiC制得的组件
将由不同级别烧结的SiC制得的尺寸为50×35×5mm的抛光盘在热压下以一个置于另一个的上部的形式形成堆叠。使用2个由粗粒SSiC材料(平均粒径约200μm)制得的盘,2个由细粒SSiC材料(平均粒径约5μm)制得的盘,和2个由具有初始中级粒径(约50μm)的SSiC复合材料制得的盘作为待连接的整体块。该堆叠在2150℃下,氮气气氛中,经受11.4MPa的负载45min。
图3显示了由6个组件连接的整体块的抛光基面部分,在仅有细粒SiC材料初始存在的部件中存在与引入力方向平行的方向上的约15%的塑性形变(在图中左侧部分的2个盘)。在连接过程中,粗粒SiC材料(图中右侧部分的2个盘)和具有初始中级粒径的SSiC材料(中间部分的2个盘)保持尺寸上的稳定(形变小于1%)。该实施例表明即使由选自不同SiC级别的组件也可以彼此无缝地连接且几乎无形变地形成整体块。
在显微镜下观察抛光基面部分的任一连接处均无边界线。即使为暴露颗粒边界,在基面部分蚀刻也未显示缝隙。相反,如图4所示,基于粗粒SSiC组件,两个盘的颗粒彼此间生长由此溶解组件界面。在相同材料对形成的连接处和不同SiC组件之间的连接处发生相同的现象。由良好的连接形成非常高的机械强度。由组件制得弯曲棒的强度在4点弯曲测试中超过290MPa。
而且,图3显示在非常高的温度下的连接操作中所有3种SSiC材料的微结构变得更粗。
实施例3扩散焊由不同类型的SSiC制得的组件
根据本发明,将由不同级别烧结的SiC制得的尺寸为50×35×5mm的抛光盘在热压下以一个置于另一个的上部的形式形成堆叠。使用2个由粗粒SSiC材料(平均粒径约200μm)制得的盘,2个由细粒SSiC材料(平均粒径约5μm)制得的盘,和2个由具有初始中级粒径约50μm的SSiC复合材料制得的盘作为待连接的整体块。与实施例2对比,该堆叠在较低的1800℃温度下,氮气气氛中,经受11.4MPa的负载45min。
在此温度下细粒SSiC的蠕变速率足够低以使所有SSiC组件彼此低形变地连接。包括细粒SSiC的所有级别的SSiC在引入力方向的塑性形变低于1%。所有SSiC材料的蠕变速率在1800℃低于2·10-5l/s。
尽管温度低,如图5所示在抛光基面部分的微观检查没有显示任何连接缝隙。微结构没有变粗。颗粒也没有一起生长。相反,连接操作将组件界面转化为作为聚结晶整体块一部分的颗粒边界。在蚀刻处理以显示界面之后,观测到相邻颗粒边界的平面。从而组件形成整体块。连接强度超过200MPa。
实施例4粗糙化和扩散焊细粒SiC组件
将由细粒烧结的SSiC(平均粒径约5μm)制得的尺寸为50×35×5mm的抛光盘在热压下以一个置于另一个的上部的形式形成堆叠。在2150℃的温度和氮气气氛下应用连接操作,其中甚至在施加最大负载11.4MPa之前,材料在此条件下在30min内被转化为平均粒径50μm的粗粒SSiC,在温度维持时间45min后和载荷下,在引入力方向的塑性形变低于1%。在此条件下粗糙的SSiC材料的蠕变速率在2150℃低于2·10-5l/s。
实施例5扩散焊具有颗粒边界的颗粒碳化硼
将由加强颗粒的碳化硼制得的抛光盘(50*50*6mm)在热压下以一个置于另一个的上部的形式形成堆叠。在2150℃和氮气气氛下,负载8MPa和维持时间45min下的连接操作实现在引入力方向的塑性形变为5%。在2150℃该材料的的蠕变速率低于8·10-5l/s。
所得组件为无缝整体块。图6显示了该组件的抛光基面部分。微观检查没有显示在连接处有任何缝隙。彼此面对的组件的颗粒没有一起生长。相反,连接操作将组件界面转化为形成聚晶体整块一部分的颗粒边界。在以暴露界面的蚀刻处理之后可以看见相邻颗粒边界的平面(图7)。
对比例6扩散焊细粒SSiC组件
由烧结的SiC(平均粒径约5μm)制得的尺寸为50×35×5mm的抛光盘在热压下以一个置于另一个的上部的形式形成堆叠。在2150℃的温度,氮气气氛下,11.4MPa负载和维持时间10min的连接操作获得在引入力方向约12%的高塑性形变的组件。该SiC材料在2150℃的蠕变速率为约2·10-4l/s。

Claims (11)

1.陶瓷组件的连接方法,其中被连接的组件包括烧结的非氧化物陶瓷,并且采用扩散焊方法在保护气体气氛存在下将组件彼此接触,并且在至少1600℃的温度下,优选超过1800℃,尤其优选超过2000℃下,以及在任选存在的负载下几乎无形变地进行连接,形成一个整体,被连接的组件在施加压力的方向的塑性形变低于5%,优选低于1%。
2.如权利要求1所述的方法,其中,所述扩散焊是热压过程。
3.如权利要求1或2所述的方法,其中至少一种被连接的组件包括在连接过程中的蠕变速率一直低于2·10-4l/s,优选一直低于8·10-5l/s,尤其优选一直低于2·10-5l/s的非氧化物陶瓷。
4.如权利要求1-3任一项所述的方法,其中至少一种被连接的组件包括二硼化钛、碳化硼、氮化硅、碳化硅、或者它们的混合物,尤其优选包括碳化硅。
5.如权利要求4所述的方法,其中至少一种被连接的组件包括粗粒的烧结的具有双峰颗粒大小分布的碳化硅,平均颗粒大小大于5
μm,优选大于20μm,尤其优选大于50μm,所述组件还包含不高于35体积%的其它材料组件,如石墨、碳化硼或其它陶瓷颗粒。
6.如权利要求1-5任一项所述的方法,其在温度大于1600℃,尤其优选大于1800℃,特别优选大于2000℃,和负载大于10kPa,优选大于1MPa,特别优选大于10MPa,并且温度保持时间优选大于10min,尤其优选大于30min下进行。
7.由非氧化物陶瓷制成的无缝连接的组件。
8.如权利要求7所述的组件,其在无缝连接处具有由采用4点法测得的大于150MPa,尤其优选大于250MPa的弯曲断裂强度。
9.如权利要求7或8所述的组件,其中在无缝连接区域中的弯曲断裂强度和在所述组件的基质材料中的弯曲断裂强度一样高。
10.如权利要求7、8或9中所述的组件,其为容器、管、反应器、辊、储存器、衬里、阀、热交换器、加热元件、镀层、或耐磨组件如滑动接触轴承或轴面密封件、闸、离合器、喷嘴或形变工具。
11.由如权利要求1-6中任一项所述的方法制备的组件作为结构组件或功能组件的用途,所述组件包括容器、管、反应器、衬里、阀、热交换器、加热元件、镀层、或耐磨组件如滑动接触轴承或轴面密封件、闸、离合器、喷嘴或形变工具。
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