CN1032486C - 形成在铁基上的涂层及其形成方法 - Google Patents

形成在铁基上的涂层及其形成方法 Download PDF

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CN1032486C
CN1032486C CN87101667A CN87101667A CN1032486C CN 1032486 C CN1032486 C CN 1032486C CN 87101667 A CN87101667 A CN 87101667A CN 87101667 A CN87101667 A CN 87101667A CN 1032486 C CN1032486 C CN 1032486C
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chromium cpd
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石井乔
小浜一
矢部久雄
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Toshiba Corp
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Abstract

一种形成在铁基金属的基体的表面上的涂层，包括含有作为主要成份的Cr2O3的表层和含有在基体和表层氧化铬之间的反应生成物并形成于表层和基体之间的界面上的中间层；本发明还提供一种形成上述涂层的方法，它包括：(1)含有Cr2O3的铬化合物溶液通过涂或浸而涂覆于基体的表面，(2)将基体在500℃到600℃的温度下进行烘焙，使铬化合物转变成Cr2O3，(3)多次重复步骤(1)和(2)。

Description

形成在铁基上的涂层及其形成方法
本发明涉及一种形成在铁基金属基体上的涂层及其形成方法，该涂层能与由纸、橡胶、塑料、树脂、陶瓷和金属组成的集合里挑选的构件实行接触。
众所周知，由于钢铁具有优良的机械性能，例如强度，延展性，韧性，硬度等等，因此相对其它金属来说，它被当作机械材料，结构材料等最基本的材料来用。
钢铁根据它们的含碳量可分为铁，钢和铸钢。再进一步，钢可以分为碳钢和合金钢，合金钢是通过在碳钢里加入各种元素而获得的并具有特殊的性能。根据它们的性能合金钢可有各种不同的用途。
由钢制成的机械零件或结构零件除了机械强度外根据它们的使用条件或环境因素还必须具有所需的性能。当钢制零件使用时并与其它零件摩擦接触时，需要耐磨和一个光滑的表面。例如，当零件(如机器的轴承零件或滑动零件)互相摩擦接触时，或当工具与其它零件接触时，就需要耐磨性和光滑的表面以便防止零件的磨损和改进相对其它零件的滑动性能。当钢制零件在有腐蚀性的诸如水、酸性物、碱性物等环境里使用时，例如就潜水泵的传动轴和转子来说就需要高的防化学变化的性能。
近年来，曾经尝试过在零件的表面形成一层不同于基体的涂层，以便除了该材料原有的性能外再根据使用条件或环境因素提供给钢制零件所需的性能。这种涂层必须具有与其它零件磨擦的耐磨性和改进相对其它零件滑动性能的光洁度，必须不损伤其它零件，必须具有防化学变化的性能并足以不在腐蚀性环境里被腐蚀。再进一步，涂层必须以很高的机械强度形成于零件的基体表面上，不会因形成而降低基体的性能并且不需在形成后进行研磨等精加工。
作为在铁或钢制零件的基体表面形成涂层的一种方法，电镀，物理蒸敷法，化学蒸敷法，火焰喷涂法等等是众所周知的。然而，这些方法不能完全满足上面提到的所有的需求，而且实际应用起来也不能尽如人意。更具体地说，用这种方法形成的涂层不具有足够的致密度，耐磨性和光洁度。涂层和基体之间的联结强度也不是足够的，涂层经常会从基体上脱落。此外还需要涂层形成后的研磨工序。
由于上述原因，提供本发明以便在机械零件表面形成一种具有良好的耐磨性、光洁度和抗化学变化的涂层，该涂层具有很高的机械强度并在不损伤基体的情况能很容易地形成于基体上，该涂层能与由纸、橡胶、塑料、树脂、陶瓷和金属组成的集合里挑选的构件实行接触。
根据本发明，提供一种形成在铁基金属的基体的表面上的涂层，它包括含有氧化铬(Cr2O3)作为主要成份的表层，一含有基体和表层里的氧化铬之间的反应生成物的中间层形成于表层和基体之间的界面上。
根据本发明，提供一种形成上述涂层的方法，它包括下述步骤：
(1)含有作为主要成份的氧化铬(Cr2O3)的铬化合物溶液通过涂或浸的手段涂覆于基体的表面；
(2)所述基体在500℃到600℃的温度下进行烘焙，在此加热下所述铬化合物转变为氧化铬(Cr2O3)；
(3)多次重复步骤(1)和(2)。
本发明的涂层能与由纸、橡胶、塑料、树脂、陶瓷或金属组成的集合中挑选的构件接触，用这种涂层所制成的机械零件包括诸如机器上的轴承或滑动零件等零件，例如，发动机的汽缸或泵体，它们都与由橡胶或合成树脂组成的O型密封圈接触。
涂层所采用的基体可以是碳钢、不锈钢或其它铁合金。
根据本发明形成于机械零件基体上的涂层具有氧化铬(Cr2O3)颗粒的致密结构，该颗粒是通过加热铬化合物转变而来的并互相完全粘结。涂层是光滑的并具有良好的耐磨性。由于析出的Cr2O3陶瓷颗粒的尺寸非常小(1微米或更小)，涂层就能是致密的、完全没有微孔的光洁层，并能形成非常薄的一层，而且基体的原有性能(例如弹性)依然能有效地利用。涂层的硬度高达HV500或更高。作为材料和氧化铬之间的反应生成物的中间层形成于涂层和基体之间的界面上。涂层可以很高的粘附强度(500公斤力/厘米2)形成于基体上。中间层的厚度介于0.5微米至3.0微米的范围内。涂层还有很高的抗腐蚀性，隔离外界物质的性质和高的防化学变化性能。
涂层里包含的氧化铬(Cr2O3)可以增加硬度和减少摩擦系数。
这种涂层可通过以下的方法制成。根据该方法，铬化合物溶液，例如CrO3的水溶液通过涂或浸的手段涂覆于基体的表面。将涂有CrO3溶液的基体在500℃到600℃(最好约550℃)的温度下烘焙作反应处理，由此在基体的表面区域内形成一含有以Cr2O3作为主要成分的涂层。500℃至600℃的烘焙温度使CrO3转变为Cr2O3。多次重复涂敷和烘焙CrO3的操作循环就能在基体的表面形成一层含Cr2O3的致密的硬的陶瓷涂层。该涂层的厚度是1到50微米。在这种方法里，厚度是由上述的操作循环重复的次数控制的。机械零件涂层的厚度推荐的是1到10微米，最好是2到6微米。由于烘焙温度介于500℃到600℃范围之间，基体的性能不会降低。
任何铬化合物，包括通过加热可以转变为Cr2O3的CrO3均可使用，这种铬化合物如NaCrO4·10H2O，Na2Cr2O7·2H2O，K2CrO4，K2Cr2O7和(NH4)2Cr2O7。此外，所述的溶液不局限于水溶液，还可以用熔盐来代替。溶液的浓度最好在10—85％之间。
本发明将通过下述例子来描述：
例1：
用奥氏体不锈钢(ASTM304)和铁素体不锈钢(ASTM430)作为基体，有八个试样，包括一个不具有涂层，一个具有根据本发明形成的涂层，一个具有根据普通方法形成的涂层，如下面表1所示：
                                              表1
试样编号 涂层的形成方法   涂层材料    涂层厚度(μm)  涂层硬度(HV)     基体材料
    1     无涂层      -   -     300  ASTM(304)
    2     无涂层      -   -     250  ASTM(430)
    3     本发明     Cr2O3  4至5     600  ASTM(304)
    4     本发明     Cr2O3  4至5     550  ASTM(430)
    5 物理蒸敷法     TiC  2至3   2.000  ASTM(304)
    6 物理蒸敷法     TiC  2至3   2.000  ASTM(430)
    7 化学蒸敷法     TiN  6至7   3.000  ASTM(304)
    8 化学蒸敷法     TiN  6至7   3.000  ASTM(430)
试样1和试样2的基体表面需要精加工，而形成涂层后的试样3和试样4不需精加工。试样5到试样8则在涂层形成后需要精加工。由于试样3和试样4的涂层是如下所述那样地形成于基体的表面。更具体地说，基体是被浸在50％的铬酸(CrO3)溶液里持续1到2分钟。当基体干燥后，在500℃到600℃温度的空气里被烘焙。将上述加工的操作过程重复16次，由此在基体表面形成约5微米厚的涂层。该涂层由含有基体和CrO3的反应生成物(FeO·Cr2O3)和作为主要成份的Cr2O3的中间层，及含有作为主要成份的从CrO3转变而来的Cr2O3的一层组成。试验这些试样是为了检查它们的耐磨性和抗化学变化性能。
耐磨性试验：通过一种高速的纤维滑动试验来检查耐磨性，其试验条件如下：纤维：    聚酯50d/48f速度：    3.5m/sec拉力：    65g试验时间：24小时试验结果如表2所示
                               表2
试样编号     涂层的形成方法 涂层材料     破坏情况
1     无涂层     — 较大的磨损痕迹持续24小时丝不断
3     本发明     Cr2O3     无磨损痕迹持续24小时丝不断
5     物理蒸敷法     TiC 较小的磨损痕迹20小时后丝断
7 化学蒸敷法 TiN     中等磨损痕迹12小时后丝断
从表2可得知，本发明的试样没有磨损痕迹并在丝运动24小时后依然不断。
耐腐蚀性试验：
试样的耐腐蚀性是通过将它们浸入盐酸溶液里然后测出样品重量的减少来进行的。
试验条件如下所述：
溶液浓度：5％，10％
温度：    环境温度
浸渍时间：24小时
试验结果如表3所示
                            表3
试样编号 涂层的形成方法                 盐酸浓度
1 无涂层     5％      10％
  0.72mg/cm2     2.5mg/cm2
    3     本发明   0     0.1mg/cm2
从表3中可以得知，本发明的试样具有良好的耐腐蚀性能。
例2
一奥氏体不锈钢(A STM304)泵体被作为基体来用，其外径为34毫米，内径为30毫米，长为100毫米，共准备两个试样。一个试样具有根据本发明形成的涂层，另一个试样具有根据一般方法形成的涂层。
更具体地说，试样9有一根据本发明形成的涂层。将基体浸在80％CrO3水溶液里持续1到2分钟。然后，将基体放在500℃到600℃温度的空气里烘焙。上述操作过程重复15次，由此在基体上形成一5微米厚的涂层。
试样10有一根据一般方法形成的涂层。通过镀铬在基体上形成一30到40微米厚的铬层。
两个试样作为泵体安装在一个试验柱塞泵里，然后就可以做内表面的耐磨试验了。具体地说，就是通过柱塞泵不断地输送2％熟石灰的水溶液。然后在300小时后测出泵体内表面涂层的磨损，并观察内表面的状态。注意在泵运转期间，由橡胶制成的并安装在传动轴末端的滑动部件以每分钟120次的速率在汽缸内往复运动。
结果是，试样9内表面的磨损是2微米，且其内表面状态没有发生变化。但试样10内表面的磨损是45微米，而且涂层几乎完全破坏并露出了基体。
根据上述的本发明，可以提供一种涂层，该涂层具有良好的耐磨性、光洁度和抗化学变化性能，并能很容易地以很高的机械强度并在不削弱基体性能的情况下形成于基体之上，该涂层能实现与某种构件的接触，所说的构件选自由纸、橡胶、塑料、树脂、陶瓷和金属组成的集合。

Claims (9)

1.一种形成在一铁基金属的基体的表面上的涂层，它包括一含有作为主要成份的氧化铬(Cr2O3)的表层，其特征在于还包括一含有在所述表层里的氧化铬和所述基体之间的反应生成物并形成于所述表层和所述基体之间的界面上的中间层。
2.根据权利要求1所述的涂层，其特征在于所述表层有一1到50微米的厚度。
3.根据权利要求1所述的涂层，其特征在于所述表层有一1到10微米的厚度。
4.根据权利要求1所述的涂层，其特征在于所述表层有一2到6微米的厚度。
5.根据权利要求1所述的涂层，其特征在于所述中间层有一0.5到3.0微米的厚度。
6.根据权利要求1所述的涂层，其特征在于所述中间层含有FeO·Cr2O3和Cr2O3。
7.一种形成由权利要求1所确定的涂层的方法，其特征在于它包括下述步骤：
(1)含有作为主要成份的氧化铬(CrO3)的铬化合物溶液通过涂或浸的手段涂覆于基体的表面；
(2)将所述基体在500℃到600℃的温度下进行烘焙，在此加热所述铬化合物使之转变为氧化铬(Cr2O3)；
(3)多次重复步骤(1)和(2)。
8.根据权利要求7所述的方法，其特征在于所述铬化合物溶液可以由铬化合物熔盐代替。
9.根据权利要求7所述的方法，其特征在于，所述铬化合物溶液的浓度最好在10—85％之间。
CN87101667A 1986-02-28 1987-02-28 形成在铁基上的涂层及其形成方法 Expired - Fee Related CN1032486C (zh)

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