CN101501246A - 热和腐蚀性负荷的功能性构件的涂层 - Google Patents
热和腐蚀性负荷的功能性构件的涂层 Download PDFInfo
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Abstract
本发明涉及一种金属的功能性构件，其承受热负荷或者热和腐蚀性负荷并在所述构件上涂覆一种涂层到至少一个表面上，其中所述涂层由具有氟化锆的粘结剂相和置入到所述粘结剂相中的材料构成。此外，本发明涉及一种用于制备这类涂层的隔离剂，以及一种涂覆所述涂层到功能性构件上的方法。
Description
技术领域
本发明涉及一种金属的功能性构件，其承受热负荷或者热与腐蚀性负荷，并在所述构件上涂覆一种涂层到至少一个表面上，其中所述涂层由粘结剂相和嵌入到所述粘结剂相中的材料构成。此外本发明涉及在功能性构件上用于制备涂层的隔离剂和此外一种在功能性构件的金属表面上产生涂层的方法。
背景技术
承受热负荷或者热和腐蚀性负荷的并且在此由介质(Medium)流通(durchstrmen)、冲击或承受所述介质的构件，发挥例如传动或隔板的功能。在所述功能中将其用流动性或膨胀性介质冲击。在此，经常发生强烈的温度波动，以致于所述构件必须满足耐热性的条件。在与流动性介质接触的部件上还经常发生沉淀，以致于大多用涂层装备这些部件。这类功能性构件的典型实例为例如活塞、汽缸盖球形罩(Zylinderkopfkalotten)以及在汽车中废气再循环管道的整个区域。除了这些构件的腐蚀性负荷外，这些构件还经受热负荷和温度波动。为了保护这类功能性构件，各种各样的涂层和涂覆方法是已知的。
由DE 101 24 434 A1已知一种制备涂层的方法以及用于来自汽车制造和机械制造领域的金属或合金(如钢、烧结金属或铝合金)的涂层。涂层的目的在于保护所述材料免于磨损和腐蚀。在此，所述涂层由无机的基质相(其至少尽可能地由磷酸盐构成)和嵌入其中的材料构成。在一个实施方式中所述涂层由磷酸铝构成的无机的基质相构成，材料(例如氧化铝或石墨)嵌入到所述基质相中。这类涂层优选通过由溶解的磷酸单铝(Monoaluminiumphosphat)和在其中分散的、粉末状的功能性材料构成的水基的凝胶或分散体涂覆到待涂覆的基底上，干燥并于150℃至500℃的典型的温度下在炉中煅烧。
另一种用于铝材料的涂层已知于DE 699 08 837 T2。在此，所述涂层涉及活塞裙的表面，其具有经硬质阳极化的涂层和在经硬质阳极化的涂层上涂覆的复合聚合物涂层。所述复合聚合物涂层在耐热聚合物基质中含有许多固态的和润滑性的微粒，所述耐热性聚合物基质可经受发动机的工作温度。在此，作为润滑剂使用已知的润滑剂-材料石墨、氮化硼、钼等。
发明内容
本发明的任务在于开发构件上的热负荷的或者热与腐蚀性负荷的功能性表面的涂层，其与功能性构件的母材形成化学键合并因此对抗内能性构件的腐蚀性和热负荷。此外，所述涂层应是容易施用的，并具有对于母材的高粘附性。此外，本发明的任务在于提供一种用于制备这类层的隔离剂，其可廉价地制备且容易地施用。本发明的另一个任务是提供一种方法，所述方法能够产生这类层，且所述方法在粘结剂和母材之间产生高粘附性。
本发明涉及用涂层装备的功能性构件的任务如下解决，即所述粘结剂相与功能性构件的母材化学结合，且所述粘结剂相由聚合物形成，所述聚合物由经聚合的氟化锆构成，其中功能性构件为内燃机的部件。通过本发明的由经聚合的氟化锆构成的粘结剂相的应用，现在获得了这样的可能性，即建立与母材的化学键合，并因此在功能性构件上产生牢固粘附的层。这类涂层提高了功能性构件的寿命并降低了(在改进的效果的情况下)耗费且高成本的用于改进所述母材的温度突变行为的方法的使用。此外，借助本发明的层避免了沉积，这又用于汽车的减排。在有利的本发明的实施方案变化中，将Al2O3和/或SiO2和/或TiO2和/或ZrO2形式的结构颗粒结合到所述粘结剂相中。在此，聚合物链包裹所述结构颗粒且将所述结构颗粒粘结到母材上。在此，所述氟化物与在母材中存在的铁或者非金属(例如铝)形成化学键。因此，在功能性构件上产生牢固粘附的层，其借助与母材的化学键和所述结构元件到聚合物链中的包裹形成对于腐蚀性负荷的高的安全性。在此硬质的结构颗粒(其作为氧化物存在)用作为磨损载体且所述粘结剂相用作为母材与结构元件之间的粘结剂。所述结构颗粒以80nm至200nm的级份存在，并在涂层中以不超过10重量％形成颗粒类材料的最大份额。所述结构颗粒具有相对粗糙的表面结构，以便一方面彼此紧紧互锁连接(sich verhaken)且同时保证在所述粘结剂相中良好的牢固性(Halt)。
优选将Al2O3和/或SiO2和/或ZnO和/或TiO2和/或ZrO2和/或CeO形式的基础颗粒与结构颗粒一起引入到所述粘结剂相中。所述基础颗粒置入到所述结构颗粒之间的空隙中。特别是通过2nm至80nm的基础颗粒尺寸，所述基础颗粒最佳适合于用作为结构颗粒之间的填充物。由此产生非常平滑的表面，其又对抗腐蚀和对抗冲击功能性构件的(在例如废气再循环管道的废气中含有的)炭黑颗粒的沉积。所述非常平滑且耐久的表面因此成就本发明的优点，即用本发明的涂层装备的功能性构件具有长的寿命。所述基础颗粒优选以1重量％至3重量％的份额存在于所述涂层中。
在其它有利的本发明的实施方案变化中，在粘结剂相中结合入氮化硼和/或镁铝硅酸盐和/或二硫化钼和/或硅酸盐矿(例如云母)形式的滑动颗粒。在所述涂层中以不超过5重量％的份额含有所述滑动颗粒。具有2μm至15μm范围(Ausdehnung)的大得多的滑动颗粒同样通过聚合物链固定或处于所述涂层中的结构颗粒之间。
作为层厚优选设计厚度为1μm和80μm之间。在功能性构件的表面上优选厚度为25μm和60μm之间。功能性构件为例如构件(如活塞、汽缸盖球形罩或汽车中的废气再循环管道)。在此功能性构件由铝合金或由钢形成。同样可能的是，在功能性构件上的本发明的涂层由铸铁，特别是GG、GGG、GGV形式的铸铁形成。
本发明涉及用于制备在功能性构件上的涂层的隔离剂的任务如下解决，即所述隔离剂由全脱盐的水形成并含有下列成分：
-成酸剂，特别是以钠碱液和/或钾碱液和/或氯化铝形式的
-由氟化锆(特别是以H2ZrF6形式的)构成的粘结剂，
-有机分散剂(例如明胶)。
借助成酸剂可以调节酸含量并以此调节所述隔离剂的pH值，并因此控制反应速度和聚合物的形成。优选调节在隔离剂中的pH值为4至5。通过使用隔离剂现在可以制备根据权利要求1所述的涂层。在优选的实施方式中在隔离剂中含有结构颗粒以及基础颗粒，其借助喷涂或浸渍所述功能部件而施加到功能性构件的材料表面上。有利的是同样引入氮化硼和/或镁铝硅酸盐和/或二硫化钼形式的滑动颗粒。在此，所述结构颗粒的级份处于80nm至200nm之间，所述基础构件的级份处于2nm至80nm之间和所述滑动颗粒的级份处于2μm至15μm之间。在此独立地(selbst
ndig)形成纳米颗粒的明胶是有利的。在从属权利要求中给出的范围粘结剂以不超过5重量％的最大份额(Grβenanteil)添加到所述隔离剂中。将不超过10重量％的结构颗粒，不超过3重量％的基础颗粒和不超过5重量％份额的滑动颗粒添加到隔离剂中。
通过结构颗粒、基础颗粒、滑动颗粒和作为粘结剂的氟化锆的添加的有针对性的选择可以制备隔离剂，其具有高的流动性并优选用简单的方法喷涂到功能性构件的表面上。
关于在功能性构件的表面上制备涂层的方法，本发明的涂层经此制备，即所述表面首先用隔离剂冲击并随后将功能性构件加热到至少200℃的温度，以便进行氟化物与母材的化学键合和粘结剂的聚合。有利地所述加热借助高频电场产生，即例如以电容或电感方式施加到功能性构件的表面上。通过直接的加热(例如在电感加热的情况下进行)，可非常均匀地加热所述表面。在此，优选的借助高频电场用于加热的频率区间为100kHz至10MHz，其中优选使用约4MHz。在用4MHz加热的情况下因此产生0.2至0.3mm的氟化物渗透深度。因此，在功能性构件的表面上产生非常好的粘附性涂层。
聚合物链一方面用于所述层的内聚力且另一方面所述聚合物链是有利的，因为其在热负荷下增长并因此提高所述层的弹性。因此，在循环的热负荷下不出现由所述涂层的裂缝形成而造成的过早的构件失效，因为本发明的涂层可弹性地跟随母材伸展。通过本发明所述层的结构可达到直至约1300℃的耐热性。所使用的氟化物粘结剂体系具有约220℃的聚合温度和830℃的玻璃化温度。在此，对母材的粘附性在接近玻璃化或者玻璃化的状态下通过对母材的化学键合而确保。但是，优选注意在功能性构件的使用区域内的运行温度低于所述玻璃化温度，由此所述涂层在弹性区域内并因此其膨胀系数类似于所述母材的膨胀系数。
Claims (19)
1.金属的功能性构件，其承受热负荷或者热和腐蚀性负荷，并在所述构件上将一种由粘结剂相和嵌入到所述粘结剂相中的材料构成的涂层涂覆到至少一个表面上，其特征在于，所述功能性构件是内燃机的部件，且所述粘结剂相与所述功能性构件的母材化学结合，并形成由经聚合的氟化锆构成的聚合物形成的粘结剂相。
2.根据权利要求1所述的功能性构件，其特征在于，嵌入到粘结剂相中的材料是80nm至200nm级份的Al2O3和/或SiO2和/或TiO2和/或ZrO2形式的结构颗粒，其中所述结构颗粒由聚合物包裹。
3.根据权利要求2所述的功能性构件，其特征在于，嵌入到粘结剂相中的材料由2nm至80nm级份的Al2O3、SiO2、ZnO、ZrO2、CeO、TiO2形式的基础颗粒形成，其中所述基础颗粒置入到结构颗粒之间的空隙中且所述基础颗粒由聚合物包裹。
4.根据权利要求1或2或2和3所述的功能性构件，其特征在于，嵌入到粘结剂相中的材料为2μm至15μm级份的氮化硼和/或镁铝硅酸盐和/或二硫化钼形式的滑动颗粒，其中所述滑动颗粒由聚合物包裹。
5.根据权利要求1-4中一项或多项所述的功能性构件，其特征在于，所述功能性构件由铝合金或钢或铸铁，特别是GG、GGG、GGV形式的铸铁形成。
6.根据权利要求5所述的功能性构件，其特征在于，所述功能性构件为含铁的构件，且涂层借助经结合的氟化铁与母材粘结。
7.根据权利要求1-4中一项或多项所述的功能性构件，其特征在于，所述层以1μm至80μm，优选25μm至60μm的厚度存在于表面上。
8.根据权利要求1-5中一项或多项所述的功能性构件，其特征在于，所述构件为活塞、汽缸盖球形罩或废气再循环管道部件。
9.用于制备在功能性构件上的涂层的隔离剂，其特征在于，所述隔离剂由全脱盐的水形成并至少含有下列成分：
-成酸剂，特别是以钠碱液和/或钾碱液和/或氯化铝形式和，
-由氟化锆构成的粘结剂。
10.根据权利要求9所述的隔离剂，其特征在于，在所述隔离剂中含有80nm至200nm级份的Al2O3和/或SiO2形式的结构颗粒的组分。
11.根据权利要求10所述的隔离剂，其特征在于，在所述隔离剂中含有2nm至80nm的级份的Al2O3和/或SiO2和/或ZnO和/或TiO2和/或ZrO2和/或CeO形式的基础颗粒的组分。
12.根据权利要求9-10中一项或多项所述的隔离剂，其特征在于，在所述隔离剂中含有2μm至15μm的级份的氮化硼和/或镁铝硅酸盐和/或二硫化钼形式的滑动颗粒的组分。
13.根据权利要求9-12中一项或多项所述的隔离剂，其特征在于，在所述隔离剂中借助成酸剂将pH值调节到4至5。
14.根据权利要求9-13中一项或多项所述的隔离剂，其特征在于，所述粘结剂的份额在隔离剂中少于或等于5重量％。
15.根据权利要求9-14中一项或多项所述的隔离剂，其特征在于，所述结构颗粒的份额在隔离剂中少于或等于10重量％。
16.根据权利要求9-15中一项或多项所述的隔离剂，其特征在于，所述基础颗粒的份额在隔离剂中少于或等于3重量％，且优选在1重量％和3重量％之间。
17.根据权利要求9-16中一项或多项所述的隔离剂，其特征在于，所述滑动颗粒的份额在隔离剂中少于或等于5重量％。
18.在根据权利要求1-8中一项或多项所述的功能性构件的金属表面上，借助根据权利要求9-17中一项或多项所述的隔离剂制备涂层的方法，其特征在于，
-首先，将所述表面用隔离剂冲击，和
-随后将功能性构件加热到至少200℃的温度，以便在隔离剂中进行氟化物与母材的化学键合和粘结剂的聚合。
19.根据权利要求18所述的方法，其特征在于，所述加热借助高频电场在100kHz至10MHz的频率范围内，优选在4MHz的频率范围内，以电感或电容方式进行。
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| CN116715983A (zh) * | 2023-06-19 | 2023-09-08 | 陕西科技大学 | 金属高温挤压成型用水性涂料、自润滑减磨涂层及制备方法 |
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| JP2009529097A (ja) | 2009-08-13 |
| JP5219845B2 (ja) | 2013-06-26 |
| DE102006010875A1 (de) | 2007-09-13 |
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