CN111492097A - 钢板表面处理用溶液组合物及利用该组合物进行表面处理的钢板 - Google Patents
钢板表面处理用溶液组合物及利用该组合物进行表面处理的钢板 Download PDFInfo
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- CN111492097A CN111492097A CN201880082759.5A CN201880082759A CN111492097A CN 111492097 A CN111492097 A CN 111492097A CN 201880082759 A CN201880082759 A CN 201880082759A CN 111492097 A CN111492097 A CN 111492097A
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- steel sheet
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- treated steel
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Classifications
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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Abstract
本发明涉及一种经表面处理的钢板,所述钢板包括:钢板;镍镀层,形成在所述钢板的至少一个表面上;以及耐蚀性薄膜层,形成在所述镍镀层上,所述耐蚀性薄膜层包含通过二氧化硅与烷氧基硅烷的水解反应而形成的生成物和丙烯酸酯类高分子,并且包含25‑65重量%的碳(C)、20‑70重量%的硅(Si)、1‑40重量%的氧(O),硅(Si)和氧的键(Si‑O键)与硅(Si)和碳(C)的键(Si‑C键)的比例为80‑95%:5‑20%。根据本发明,通过在钢板表面上涂覆本发明中提供的组合物,从而在不改变钢板的组成的情况下,可以提供对硫酸的耐蚀性。此外,根据本发明的表面处理组合物向构造物提供对硫酸和盐酸的优异的耐蚀性,从而可以延长钢板的寿命。并且,通过在钢板和涂层之间包括镍镀层,从而可以改善钢板的局部腐蚀。
Description
技术领域
本发明涉及一种对硫酸等酸的抗性优异的钢板的表面处理组合物及应用所述表面处理组合物的涂覆钢板。
背景技术
通常,在燃烧包含硫等的燃料时,产生硫氧化物、氮氧化物等,并且当硫氧化物或氮氧化物等遇到水分时,生成硫酸或硝酸等强酸。这些酸在露点以下的温度下附着于金属等构造物的表面,并发生促进腐蚀的露点腐蚀。因此,火力发电厂的热交换器、导管(Duct)等设备会暴露在这种由强酸导致的腐蚀环境中。
为了降低这种露点腐蚀,相关企业使用高价的不锈钢或搪瓷钢板等,或者使用相对低价且对露点腐蚀的抗性高的耐硫酸钢等。腐蚀反应发生在构造体的表面,但是目前除了搪瓷钢板以外的大部分材料是表面上没有额外的涂层的状态下使用。
用于防止这种露点腐蚀的技术有韩国专利申请号第2013-0151739号、第2013-0145717号、第2013-0141627号、第2013-0130161号等,但是这些都是通过调整钢板自身的成分等来提高对强酸的耐蚀性的技术,与在钢板表面形成涂层来抑制这种露点腐蚀的技术是不同的。
发明内容
要解决的技术问题
本发明的目的在于,通过在钢板表面进行涂覆,而不是通过调整钢板自身的成分,从而提高包括如上所述的露点腐蚀的对强酸的耐蚀性。此外,提供一种局部腐蚀问题得到改善的经表面处理的钢板。
技术方案
根据本发明的一个方面,提供一种经表面处理的钢板,所述钢板包括:钢板;镍镀层,形成在所述钢板的至少一个表面上;以及耐蚀性薄膜层,形成在所述镍镀层上,所述耐蚀性薄膜层包含通过二氧化硅与烷氧基硅烷的水解反应而形成的生成物和丙烯酸酯类高分子,并且包含25-65重量%的碳(C)、20-70重量%的硅(Si)、1-40重量%的氧(O),硅(Si)和氧的键(Si-O键)与硅(Si)和碳(C)的键(Si-C键)的比例为80-95%:5-20%。
所述耐蚀性薄膜层可以由钢板表面处理用溶液组合物形成,所述钢板表面处理用溶液组合物包含:30-50重量%的胶态二氧化硅,其包含5-20nm尺寸的二氧化硅;40-60重量%的包含3个以上烷氧基的硅烷;5-15重量%的丙烯酸酯类有机单体;以及0.01-1重量%的酸(acid)。
所述胶态二氧化硅中的二氧化硅的含量可以为10-45重量%。
所述硅烷可以为选自乙烯基三甲氧基硅烷(Vinyl trimethoxy silane)、乙烯基三乙氧基硅烷(Vinyl triethoxy silane)、乙烯基三异丙氧基硅烷(Vinyl tri-isopropoxy silane)、3-甲基丙烯酰氧基丙基三甲氧基硅烷(3-methacryloxypropyltrimethoxy silane)、2-缩水甘油醚氧基丙基三甲氧基硅烷(2-Glycidyloxy propyltrimethoxy silane)、2-缩水甘油醚氧基丙基三乙氧基硅烷(2-Glycidyloxy propyltriethoxy silane)、2-氨基丙基三乙氧基硅烷(2-aminopropyl triethoxy silane)、2-脲基烷基三乙氧基硅烷(2-ureidoalkyl triethoxy silane)、四乙氧基硅烷(tetraethoxysilane)、三乙氧基苯基硅烷(Triethoxyphenylsilane)和三甲氧基苯基硅烷(Trimethoxyphenylsilane)中的至少一种。
所述有机单体可以为选自冰晶级丙烯酸(Acrylic acid glacial)、丙烯酸甲酯(Methyl acrylate)、丙烯酸乙酯(Ethyl acrylate)、丙烯酸丁酯(Butyl acrylate)、丙烯酸-2-乙基己酯(2-Ethylhexyl acrylate)、丙烯酸异丁酯(Isobutyl acrylate)、丙烯酸叔丁酯(Tertiary butyl acrylate)、甲基丙烯酸叔丁酯(Tertiary butyl methacrylate)、丁二醇单丙烯酸酯(Butanediol monoacrylate)、月桂醇丙烯酸酯(Lauryl acrylate)、丙烯酸二甲氨基乙酯(Dimethylaminoethyl acrylate)和二氢二环戊二烯基丙烯酸酯(Dihydrodicyclopentadienyl acrylate)中的至少一种。
所述酸可以为选自乙酸、甲酸、乳酸、葡萄糖酸、硫酸、硝酸、盐酸和氢氟酸中的一种以上。
所述钢板表面处理用溶液组合物还可以包含1-15重量%的溶剂。
所述溶剂可以为选自甲醇、乙醇、2-丙醇、2-甲氧基丙醇和2-丁氧基乙醇中的至少一种。
所述钢板表面处理用溶液组合物还可以包含0.1-5.0重量%的具有环形结构的有机树脂。
所述具有环形结构的有机树脂可以为选自聚氨酯、氨基改性酚醛树脂、聚酯树脂、环氧树脂和聚乙烯醇缩丁醛中的至少一种或两种以上的混合树脂。
所述耐蚀性薄膜层可以具有0.1-50μm的厚度。
所述镍镀层可以具有0.0005-1.12μm的厚度。
所述镍镀层可以具有5-10000mg/m2的附着量。
所述钢板可以为耐硫酸钢。
以重量%计,所述耐硫酸钢可以包含:C:0.2%以下(0除外)、Si:0.5%以下(0除外)、Mn:1.5%以下(0除外)、S:0.02%以下、P:0.02%以下、Al:0.1%以下、Cu:0.1-0.5%、余量的Fe和其它不可避免的杂质,并且所述耐硫酸钢还可以进一步包含:Co:0.03-0.1%、Ni:0.3%以下(0除外)和Sb:0.3%以下(0除外)中的至少一种。而且,所述耐硫酸钢的表面下形成100-300nm厚度的富集层,所述富集层可以为选自Cu、Co、Ni和Sb中的至少一种的富集层。
此外,以重量%计,所述耐硫酸钢可以是包含:C:0.03-0.1%、Si:0.15-0.35%、Mn:0.5-1.2、S:0.01%以下、P:0.015%以下、Al:0.02-0.06、N:0.004%以下、Cu:0.2-0.4%、余量的Fe和其它不可避免的杂质的钢板,并且还可以包含:Ni:0.1-0.25%、Sb:0.05-0.2%、Co:0.03-0.1%中的至少一种,所述耐硫酸钢的表面下可以形成100-300nm厚度的富集层,所述富集层可以为选自Cu、Co、Ni和Sb中的至少一种的富集层。
有益效果
根据本发明的一个实施方案,通过在钢板表面上涂覆本发明中提供的组合物,从而在不改变钢板的组成的情况下,可以提供对硫酸的耐蚀性。
此外,根据本发明的表面处理组合物向构造物提供对硫酸和盐酸的优异的耐蚀性,从而可以延长钢板的寿命。
并且,通过在钢板和涂层之间包括镍镀层,从而可以改善钢板的局部腐蚀。
附图说明
图1的(a)示出对未形成本发明的镍镀层的比较例进行72小时、50%的硫酸腐蚀评价后的照片,(b)示出对形成本发明的镍镀层的实施例进行96小时、50%的硫酸腐蚀评价后的照片。
最佳实施方式
本发明的目的在于,向钢板提供对硫酸、盐酸等强酸的耐蚀性,并在钢板上形成镍镀层以改善局部腐蚀效果,并且通过向钢板赋予对硫酸等强酸具有耐蚀性的表面处理,即,通过涂覆来提供耐酸性的特性,而不是通过调整钢板自身的成分来提供耐酸性钢板。
为此,本发明提供一种涂覆有可以赋予耐酸性的特性的表面处理用溶液组合物的钢板,根据本发明的一个方面,提供一种经表面处理的钢板,所述钢板包括:钢板;镍镀层,形成在所述钢板的至少一个表面上;以及耐蚀性薄膜层,形成在所述镍镀层上,所述耐蚀性薄膜层包含通过二氧化硅与烷氧基硅烷的水解反应而形成的生成物和丙烯酸酯类高分子,并且包含25-65重量%的碳(C)、20-70重量%的硅(Si)、1-40重量%的氧(O),硅(Si)和氧的键(Si-O键)与硅(Si)和碳(C)的键(Si-C键)的比例为80-95%:5-20%。
此外,所述耐蚀性薄膜层可以由钢板表面处理用溶液组合物形成,所述钢板表面处理用溶液组合物包含:30-50重量%的胶态二氧化硅,其包含5-20nm尺寸的二氧化硅;40-60重量%的包含3个以上烷氧基的硅烷;5-15重量%的丙烯酸酯类有机单体;以及0.01-1重量%的酸(acid)。
本发明中提供的表面处理用溶液组合物包含胶态二氧化硅、硅烷、有机单体等。
本发明的表面处理用溶液组合物中包含的所述胶态二氧化硅对钢板表面形成致密的结构的薄膜,其为形成本发明的钢板的表面处理薄膜的主要成分,向薄膜提供硬度。此外,所述胶态二氧化硅在形成所述薄膜的过程中与硅烷进行化学结合,在干燥和固化的过程中涂覆在钢板表面,从而起到向钢板提供耐酸性的作用。
所述胶态二氧化硅可以使用具有纳米尺寸的颗粒尺寸的胶态二氧化硅,例如,可以使用颗粒尺寸为5-50nm的胶态二氧化硅。当所述胶态二氧化硅的颗粒尺寸小于5nm时,二氧化硅的表面积过宽,与其进行反应的硅烷不足,因此耐酸性变差。另外,当胶态二氧化硅的颗粒尺寸超过50nm时,二氧化硅之间的孔隙率(porosity)高,因此具有耐酸性降低的问题。更优选地,所述胶态二氧化硅具有5-20nm的颗粒尺寸。
所述胶态二氧化硅中所包含的二氧化硅的含量优选为10-45重量%。当所述二氧化硅的含量小于10重量%时,由于二氧化硅的含量不足,可能发生薄膜的耐蚀性变差的问题,当所述二氧化硅的含量超过45重量%时,具有过多的二氧化硅颗粒发生沉淀的问题。
相对于100重量份的金属表面处理用溶液组合物,可以包含30-50重量份的所述胶态二氧化硅。将其以二氧化硅的含量表示时,相对于100重量份的总组合物,二氧化硅的含量可以为3.0-22.5重量份。当所述胶态二氧化硅的含量小于30重量份时,无法与烷氧基硅烷进行充分结合,导致硬度降低,并且可能无法确保对酸的耐蚀性。另一方面,当所述胶态二氧化硅的含量超过50重量份时,由于未与硅烷结合的二氧化硅的残留,涂膜形成能力可能会降低,由此可能无法确保对酸的耐蚀性。
本发明的金属表面处理用溶液组合物包含硅烷。所述硅烷与二氧化硅进行溶胶-凝胶反应来结合,并且硅烷之间进行交联,在干燥过程中与钢板表面进行反应,从而起到使薄膜附着于钢板的作用。因此,可以使提供对酸的耐蚀性的二氧化硅在钢板表面坚固地形成薄膜并保持,从而有助于增加耐酸性。
对所述硅烷不作特别限定,但是优选为具有烷氧基基团的烷氧基硅烷,并且使用烷氧基基团为3个以上的烷氧基硅烷时,可以与二氧化硅、硅烷、钢板进行结合反应,从而可以提高薄膜对钢板的粘附性,并且可以形成致密的涂层,因此在可以提高对酸的耐蚀性的方面更为优选。
如上所述的烷氧基硅烷例如可以包含选自乙烯基三甲氧基硅烷(Vinyltrimethoxy silane)、乙烯基三乙氧基硅烷(Vinyl triethoxy silane)、乙烯基三异丙氧基硅烷(Vinyl tri-isopropoxy silane)、3-甲基丙烯酰氧基丙基三甲氧基硅烷(3-methacryloxypropyl trimethoxy silane)、2-缩水甘油醚氧基丙基三甲氧基硅烷(2-Glycidyloxy propyl trimethoxy silane)、2-缩水甘油醚氧基丙基三乙氧基硅烷(2-Glycidyloxy propyl triethoxy silane)、2-氨基丙基三乙氧基硅烷(2-aminopropyltriethoxy silane)、2-脲基烷基三乙氧基硅烷(2-ureidoalkyl triethoxy silane)、四乙氧基硅烷(tetraethoxysilane)、三乙氧基苯基硅烷(Triethoxyphenylsilane)、三甲氧基苯基硅烷(Trimethoxyphenylsilane)、甲基三甲氧基硅烷和它们的混合物中的一种以上,所述烷氧基硅烷可以在水解后稳定化,因此更为优选。
本发明的金属表面处理用溶液组合物中,相对于100重量份的金属表面处理组合物,可以包含40-60重量份的所述烷氧基硅烷。当所述烷氧基硅烷小于40重量份时,由于无法与胶态二氧化硅和钢板形成充分的结合,从而涂膜形成能力降低,由此可能无法确保对酸的耐蚀性。另外,当所述烷氧基硅烷超过60重量份时,可能会排出由于热分解而生成的有机气体,并且由于残留大量的硅烷醇,阻碍涂膜的粘附性,由此可能无法确保耐蚀性。
所述烷氧基硅烷和二氧化硅形成通过溶胶-凝胶反应形成的钢板的表面处理薄膜,由此形成的薄膜具有坚硬的特性,因此优选在无机薄膜内赋予薄膜的柔韧性。因此,本发明的金属表面处理用溶液组合物包含有机单体。
所述二氧化硅与烷氧基硅烷进行结合反应的条件为强酸性条件,在这种条件下单体进行高分子反应而成为高分子。由这种单体生成的高分子填充坚硬的无机物之间,以提高涂膜形成能力,并且提供耐水性,而且可以向无机物薄膜提供柔韧性。此外,所述单体在干燥过程中发生进一步的聚合反应,但是在低于烷氧基硅烷和硅烷的固化过程的温度下发生,因此还起到降低整体固化温度的作用。
所述有机单体只要是可以在二氧化硅与硅烷进行结合的反应条件下聚合的有机单体,则不作特别限定,但是更优选使用丙烯酸酯类单体。所述丙烯酸酯类单体在二氧化硅与硅烷发生反应的酸性条件下发生聚合反应,并且在聚合反应后生成的高分子的颗粒尺寸具有适当的尺寸,并不具有过大的尺寸,因此优选。
此外,所述丙烯酸酯类单体通过所述烷氧基硅烷与二氧化硅的溶胶-凝胶反应而生成醇成分,所述醇成分提高单体的聚合速度,从而可以促进聚合反应。此外,具有如下优点,即容易调节固化密度和硬度(Hardness),并且提高薄膜的透明度。当使用除此之外的其它阳离子(cation)类型的单体时,所得到的高分子的颗粒过大,从而可能发生严重的凝胶化。
所述丙烯酸酯类单体的实例可以列举冰晶级丙烯酸(Acrylic acid glacial)、丙烯酸甲酯(Methyl acrylate)、丙烯酸乙酯(Ethyl acrylate)、丙烯酸正丁酯(N-Butylacrylate)、丙烯酸-2-乙基己酯(2-Ethylhexyl acrylate)、丙烯酸异丁酯(Isobutylacrylate)、丙烯酸叔丁酯(Tertiary butyl acrylate)、甲基丙烯酸叔丁酯(Tertiarybutyl methacrylate)、丁二醇单丙烯酸酯(Butanediol monoacrylate)、月桂醇丙烯酸酯(Lauryl acrylate)、丙烯酸二甲氨基乙酯(Dimethylaminoethyl acrylate)和二氢二环戊二烯基丙烯酸酯(Dihydrodicyclopentadienyl acrylate)等,这些可以单独使用或混合两种以上使用。
所述有机单体在涂覆时有助于涂膜的形成和交联反应,相对于100重量份的金属表面处理用溶液组合物,可以包含5-15重量份的所述有机单体。相对于100重量份的金属表面处理用溶液组合物,当所述有机单体小于5重量份时,由于无法与二氧化硅和烷氧基硅烷聚合物形成充分的结合,从而涂膜形成能力可能会降低,由此可能会无法确保耐蚀性。另外,当所述有机单体超过15重量份时,由于没有反应的残留单体,耐水性或对酸的耐蚀性可能会降低。
本发明的金属表面处理用溶液组合物还包含用于调节酸度的酸。所述酸起到帮助烷氧基硅烷的水解反应且提高烷氧基硅烷的稳定性的作用,因此优选将溶液的酸度调节为1-5的pH范围。为此,相对于100重量份的金属表面处理组合物,可以包含0.01-1.00重量份的所述酸。相对于100重量份的金属表面处理用溶液组合物,当所述酸的含量小于0.01重量份时,水解时间增加,因此整体溶液组合物的溶液稳定性可能会降低。相对于100重量份的金属表面处理用溶液组合物,当所述酸的含量超过1.00重量份时,可能发生钢板的腐蚀,并且可能难以控制树脂的分子量。
对所述酸的具体的种类不作特别限定,但本发明的金属表面处理用溶液组合物中优选可以包含选自乙酸、甲酸、乳酸、葡萄糖酸等有机酸,以及硫酸、硝酸、盐酸、氢氟酸等有机-无机酸以及它们的混合物中的一种以上。
本发明的金属表面处理用溶液组合物中包含溶剂。所述溶剂起到调节硅烷对水的相容性和水解性、树脂组合物对金属表面的浸润性(Wetting)、干燥速度等的作用,相对于100重量份的金属表面处理组合物,可以包含1-15重量份的溶剂。当所述溶剂的含量小于1重量份时,相容性降低,从而涂液的储藏性降低,并且涂覆后可能无法确保耐蚀性。另外,相对于100重量份的所述金属表面处理组合物,当所述溶剂的含量超过15重量份时,由于粘度过度降低,从而溶液的稳定性降低,并且涂覆后可能无法确保耐蚀性。
在本发明的金属表面处理用溶液组合物中,对所述溶剂的具体种类不作特别限定,但是优选可以包含选自甲醇、乙醇、2-丙醇、2-甲氧基丙醇和2-丁氧基乙醇等中的一种以上。
并且,本发明还可以包含有机树脂。所述有机树脂起到增加与待涂覆的基材的附着性,并且提高常温干燥性的作用,相对于100重量份的金属表面处理组合物,优选包含0.1-5.0重量份的有机树脂。当所述有机树脂的含量小于0.1重量份时,添加有机树脂而引起的协同效应微小,当所述有机树脂的含量超过5.0重量份时,耐水性降低,因此可能发生涂膜剥离现象等。
在本发明的金属表面处理组合物中,所述有机树脂优选使用树脂结构内具有环形结构的树脂。树脂结构内的环形结构在各种反应中相对稳定,从而有助于提高耐酸性。
树脂结构内具有这种环形结构的有机树脂例如可以列举聚氨酯、氨基改性酚醛树脂、聚酯树脂、环氧树脂和聚乙烯醇缩丁醛等,可以使用所述各树脂的混合形态,并且可以单独使用或混合使用这些树脂。
将如上所述的根据本发明的金属表面处理用溶液组合物涂覆在钢板表面并进行干燥,从而可以形成对酸具有优异的耐蚀性的表面处理薄膜。所述涂覆可以采用通常使用的涂覆法,并不作特别限定。例如,可以采用辊涂、喷涂、沉积、喷射挤压或沉积挤压等方法,根据需要还可以混合使用两种以上的方法。
另外,所述干燥可以采用热风干燥炉或感应加热炉的方法来进行,以基材钢板最终达到温度(PMT)为基准,所述干燥可以在150-420℃的温度范围进行。以PMT为基准,当所述干燥温度没有达到150℃以上的温度时,无法形成完整的固体形状的薄膜层,并且在后续工序中液态的残留溶液被去除,因此可能无法确保所期望的耐蚀性。此外,以PMT为基准,当所述干燥温度超过420℃时,薄膜层内的有机树脂层氧化(表示燃烧)而使得薄膜层结构发生变化,并且可能无法确保所期望的耐蚀性。为此,例如,通过所述热风干燥炉进行干燥时,可以将热风干燥炉的内部温度设置为150-420℃来进行干燥。
对根据本发明的钢板的表面处理涂覆不作特别限定,可以以连续工序实现,此时,连续工序速度例如可以以60-180mpm(m/分钟)来进行。
由此得到的表面处理涂覆钢板在干燥后可以具有0.1-50μm的薄膜厚度。当薄膜的厚度小于0.1μm时,薄膜不充足,因此具有耐蚀性不足的问题,当薄膜的厚度超过50μm时,在所述涂覆工序中操作时未能充分干燥,因此具有可能无法形成坚固的薄膜的问题。
所述薄膜为有机无机复合薄膜,根据本发明的薄膜是通过二氧化硅与烷氧基硅烷的水解反应结合,并且烷氧基硅烷的其它烷氧基与钢板结合而在钢板表面形成坚固的薄膜。因此,根据本发明的薄膜可以被解释为在钢板表面上存在烷氧基硅烷与二氧化硅的水解反应生成物。在如上所述的水解反应等过程中生成醇,但该醇会在干燥过程中挥发。这种薄膜向钢板提供耐蚀性,即提供对酸的优异的耐蚀性。
另外,本发明的有机单体经过聚合以聚合物存在。所述有机单体为丙烯酸酯类单体,在薄膜中作为所述有机单体的聚合物的丙烯酸酯类高分子存在于钢板表面。
如上所述,将本发明的钢板表面处理用溶液组合物涂覆在钢板表面而形成的有机无机复合薄膜包含25-65重量%的碳(C)、20-70重量%的硅(Si)和1-40重量%的氧(O)。这可以通过电子探针微量分析(Electron probe micro-analysis,EPMA)、能量色散型X射线光谱(Energy-dispersive X-ray spectroscopy,EDS)等分析方法来确认。
其中,硅与氧或碳结合而存在,所述硅和氧结合的Si-O键与硅和碳结合的Si-C键之间的比例为80-95%(Si-O)比5-20%(Si-C)的范围。
另外,本发明中,当还包含有机树脂时,所述有机树脂可以以0.1-5.0重量%的含量包含在薄膜内。本发明的所述薄膜即使被应用在通常的钢板,即应用在镀锌系钢板,也可以得到对硫酸等的优异的耐蚀性。尤其,对于通常的提高对硫酸等的耐蚀性的钢,即,对于暴露在酸性的腐蚀环境中时在钢表面形成薄薄的薄膜而对酸具有强耐蚀性的耐硫酸钢应用本发明的薄膜时,与钢自身对硫酸等的耐蚀性一同起到协同效应,从而可以得到显著优异的硫酸耐蚀性。
对所述耐硫酸钢不作特别限定,例如,以重量%计,可以是包含C:0.2%以下(0除外)、Si:0.5%以下(0除外)、Mn:1.5%以下(0除外)、S:0.02%以下、P:0.02%以下、Al:0.1%以下、N:0.008%以下、Cu:0.1-0.5%、余量的Fe和其它不可避免的杂质的钢板。此时,还可以包含Co:0.03-0.1%、Ni和Sb:0.3%以下(0除外),在这种情况下,所述耐硫酸钢的表面下形成100-300nm厚度的富集层,所述富集层可以为选自Cu、Co、Ni和Sb中的至少一种的富集层。
更优选地,例如,以重量%计,所述耐硫酸钢可以是包含C:0.03-0.1%、Si:0.15-0.35%、Mn:0.5-1.2、S:0.01%以下、P:0.015%以下、Al:0.02-0.06、N:0.004%以下、Cu:0.2-0.4%、余量的Fe和其它不可避免的杂质的钢板。此时,还可以包含Ni:0.1-0.25%、Sb:0.05-0.2%、Co:0.03-0.1%中的一种,所述耐硫酸钢的表面下形成100-300nm厚度的富集层,所述富集层可以为选自Cu、Co、Ni和Sb中的至少一种的富集层。
根据本发明的涂覆有表面处理用溶液组合物的钢板自身的耐蚀性优异,但由于表面处理涂覆的特性,当长期暴露在腐蚀环境中时,可能发生局部腐蚀。因此,在本发明中,在所述钢板表面上涂覆所述表面处理用溶液组合物之前,可以包括在钢板的至少一个表面上形成镍镀层的步骤。
对形成镍镀层的方法不作特别限定,可以利用公知的方法。另外,所述镍镀层优选具有5-10000mg/m2的附着量,当镍镀层的附着量小于5mg/m2时,可能无法确保通过镀镍抑制局部腐蚀的效果。另一方面,当镍镀层的附着量超过10000mg/m2时,生产成本过高,因此可能存在无法确保经济性的问题。
所述镍镀层优选具有0.0005-1.12μm的厚度。当所述镍镀层的厚度小于0.0005μm时,可能没有改善局部腐蚀的效果,当所述镍镀层的厚度超过1.12μm时,由于过多的镀覆量,生产成本高,因此收益性可能会降低。
具体实施方式
实施例
下面,通过根据本发明的实施例和未根据本发明的比较例来更详细地说明本发明,但是本发明的范围并不受限于以下提出的实施例。
制造例
形成镍镀层的钢板
如下在钢板表面上形成镍层:在55℃下,在镍浓度为30g/L的镀覆溶液中施加7.7kA的电流,并通过电镀方式进行镀覆。
涂覆有表面处理组合物的钢板
在胶态二氧化硅Ludox HSA(固含量为30%、颗粒尺寸为12nm、W.R.Grace&Co.-Conn.公司)中分别添加四乙氧基硅烷、作为溶剂的乙醇和作为酸度调节剂的乙酸,然后进行冷却以使温度不超过约50℃,并搅拌约5小时。
此时,胶态二氧化硅通过硅烷发生表面改性,硅烷则发生水解。充分反应后,分别添加作为单体的丙烯酸乙酯和作为有机树脂的聚(甲基)丙烯酸,然后进一步反应约24小时。
使用各表面处理组合物,通过辊涂的方式将形成所述镍镀层的钢板(POSCO公司制造的ANCOR-CS钢)进行涂覆,然后放入约250℃的热风干燥炉中并以钢板的PMT 250℃进行加热,将所述组合物进行干燥及固化,从而分别制造经表面处理的钢板。
将制造的钢板的镍附着量、涂层的厚度和涂层的各成分的含量示于下述表1中。
[表1]
实验例
1.硫酸耐蚀性
将所述表面处理钢板浸渍在保持70的50体积%的硫酸水溶液中6小时,然后观察腐蚀特性。其评价基准为如下。
○:小于15mg/cm2/小时
△:15mg/cm2/小时以上且小于65mg/cm2/小时
×:65mg/cm2/小时以上
2.复合耐蚀性
将所述表面处理钢板浸渍在保持60的16.9体积%的硫酸和0.35体积%的盐酸的混合水溶液中6小时,然后观察在硫酸-盐酸复合腐蚀条件下的腐蚀特性。其评价基准为如下。
○:小于3mg/cm2/小时
△:3mg/cm2/小时以上且小于6mg/cm2/小时
×:6mg/cm2/小时以上
3.最小厚度(局部腐蚀性)
将所述表面处理钢板浸渍在保持70的50体积%的硫酸水溶液中96小时来进行腐蚀,然后以横向和竖向各8个点的方式,总共测量64个点的厚度,并观察最薄的厚度。其评价基准为如下。
○:0.10mm以上
△:0.05mm以上且小于0.10mm
×:小于0.05mm
4.涂膜粘附性
将所述表面处理钢板切割成150cm×75cm(横向×纵向)的尺寸而制造试片,并利用横切导板(cross cut guide)在所述试片的表面上以1mm的间隔在横向和纵向分别划线,以形成100个格,利用埃里克森(erichsen)试验机将所述形成100个格的部分向上推到6mm的高度,然后在向上推的部位粘贴剥离胶带(NB-1,Ichiban公司(制造)),然后取下并观察埃里克森部分是否剥离。其评价基准为如下。
○:表面没有发生剥离的情况
△:表面的100个格中有1-3个格剥离的情况
×:表面的100个格中有超过3个格剥离的情况
5.加工后的硫酸耐蚀性
将所述表面处理钢板制造成直径为38mm尺寸的钢板,然后利用埃里克森杯突(Cupping)试验仪加工成7mm的高度,然后浸渍在保持70的50体积%的硫酸水溶液中6小时,然后观察试片的腐蚀减量。其评价基准为如下。
○:小于15mg/cm2/小时
△:15mg/cm2/小时以上且小于65mg/cm2/小时
×:65mg/cm2/小时以上
将对所述实施例1-4和比较例1-10中制造的表面处理钢板的物理性能进行测量的结果记载于下述表2中。
[表2]
如上述表2中所示,可以知道根据本发明的实施例1-4的硫酸耐蚀性、复合耐蚀性、涂膜粘附性和加工后的硫酸耐蚀性非常优异。此外,在涂覆和干燥过程中没有发生鼓泡现象等表面缺陷,从而确保了非常优异的表面品质。并且,在50%的硫酸中进行96小时的腐蚀评价后显示出0.10mm以上的最小厚度,由此可以确认通过镍镀层改善了局部腐蚀性。
但是,可以知道比较例1的硫酸耐蚀性和复合耐蚀性显著降低。这是因为由于添加过量的胶态二氧化硅,在与硅烷的反应中剩下大量的残留二氧化硅,从而阻碍了薄膜的形成。
并且,比较例2也显示出硫酸耐蚀性和复合耐蚀性降低的结果。这是因为由于硅烷的含量不足,胶态二氧化硅的表面像比较例1一样没有得到充分的改性,由此大量的残留二氧化硅阻碍了薄膜的形成。
另外,比较例3是添加过量的酸度调节剂的情况,可以知道通过硅烷改性的二氧化硅和单体以及有机树脂中的有机无机混合树脂的分子量过度增加,从而发生溶液的凝胶化,或者即使进行涂覆,硫酸耐蚀性或复合耐蚀性也会降低。此外,由于残留酸度调节剂,还可能发生钢板的腐蚀。
此外,在比较例4中,可以知道由于不包含溶剂,在溶液组合物的制备过程中容易发生凝胶化,并且即使进行涂覆,硫酸耐蚀性和复合耐蚀性也会降低。
比较例5和比较例6分别是添加过量的单体和有机树脂的情况,可以知道如上所述相对于无机成分,有机成分的含量过量时,硫酸耐蚀性和复合耐蚀性降低。
比较例7是所添加的硅烷含量为过量的情况,可以知道在溶液组合物的制备过程中会排出由于热分解而生成的有机气体,并且由于大量的残留硅烷,涂覆后的耐硫酸性降低。
比较例8的涂层的厚度不足,因此可以知道硫酸耐蚀性、复合耐蚀性和加工后的硫酸耐蚀性不足。
另外,比较例9的镍的镀覆量不足,因此可以知道最小厚度(局部腐蚀性)不足。
此外,比较例10的涂层的厚度过厚,因此可以知道由于加工过程中发生的涂层裂纹,涂膜粘附性和加工后的硫酸耐蚀性差。
另外,图1的(a)示出对未形成本发明的镍镀层的比较例进行72小时、50%的硫酸腐蚀评价后的照片,(b)示出对形成本发明的镍镀层的实施例进行96小时、50%的硫酸腐蚀评价后的照片。可以确认未形成镍镀层的(a)中左侧边缘脱落,但形成镍镀层的(b)在相同条件下进行96小时的评价后也没有脱落的部分。
以上,对本发明的实施例进行了详细的说明,但本发明的权利范围并不限定于此,在不脱离权利要求书中记载的本发明的技术思想的范围内可以进行各种修改和变形,这对于本领域技术人员而言是显而易见的。
Claims (19)
1.一种经表面处理的钢板,其包括:
钢板;
镍镀层,形成在所述钢板的至少一个表面上;以及
耐蚀性薄膜层,形成在所述镍镀层上,
所述耐蚀性薄膜层包含通过二氧化硅与烷氧基硅烷的水解反应而形成的生成物和丙烯酸酯类高分子,
并且包含25-65重量%的碳(C)、20-70重量%的硅(Si)、1-40重量%的氧(O),
硅(Si)和氧的键(Si-O键)与硅(Si)和碳(C)的键(Si-C键)的比例为80-95%:5-20%。
2.根据权利要求1所述的经表面处理的钢板,其中,所述耐蚀性薄膜层由钢板表面处理用溶液组合物形成,所述钢板表面处理用溶液组合物包含:
30-50重量%的胶态二氧化硅,其包含5-20nm尺寸的二氧化硅;
40-60重量%的包含3个以上烷氧基的硅烷;
5-15重量%的丙烯酸酯类有机单体;以及
0.01-1重量%的酸。
3.根据权利要求2所述的经表面处理的钢板,其中,所述胶态二氧化硅中的二氧化硅的含量为10-45重量%。
4.根据权利要求2所述的经表面处理的钢板,其中,所述硅烷为选自乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三异丙氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、2-缩水甘油醚氧基丙基三甲氧基硅烷、2-缩水甘油醚氧基丙基三乙氧基硅烷、2-氨基丙基三乙氧基硅烷、2-脲基烷基三乙氧基硅烷、四乙氧基硅烷、三乙氧基苯基硅烷和三甲氧基苯基硅烷中的至少一种。
5.根据权利要求2所述的经表面处理的钢板,其中,所述有机单体为选自冰晶级丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸-2-乙基己酯、丙烯酸异丁酯、丙烯酸叔丁酯、甲基丙烯酸叔丁酯、丁二醇单丙烯酸酯、月桂醇丙烯酸酯、丙烯酸二甲氨基乙酯和二氢二环戊二烯基丙烯酸酯中的至少一种。
6.根据权利要求2所述的经表面处理的钢板,其中,所述酸为选自乙酸、甲酸、乳酸、葡萄糖酸、硫酸、硝酸、盐酸和氢氟酸中的一种以上。
7.根据权利要求2所述的经表面处理的钢板,其中,所述钢板表面处理用溶液组合物还包含1-15重量%的溶剂。
8.根据权利要求7所述的经表面处理的钢板,其中,所述溶剂为选自甲醇、乙醇、2-丙醇、2-甲氧基丙醇和2-丁氧基乙醇中的至少一种。
9.根据权利要求2所述的经表面处理的钢板,其中,所述钢板表面处理用溶液组合物还包含0.1-5.0重量%的具有环形结构的有机树脂。
10.根据权利要求9所述的经表面处理的钢板,其中,所述具有环形结构的有机树脂为选自聚氨酯、氨基改性酚醛树脂、聚酯树脂、环氧树脂和聚乙烯醇缩丁醛中的至少一种或两种以上的混合树脂。
11.根据权利要求1所述的经表面处理的钢板,其中,所述耐蚀性薄膜层具有0.1-50μm的厚度。
12.根据权利要求1所述的经表面处理的钢板,其中,所述镍镀层具有0.0005-1.12μm的厚度。
13.根据权利要求1所述的经表面处理的钢板,其中,所述镍镀层具有5-10000mg/m2的附着量。
14.根据权利要求1所述的经表面处理的钢板,其中,所述钢板为耐硫酸钢。
15.根据权利要求14所述的经表面处理的钢板,其中,以重量%计,所述耐硫酸钢包含:C:0.2%以下且0除外、Si:0.5%以下且0除外、Mn:1.5%以下且0除外、S:0.02%以下、P:0.02%以下、Al:0.1%以下、N:0.008%以下、Cu:0.1-0.5%、余量的Fe和其它不可避免的杂质。
16.根据权利要求15所述的经表面处理的钢板,其中,以重量%计,所述耐硫酸钢还包含:Co:0.03-0.1%、Ni:0.3%以下且0除外和Sb:0.3%以下且0除外中的至少一种。
17.根据权利要求14所述的经表面处理的钢板,其中,以重量%计,所述耐硫酸钢包含:C:0.03-0.1%、Si:0.15-0.35%、Mn:0.5-1.2、S:0.01%以下、P:0.015%以下、Al:0.02-0.06、N:0.004%以下、Cu:0.2-0.4%、余量的Fe和其它不可避免的杂质。
18.根据权利要求17所述的经表面处理的钢板,其中,以重量%计,所述耐硫酸钢还包含:Co:0.03-0.1%、Ni:0.1-0.25%和Sb:0.05-0.2%中的至少一种。
19.根据权利要求16或18所述的经表面处理的钢板,其中,所述耐硫酸钢的表面下形成100-300nm厚度的富集层,所述富集层为选自Cu、Co、Ni和Sb中的至少一种的富集层。
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EP3730675B1 (en) | 2022-08-24 |
EP3730675A1 (en) | 2020-10-28 |
JP2021507991A (ja) | 2021-02-25 |
KR20190076647A (ko) | 2019-07-02 |
JP7281467B2 (ja) | 2023-05-25 |
CN111492097B (zh) | 2023-10-24 |
WO2019124865A1 (ko) | 2019-06-27 |
EP3730675A4 (en) | 2021-03-31 |
KR102065224B1 (ko) | 2020-01-10 |
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