CN106011743A - 一种合金材料表面锰铬陶瓷涂层的制备方法 - Google Patents
一种合金材料表面锰铬陶瓷涂层的制备方法 Download PDFInfo
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Abstract
本发明涉及一种合金材料表面锰铬陶瓷涂层制备方法。采用两步包埋渗技术,先后将Mn、Cr元素渗入合金表层,使Mn、Cr元素呈特定的浓度梯度分布,随后再通过低氧分压法在合金材料表面氧化形成致密的锰铬陶瓷涂层。该技术可以使涂层具有较高的厚度,有效地提高合金材料的抗高温氧化、渗碳及结焦性能,并具有长久的服役寿命。
Description
技术领域
本发明涉及陶瓷涂层技术领域,具体的说,是一种合金材料表面锰铬陶瓷涂层的制备方法。
背景技术
传统高温合金采用铬镍等合金元素提高材料的抗高温氧化、抗渗碳性能。在高温下,合金元素表面形成各种氧化物如Cr2O3、NiO等在一定程度上能够保护基体材料免于高温侵蚀。但是在较高温度下,合金材料表面Cr2O3氧化层蒸汽压较高,仍易于挥发、剥落,从而失去对基体材料的保护作用。
HP40、HK40、35Cr45Ni、Incoloy 800等高温合金是石化行业乙烯裂解炉、制氢炉等常用的炉管材料,炉管运行在富含CO、CO2、CH4及其他碳氢化合物的高温气氛环境中,合金氧化物与碳发生反应生成脆性的碳化物,从而失去对基体合金的保护作用;裸露的基体Fe、Ni元素与高温烃类接触,能够催化焦垢的形成与生长,造成严重的结焦。明显缩短运行周期,对生产造成非常大的影响。
因此在合金材料的表面制备更加稳定的保护膜,从而提高材料的抗高温氧化、抗渗碳、抗结焦性能,是非常具有现实意义的。以乙烯裂解炉炉管为例,在长期的高温裂解气环境下,炉管内表面面临非常严重的渗碳和结焦问题。目前对炉管表面的渗碳和结焦最有效的方法是利用惰性涂层隔绝起催化结焦作用的铁镍元素与裂解原料接触,主要有以下几种:(1)通过物理或化学方法在炉管表面涂覆一层抑制结焦涂层;(2)通过基体成分原位氧化技术在炉管表面形成一层稳定的保护层。
美国专利US 6139649中,Alon Surface Technologies公司在炉管表面形成了具有三层结构的抑制结焦涂层。第一层采用铬硅沉积,第二层涂覆铝、镁、硅和锰,第三层涂覆碱土金属,用氩气和氮气处理形成稳定的氧化物层。
中国科学院金属研究所开发了一种新型抗结焦复合炉管。炉管主体材料为耐热钢,内壁为SiO2、BaO、CaO、Al2O3混合物在1200℃下烧结而成的陶瓷烧结层。
中国CN100497529C、US6514563、CN1399670等专利中,将结焦抑制剂和抑制结焦涂层技术结合形成抑制结焦在线涂覆预处理涂层。
NOVA公司在专利US715697、US6824883、US2006086431等中公开了炉管内形成锰铬陶瓷(MnxCr3-xO4(0.5≤x≤1.5))保护层的方法。中国专利CN101565807A、CN101565808A将H2、CO、N2等气体引入水蒸气,采用高温氧化在炉管材料表面制备出MnxCr3-xO4(0.5≤x≤1.5)陶瓷涂层。专利CN102719783A将H2、N2等气体通过水或者其他电解质溶液引入水蒸气,以两步加热保温的方法在炉管表面制备出了MnxCr3-xO4(0.5≤x≤1.5)陶瓷涂层。研究发现锰铬陶瓷在高温热裂解环境中比氧化铬稳定,但在循环结焦清焦过程中,锰铬陶瓷会发生缓慢的渗碳,其抗结焦、抗渗碳能力下降。
中国专利CN103788986A通过辉光放电和氧化相结合的方法在炉管表面形成锰铬陶瓷涂层或锰铝陶瓷涂层,可减少裂解炉管的结焦和渗碳。由于涂层中存在MnO、Fe、Ni,增加了涂层渗碳、结焦的倾向。
采用上述方法制备陶瓷保护层能对基体起到一定的保护作用,但是也存在以下不足:基体中原始锰含量较低,直接通过低氧分压原位氧化的方法制备获得的陶瓷涂层较薄(~1微米),随着炉管内物料高速冲刷、循环结焦和清焦、碳化等因素综合作用,涂层容易失效;同时,陶瓷涂层的Mn来自于基体原始母材,Mn的外迁会导致靠近涂层处基体贫Cr、Mn,一旦保护层破坏,渗碳和结焦更容易加速进行。采用直接烧结形成玻璃或陶瓷涂层工艺,获得的涂层与基体结合力相对较低,容易脱落失效。
发明内容
本发明的目的在于克服现有技术的不足,提供一种合金材料表面锰铬陶瓷涂层的制备方法。本技术可以在合金材料表面形成致密、稳定的保护性涂层。涂层几乎完全由锰铬陶瓷组成且具有较高的厚度。同时陶瓷涂层下方区域富Cr、Mn元素,使涂层具备一定的自修复能力。该涂层能有效地提高合金材料的抗高温氧化、抗渗碳、抗结焦性能。
本发明的目的是通过以下技术方案来实现的:
一种合金材料表面锰铬陶瓷涂层的制备方法,其具体步骤为:
(1)将合金材料表面做碱洗酸洗进行除油除锈预处理;
所述的合金材料成分以质量百分比计,为:Cr 10~35%,Ni 10~50%,Si0.2~3%,Mn 0.05~2%,微量元素0.01~5%,余量为Fe;微量元素为Nb、Ti、Mo、W、Al、C、稀土元素中的一种或几种。
(2)将材料置于渗箱中加入渗锰剂进行渗锰处理;
渗锰剂成分以质量百分比计为:锰粉或锰铁粉10~40%,活化剂氯化铵或氟化钠中的一种或两种1~5%,余量为Al2O3粉;
所用粉末粒度为100~400目;渗锰处理温度为800~1000℃,加热处理时间为2~10h;渗锰层深度为50~200μm;
(3)将材料表面清理,置于渗箱中加入渗铬剂进行渗铬处理。
渗铬剂成分以质量百分比计为:铬粉或铬铁粉10~60%,活化剂氯化铵1~5%,余量为Al2O3粉,所用粉末粒度为100~400目;
渗铬处理温度为950~1100℃;热处理时间为1~5h;渗铬层深度为50~200μm。
(4)将材料表面清理,置入热处理炉中,然后通入水蒸气与还原性气体或惰性气体的混合气进行高温低氧分压法氧化,获得陶瓷涂层;
表面清理采用浓度为5%的NaOH水溶液,对渗后材料进行清洗,然后用清水冲洗后热空气吹干;
还原性气体选自氢气、一氧化碳中的一种或两种,惰性气体选自氮气、氦气、氩气中的一种或多种;
混合气体中水蒸气的摩尔分数为0.1~10%。
低氧分压法氧化热处理制度为:升温速率5~30℃/min,炉温升至800~1200℃保温5~15h,然后随炉降温冷却。
所获得的陶瓷涂层外层是锰铬陶瓷,成分为MnxCr3-xO4(0.5≤x≤1.5);涂层下为氧化硅过渡层;锰铬陶瓷涂层厚度为5um~25um。
与现有技术相比,本发明的积极效果是:
(1)锰铬陶瓷涂层是由渗层原位氧化生长得到的,因此与基体结合强度高。
(2)锰铬陶瓷所需的Mn、Cr元素主要来源于氧化前的渗锰再渗铬工艺,可以确保表面富铬氧化的同时,渗层内渗入的锰元素向外表面扩散氧化,形成锰铬陶瓷涂层。由于表层区锰含量较多,反应生成的涂层可以具有较高的厚度,提高使用保护寿命。
(3)Mn、Cr元素来源于渗锰再渗铬工艺,不消耗基体合金材料的某些元素组分,避免了基体中Cr、Mn元素贫化区的产生,有利于基体组织性能的稳定性。
(4)涂层完全由抗结焦、抗渗碳的锰铬陶瓷涂层构成,不含MnO、Fe、Ni等非抗结焦、抗渗碳的物相,因此具有非常优异的抗结焦、抗渗碳、抗氧化性能。
(5)采用先渗铬、后渗锰工艺,在渗层内形成外铬内锰的浓度分布,避免高温氧化气氛下Mn扩散速度快,在外表面优先形成疏松MnO、MnO2等锰的氧化层,使得外表面锰铬浓度含量相匹配,形成以MnCr2O4为主的陶瓷涂层结构。
附图说明
图1涂层的XRD分析;
图2涂层表面形貌SEM图;
图3涂层表面元素分析EDX图;
图4涂层截面形貌;
图5涂层截面元素分布图;
图6涂层表面结焦形貌图;
图7无涂层材料表面结焦形貌图。
具体实施方式
以下提供本发明一种合金材料表面锰铬陶瓷涂层的制备方法的具体实施方式。
实施例1
实例在ZG45Cr35Ni25NbM合金材料表面制备陶瓷涂层。
将ZG45Cr35Ni25NbM合金材料采用碱洗、酸洗处理,进行表面除油除锈后,与渗锰剂一起放入渗锰罐中,渗锰罐用耐火泥封好,然后将渗罐放入马弗炉中进行高温渗锰处理。热处理温度为950℃,升温速率为10℃/min,保温时间为6h。待渗罐温度降到室温,取出合金材料,清除表面附着的渗锰剂,与渗铬剂一起放入渗铬罐中,渗铬罐用耐火泥封好,然后将渗罐放入马弗炉中进行高温渗铬处理。热处理温度为1050℃,升温速率为10℃/min,保温时间为2h。待渗罐温度降到室温,取出合金材料,用5%的NaOH水溶液清洗,后用清水清洗吹干。再置于管式加热炉中,氢气作为保护气氛,氢气经温度为20℃的去离子水后,再通入管式加热炉中,气体流速为100ml/min,。将管式加热炉以5℃/min的升温速率加热到1050℃,保温10h,后随炉冷却至室温,关闭气体。
经渗锰、渗铬和氧化处理后,试样表面形成了锰铬陶瓷涂层,厚度为7~10um。
以ZG45Cr35Ni25NbM合金材料为例,采用本发明制备的陶瓷涂层的XRD分析如图3所示。图1表明合金材料表面形成了几乎完全为MnCr2O4的陶瓷涂层。图2为陶瓷涂层的表面形貌。图3为陶瓷涂层表面EDS元素分析,表明外层由Mn、Cr、O三种元素组成。图4和图5为涂层的截面形貌和元素分布。图6和图7分别为陶瓷涂层与原始合金材料表面在模拟乙烯裂解气氛下的结焦形貌图,陶瓷表面焦层为颗粒状焦,原始合金材料表面布满大量的丝状催化焦。
该涂层可有效地抑制材料在高温、富碳、烃类环境下的氧化、渗碳和结焦,延长材料的使用寿命。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员,在不脱离本发明构思的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围内。
Claims (10)
1.一种合金材料表面锰铬陶瓷涂层的制备方法,其特征在于,其具体步骤为:
(1)将合金材料表面碱洗酸洗做除油除锈预处理;
(2)将材料置于渗箱中加入渗锰剂进行渗锰处理;
(3)将材料表面清理,置于渗箱中加入渗铬剂进行渗铬处理。
(4)将材料表面清理,置入热处理炉中,然后通入水蒸气与还原性气体或惰性气体的混合气进行高温低氧分压法氧化,获得陶瓷涂层。
2.如权利要求1所述的一种合金材料表面锰铬陶瓷涂层的制备方法,其特征在于,在所述的步骤(1)中,所述的合金材料成分以质量百分比计,为:Cr 10~35%,Ni 10~50%,Si 0.2~3%,Mn 0.05~2%,微量元素0.01~5%,余量为Fe;微量元素为Nb、Ti、Mo、W、Al、C、稀土元素中的一种或几种。
3.如权利要求1所述的一种合金材料表面锰铬陶瓷涂层的制备方法,其特征在于,在所述的步骤(2)中,渗锰剂成分以质量百分比计为:锰粉或锰铁粉10~40%,活化剂氯化铵或氟化钠中的一种或两种1~5%,余量为Al2O3粉。
4.如权利要求1所述的一种合金材料表面锰铬陶瓷涂层的制备方法,其特征在于,在所述的步骤(2)中,所用粉末粒度为100~400目;渗锰处理温度为800~1000℃,加热处理时间为2~10h;渗锰层深度为50~200μm。
5.如权利要求1所述的一种合金材料表面锰铬陶瓷涂层的制备方法,其特征在于,在所述的步骤(3)中,渗铬剂成分以质量百分比计为:铬粉或铬铁粉10~60%,活化剂氯化铵1~5%,余量为Al2O3粉,所用粉末粒度为100~400目。
6.如权利要求1所述的一种合金材料表面锰铬陶瓷涂层的制备方法,其特征在于,在所述的步骤(3)中,渗铬处理温度为950~1100℃;热处理时间为1~5h;渗铬层深度为50~200μm。
7.如权利要求1所述的一种合金材料表面锰铬陶瓷涂层的制备方法,其特征在于,在所述的步骤(4)中,表面清理采用浓度为5%的NaOH水溶液,对渗后材料进行清洗,然后用清水冲洗后热空气吹干;还原性气体选自氢气、一氧化碳中的一种或两种,惰性气体选自氮气、氦气、氩气中的一种或多种。
8.如权利要求1所述的一种合金材料表面锰铬陶瓷涂层的制备方法,其特征在于,在所述的步骤(4)中,混合气体中水蒸气的摩尔分数为0.1~10%。
9.如权利要求1所述的一种合金材料表面锰铬陶瓷涂层的制备方法,其特征在于,在所述的步骤(4)中,低氧分压法氧化热处理制度为:升温速率5~30℃/min,炉温升至800~1200℃保温5~15h,然后随炉降温冷却。
10.如权利要求1所述的一种合金材料表面锰铬陶瓷涂层的制备方法制备的陶瓷涂层,其特征在于,所获得的陶瓷涂层外层是锰铬陶瓷,成分为MnxCr3-xO4(0.5≤x≤1.5);涂层下为氧化硅过渡层;锰铬陶瓷涂层厚度为5um~25um。
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