CN101274366A - 热喷涂粉末、热喷涂涂层、以及炉底辊 - Google Patents
热喷涂粉末、热喷涂涂层、以及炉底辊 Download PDFInfo
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Abstract
一种热喷涂粉末,含有30~50mass%的碳化铬,剩余的为含有铬、铝、镱、以及钴和镍两者中的至少一种的合金。该热喷涂粉末具有20~60μm的平均粒径。该热喷涂粉末可以含有20mass%或更少的氧化镱以代替所述合金中的一部分。一种通过热喷涂该热喷涂粉末而形成的热喷涂涂层,尤其是一种通过高速火焰喷涂该热喷涂粉末而形成的热喷涂涂层适用于炉底辊。
Description
技术领域
本发明涉及一种热喷涂粉末、一种由该热喷涂粉末获得的热喷涂涂层、以及一种包括该由热喷涂粉末获得的热喷涂涂层的炉底辊。
背景技术
用于传送钢板的所谓的炉底辊位于热处理熔炉例如钢板连续退火炉中。钢板在保持N2/H2等还原气氛下的炉中进行热处理。这时,在某些情况下,由于辊和钢板之间的反应,在炉底辊的表面上会形成被称为积聚物的沉积物。当炉底辊的表面上形成积聚物时,在该炉底辊上传送的钢板的表面会形成压痕等,从而会造成钢板的质量下降。因此,当炉底辊的表面上形成积聚物时,需要立即停止熔炉的运作并且清理炉底辊的表面,于是生产效率会显著下降。因此,传统上通过在炉底辊的表面形成热喷涂涂层来防止积聚物的形成。
同时,近年来,对高强度钢的需求与日俱增。高强度钢比普通钢包含更大量的作为固态溶液增强元素的元素例如锰(Mn)和硅(Si)。由于这些元素较易氧化,故在高强度钢的表面上会形成富含这些元素氧化物的层。由于富含锰的层通过与形成于炉底辊表面上的热喷涂涂层反应而特别易于形成积聚物,故该类锰积聚物对用于传送高强度钢板的炉底辊会造成问题。随着对钢板质量的要求变得越来越严格,积聚物的问题变得愈发明显。因此,人们发展了一种针对该热喷涂涂层的热喷涂粉末以解决这些问题(参见,例如日本专利申请Nos.2005-206863和2003-27204)。
对于用于熔炉中的高温区域(例如,900℃或更高)的炉底辊表面的热喷涂涂层,尤其需要较高的抗积聚性。同时,该热喷涂涂层还需要具有较高的抗热冲击性,可以防止由例如其上经过的钢板所带来的热冲击而造成分离。然而,在现在的情况下,尚未获得满足这些要求的热喷涂涂层。
发明内容
因此,本发明的目的在于提供一种能够形成适用于炉底辊的热喷涂涂层的热喷涂粉末、一种由该热喷涂粉末获得的热喷涂涂层、以及一种包括该热喷涂涂层的炉底辊。
为了实现上述目标并且根据本发明的第一个方面,提供了一种热喷涂粉末。该热喷涂粉末含有30~50mass%的碳化铬,剩余的为含有铬、铝、镱、以及钴和镍两者中的至少一种的合金。该热喷涂粉末具有20~60μm的平均粒径。
根据本发明的第二个方面,提供了一种由高速火焰喷涂根据本发明第一个方面的热喷涂粉末获得的热喷涂涂层。
根据本发明的第三个方面,提供了一种在其表面具有根据本发明第二个方面的热喷涂涂层的炉底辊。
通过如下说明、以及以实施例的方式对本发明的原理进行说明,可使本发明的其他方面和优点变得显而易见。
具体实施方式
在下文中,将对本发明的一个实施方式进行描述。
根据本实施方式的热喷涂粉末含有30~50mass%的碳化铬,剩余的为合金。换句话说,该热喷涂粉末含有30~50mass%的碳化铬和50~70mass%的合金。该合金含有铬、铝、镱、以及钴和镍两者中的至少一种。更具体的说,关于该合金,可以使用CoCrAlY合金、NiCrAlY合金、CoNiCrAlY合金、以及NiCoCrAlY合金中的任意一种。从提高由该热喷涂粉末获得的热喷涂涂层的抗积聚性考虑,在合金中的铬含量、铝含量和镱含量分别优选为15~25mass%、6~12mass%和0.3~1mass%。
该热喷涂粉末中的碳化铬的含量必须为30mass%或更多(换句话说,在该热喷涂粉末中合金的含量为70mass%或更少)。当碳化铬的含量增大时,由该热喷涂粉末获得的热喷涂涂层的抗积聚性会更好。这是由于热喷涂粉末中的碳化铬即使与富含锰的层接触时,其形成反应层的可能性也较小,从而可以抑制形成积聚物。此外,当碳化铬的含量增大时,由该热喷涂粉末获得的热喷涂涂层的硬度会增大,并且该热喷涂涂层的耐磨性也因此而增大。从这点考虑,如果该热喷涂粉末中的碳化铬的含量为30mass%或更多,那么由该热喷涂粉末可以获得具有出色的抗积聚性和耐磨性的适用于炉底辊的热喷涂涂层。为了进一步显著提高由该热喷涂粉末获得的热喷涂涂层的抗积聚性和耐磨性,该热喷涂粉末中的碳化铬的含量优选为33mass%或更多,并且进一步优选为35mass%或更多。换句话说,该热喷涂粉末中的合金的含量优选为67mass%或更少,并且进一步优选为65mass%或更少。
此外,热喷涂粉末中的碳化铬的含量必须为50mass%或更少(换句话说,该热喷涂粉末中的合金的含量为50mass%或更多)。当碳化铬的含量减少时,由该热喷涂粉末获得的热喷涂涂层的粗糙度得到改善,并且该热喷涂涂层的抗热冲击性也因此得到提高。从这点考虑,如果该热喷涂粉末中的碳化铬的含量为50mass%或更少,那么由该热喷涂粉末可以获得具有出色的抗热冲击性的适用于炉底辊的热喷涂涂层。为了进一步显著提高由该热喷涂粉末获得的热喷涂涂层的抗热冲击性,该热喷涂粉末中的碳化铬的含量优选为47mass%或更少,并且进一步优选为45mass%或更少。换句话说,该热喷涂粉末中的合金的含量优选为53mass%或更多,并且进一步优选为55mass%或更多。
该热喷涂粉末必须具有20μm或更大的平均粒径。当该热喷涂粉末的平均粒径增大时,该热喷涂粉末中含有的在热喷涂时会造成过熔的精细颗粒的量会减少,于是在热喷涂该热喷涂粉末期间发生所谓的溅射现象的可能性较小。术语“溅射”指的是通过将过熔的热喷涂粉末粘附并沉积在热喷涂装置中的喷嘴内壁上而形成的沉积物从内壁脱落,并且混入到在热喷涂该热喷涂粉末期间形成的热喷涂涂层中的现象。由于该沉积物长时间暴露于喷嘴中的火焰中而劣化例如氧化,故当溅射发生时,由该热喷涂粉末获得的热喷涂涂层的性能包括抗积聚性会下降。从这点考虑,如果该热喷涂粉末具有20μm或更大的平均粒径,那么可以显著抑制该热喷涂涂层的抗积聚性因发生溅射而下降。为了进一步显著抑制该热喷涂涂层的抗积聚性因发生溅射而下降,该热喷涂粉末优选具有23μm或更大的平均粒径,并且进一步优选为25μm或更大。
该热喷涂粉末必须具有60μm或更小的平均粒径。当该热喷涂粉末的平均粒径减小时,由该热喷涂粉末获得的热喷涂涂层的密度会增大,于是该热喷涂涂层的性能包括抗积聚性和耐磨性得到提高。当热喷涂涂层具有较差的密度时,涂层表面上的开孔会作为起始点而形成积聚物。从这点考虑,如果该热喷涂粉末具有60μm或更小的平均粒径,那么由该热喷涂粉末可以获得具有出色的抗积聚性和耐磨性的适用于炉底辊的热喷涂涂层。为了进一步显著提高由该热喷涂粉末获得的热喷涂涂层的抗积聚性和耐磨性,该热喷涂粉末优选具有57μm或更小的平均粒径,并且进一步优选为55μm或更小。
构成该热喷涂粉末的颗粒优选为经粒化并且烧结的颗粒。与经熔融并且碾碎的颗粒以及经烧结并且碾碎的颗粒相比,经粒化并且烧结的颗粒的优点在于它们具有较好的流动性,从而在制备时其内混有更少的杂质。因此由具有经粒化并且烧结的颗粒的该热喷涂粉末获得的热喷涂涂层具有均一的结构,于是该热喷涂涂层的性能包括抗积聚性得到提高。该经粒化并且烧结的颗粒是通过例如将包含碳化铬粉末和合金粉末的原料粉末粒化并且烧结,接着粉碎成更小的颗粒,并且根据需要将获得的粉末进行分类而制得的。经熔融并且碾碎的颗粒是通过将原料粉末熔融,使熔融的粉末冷却并固化,然后碾碎,并且根据需要将获得的粉末进行分类而制得的。经烧结并且碾碎的颗粒是通过将原料粉末烧结并且碾碎,并且根据需要将获得的粉末进行分类而制得的。
当该热喷涂粉末包含经粒化并且烧结的颗粒时,经粒化并且烧结的颗粒的原料粉末优选具有15μm或更小的平均粒径。当原料粉末的平均粒径减小时,由该热喷涂粉末获得的热喷涂涂层中的各个碳化铬颗粒的尺寸和各个合金部分的尺寸也减小,于是该热喷涂涂层的均一性得到提高。从这点考虑,如果原料粉末具有15μm或更小的平均粒径,那么由该热喷涂粉末可以获得具有特别高的均一性的热喷涂涂层。
当该热喷涂粉末包含经粒化并且烧结的颗粒时,经粒化并且烧结的颗粒优选具有10MPa或更大的抗碎强度。当经粒化并且烧结的颗粒的抗碎强度增大时,该热喷涂粉末中的经粒化并且烧结的颗粒的破裂得到抑制。当该热喷涂粉末从粉末进料器中被送入热喷涂装置时,或当送入热喷涂装置中的该热喷涂粉末被注入热喷涂火焰中时,在用于连接粉末进料器和热喷涂装置的管子中会发生这种破裂。当经粒化并且烧结的颗粒发生破裂时,该热喷涂粉末中会形成在热喷涂期间导致过熔的精细颗粒,于是在热喷涂该热喷涂粉末期间可能会发生溅射。从这点考虑,如果经粒化并且烧结的颗粒具有10MPa或更大的抗碎强度,那么可以显著抑制经粒化并且烧结的颗粒的破裂,从而可以抑制溅射的发生。
本实施方式的热喷涂粉末被用于通过高速火焰喷涂例如HVOF形成热喷涂涂层的目的。与其他热喷涂方法相比,在高速火焰喷涂的情况下,获得的热喷涂涂层具有出色的密度、结构均一性、以及更少的受热劣化,并且由该热喷涂粉末形成的热喷涂涂层具有出色的抗积聚性和抗热冲击性。因此,优选通过高速火焰喷涂对本实施方式的热喷涂粉末进行热喷涂。
由热喷涂粉末获得的热喷涂涂层形成于,比如炉底辊的表面上。形成于炉底辊表面上的热喷涂涂层是通过高速火焰喷涂热喷涂粉末形成的。从获得出色的抗积聚性和出色的抗热冲击性考虑,该热喷涂涂层优选具有40~300μm的厚度。
根据本实施方式,可以获得下列优点。
本实施方式的热喷涂粉末含有30~50mass%的碳化铬,剩余的为含有铬、铝、镱、以及钴和镍两者中的至少一种的合金,并且具有20~60μm的平均粒径。因此,由该热喷涂粉末获得的热喷涂涂层具有出色的抗积聚性和耐磨性,从而适用于炉底辊的用途。换句话说,该热喷涂粉末可以形成同时满足当用于热处理熔炉的高温区域时所需要的抗积聚性和抗热冲击性并且适用于炉底辊的热喷涂涂层。
上述实施方式可以修改如下。
本实施方式的热喷涂粉末可以含有氧化镱以代替一部分合金。由于氧化镱具有化学稳定性并且具有较高的惰性,故通过加入氧化镱,可以提高由该热喷涂粉末获得的热喷涂涂层的抗积聚性。该热喷涂粉末中的氧化镱含量越少,由该热喷涂粉末获得的热喷涂涂层的密度和抗热冲击性提高得越大。因此,该热喷涂粉末中的氧化镱的含量优选为20mass%或更少,并且进一步优选为15mass%或更少。
接下来,将参考实施例和对照例对本发明进行详细描述。
在实施例1~15和对照例1~6中,制备了分别包含经粒化并且烧结的含有Cr3C2和合金并且根据需要进一步含有Y2O3的颗粒的热喷涂粉末。在实施例16中,制备了包含Cr3C2粉末、Y2O3粉末和合金粉末的混合物的热喷涂粉末。然后,将各个热喷涂粉末进行热喷涂以形成热喷涂涂层。各个实施例和对照例的细节如表1所述。
表1中“Cr3C2含量”一栏所示为在各个实施例和对照例的热喷涂粉末中的Cr3C2含量。
表1中“Y2O3含量”一栏所示为在各个实施例和对照例的热喷涂粉末中的Y2O3含量。
表1中“合金组合物”一栏所示为在各个实施例和对照例的热喷涂粉末中的合金组合物。
表1中“热喷涂粉末的平均粒径”和“原料粉末的平均粒径”两栏分别为在各个实施例和对照例的热喷涂粉末中的热喷涂粉末的平均粒径和热喷涂粉末的原料粉末的平均粒径的测量结果。HORIBA有限公司生产的激光衍射/散射粒径测定装置“LA-300”被用于测量平均粒径。这里的“平均粒径”是指由具有最小粒径的颗粒开始升序累计各个颗粒的体积,直到颗粒的累积体积为所有颗粒的累计体积的50%时,最后所累计的颗粒的粒径。
在表1的“热喷涂粉末的种类”一栏中,“经粒化并且烧结”是指热喷涂粉末包含经粒化并且烧结的颗粒,并且“混和”是指热喷涂粉末包含Cr3C2粉末、Y2O3粉末和合金粉末的混合物。
表1中的“抗碎强度”一栏所示为在实施例1~15和对照例1~6中的各个热喷涂粉末中经粒化并且烧结的颗粒的抗碎强度的测量结果。具体的说,抗碎强度是指根据公式:σ=2.8×L/π/d2计算的各个热喷涂粉末中的经粒化并且烧结的颗粒的抗碎强度σ[MPa]。在上述公式中,L和d分别是指热喷涂粉末的临界载荷[N]和平均粒径[mm]。术语“临界载荷”是指用压头向经粒化并且烧结的颗粒施加以恒定速率增大的压力负载时,在压头的位移陡增的瞬间施加在经粒化并且烧结的颗粒上的压缩负载的量。Shimadzu公司生产的微压缩测试仪“MCTE-500”被用于测定该临界负载。
表1中的“热喷涂方法”一栏所示为热喷涂各个实施例和对照例中的热喷涂粉末以获得热喷涂涂层时使用的热喷涂方法。在该栏中,“HVOF”是指在如表2所示的条件下进行的高速火焰喷涂,并且“等离子”是指在如表3所示的条件下进行的等离子热喷涂。
表1中的“涂层厚度”一栏所示为由各个实施例和对照例的热喷涂粉末获得的热喷涂涂层的厚度的测量结果。
表1中的“溅射”一栏所示为当热喷涂各个实施例和对照例中的热喷涂粉末以获得热喷涂涂层时发生溅射的情况的评估结果。具体的说,在通过使用热喷涂装置连续进行10分钟和20分钟的热喷涂后,观察各个热喷涂粉末与热喷涂装置的喷嘴内壁的粘结情况。然后,对各个热喷涂粉末进行评估,将即使进行连续热喷涂20分钟后也没有发现粘结的情况定为“好(G)”,将进行连续热喷涂10分钟后没有发现粘结,但进行连续热喷涂20分钟后发现粘结的情况定为“中(F)”,并且将进行连续热喷涂10分钟后发现粘结的情况定为“差(P)”。
表1中的“粘附效率”一栏所示为当热喷涂各个实施例和对照例的热喷涂粉末以获得热喷涂涂层时粘附效率(热喷涂率)的评估结果。具体的说,对各个热喷涂粉末进行评估,当通过将获得的热喷涂涂层的重量除以使用的热喷涂粉末的重量所测得的粘附效率的数值为35%或更大时将其定为“好(G)”,当数值为30%或更大并且小于35%时将其定为“中(F)”,并且当数值小于30%时将其定为“差(P)”。
表1中的“硬度”一栏所示为对各个实施例和对照例中获得的热喷涂涂层所测得的硬度的评估结果。具体的说,对各个热喷涂粉末进行评估,当使用由Shimadzu公司生产的微硬度测试仪“HMV-1”以2N的负载测定热喷涂涂层横截面的Vickers硬度值为500或更大时将其定为“好(G)”,当数值为450或更大并且小于500时将其定为“中(F)”,并且当数值小于450时将其定为“差(P)”。
表1中的“孔隙率”一栏所示为对各个实施例和对照例中获得的热喷涂涂层所测得的孔隙率的评估结果。具体的说,对各个热喷涂粉末进行评估,当通过图像分析测定镜面抛光后的热喷涂涂层的横截面所测得的孔隙率数值为2.0%或更小时将其定为“好(G)”,当数值大于2.0%并且为3.0%或更小时将其定为“中(F)”,并且当数值大于3.0%时将其定为“差(P)”。
表1中的“耐磨性”一栏所示为在各个实施例和对照例中获得的热喷涂涂层的耐磨性的评估结果。具体的说,在根据日本工业标准(JIS)H8682-1对各个热喷涂涂层进行干磨削测试,并且对用作标准样品的由碳钢(SS400)制成的平板进行相同的干磨削测试后,当热喷涂涂层的磨损重量与标准样品的磨损重量的比值为0.4或更小时,将该热喷涂涂层评估为“好(G)”,当比值大于0.4并且为0.5或更小时,将该热喷涂涂层评估为“中(F)”,并且当比值大于0.5时,将该热喷涂涂层评估为“差(P)”。在上述干磨削测试中,使用Suga磨削测试仪,在30.9N的负载下,使用US CAMI(砂纸制造协会)标准中的CP180砂纸摩擦各个热喷涂涂层和标准样品的表面预定的次数。
表1中的“抗热冲击性”一栏所示为对各个实施例和对照例中获得的热喷涂涂层的抗热冲击性的评估结果。具体的说,重复加热和冷却循环,即,将在由耐热铸钢(SCH11)制成的基底的表面上形成各个热喷涂涂层所制得的样品,在1000℃的空气中加热30分钟,然后在水中冷却。然后,对各个热喷涂涂层进行评估,如果热喷涂涂层即使重复该加热和冷却循环20次时也没有发生分离,则将其定为“好(G)”,如果重复循环15次或更多并且小于20次时热喷涂涂层发生了分离,则将其定为“中(F)”,如果重复循环小于15次时发生了分离,则将其定为“差(P)”。
表1中的“抗积聚性”一栏所示为对各个实施例和对照例中获得的热喷涂涂层的抗积聚性的评估结果。具体的说,通过在由不锈钢(SUS304)制成的基底的表面上形成各个热喷涂涂层来制得样品。在两个样品的热喷涂涂层之间夹着作为积聚补给物的氧化锰粉末,并且将制得的样品在1000℃的N2/3 vol% H2气氛中加热100小时。在将各个样品的横截面抛光后,使用由HORIBA有限公司生产的能量散射X光分析仪“EDX”测定热喷涂涂层中的锰扩散层的厚度。然后,对各个热喷涂涂层进行评估,当扩散层的厚度为20μm或更小时将其定为“好(G)”,当厚度大于20μm并且为50μm或更小时将其定为“中(F)”,并且当厚度大于50μm时将其定为“差(P)”。
表1
表1(续)
表2
表3
如表1所示,实施例1~16中的各个热喷涂涂层在抗热冲击性和抗积聚性的评估方面均为“好”或“中”,因此实际上获得了令人满意的结果。相反,对照例1~6中的各个热喷涂涂层在抗热冲击性和抗积聚性的评估方面至少有一个“差”,因此实际上没有获得令人满意的结果。
Claims (6)
1.一种热喷涂粉末,其特征在于,所述热喷涂粉末包含30~50mass%的碳化铬,剩余的为含有铬、铝、镱、以及钴和镍两者中的至少一种的合金,其中所述热喷涂粉末具有20~60μm的平均粒径。
2.如权利要求1所述的热喷涂粉末,其特征在于,所述热喷涂粉末包含20mass%或更少的氧化镱以代替部分所述合金。
3.如权利要求1或2所述的热喷涂粉末,其特征在于,所述热喷涂粉末包含由平均粒径为15μm或更小的原料粉末形成的经粒化并烧结的颗粒,所述经粒化并烧结的颗粒具有10MPa或更大的抗碎强度。
4.一种热喷涂涂层,其特征在于,所述热喷涂涂层通过高速火焰喷涂如权利要求1或2所述的热喷涂粉末而形成。
5.一种炉底辊,其特征在于,所述炉底辊的表面上形成有如权利要求4所述的热喷涂涂层。
6.如权利要求5所述的炉底辊,其特征在于,所述热喷涂涂层具有40~300μm的厚度。
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Cited By (4)
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CN101736279B (zh) * | 2008-11-05 | 2012-07-18 | 沈阳黎明航空发动机(集团)有限责任公司 | 一种超音速火焰喷涂自润滑耐磨涂层工艺 |
CN102039416A (zh) * | 2009-10-10 | 2011-05-04 | 湖北嘉裕管业股份有限公司 | 一种矿山公路机械用工具齿的碳化钨镍钼铁硼多元合金涂层方法 |
CN102586711A (zh) * | 2012-03-11 | 2012-07-18 | 赣州章源钨业新材料有限公司 | 一种新型高钴热喷涂粉末及其制备工艺 |
CN112095070A (zh) * | 2020-10-20 | 2020-12-18 | 西安交通大学 | 一种应用于等离子喷涂的含铝的金属粉末 |
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KR20080087740A (ko) | 2008-10-01 |
DE102008015789B4 (de) | 2015-10-29 |
KR101475764B1 (ko) | 2014-12-23 |
JP2008240072A (ja) | 2008-10-09 |
US20080241522A1 (en) | 2008-10-02 |
TWI428471B (zh) | 2014-03-01 |
US7776450B2 (en) | 2010-08-17 |
CN101274366B (zh) | 2012-02-15 |
DE102008015789A1 (de) | 2008-10-16 |
TW200916603A (en) | 2009-04-16 |
JP5058645B2 (ja) | 2012-10-24 |
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