CN117626274A - 一种硫酸-植酸复配除锈剂及其制备和应用 - Google Patents
一种硫酸-植酸复配除锈剂及其制备和应用 Download PDFInfo
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- CN117626274A CN117626274A CN202311475946.9A CN202311475946A CN117626274A CN 117626274 A CN117626274 A CN 117626274A CN 202311475946 A CN202311475946 A CN 202311475946A CN 117626274 A CN117626274 A CN 117626274A
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- sulfuric acid
- iron
- rust remover
- phytic acid
- corrosion
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000000467 phytic acid Substances 0.000 title claims abstract description 50
- 229940068041 phytic acid Drugs 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 93
- 230000007797 corrosion Effects 0.000 claims abstract description 62
- 238000005260 corrosion Methods 0.000 claims abstract description 62
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052742 iron Inorganic materials 0.000 claims abstract description 40
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 27
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 26
- 239000003112 inhibitor Substances 0.000 claims abstract description 18
- 229910001018 Cast iron Inorganic materials 0.000 claims description 41
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 37
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- NWBJYWHLCVSVIJ-UHFFFAOYSA-N N-benzyladenine Chemical compound N=1C=NC=2NC=NC=2C=1NCC1=CC=CC=C1 NWBJYWHLCVSVIJ-UHFFFAOYSA-N 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000013535 sea water Substances 0.000 description 6
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- 229910002588 FeOOH Inorganic materials 0.000 description 5
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
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- -1 acyl acetone Chemical compound 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
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- 150000002739 metals Chemical class 0.000 description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011086 high cleaning Methods 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- 229910021646 siderite Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
- 229910006540 α-FeOOH Inorganic materials 0.000 description 1
Classifications
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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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
- C23G1/065—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors sulfur-containing compounds
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/081—Iron or steel solutions containing H2SO4
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/088—Iron or steel solutions containing organic acids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
本发明公开了一种硫酸‑植酸复配除锈剂及制备方法和应用。该复配除锈剂不仅对可充分去除铁及铁合金表面的腐蚀产物,同时可在基体表面成膜以达到缓蚀的目的。其主要成分为硫酸与植酸,并加入适量的缓蚀剂配制而成。与传统的无机酸除锈剂相比,该复配除锈剂具有操作安全,使用方便等优点,其反应较传统无机酸除锈剂温和;同时该复配除锈剂免除了传统无机酸已损害铁基体的缺点,其在除锈的同时可在铁器表面形成保护膜层,阻碍硫酸对铁基体的侵蚀,从而达到除锈‑缓蚀的双重目的,有效延长铁合金的使用寿命以及保护铁质文物的多样性。
Description
技术领域
本发明涉及一种除锈剂及其制备和应用,尤其涉及一种硫酸-植酸复配除锈剂及其制备和应用,其用途尤其代指铸铁及铁质文物表面清洗。
背景技术
历史文物是文化最直接的反应,是古人留给后人的一笔宝贵的历史财富;而金属文物,更是一笔重要的物质文化遗产。但由于近年来社会科技的发展,环境中的污染物质与日俱增,使得生活中的金属制品皆受到了不同程度的腐蚀,造成了严重的经济损失。据不完全统计,国家每年由于金属腐蚀的直接损失占到了国民经济总产值的2%-4%。而金属文物由于其表面较为脆弱,更易受到不同介质中污染物质的侵蚀。其中,以铁质文物为代表的活泼金属所制的文物腐蚀更为严重。与青铜文物相比,我国使用铁器的时间相对较晚,早期的铁器多以天然铁-陨铁为主。春秋战国时期,炼铁技术得到较大提升,铁器逐渐代替了铜器成为各朝兵器和农具的首选。但由于古代的炼铁技术不及现代,冶炼使用的铁多为含碳量较高的铸铁,导致其较其他铁合金而言更易被腐蚀。这是由于钢铁材料的腐蚀主要是由于与环境中的氧气或者水分子反应,形成氧化铁,这种现象叫做氧化或者说是锈蚀。而碳可以降低铁的氧化电位,也就是使得氧化反应更容易进行。含碳量较高的铁,如铸铁,会在其微观结构中形成许多分散的碳质颗粒。这些碳质颗粒可以形成许多微小的电池系统,即它们本身与周围的铁基体形成腐蚀微电池(也称为局部电池)。在这种腐蚀微电池中,铁基体作为阳极,比碳颗粒更容易被氧化(失去电子)。因此,碳颗粒的存在加快了铁的腐蚀速度。此外,铁和碳的组合也可以形成一些更易腐蚀的相,如铁素体。当在含碳量较高的铁中形成这些易腐蚀的相时,将会加速腐蚀过程。而在相对复杂的环境中,铸铁的腐蚀现象更为严重。以厦门胡里山炮台为例,根据对其腐蚀产物的分析发现,其主要成分为针铁矿(α-Fe2O3),纤铁矿(γ-Fe2O3),磁铁矿(Fe3O4)以及三种FeOOH(α-FeOOH,β-FeOOH,γ-FeOOH)。而SEM-EDS检测发现,其表面锈层一般较为疏松,常存在大量孔洞,而在孔洞中,EDS测试发现了大量Cl-的存在。由于Cl-的离子半径较小且电负性较强,其对于铁表面较薄的氧化物膜具有较强的穿透力,使得铁表面腐蚀的阳极反应加速,生成可溶性Fe2+的氯化物,并与空气中氧气反应最终生成Fe3+。此外,Cl-的不断侵蚀会加速铁器表面保护性氧化物的破坏性溶解。如不及时处理,Cl-最终会不断侵蚀铁器直至文物彻底损坏,对考古研究造成难以挽回的损失。因此,不论是出于保护金属文物及其他金属制品的目的,还是贯彻“可持续发展”这一发展理念,对金属的清洗除锈和缓蚀防护都是国家的研究重点。传统的清洗多以酸性较强的无机酸为主。如中国专利公告了一种“用浓盐酸或浓硫酸除去钢铁器件上的铁锈的新方法”(公开号CN101451244A),便是利用浓盐酸和浓硫酸作为除锈主料,同时辅以尿素、硫酸铵等添加剂对钢材表面的锈蚀进行清理。该清洗方法虽除锈效果优异,但也存在明显不足。专利向酸中添加尿素等添加剂以抑制酸雾的产生,但忽视了无机强酸对于金属基体的侵蚀。由于铁在盐酸等强酸中的反应较为剧烈,如不对反应条件加以控制。铁器在进行除锈清洗时极易发生“氢脆”现象——铁与酸反应生成氢气,氢气分子能进入金属晶格内,并在内部扩散。当这些内部的氢气达到一定的浓度时,就可能在金属内部形成小的气泡,导致金属的内部结构受到破坏,使得金属的强度和韧性降低。同时浓盐酸清洗时会引入新的Cl-,使得铁器产生二次腐蚀。因此,该专利的应用范围十分有限,只可用于清洗本身耐蚀性较强的不锈钢等钢材,对于碳钢等含碳量较高的铁合金则须谨慎使用,而对于本身较为脆弱的铸铁文物则完全不适用。因此除无机酸外,近年来金属文物的除锈重点逐渐转变为有机酸。如中国专利曾公开了一种氨基磺酸除锈剂(CN111690941A),以氨基磺酸、氯盐,柠檬酸,酒石酸,助溶剂,阴离子表面活性剂及水配制而成。在普碳钢和低合金钢上实现了良好的清洗效果,同时具有清洗容量高,清洗速度快等优点。但其缺点仍不可忽视,如氨基磺酸等有机酸虽对铁的侵蚀效果较弱,但由于其酸性相对较弱,只适用于清洗腐蚀情况较为简单的钢材,而对于腐蚀较为复杂的铁质文物、特别是铸铁文物则除锈效果较差,而作为表面活性剂加入的氯盐,可能会在清洗过程中进入铁基体表面的空隙中,对铁器造成二次腐蚀;且专利所用的环己酮、酰丙酮等皆为致癌物,可能会对人体造成危害,若直接排放会造成环境污染,不符合“可持续发展”这一发展理念。
发明内容
本发明的目的是为了改进现有技术的不足而提供了一种硫酸-植酸复配除锈剂,本发明还提供了上述硫酸-植酸复配除锈的制备方法,本发明还提出了硫酸-植酸复配除锈的应用。
本发明的技术方案为:本发明以硫酸与植酸为主,缓蚀剂为辅,在保证硫酸本身较好的除锈效果的同时降低硫酸对铁基体的侵蚀,同时在铁基体表面成膜阻碍其他腐蚀因素的进入,避免二次腐蚀与“氢脆”现象的发生。同时与传统无机与有机除锈剂不同,该种硫酸-植酸复配除锈剂不仅对FeO及Fe2O3等常见的铸铁腐蚀产物去除效果较好,对于铁在复杂环境中产生的腐蚀产物,如在海洋中生成的FeOOH,其除锈效果仍可达到98%以上。因此,该发明所提出的硫酸-植酸复配除锈剂,不仅保留了传统无机强酸较好的除锈效果,同时避免了无机强酸对铁基体造成的危害,从而达到1+1>2的效果因此该除锈剂较其他除锈剂具备更好的除锈效率和更广的适用范围:不仅能够用于日常生活中铁合金除锈,对于那些埋藏年代久远,表面较为脆弱且腐蚀产物较为复杂的铸铁文物的除锈工作也同样适用。本发明提出的新型硫酸-植酸体系,在以硫酸为除锈主料的基础上加入植酸与缓蚀剂,使得该发明在具备上述单一清洗剂优点的同时有效避免了其存在的缺陷。
本发明的具体技术方案:一种硫酸-植酸复配除锈剂,以硫酸为基底,辅以植酸,并加入缓蚀剂以减缓其对铁基体的侵蚀,以去离子水为溶剂得到新型除锈剂。其特征在于:其原料组分及各组分的质量百分比分别为:浓硫酸3~5%,纯植酸0.1~0.2%,缓蚀剂0.01~0.1%,余量为去离子水。
优选所述的缓蚀剂为硫脲、6-苄基氨基嘌呤(BAP)或十六烷基三甲基溴化铵(CTAB)等传统有机缓蚀剂中的一种或多种。
本发明还提供了一种制备上述的硫酸-植酸复配除锈剂的方法,其特征在于:按照配比配好溶液,在室温环境下进行搅拌,其中搅拌速率为400~600r/min,搅拌时间为10~30min。
本发明还提供了上述的硫酸-植酸复配除锈剂在铁质文物中的应用。具体步骤为:将需进行除锈处理的铸铁完全浸没于硫酸-植酸复配除锈液中,在室温下进行反应,反应1h~3h。处理完毕后,对处理后的铸铁进行红外光谱仪及SEM表征,证明其表面锈蚀已被完全去除;并进行失重实验及电化学实验测试其耐蚀性。
有益效果:
与传统的无机酸除锈剂相比,本发明采用的除锈剂具有明显优势:
(1)本发明中采用的植酸与硫脲均为非危险品,使用起来较为方便安全,且植酸广泛存在于农作物中,易于制取。
(2)植酸与硫脲皆对金属具有良好的螯合性,不会对铁基体产生损害或导致其褪色。同时植酸作为有机强酸,将其加入硫酸中进行复配后不会影响硫酸本身的酸性,使得除锈反应能够正常进行。同时植酸与硫脲可与反应析出的铁离子进行络合沉淀在铁基体表面,形成植酸-硫脲复配膜,使得硫酸在除锈完成后无法进一步与铁基体反应而对铁基体造成伤害。
附图说明
图1为实施例1中铸铁在海洋环境中腐蚀后的XRD分析图;
图2为实施例1中铸铁在海洋环境中腐蚀后的SEM分析图;其中2(a)为放大300倍,图2(b)为放大1000倍;
图3为实施例1中铸铁在添加硫脲的硫酸-植酸溶液中的交流阻抗图;
图4为实施例1中铸铁在添加硫脲的硫酸-植酸溶液中的极化曲线图;
图5为实施例1中铸铁在添加不同比例植酸/硫脲的硫酸溶液中的傅里叶红外光谱(FTIR);
图6为实施例1中铸铁在添加不同比例植酸/硫脲的硫酸溶液中的SEM分析图;
图7为实施例2中铸铁在添加BAP的硫酸-植酸溶液中的交流阻抗图;
图8为实施例2中铸铁在添加BAP的硫酸-植酸溶液中的极化曲线图;
图9为实施例3中铸铁在添加CTAB的硫酸-植酸溶液中的交流阻抗图;
图10为实施例3中铸铁在添加CTAB的硫酸-植酸溶液中的极化曲线图。
具体实施方式
以下实施例中所用原料为:质量浓度为98%浓硫酸、BR纯植酸(上海源叶公司生产)、AR分析纯缓蚀剂
实施例1
海洋环境下铸铁金属腐蚀产物分析表征及除锈剂除锈&分析
按照以下标准加入原料后,在室温下以600r/min搅拌30min后得到模拟海水溶液
表1模拟海水配方
将处理后的铸铁试片片放入其中在35℃环境下水浴反应30d,收集腐蚀产物进行表征。
从铜片腐蚀形貌可以看出,在海洋环境下,铸铁表面生成了一层疏松多孔的棕黄色沉淀物,从图1XRD物相分析结果发现其主要成分为FeOOH,同时还存在少量FeCl3,证明在海洋环境下,主要表现为O2、H2O及Cl-的腐蚀,其中Fe会失去电子生成Fe2+,其会在O2的氧化为Fe3+,并与O2、H2O进一步反应生成FeOOH,其分解后即会转化为Fe2O3与Fe3O4。SEM测试(见图2)发现,铸铁在模拟海水中表面生成大量颗粒状物质,对比XRD图及肉眼观察可知此为表面疏松多孔的Fe2O3与Fe3O4,其分布较为杂乱。
按照硫酸质量比5%,BR纯植酸质量比0.1%,缓蚀剂(硫脲)质量比0.1%,水余量称取原料,在室温下以600r/min均匀搅拌20min配置得到除锈剂溶液;
将在模拟海水溶液中经充分腐蚀的铸铁放入配制好的硫酸-植酸复配除锈剂中浸没,在室温环境下反应2h,后取出干燥,计算发现除锈剂对海洋中铸铁腐蚀产物去除效率达98.33%。而后捞出干燥后进行电化学测试发现,其在硫酸溶液中的缓蚀效果同样存在,从图3拟合得到阻抗值为128Ω·cm2,而从图4拟合得到自腐蚀电流密度为8.08×10-5A·cm-2,与空白样相比,缓蚀效率为95.49%。将处理后的铸铁进行傅里叶红外光谱分析(FTIR)
图5为植酸/硫脲/植酸-硫脲复配缓蚀剂的FTIR图,分析发现,在加入植酸后,3226cm-1的吸收峰表现为水O-H和羟基O-H的伸缩振动,1632cm-1处的吸收峰为水O-H的弯曲振动,1346cm-1处的吸收峰为C-H的变角振动,1095cm-1处的吸收峰为PO2的对称伸缩振动和P-(OH)2的反对称伸缩振动,1017cm-1处的吸收峰为P-O-C中C-O的伸缩振动,893cm-1处的吸收峰为P-O的伸缩振动和P-(OH)2的对称伸缩振动。而加入硫脲后,复合膜层的O-H所在吸收峰相比单一植酸有一定程度的偏移,且多了硫脲基团的存在。在3229cm-1处的吸收峰为水O-H和氨基N-H的伸缩振动,1631cm-1处的吸收峰为水O-H的弯曲振动和氨基NH2的变角振动,1344cm-1处的吸收峰可能为C-N的伸缩振动,1020cm-1处的吸收峰为C=S的伸缩振动。ATR分析发现当植酸与硫脲复配后,两者的官能团均存在于试片表面;证明了在5%硫酸溶液中加入植酸-硫脲复配缓蚀剂后,二者均可在铸铁表面形成膜层,有效提高铸铁在硫酸中的缓蚀。
将中处理后的铸铁进行SEM分析
图6为未添加(图6(a))及添加了硫脲(图6(b))的硫酸-植酸复配缓蚀剂对铸铁腐蚀的SEM图,从图6(a)中发现,未添加硫脲时,单一植酸仍可在铸铁表面形成植酸转化膜,但整体较为疏松,孔隙较多,使得其对铸铁的保护效果较为有限。而在添加了硫脲后从图6(b)发现,其与植酸复配形成了一层较为致密的植酸-硫脲钝化膜,有效提高了铸铁在硫酸中的缓蚀效果。
实施例2
按照硫酸质量比3%,BR纯植酸质量比0.1%,缓蚀剂(BAP)质量比0.01%,水余量称取原料,以600r/min均匀搅拌15min配置得到除锈剂溶液。
将在模拟海水溶液中经充分腐蚀的铸铁(同实施例1)放入配制好的硫酸-植酸复配除锈剂中浸没,在室温环境下反应1.5h,后取出干燥,计算发现除锈剂对海洋中铸铁腐蚀产物去除效率达95.31%。而后捞出干燥后进行电化学测试发现,其在硫酸溶液中的缓蚀效果同样存在,从图7拟合得到阻抗值为28Ω·cm2,而从图8拟合得到自腐蚀电流密度为3.39×10-4A·cm-2,与空白样相比,缓蚀效率为81.06%。
实施例3
按照98%硫酸浓质量比4%,BR纯植酸质量比0.15%,缓蚀剂(CTAB)质量比0.05%,水余量称取原料,以500r/min均匀搅拌15min配置得到除锈剂溶液。
将在模拟海水溶液中经充分腐蚀的铸铁(同实施例1)放入配制好的硫酸-植酸复配除锈剂中浸没,在室温环境下反应2.5h,后取出干燥,计算发现除锈剂对海洋中铸铁腐蚀产物去除效率达96.44%。而后捞出干燥后进行电化学测试发现,其在硫酸溶液中的缓蚀效果同样存在,从图9拟合得到阻抗值为34Ω·cm2,而从图10拟合得到自腐蚀电流密度为3.14×10-4A·cm-2,与空白样相比,缓蚀效率为82.46%。
Claims (5)
1.一种硫酸-植酸复配除锈剂,其特征在于:其原料组分及各组分的质量百分比分别为:浓硫酸3~5%,纯植酸0.1~0.2%,缓蚀剂0.01~0.1%,余量为去离子水。
2.根据权利要求1所述的硫酸-植酸复配除锈剂,其特征在于所述的缓蚀剂为硫脲、6-苄基氨基嘌呤或十六烷基三甲基溴化铵中的一种或几种。
3.一种制备如权利要求1所述的硫酸-植酸复配除锈剂的方法,其具体步骤为:按照配比配好溶液,进行搅拌,其中搅拌速率为400~600r/min,搅拌时间为10~30min。
4.一种如权利要求1所述的硫酸-植酸复配除锈剂在铁质文物中的应用。
5.根据权利要求4所述的应用,其特征在于:将需进行除锈处理的铸铁浸没于硫酸-植酸复配除锈剂中,进行反应1h~3h。
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