CN102944601A - 用于测量铸铁熔体中的氧含量的传感器 - Google Patents

用于测量铸铁熔体中的氧含量的传感器 Download PDF

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CN102944601A
CN102944601A CN2012103110470A CN201210311047A CN102944601A CN 102944601 A CN102944601 A CN 102944601A CN 2012103110470 A CN2012103110470 A CN 2012103110470A CN 201210311047 A CN201210311047 A CN 201210311047A CN 102944601 A CN102944601 A CN 102944601A
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丹尼·哈贝茨
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Abstract

本发明涉及通过电化学测量元件来测量铸铁熔体中的氧含量的传感器，其中所述电化学测量元件包括固体电解质管，所述传感器的特征在于：二氧化锆层被施加于所述固体电解质管的外表面上。本发明的传感器可使得现有技术得到改善。

Description

用于测量铸铁熔体中的氧含量的传感器
本申请是申请号为200880002846.1、申请日为2008年1月14日、发明名称为“影响铸铁性质的方法”的专利申请的分案申请。
技术领域
本发明涉及通过向铸铁熔体中加入镁从而影响铸铁性质的方法。
本发明还涉及通过电化学测量元件来测量铸铁熔体中的氧含量的传感器，其中所述电化学测量元件包括固体电解质管。
背景技术
一般来说，铸铁熔体中的游离镁的含量被认为是在镁处理的铸铁中形成球状石墨或蠕虫状石墨的决定因素。目前用于调控可锻铸铁生产过程的方法包括借助光谱分析样品来确定镁的总含量，即游离镁和结合镁的总含量。但是，这种方法所提供的信息并不完整，因为该方法不能得知游离镁的含量，而且这种测量方式也不能提供关于氧活度的任何信息。然而，同游离镁一样，氧活度也是形成石墨形态的决定因素。所谓的可锻铸铁是这样的常规灰铸铁，其经过球化添加剂的处理，因而铸铁中的绝大部分石墨碳都是所谓的粒状石墨或球状石墨。由于颗粒的形态、尺寸及数目这些参数会影响到铸铁的机械性能，因此必须从这些方面对铸铁中的粒状石墨进行分析。目视分析方式复杂或带有主观性，即使在部分自动化的分析中也是如此。这方面的测量方式是已知的，例如可从专利文献US 5,675,097中得知。专利文献DE 19928456A1描述了确定铸铁中石墨的空间结构的测量方法，该测量方法基于氧的测定，并且没有目视分析方法的缺陷。这样，反应会更为迅速，并且对生产过程的特定影响会提高产率，或者减少铸造过程中所产生的废料。铸铁的质量可以得到良好地控制。
可通过（例如）对白口硬化样品进行金相分析或光谱分析、或者还可通过热分析来证实铸铁中镁处理的成效。
一般来说，用纯镁或镁合金来促进铸铁的球状形态。所加入的镁中的一部分从铁中提取氧和硫；剩余部分的镁，即所谓的游离镁部分，控制氧活度。熔体中游离镁的含量是铸铁球化率的决定因素。随着时间的推移，熔体中的游离镁含量减少，而氧活度提高。这会对铸铁的结构以及机械性能造成影响。
从（例如）专利文献DE 10310387B3中可得知用来测定金属熔体氧活度的传感器。在该专利文献中披露了一种外表面上具有涂层的固体电解质管，该涂层是由锆酸钙和氟化物的混合物形成的，从而可测量（例如）铁熔体中的硫、硅或碳的浓度。
发明内容
本发明的目的是提出一种方法以及用于调控该方法的传感器，通过这种方法和这种传感器可使得现有技术得到改善，并且使铸铁的机械性能在液相时就受到特定的影响。
该问题通过独立权利要求的技术特征而得以解决。在从属权利要求中示出了有利的实施方案。具体而言，本发明方法的特征在于：对铸铁熔体中的氧含量进行测量；并且向铸铁熔体中加入镁，直至在约1,420℃的温度（参考温度）下铸铁熔体中的氧含量达到约0.005ppm至0.2ppm为止。由于测量氧比目前可能的测量镁的方式更为精确（镁在熔体中以游离镁和结合镁的形式存在，因此不可能对镁作出精确的分析），因此能够更为精确地决定铸铁的机械性能。本领域的技术人员可以检测并利用低氧含量下存在些许大石墨颗粒与较高氧含量下存在众多小石墨颗粒这二者之间的相互关系。这样，如专利文献US5,675,097中已描述的那样，可以与机械性能（例如抗拉强度、延伸率以及变形阻力）相关联。出乎意料的是，已经表明，当加入镁直至氧含量低于0.1ppm、优选为介于0.08ppm和0.1ppm之间时，铸铁具有最大的延伸率。当氧含量更低或更高时，铸铁的延伸率会再次降低。有利的是，向铸铁熔体中加入约200ppm至750ppm的镁，以达到所需的氧含量。
本发明传感器的特征在于：二氧化锆层被施加于固体电解质管的外表面上。特别是，可采用氧化钙、氧化钇和/或氧化镁使该层中的二氧化锆稳定。有利的是，使用至多30重量%的氧化钙、至多25重量%的氧化镁和/或至多52重量%的氧化钇来使该层稳定。特别有利的是，使用约4重量%至6重量%的氧化钙来使该层稳定。有利的是，该传感器的该层是等离子喷镀的。优选的是，该层的厚度为约30μm至50μm，尤其为约40μm。其上设置有该层的固体电解质管优选为可被约2重量%的氧化镁稳定的二氧化锆管。
附图说明
下面参照附图对本发明的一个示例性实施方案进行说明。在这些附图中：
图1示出石墨颗粒的数目与氧含量（氧活度aO）之间的关系；
图2示出相对延伸率与氧含量之间的关系；
图3示出本发明的传感器头的剖面图；并且
图4示出另一实施方案的传感器的部分剖面。
具体实施方式
图1示出石墨颗粒的数目随着氧含量（氧活度aO）的升高而增加。因此，可通过加入镁来调节氧含量，进而调整石墨颗粒的数目。因此，铸铁的性质在熔体状态下就已受到特定的影响。当氧活度介于约0.10ppm和0.12ppm之间时能获得最大的球化率（该数据在1,420℃下有效）。当氧活度降至低于0.10ppm时，球化率降低。这与铸造生产实践中的已知经验（即，过高的镁含量会对球化率产生不利的影响）相符。
图2示出铸铁的相对延伸率与氧含量之间的关系。显然，当氧活度约为0.08ppm时，延伸率最大。当氧活度较低时，延伸率略微降低，这可能是由于此时的球化率较小所致。如果氧活度超过该最佳值，则延伸率会稳定降低。该图表明，可通过加入镁来调控铸铁熔体中的氧含量，进而影响铸铁的相对延伸率。
图3示出了本发明的传感器。在金属管1中，电线2（Cu/CuNi/导体）被设置在填砂3中。电线通过连接件4与矛状物或另一固定器相连，再和分析器单元相连。电线2的另一端与热电偶5以及电化学测量元件6相连。电化学测量元件6具有固体电解质管（ZrO2元件），该固体电解质管具有作为外套的钢质冲击屏蔽层。ZrO2元件的外表面上具有用5重量%的氧化钙稳定的二氧化锆层。该层的厚度为约40μm。由于固体电解质管基本上是已知的，因此在图中未示出其细节。
热电偶5固定在热电偶密封粘结剂7内的适当位置上。测量元件6也固定在粘结剂8内的适当位置上；设置于传感器内部的测量元件6的端部被密封塞9封闭，其中电触头穿过该密封塞9。两个传感器元件5和6通过塑料夹10连接在一起。电线以延伸贯通绝热部件11的方式穿过金属管1的内部。在传感器的浸入端，砂体12被设置在金属管1的外部以对金属管1加以保护。
图4示出了一种类似的装置，其中示出了位于载体管13内的传感器的接触件。载体管13由纸板形成，并且在载体管13朝向砂体12的前侧，包围着由铸造用砂或水泥形成的防溅管14。为了在输送以及浸入熔体的过程中起到保护作用，传感器元件5和6本身最初被金属帽15包住，该金属帽15会在传感器浸入金属熔体过程中或浸入之后发生熔融，从而使传感器元件5和6暴露出来。

Claims (8)

1.一种通过电化学测量元件来测量铸铁熔体中的氧含量的传感器，该电化学测量元件包括固体电解质管，所述传感器的特征在于：二氧化锆层被施加于所述固体电解质管的外表面上。
2.根据权利要求1所述的传感器，其特征在于：所述二氧化锆层中的二氧化锆被氧化钙、氧化钇和/或氧化镁所稳定。
3.根据权利要求2所述的传感器，其特征在于：所述二氧化锆层被至多30重量%的氧化钙、或至多25重量%的氧化镁、或至多52重量%的氧化钇所稳定。
4.根据权利要求3所述的传感器，其特征在于：所述二氧化锆层被约4重量%至6重量%的氧化钙所稳定。
5.根据权利要求1至4中任意一项所述的传感器，其特征在于：所述二氧化锆层是等离子喷镀的。
6.根据权利要求1至5中任意一项所述的传感器，其特征在于：所述二氧化锆层的厚度为约30μm至50μm，尤其为约40μm。
7.根据权利要求1至6中任意一项所述的传感器，其特征在于：所述固体电解质管被设计为二氧化锆管。
8.根据权利要求7所述的传感器，其特征在于：所述二氧化锆管被约2重量%的氧化镁所稳定。
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