CN108884548A - 材料、使用该材料的保存容器、安装于该保存容器的阀以及ClF的保存方法、ClF容器的使用方法 - Google Patents

材料、使用该材料的保存容器、安装于该保存容器的阀以及ClF的保存方法、ClF容器的使用方法 Download PDF

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Publication number
CN108884548A
CN108884548A CN201780021008.8A CN201780021008A CN108884548A CN 108884548 A CN108884548 A CN 108884548A CN 201780021008 A CN201780021008 A CN 201780021008A CN 108884548 A CN108884548 A CN 108884548A
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China
Prior art keywords
clf
valve
preservation container
gas
passivating film
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Pending
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CN201780021008.8A
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English (en)
Inventor
泷泽浩树
菊池翔
涩泽幸伸
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Kanto Denka Kogyo Co Ltd
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Kanto Denka Kogyo Co Ltd
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Publication of CN108884548A publication Critical patent/CN108884548A/zh
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    • 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
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • 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
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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    • 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
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • 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
    • C23C8/00Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
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    • 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
    • C23C8/00Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • 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
    • C23C8/00Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10Oxidising
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16KVALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
    • F16K1/00Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces
    • F16K1/02Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces with screw-spindle
    • F16K1/04Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces with screw-spindle with a cut-off member rigid with the spindle, e.g. main valves
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16KVALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
    • F16K1/00Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces
    • F16K1/30Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces specially adapted for pressure containers
    • F16K1/301Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces specially adapted for pressure containers only shut-off valves, i.e. valves without additional means
    • F16K1/302Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces specially adapted for pressure containers only shut-off valves, i.e. valves without additional means with valve member and actuator on the same side of the seat
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16KVALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
    • F16K1/00Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces
    • F16K1/30Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces specially adapted for pressure containers
    • F16K1/301Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces specially adapted for pressure containers only shut-off valves, i.e. valves without additional means
    • F16K1/303Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces specially adapted for pressure containers only shut-off valves, i.e. valves without additional means with a valve member, e.g. stem or shaft, passing through the seat
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16KVALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
    • F16K1/00Lift valves or globe valves, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces
    • F16K1/32Details
    • F16K1/34Cutting-off parts, e.g. valve members, seats
    • F16K1/36Valve members
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F16KVALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
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    • F16K41/02Spindle sealings with stuffing-box ; Sealing rings
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    • F17C1/00Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
    • F17C1/10Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge with provision for protection against corrosion, e.g. due to gaseous acid
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    • F17CVESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
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    • F17C2205/0382Constructional details of valves, regulators
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    • F17C2205/03Fluid connections, filters, valves, closure means or other attachments
    • F17C2205/0388Arrangement of valves, regulators, filters
    • F17C2205/0394Arrangement of valves, regulators, filters in direct contact with the pressure vessel
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17CVESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
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Abstract

在材料的至少一部分具有由于与含有ClF的气体接触而产生的氟化物的钝化膜(28)。

Description

材料、使用该材料的保存容器、安装于该保存容器的阀以及 ClF的保存方法、ClF容器的使用方法
技术领域
本发明涉及材料、使用该材料的保存容器、安装于该保存容器的阀以及ClF的保存方法、ClF容器的使用方法。
背景技术
在半导体、LCD(Liquid Crystal Display,液晶显示器)、PDP(Plasma DisplayPanel,等离子显示面板)等的制造工序中,在半导体基板的表面蚀刻电路图案的蚀刻处理、用于清洁半导体制造装置或液晶制造装置的内部面的清洗处理中,大量使用氟系气体。
此外,在专利文献1中公开有如下技术:在半导体制造装置的清洗中,作为氟系气体,使用ClF3(三氟化氯)。
(现有技术文献)
(专利文献)
专利文献1:日本特开2010-147118号公报
发明内容
(发明所要解决的问题)
然而,在高温下,由于含有氟化氯的氟系气体具有高反应性,因此在蚀刻或清洗时不易抑制氟系气体的反应。另外,在高温下使用氟系气体的情况下,存在氟系气体若与上述装置的构成部件接触则会激烈反应而形成化合物,构成部件会由于腐蚀受到严重损伤的问题。
由此,可以考虑在上述的蚀刻或清洗中使用作为氟化氯的ClF(一氟化氯)。ClF与其他的作为氟系气体的ClF3(沸点:11.75℃)或ClF5(五氟化氯,沸点:-14℃)相比具有极低的沸点(-100.1℃),因此在从低温到高温的范围内能够以比较稳定的性状而使用。
然而,ClF除具有极低的沸点之外,也是具有极高反应性的有毒腐蚀性气体。因此,关于通过抑制接触ClF的氟化反应及吸附来抑制ClF的浓度下降,能够操作高纯度且安全的ClF的材料、使用该材料的保存容器、安装于该保存容器的阀以及ClF的保存方法、ClF的保存容器的使用方法,依然存在问题。
本发明鉴于以上问题而作出的,其目的在于提供通过抑制ClF的氟化反应及吸附来抑制ClF的浓度下降,能够实现高纯度且安全的ClF的操作的材料、使用该材料的保存容器、安装于该保存容器的阀,以及ClF的保存方法、ClF的保存容器的使用方法。
(用于解决问题的方案)
为了达成上述目的,本发明的材料的特征在于至少一部分具有由于与含有ClF的气体的接触而产生的氟化物的钝化膜。
优选地,所述钝化膜具有5nm~50nm的膜厚度。
优选地,所述气体还含有从ClF3和F2中选择的至少一种。
优选地,在锰钢、不锈钢、铬钼钢、铝合金、镍合金、钴合金、金、树脂中的至少一种上形成所述钝化膜。
另外,本发明的保存容器的特征在于由上述材料构成,且具有形成有所述钝化膜的内部面。
优选地,具有安装于所述保存容器的阀,所述阀具有所述气体的流路、开口有所述流路的阀座、以及通过与所述阀座接触和分离而将所述流路开闭的阀体,在所述流路和所述阀座及阀体的至少接触气体的部位形成有所述钝化膜。
优选地,所述阀体具有在关闭所述流路时按压于所述阀座的气体封闭面;所述气体封闭面具有2μm~10μm的金镀层。
优选地,所述金镀层进行了封孔处理。
优选地,所述金镀层进行了氧化处理。
优选地,所述钝化膜形成在所述金镀层上。
优选地,所述阀体为碟片型。
优选地,所述阀体为隔膜。
另外,本发明的材料的制造方法的特征在于,在材料的表面形成有与含有ClF的气体接触而由所述材料的氟化物形成的钝化膜。
优选地,所述气体中所述ClF的浓度为1重量%~100重量%。
另外,本发明的ClF的保存方法的特征在于,将ClF填充于通过导入含有ClF的气体而在内部面形成有氟化物的钝化膜的保存容器中并保存。
优选地,在所述保存容器中填充而保存的ClF的浓度为1重量%~100重量%。
另外,本发明的ClF的保存容器的使用方法是作为通过导入含有ClF的气体而在内部面形成有氟化物的钝化膜的保存容器的使用方法,所述使用方法包括:填充工序,将CIF填充于所述保存容器的内部;使用工序,在所述填充工序后,使填充的所述ClF从所述保存容器流出而使用所述ClF;以及净化工序,在所述使用工序后,通过抽真空将所述保存容器减压之后,在所述保存容器中填充惰性气体。
(发明的效果)
根据本发明,能够提供通过抑制填充于保存容器中的ClF的氟化反应及吸附来抑制所填充的ClF的浓度下降,能够实现高纯度且安全的ClF的操作的材料、使用该材料的保存容器、安装于该保存容器的阀,以及ClF的保存方法、ClF的保存容器的使用方法。
附图说明
图1为使用本发明的一个实施方式的材料的储气瓶2的局部剖视图。
图2为将在图1的阀中阀体从阀座分离的状态放大示出的图。
图3为按时间顺序示出图1的储气瓶的使用方法的流程图。
具体实施方式
以下,基于附图对本发明的一个实施方式进行说明。
图1为使用本发明的一个实施方式的材料的储气瓶2的局部剖视图。储气瓶2是具有用于保存ClF的耐压性的保存容器,包括:在上部具有开口4的器壁6、安装于开口4的圆筒状的封口件8、安装于封口件8的阀10。
器壁6及封口件8由例如锰钢、不锈钢、铬钼钢、镍合金、铝合金中的至少一种金属材料形成。上述不锈钢只要是具有对ClF的耐腐蚀性的即可,并无特殊限制,但可以使用奥氏体系列、马氏体系列、铁素体系列或者除此以外的类型的不锈钢。
阀10包括:作为阀主体的主体12、形成于主体12内的气体的流路14、开口有流路14的阀座16、碟片型(圆盘型)的阀体18、下端结合于阀体18的阀轴20、与阀轴20的上端结合的手动式的把手21等。阀轴20利用安装于主体12内的压盖衬垫22而被轴封,在阀座16设置有碟片衬垫24。通过旋转把手21使阀轴20旋转,进而通过阀体18经由碟片衬垫24与阀座16接触和分离来使流路14开闭。此外,阀10可以为全金属阀,在该情况下不存在碟片衬垫24,通过将阀体18与阀座16直接接触和分离来使流路14开闭。
主体12由例如不锈钢、镍合金、钴合金中的至少一种金属材料形成,形成有利用螺纹接合安装于封口件8的内部面8a的下连接部12a和利用螺纹接合而安装有未图示的盖状的封闭栓的横连接部12b。压盖衬垫22及碟片衬垫24由例如PCTFE(polychlorotrifluoroethylene,聚三氟氯乙烯)、PTFE(Polytetrafluoroethylene,聚四氟乙烯)等树脂材料形成为环状。
图2为将在图1的阀10中阀体18从阀座16分离的状态放大示出的图。在阀体18的下端,形成有在阀10的关闭状态下堵塞流路14来封闭气体的密封面18a。在密封面18a上形成有层厚为2μm~10μm程度的金镀层26。金镀层26进行了用处理剂堵塞形成于金镀层26的销孔的封孔处理。另外,可以对金镀层26进行氧化处理来形成氧化膜。上述封孔处理及氧化处理能够提高密封面18a对ClF的耐腐蚀性。
另外,本实施方式的阀体18形成为如上述的碟片型。由此,阀体18的密封面18a对阀座16的碟片衬垫24的按压以平坦面的面接触形式进行。据此,与针形阀体与阀座的按压以线接触的形式进行的针阀(未图示)等的情况相比,在阀10的情况下,阀体18的密封面18a对阀座16的碟片衬垫24按压时的密封面18a的表面压力能够下降。由此,可有效地抑制金镀层26从密封面18a剥离。另外,能够有效地避免阀10的开闭时的密封面18a的物理损伤,抑制密封面18a的劣化,进而提高阀10对ClF的耐腐蚀性。
在此,如1及2所示,在本实施方式中,在储气瓶2的器壁6的内部面6a、面向储气瓶2内的封口件8的内端面8b、阀10的流路14、具有形成有金镀层26的密封面18a的阀体18、具有碟片衬垫24的阀座16等的包括封口件8及阀10的储气瓶2的接触气体部的全部区域中,形成有氟化物的钝化膜28。
利用使上述接触气体部与含有ClF的气体(以下,也称为使用气体)接触的所谓钝化处理来形成该钝化膜28,其具有5nm以上、优选为5nm~50nm左右的膜厚度。具体而言,钝化膜28的膜厚度形成为:在作为使用气体的ClF与接触气体部接触时,作为能够抑制由氟化反应导致材料的腐蚀、损伤的下限值为5nm以上。另外,若考虑形成钝化膜28的成本(后述的处理时间、ClF的使用量等),钝化膜28的膜厚度的上限值优选为50nm。
关于钝化处理,在阀10的开状态下,将未图示的配管和使用气体供给源连接于阀10的主体12的横连接部12b,将使用气体导入储气瓶2。以如下成分的使用气体及处理条件进行钝化处理。
·使用气体:仅ClF,或者,在含有ClF的基础上,还从ClF3和F2中选择一种以上的气体(作为基础气体,也可以混合N2(氮气)以及其他的惰性气体)
·使用气体的ClF浓度:1重量%~100重量%
·处理时间(使用气体的接触时间):6小时以上
·处理温度:10℃~100℃左右
·处理压力:0MPaG~0.1MPaG左右
ClF的浓度越高则能够越迅速地形成钝化膜28,且钝化膜28的膜质越坚固。另外,处理时间越长则钝化膜28的膜质越坚固。此外,所谓接触气体时间是指从与使用气体接触的瞬间开始计数的时间。
另外,处理温度越高则能够越迅速地形成钝化膜28,且钝化膜28的膜质越坚固。但是,若处理温度过高则接触气体部的金属腐蚀的可能性升高,因此,处理温度优选为上述温度范围。另外,由于ClF对金属的吸附性强,因此即使在低温下也能够容易地形成钝化膜28。另外,处理压力越高则能够越迅速地形成钝化膜28,且钝化膜28的膜质越坚固。但是,若处理压力过高则使用气体的操作变得困难、危险,因此处理压力优选为上述范围。此外,从钝化处理结束后的储气瓶2酌情排出使用气体、利用真空泵减压及惰性气体的填充,在多次重复上述循环净化后,储气瓶2变为实际可使用的状态。
图3为按时间顺序示出进行上述钝化处理后的储气瓶2的使用方法的流程图。
<填充工序:S1>
首先,在步骤S1中,将含有ClF的气体(以下,简称为ClF,或者保存气体)填充于形成有钝化膜28的处于可使用状态的储气瓶2的内部并保存。具体而言,在阀10的打开状态下,将未图示的保存气体供给源连接于阀10的横连接部12b,将保存气体导入储气瓶2。在填充了保存气体后,关闭阀10从而将保存气体密封保存在储气瓶2内。
<使用工序:S2>
接下来,在步骤S2中,将填充有保存气体的储气瓶2搬运至保存气体的使用处并使用。具体而言,将未图示的保存气体供给对象连接于阀10的横连接部12b,打开阀10,使保存气体从储气瓶2流出并供给至保存气体供给对象。在使用了保存气体后,关闭阀10,从使用处回收储气瓶2。
<净化工序:S3>
接下来,在步骤3中,在收回的储气瓶2的阀10的横连接部12b连接未图示的净化装置。然后,利用净化装置在将储气瓶2抽真空以减压的同时,排出在储气瓶2内微量残留的保存气体后,向储气瓶2填充惰性气体。
所谓惰性气体,是氮或者氩、氦、氖、氙、氪等的拥有稳定原子核种类的稀有气体,是指在化学合成、化学分析或反应性高的物质的保存方面所使用的反应性低的气体。由于这种低反应性,因此常用于使得不发生不期望的化学反应的用途方面。
具体而言,净化装置包括未图示的真空泵,构成为能够实施循环净化,该循环净化指多次重复从利用该真空泵减压至-0.1MPaG左右,然后填充惰性气体至常压状态的一系列的减压及惰性气体的填充。由于ClF容易浸透、吸附于金属,且不容易去除吸附的ClF,因此为了防止储气瓶2的劣化,在使用了储气瓶2后,将利用重复惰性气体填充和使用真空泵减压的循环净化实施10次以上。关于该循环净化的次数,通过根据吸附于储气瓶2的ClF的吸附量来设定次数,据此,能够确实地去除吸附于储气瓶2的ClF,使储气瓶2以无腐蚀的状态长期使用。
另外,储气瓶2的接触气体部与ClF接触后,容易因空气中的水分而腐蚀、劣化。因此,阀10关闭,移除与阀10的主体12的横连接部12b连接的上述配管,将移除的配管收纳于另行准备的干燥器等的未图示的容器中,用氮等的惰性气体进行净化后保管。另外,在横连接部12b安装上述封闭栓。据此,能够防止上述配管及横连接部12b因暴露于空气中而导致的腐蚀。此外,虽然没有特殊规定,但是利用惰性气体对上述配管的净化量越大越好,且净化时间越长越好。此外,由每一次净化的惰性气体量与净化次数来规定所谓净化量。
以下,参照表1~4,对涉及对ClF的耐久性进行的实验1~4的实施例1~7和比较例1~5进行比较说明。此外,本发明并不限于这些各个例子的结果。
<实验1>
在设想为阀10的阀体18的试样上形成金镀层,如表1所示,通过改变金镀层的层厚、对金镀层的封孔处理、氧化处理的有无,以试样的重量变化、表面腐蚀度、金镀层剥离的有无作为指标来确认这些变化对ClF的耐久性的影响程度。此外,根据试样的重量变化、表面积、实验时间计算表面腐蚀度。因此,在由于金镀层的腐蚀导致试样的重量减少的情况下为负值。另外,此处所谓的腐蚀是定义为包括例如在金镀层形成氟化物或者氯化物,或者渗透,其结果导致金镀层变色或者金镀层剥离的现象。
[表1]
(实施例1)
·金镀层的层厚:7.3~8.4μm
·对金镀层的封孔处理:无
·对金镀层的氧化处理:无
对如上条件的试样实施ClF的压缩/拉伸试验的结果:
·试样的重量变化:增加0.009%
·试样的表面腐蚀度:0.0014mg/cm2·h
得到如上的结果,最终
·金镀层从试样剥离:无
如上,合格。
(实施例2)
·金镀层的层厚:2.5~2.6μm
·对金镀层的封孔处理:有
·对金镀层的氧化处理:无
对如上条件的试样实施ClF的压缩/拉伸试验的结果:
·试样的重量变化:增加0.002%
·试样的表面腐蚀度:0.0003mg/cm2·h
得到如上的结果。通过对金镀层进行封孔处理,与实施例1的情况相比,虽然金镀层的层厚薄至约1/3,但是试样的重量变化、表面腐蚀度两者都能够降至约1/4,能够大幅度地抑制由ClF导致的金镀层的腐蚀。从而,最终
·金镀层从试样剥离:无
如上,合格。
(实施例3)
·金镀层的层厚:2.5~2.6μm
·对金镀层的封孔处理:无
·对金镀层的氧化处理:有
对如上条件的试样实施ClF的压缩/拉伸试验的结果:
·试样的重量变化:增加0.014%
·试样的表面腐蚀度:0.0021mg/cm2·h
得到如上的结果。通过对金镀层进行氧化处理,与实施例1的情况相比,虽然金镀层的层厚薄至约1/3,但是试样的重量变化、表面腐蚀度两者都增加至约1.5倍。这是因为虽然在金镀层的表面形成了氧化膜,但是利用该氧化膜可抑制由ClF导致的金镀层的腐蚀。从而,最终
·金镀层从试样剥离:无
如上,合格。
(实施例4)
·金镀层的层厚:2.5~2.6μm
·对金镀层的封孔处理:无
·对金镀层的氧化处理:无
对如上条件的试样实施ClF的压缩/拉伸试验的结果:
·试样的重量变化:减少0.005%
·试样的表面腐蚀度:-0.0008mg/cm2·h
得到如上的结果。在该情况下,因为试样的重量减少且试样的表面腐蚀度变为负值,因此金镀层的腐蚀继续进行。从而,最终
·金镀层从试样剥离:有
如上。但是,在本例中的金镀层的剥离为微量,在后述的实验2中的泄漏实验的结果明确了没有发生泄漏,因此做出合格的判定。
(比较例1)
·金镀层的层厚:0.3μm
·对金镀层的封孔处理:无
·对金镀层的氧化处理:无
对如上条件的试样实施ClF的压缩/拉伸试验的结果:
·试样的重量变化:减少0.009%
·试样的表面腐蚀度:-0.0014mg/cm2·h
得到如上的结果。在该情况下,因为试样的重量减少且试样的表面腐蚀度变为负值,因此金镀层的腐蚀继续进行。从而,最终
·金镀层从试样剥离:有
如上,不合格。
在如上的实验1中,得出金镀层厚的试样能够防止金镀层的剥离且对ClF的耐久性变高的结果。另外,如实施例4所明确的那样,存在即使产生了金镀层的微量的剥离也不产生泄漏的情况,明确了优选形成至少具有2μm~10μm的层厚的金镀层。
另外,在具有实施了封孔处理或者氧化处理的金镀层的试样中,即使金镀层薄,也能够抑制试样的表面腐蚀,其结果是防止了金镀层的剥离。可知试样随着腐蚀的继续进行而重量会逐渐增加的倾向,金镀层发生了剥离的试样则由于剥离的金镀层而导致重量减少。
综上,能够确认如下事实:通过使形成于阀10的阀体18的密封面18a的金镀层26的层厚至少为2μm~10μm左右的层厚,并对金镀层26实施封孔处理或者氧化处理,能够使得阀10对ClF的耐久性变高,能够安全地进在储气瓶2中的ClF的保存及操作。此外,虽然实施例中没有提及,当然地,也可以对金镀层26实施封孔处理和氧化处理二者,在这种情况下也能够防止金镀层26的剥离。
<实验2>
将ClF填充于储气瓶2,在关闭未图示的实验用阀的状态下,如表2所示,进行3次将阀10或者针阀开闭2000次的实验。之后,从储气瓶2移除实验用阀,将ClF从储气瓶2排出之后,进行储气瓶2的循环净化。之后,将He(氦)填充于储气瓶2,将He泄漏检验器连接于储气瓶2,测定泄漏速率。
[表2]
(实施例5)
·阀体:碟片型
·第一次泄漏速率:3.3×10-9Pa·m3/sec
·第二次泄漏速率:2.7×10-9Pa·m3/sec
·第三次泄漏速率:3.1×10-9Pa·m3/sec
得到如上结果,全部测定均为
·泄漏:无
如上,合格。
(比较例2)
·阀体:针型
·第一次泄漏速率:1.3×10-8Pa·m3/sec
·第二次泄漏速率:1.2×10-4Pa·m3/sec
·第三次泄漏速率:1.0×10-3Pa·m3/sec以上
得到如上结果,第一次的测定为
·泄漏:无
第二次及第三次的测定为
·泄漏:有
如上,因此最终为不合格。
在如上实验2中,在储气瓶2上安装有阀体18为针型的针阀的情况下,在2000次的开闭实验后存在发生泄漏的情况。与之相对,在储气瓶2上安装有阀体18为碟片型的阀10的情况下,在2000次的开闭实验后也没有泄漏。因此,能够确认:如图1所示的阀体18使用碟片型的阀10,能够抑制金镀层26的剥离及避免密封面18a的物理性损伤,能够安全地进行储气瓶2中的ClF的保存及操作。
<实验3>
如表3所示,以如下的条件对试样实施利用ClF的钝化处理与利用F2的钝化处理时,测定钝化膜的膜厚度是否出现差异。
·使用气体的ClF浓度:1重量%~100重量%左右
·处理时间(使用气体的接触时间):6小时以上
·处理温度:10℃~100℃左右
·处理压力:0MPaG~0.1MPaG左右
[表3]
(实施例6)
在试样上形成的利用ClF产生的钝化膜的膜厚度为4nm。
(比较例3)
在试样上形成的利用F2产生的钝化膜的膜厚度为8nm,通过同一条件的钝化处理,形成了2倍的膜厚度的钝化膜。
在如上的实验3中,由于经由利用ClF的钝化处理能够形成比较薄的钝化膜,因此,能够对例如阀10的阀体18、阀座16、碟片衬垫24等形成不易受到摩擦的影响、尽可能不影响阀10的密封性能的薄的钝化膜28。因此,能够确认利用ClF的钝化处理在ClF的保存、操作中有效。
在此,利用ClF产生的钝化膜28的膜厚度会根据与导入气体接触的金属等的材料的种类、材料的表面粗糙度、导入气体的使用条件等而变化。虽然在本实验结果中,利用ClF产生的钝化膜的膜厚度为4nm,但是该结果只是在实验3中所采用的条件下的结果,在不同条件下的情况下,明确为优选钝化膜28至少具有5nm~50nm的膜厚度。
<实验4>
将ClF填充于储气瓶2,之后使ClF从储气瓶2流出而形成储气瓶2的使用后的状态。在阀10为关闭状态下,将未图示的实验用阀、未图示的净化装置依次连接于阀10的主体12的横连接部12b。然后,打开实验用阀,利用净化装置将储气瓶2抽真空以减压至-0.1MPaG并保持(60秒),排出微量地残留于储气瓶2内的ClF后,将氮填充于储气瓶2。
净化装置进行重复利用真空泵减压及惰性气体的填充的循环净化。之后,移除净化装置,而代之以连接未图示的气体检测器。然后,打开实验用阀,如表4所示,针对每次循环净化测定储气瓶2内的ClF的残留量,判断ClF检测的有无。
[表4]
(实施例7)
·循环净化次数:100
·减压保持时间:60秒
此时,
·ClF检测:无
如上,合格。
(比较例4)
·循环净化次数:50
·减压保持时间:60秒
此时,
·ClF检测:有(2ppm以上)
如上,不合格。
(比较例5)
·循环净化次数:70
·减压保持时间:60秒
此时,
·ClF检测:有(2ppm以上)
如上,不合格。
在此,未检测出残留ClF的循环净化次数根据与导入气体接触的金属等的材料的种类、材料的表面粗糙度、导入气体的使用条件等而变化。在本实验结果中,在循环净化次数为50次、70次的情况下,检测出了ClF,不能视作合格。但是,该结果只是在实验4中所采用的条件下的结果,在不同条件下的情况下,明确了也存在循环净化的次数仅实施至少为10次以上即可的情况。
在如上述实验4中,确认了通过实施重复减压保持(在-0.1MPaG下60秒)、在常压以上填充氮的循环净化规定次数(至少10次以上),能够完全地将ClF从储气瓶2吹出。为了完全地吹出、安全地操作ClF,明确了要必须进行与储气瓶2和阀10的ClF附着量相对应的充分的循环净化。
在如上所述的本实施方式中,通过预先在与储气瓶2、构成储气瓶2的封口件8和阀10的接触气体部形成钝化膜28,能够抑制被填充于储气瓶2内的ClF的氟化反应及吸附,能够抑制保存的ClF的浓度下降。由此,能够提供能够实现高纯度且安全的ClF的操作的储气瓶2、安装于该储气瓶2的阀10,以及,使用该储气瓶2的ClF的保存方法、保存ClF的储气瓶2的使用方法。
以上是对本发明的一个实施方式的说明,但是,本发明不限于此,在不脱离本发明的主旨的范围内能够进行各种变更。
例如,不限于储气瓶2,在各种部件或装置的材料的至少一部分形成钝化膜28,至少能够抑制与该材料接触的ClF的氟化反应。
另外,替代具有碟片型的阀体18的阀10,也可以使用未图示的隔膜阀。关于隔膜阀,由于一般而言阀内的死区(dead space)小,因此能够更加高效地实施阀的接触气体部的惰性气体的置换,即循环净化。
(附图标记说明)
2:储气瓶(保存容器);6a:内部面;10:阀;14:流路;16:阀座;18:阀体;18a:密封面;26:金镀层;28:钝化膜。

Claims (17)

1.一种材料,其特征在于,在至少一部分具有由于与含有ClF的气体接触而产生的氟化物的钝化膜。
2.根据权利要求1所述的材料,其特征在于,所述钝化膜具有5nm~50nm的膜厚度。
3.根据权利要求1或2所述的材料,其特征在于,所述气体还含有从ClF3和F2中选择的至少一种。
4.根据权利要求1~3中任一项所述的材料,其特征在于,在锰钢、不锈钢、铬钼钢、镍合金、铝合金、钴合金、金及树脂中的至少一种上形成所述钝化膜。
5.一种保存容器,其特征在于,利用根据权利要求1~4中任一项所述的材料制成,且具有形成有所述钝化膜的内部面。
6.根据权利要求5所述的保存容器,其特征在于,
包括被安装于所述保存容器的阀,
所述阀具有
所述气体的流路;
所述流路所开口的阀座;以及
通过与所述阀座接触和分离而将所述流路开闭的阀体,
在所述流路和所述阀座及阀体的接触气体部形成有所述钝化膜。
7.根据权利要求6所述的保存容器,其特征在于,
所述阀体具有在关闭所述流路时按压于所述阀座的密封面,
所述密封面具有2μm~10μm的金镀层。
8.根据权利要求7所述的保存容器,其特征在于,所述金镀层进行了封孔处理。
9.根据权利要求7或8所述的保存容器,其特征在于,所述金镀层进行了氧化处理。
10.根据权利要求7~9中任一项所述的保存容器,其特征在于,所述钝化膜形成在所述金镀层上。
11.根据权利要求6~10中任一项所述的保存容器,其特征在于,所述阀体为碟片型。
12.根据权利要求6~10中任一项所述的保存容器,其特征在于,所述阀体为隔膜。
13.一种材料的制造方法,其特征在于,在材料的表面形成有与含有ClF的气体接触而由所述材料的氟化物所形成的钝化膜。
14.根据权利要求13所述的材料的制造方法,其特征在于,所述气体中的所述ClF的浓度为1重量%~100重量%。
15.一种ClF的保存方法,其特征在于,将ClF填充于通过导入含有ClF的气体而在内部面形成有氟化物的钝化膜的保存容器中并保存。
16.根据权利要求15所述的ClF的保存方法,其特征在于,填充于所述保存容器而保存的ClF的浓度为1重量%~100重量%。
17.一种ClF的保存容器的使用方法,所述保存容器通过导入含有ClF的气体而在内部面形成有氟化物的钝化膜,所述使用方法的特征在于,包括
填充工序,将CIF填充于所述保存容器的内部并保存;
使用工序,在所述填充工序后,使填充的所述ClF从所述保存容器流出而使用;以及
净化工序,在所述使用工序后,通过抽真空将所述保存容器减压之后,在所述保存容器中填充惰性气体。
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