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CN111172555B - 一种制氟用碳阳极板 - Google Patents

一种制氟用碳阳极板 Download PDF

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CN111172555B
CN111172555B CN202010075403.8A CN202010075403A CN111172555B CN 111172555 B CN111172555 B CN 111172555B CN 202010075403 A CN202010075403 A CN 202010075403A CN 111172555 B CN111172555 B CN 111172555B
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carbon
plate
silicon carbide
carbon anode
anode plate
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CN111172555A (zh
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刘坤
杭颂
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EIGHTH RESEARCH INSTITUTE OF NUCLEAR TECHNOLOGY
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/24Halogens or compounds thereof
    • C25B1/245Fluorine; Compounds thereof
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051Electrodes formed of electrocatalysts on a substrate or carrier
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds

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Abstract

本发明涉及一种制氟用碳阳极板,由碳板、以及沉积在碳板表面的碳/碳化硅掺杂涂层组成。与现有技术相比,本发明采用特殊处理工艺,在碳阳极板表面形成保护层,可以提高表面抗腐蚀性,延缓碳阳极表层钝化层的形成,有助于延长碳阳极的运行寿命。

Description

一种制氟用碳阳极板
技术领域
本发明属于碳阳极板技术领域,涉及一种制氟用碳阳极板。
背景技术
单质氟气在核工业、集成电路行业发挥重要作用,中温电解制氟工艺是当前唯一实现工业化生产的单质氟气制备工艺,此工艺主要以无定型碳材料作为阳极材料。
碳阳极在电解槽内安装方式包含夹板式和螺杆式,其中,螺杆式主要用于10KA电解槽,目前,国内螺杆式安装用碳阳极板寿命普遍较短,绝大多数产品,在6~8KA工况下稳定运行寿命难以达到6个月,已经成为制约国内电解制氟工艺发展的瓶颈。
导致碳阳极板无法持续运行的主要原因是开裂,导致开裂的原因众多,其中较为典型的是碳阳极板腐蚀、极化,因此,解决上述问题将有助于延长碳阳极板运行寿命。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种制氟用碳阳极板。采用特殊处理工艺,在碳阳极板表面形成保护层,可以提高表面抗腐蚀性,延缓碳阳极表层钝化层的形成,有助于延长碳阳极的运行寿命。
本发明的目的可以通过以下技术方案来实现:
一种制氟用碳阳极板,由碳板、以及沉积在碳板表面的碳/碳化硅掺杂涂层组成。
进一步的,所述的碳/碳化硅掺杂涂层中,碳化硅质量含量不超过90%。
进一步的,所述的碳/碳化硅掺杂涂层的厚度不超过10μm。
进一步的,所述的碳/碳化硅掺杂涂层通过以下方法沉积得到:
将碳板置于气相沉积炉内,通以由CH4、SiCl4、H2和N2组成的混合气体,高温沉积,即完成。
更进一步的,混合气体中,CH4、SiCl4、H2和N2的体积含量分别为30%、5%、5%和60%。
更进一步的,混合气体通入气相沉积炉的流速为200L/h。
更进一步的,高温沉积的工艺条件为:维持炉内气压为10KPa,在1200℃下沉积30小时。
本发明的创新之处在于,在同传统碳涂层中掺杂碳化硅,提高产品耐氢氟酸腐蚀的能力,同时,碳化硅涂层的存在,有助于防止连续氟化石墨钝化层的形成。在各组分配比中,SiCl4和H2的占比需适当控制,应维持在较低的水平,原因在于,当上述两种气体含量过高时,有助于碳化硅涂层的形成,不利用碳涂层的形成,但碳化硅的导电性明显比碳差,因此当碳化硅含量过高时,制品导电性降低明显,反而产生不利影响。
进一步的,所述的碳板在沉积前,先进行表面抛光、超声波清洗和烘干。
与现有技术相比,本发明具有以下优点:
(1)本发明所述的碳/碳化硅涂层比纯无定型碳抗腐蚀性更好;
(2)更难以形成连续氟化石墨钝化层,抗极化性能更好。
具体实施方式
下面结合具体实施例对本发明进行详细说明。本实施例以本发明技术方案为前提进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
以下各实施例中,若无特别说明的原料或处理技术,则表明均为本领域的常规市售产品或常规处理技术。
实施例1:
取密度1.75g/cm3、石墨化度为0、尺寸为600mm╳300mm╳70mm的碳板,碳板经表面抛光和超声波清洗后烘干,将烘干后的碳板置于气相沉积炉内,将体积配比为:30%CH4、5%SiCl4、5%H2和60%N2的混合气体,以200L/h流速进入沉积炉,同时将炉内气压维持在10KPa,在1200℃下沉积30小时。经测试涂层厚度约为4~5μm。
对比例1:
取密度1.75g/cm3、石墨化度为0、尺寸为600mm╳300mm╳70mm的碳板,碳板经表面抛光和超声波清洗后烘干,将烘干后的碳板置于气相沉积炉内,充入N2作为保护气氛,N2以200L/h流速进入沉积炉,同时将炉内气压维持在10KPa,在1200℃下处理30小时。
将对比例1与实施例1中的碳阳极板同时放入同一电解槽中运行,在660A工况下运行1个月,取出后在PH值为11、温度为100℃的KOH水溶液中浸泡一周后,取出用纯水将表面冲洗干净后迅速吹干,分别在表面相同位置制取4个直径为10mm,厚度为3mm的样品,经XPS测试,实例1中未氟化碳原子含量为50%,对比例1中未氟化碳原子含量为23.3%,测试结果表明,实例1中涂层有效防止氟化石墨层的形成,有助于提高产品抗腐蚀、抗极化性能。
以上各实施例中,所得碳板优选以粒径小于20μm的骨料生产得到。所采用的骨料的具体来源为:首先购瑞成300目的粉焦(即石油焦粉),利用超细立磨磨粉机再加工,经800目标准筛筛选得到最终骨料。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。

Claims (2)

1.一种制氟用碳阳极板,其特征在于,由碳板、以及沉积在碳板表面的碳/碳化硅掺杂涂层组成;
所述的碳/碳化硅掺杂涂层中,碳化硅质量含量不超过90%;
所述的碳/碳化硅掺杂涂层的厚度不超过10μm;
所述的碳/碳化硅掺杂涂层通过以下方法沉积得到:
将碳板置于气相沉积炉内,通以由CH4、SiCl4、H2和N2组成的混合气体,高温沉积,即完成;
混合气体中,CH4、SiCl4、H2和N2的体积含量分别为30%、5%、5%和60%;
混合气体通入气相沉积炉的流速为200L/h;
高温沉积的工艺条件为:维持炉内气压为10KPa,在1200℃下沉积30小时。
2.根据权利要求1所述的一种制氟用碳阳极板,其特征在于,所述的碳板在沉积前,先进行表面抛光、超声波清洗和烘干。
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3925577A (en) * 1972-11-24 1975-12-09 Westinghouse Electric Corp Silicon carbide coated graphite members and process for producing the same
US5364513A (en) * 1992-06-12 1994-11-15 Moltech Invent S.A. Electrochemical cell component or other material having oxidation preventive coating
CN101220485A (zh) * 2007-10-17 2008-07-16 中南大学 制氟碳阳极化学气相沉积热解碳抗极化涂层制备方法
CN102277560A (zh) * 2011-08-23 2011-12-14 南京理工大学 化学气相沉积SiC/C梯度表面涂层提高石墨电极抗氧化性的方法
CN102515871A (zh) * 2011-11-23 2012-06-27 西安超码科技有限公司 一种炭/炭加热器抗冲刷C/SiC涂层的制备方法
CN104119108A (zh) * 2014-08-08 2014-10-29 苏州宏久航空防热材料科技有限公司 一种复合陶瓷石墨电极的制备方法
CN105152687A (zh) * 2015-07-13 2015-12-16 清华大学 一种多孔碳化硅涂层及其制备方法
CN105732044A (zh) * 2016-02-03 2016-07-06 深圳市商德先进陶瓷有限公司 高纯度碳化硅陶瓷制造方法和陶瓷基材

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3925577A (en) * 1972-11-24 1975-12-09 Westinghouse Electric Corp Silicon carbide coated graphite members and process for producing the same
US5364513A (en) * 1992-06-12 1994-11-15 Moltech Invent S.A. Electrochemical cell component or other material having oxidation preventive coating
CN101220485A (zh) * 2007-10-17 2008-07-16 中南大学 制氟碳阳极化学气相沉积热解碳抗极化涂层制备方法
CN102277560A (zh) * 2011-08-23 2011-12-14 南京理工大学 化学气相沉积SiC/C梯度表面涂层提高石墨电极抗氧化性的方法
CN102515871A (zh) * 2011-11-23 2012-06-27 西安超码科技有限公司 一种炭/炭加热器抗冲刷C/SiC涂层的制备方法
CN104119108A (zh) * 2014-08-08 2014-10-29 苏州宏久航空防热材料科技有限公司 一种复合陶瓷石墨电极的制备方法
CN105152687A (zh) * 2015-07-13 2015-12-16 清华大学 一种多孔碳化硅涂层及其制备方法
CN105732044A (zh) * 2016-02-03 2016-07-06 深圳市商德先进陶瓷有限公司 高纯度碳化硅陶瓷制造方法和陶瓷基材

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