EP1281790B1 - Dampfphasen-Korrosionsinhibitoren und Verfahren zu deren Zubereitung - Google Patents

Dampfphasen-Korrosionsinhibitoren und Verfahren zu deren Zubereitung Download PDF

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Publication number
EP1281790B1
EP1281790B1 EP02013016A EP02013016A EP1281790B1 EP 1281790 B1 EP1281790 B1 EP 1281790B1 EP 02013016 A EP02013016 A EP 02013016A EP 02013016 A EP02013016 A EP 02013016A EP 1281790 B1 EP1281790 B1 EP 1281790B1
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Prior art keywords
corrosion
vci
material combination
inhibiting material
combination according
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Expired - Lifetime
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EP02013016A
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German (de)
English (en)
French (fr)
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EP1281790A1 (de
Inventor
Georg Prof. Dr. Reinhard
Urte Dr. Ludwig
Gerhard Hahn
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Excor Korrosionsforschung GmbH
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Excor Korrosionsforschung GmbH
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Classifications

    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/02—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in air or gases by adding vapour phase inhibitors

Definitions

  • the invention relates to substance combinations as vapor-phase corrosion inhibitors (volatile corrosion inhibitors, VCI) for the protection of common utility metals, such as iron, chromium, Nickel, tin, zinc, aluminum, copper and their alloys, against atmospheric corrosion.
  • VCI volatile corrosion inhibitors
  • these vapor phase inhibitors (VPI) or volatile corrosion inhibitors (VCI) are selected according to the type of metal to be protected and packaged as a powder packaged in pouches of a material which is permeable to the vaporous VPIs ( See, for example: HH Uhlig, corrosion and corrosion protection, Akademie-Verlag Berlin, 1970, pp 247-249, K.
  • Modern packaging materials for corrosion protection included the VCI either in tablet form within porous Foam capsules or as a fine powder within polymers Support materials.
  • VCI in the US patents 3,836,077, US 3,967,926, US 5,332,525, US 5,393,457, US 4,124,549, US 4,290,912, US 5,209,869, JP 4,124,549, EP 0.639.657 and DE-OS 3,545,473 various variants proposed the VCI in capsules or air-permeable plastic films to bring in, either by inclusion in by separating a foam created cavities with subsequent Cover same with a gas-permeable Material or by adding the VCI to the melt, Spray or bubble extrusion provided polymer melt, so that a packaging material (film or hard material) is produced, because of the structure-related porosity, the VCI components can continuously sublimate.
  • VCI during foaming of polymeric solids e.g. in JP 58,063,732, US 4,275,835 and DD 295,668.
  • Farther VCI-containing packaging can be produced, by placing the VCI components in a suitable solvent dissolved and applied to the packaging material in question become.
  • Process of this kind with different active ingredients and solvents are e.g. in JP 61,227,188, JP 62,063,686, JP 63,028,888, JP 63,183,182, JP 63,210,285, DE-PS 1521900 and US 3,887,481.
  • VCI packaging materials produced in this way are the active ingredients usually only loose in the structural cavities of the carrier material paper, cardboard, foam etc. stored contain, there is a risk of mechanical Abspreitens and trickle out the drug particles, so not can be ensured that the pretreated support materials at the time of its application for corrosion protection even the required specific surface concentration to own VCI.
  • US Pat. No. 5,958,115 is incorporated herein by reference described corrosion inhibiting composite material, the a mixture of a metal oxide sol, the sublimation capable Corrosion inhibitors and other additives exists and on the carrier material a firmly adhering, sufficiently porous Gel film of the metal oxides used and additives forms, from the corrosion inhibitors (VCI) with a uniform, long-term emission rate.
  • VCI corrosion inhibitors
  • a corrosion inhibitor is a "chemical Substance that in presence with a suitable concentration reduces the corrosion rate in a corrosive system, without the concentration of any other corroding To change funds decisively.
  • the use of the The term inhibitor should be defined by the nature of the metal and its environment, in which it is effective, be specified. " (“chemical substance which decreases the corrosion rate when Present in the corrosion system at a specific concentration whithout significantly changing the concentration of any other corrosive agent; the use of the term inhibitor should be qualified by the nature of the metal and the environment in which it is effective "(see Corrosion of metals and alloys - Terms and definitions; ISO 8044-1986).
  • VCI The main principle of the application of VCI is the maintenance, or reinforcement of the inherent, mostly limited protective Primary oxide layer, which is on each metal by contact with the atmosphere is very fast, but purely visual without optical aids is imperceptible (K. Barton, cit .; E. Kunze (ed.), Corrosion and Corrosion Protection, Volume 3, Wiley-VCH, Berlin, Weinheim, New York 2001, p. 1680 ff.).
  • the passivatable where for the maintenance or reproduction of the protective primary oxide layer is a sufficiently strong oxidizing agent is needed and those referred to as non-passivatable Metals where the passive oxide layer just through the Action of strong oxidizing agents such chemical and / or structural changes undergoes that liability on the substrate and thus also the corrosion protection effect get lost.
  • the primary oxide layer consists, for example, mainly of Fe (III) oxides. If moistening of the metal surface occurs, as is the case, for example, when a condensed water film is formed in rooms saturated with water due to temperature reduction, without a sufficiently strong oxidizing agent acting at the same time, the corrosion of the metal begins by precipitating these oxides in Fe (II).
  • the copper whose primary oxide layer is sensitive to further oxidation.
  • Its primary oxide layer is known to consist mainly of the oxide Cu 2 O and is stable only in aqueous media containing no strong oxidant, regardless of pH.
  • the oxide CuO develops relatively quickly, perceptible as a black deposit, which due to its crystal lattice dimensions can not grow together with the metal substrate (no epitaxy) and therefore does not protect against corrosion.
  • the nitrites have already proven to be versatile as salts of nitrous acid. Therefore, they have long been used as vapor phase inhibitors.
  • the relatively volatile dicyclohexylammonium nitrite has been used for more than 50 years as a vapor phase inhibitor (see Uhlig, Barton, Rozenfeld, Kunze, loc cit.) And is mentioned as part of VCI compositions in numerous patents (eg: US-PS 2,419. 327, US Patent 2,432,839, US Patent 2,432,840, US Patent 4,290,912, US Patent 4,973,448, JP 02085380, JP 62109987, JP 63210285 A, DE-PS 4040586).
  • This is not only behind the unfolding of the passivator effect of the nitrite, but also endangers the stability of the passive oxide of zinc and aluminum materials.
  • the oxides of these metals are only stable in the neutral range and undergo increasing dissolution with zinc> or aluminate formation at pH> 8: ZnO + H 2 O + OH - ⁇ Zn (OH) 3 - Al 2 O 3 + H 2 O + 5 OH - ⁇ 2 Al (OH) 4 -
  • VCI packaging materials In an effort to create VCI packaging materials, the not only for ferrous metals, but at least for galvanized Steels and aluminum materials were applicable tries to formulate VCI combinations that are not just a-nitrites, but also contain components that condensed in Intervene in water films on metal surfaces in a pH-regulating manner, so it's not the described resolution of the passive oxide layers comes.
  • nitrite-amine mixtures with other sublimation-capable substances, such as the salts of moderate to weak, saturated or unsaturated carboxylic acids, cf. eg US 2,419,327, US 2,432,839, 2,432,840, DE 814,725.
  • sublimation-capable substances such as the salts of moderate to weak, saturated or unsaturated carboxylic acids, cf. eg US 2,419,327, US 2,432,839, 2,432,840, DE 814,725.
  • the carboxylates in question are known to build in aqueous media or Kondenswasserfilmen on metal surfaces with or without the simultaneous presence of an amine depending on the particular carboxylic acid / salt system pH buffer systems higher buffer capacity and thus hinder the reducibility of oxidizing agents, resulting from the abovementioned reduction reactions in principle becomes clear for nitrite.
  • VCI combinations which also contain an amine or amine carboxylate in addition to an oxidizing agent such as nitrite, chromate or an organic nitro compound, can only be successful in practical implementation if the passivating oxidizing agent is used at excessive concentrations.
  • concentration ranges in which the VCI combinations according to the invention can be used are usually stated very generously.
  • Such oxidant-containing VCI combinations are described, for example, in US Pat. No. 600,328, where it is recommended to use as much of an organic nitrite salt as possible, or in DE-PS 814 725, in which nitrite salts of organic nitrogen-containing bases (eg.
  • Carboxylates, piperidines, oxazines or morpholines are proposed under the condition that at least 0.5 to 20 g of nitrite / m 2 packaging material are applied and reliable protection is given only if at least 35 to 600 g / m 3 Interior of the packaging were emitted.
  • Patent 4,973,448 Blends of Benzotriazole with organic carbonates, phosphates and amines, JP 62063686 and JP 63210285 A finally mixtures of benzotriazole with alkali and amine salts of aromatic carboxylic acids.
  • JP-PS 03079781 proposed instead of the substance combinations triazole / amine only to use alkylaminotriazoles.
  • 3-amino-1,2,4-triazole and 3-amino-5-methyl-1,2,4-triazole a higher volatilization rate,
  • Corrosion protection effect such as the benzoyl and tolyltriazole.
  • the object of the invention is compared to those listed above Disadvantages of conventional corrosion inhibitors improved sublimation-capable, corrosion-inhibiting substances and Indicate substance combinations, in particular among the practical interesting climatic conditions within of technical packaging and analogue closed spaces with sufficient speed from a corresponding depot sublime and after adsorption and / or condensation the surface of metals in this room there to provide conditions under which the usual utility metals reliably protected against atmospheric corrosion.
  • the object of the invention is also to provide methods for Production or processing of such substances and substance combinations for the production of improved VCI packaging materials indicated.
  • component (5) a bicyclic terpene or aliphatic substituted naphthalene, which contributes to that consisting of representatives of components (1) to (4) Fabric combinations even at relatively low temperatures and in air with permanently high levels of relative humidity always results in a sufficiently high emission rate and thus the reliability of the VCI corrosion protection is further improved.
  • these substance combinations are directly in the form corresponding powdered mixtures used or according to methods known per se in the context of production incorporated by VCI packaging means, so that these packaging materials act as a VCI depot and the anti-corrosion properties the substance combinations according to the invention especially can be advantageous to unfold.
  • the invention also provides the use of said Substance combinations as vapor-phase corrosion inhibitors in Packaging or when stored indoors Protection of common use metals, such.
  • common use metals such as iron, chromium, Nickel, tin, zinc, aluminum, copper and their alloys against atmospheric corrosion.
  • the substance combinations according to the invention are mainly used to the wide range the usual utility metals and their alloys in Packaging and during storage in analog enclosed spaces from atmospheric corrosion protect.
  • the invention also relates to a corrosion-inhibiting Material containing a component that is an inorganic Salt of nitrous acid is and due to its oxidizing power on passivatable metals the spontaneous formation of a Passive oxide layer causes another component, the one polysubstituted phenol and, owing to its properties, insoluble in water, but with a passive oxide covered metal surfaces to be well adsorbed, to Stabilization of such metal surfaces contributes to corrosion, a component which is an aliphatic ester of a dihydroxybenzoic acid and surprisingly both Effect of nitrites as a passivator is supported as well adsorptive stabilization of passive oxide layers, a component containing a tocopherol (2,5,7,8-tetramethyl-2- (4 ', 8', 12'-trimethyltridecyl) Chroman-6-ol) and because of her Property of acting as an antioxidant, surprisingly the attack of atmospheric oxygen or of nitrite Component (1) inhibited in non-passivatable metals
  • inventively provided components are advantageously only substances that are after themselves easily and safely process known methods and in the proportions to be applied as non-toxic and Environment are not endangering. They are suitable for that especially for the production of anti-corrosive packaging materials, the on a large scale cost and without risk potential are applicable.
  • the substance combinations according to the invention are preferably formulated within the following proportions by weight: Component (1) 0.1 to 40% Component (2) 0.5 to 40% Component (3) 0.5 to 40% Component (4) 0.5 to 40% or when using all five components Component (1) 0.1 to 40% Component (2) 0.5 to 30% Component (3) 0.5 to 20% Component (4) 0.5 to 20% Component (5) 0.1 to 10%.
  • the mason jars with the metal samples, the deionized water and the invention Fabric combination were sealed, for which use a lid with a sealing ring and a clamp were. After 16 h waiting time at room temperature could the so-called build-up phase of the VCI components within the vessel considered complete.
  • the reference system is therefore only for VCI corrosion protection of Cu base materials gegak. From the described example comes in comparison to the VCI effect the combination of substances according to the invention over the usual Useful metals very beneficial effect.
  • An aqueous-alcoholic acidic sol which was obtained according to DE-OS 19708285 from 50 ml of tetraethoxysilane, 200 ml of ethanol and 100 ml of 0.01N hydrochloric acid by stirring for 20 hours at room temperature and then 4.2% solids content in 70% ethanol at pH ⁇ 4, was mixed with 50 ml of 5% solution of the combination of substances according to the invention and thus paper (kraft paper 70 g / m 2 ) coated by wet rolling. Immediately after drying the thus prepared VPI paper in air, it was tested for anti-corrosive effect as compared with a commercial anticorrosive paper serving as a reference system (R2).
  • R2 commercial anticorrosive paper serving as a reference system
  • the reference system (R2) contained, according to chemical analysis, the active ingredients dicyclohexylamine nitrite, cyclohexylamine cyprylate and benzotriazole, the total proportion being approximately comparable to that of the substance combination according to the invention.
  • Example 1 It came as in Example 1 again test specimens in ring form (Standard blanks) made of low alloy steel 100Cr6, cast iron GG125, AlMg1SiCu and Cu-SF for application and also the Test ritual was analogous to that described in Example 1.
  • VCI powder blends now the individual mason jars with the VCI paper were lined, each one circular blank with ⁇ 8 cm on the ground, a coat of 13 x 28 cm and another circular cut with ⁇ 9 cm for the lid. Then were the test specimen rack and the beaker with the deionized water placed, the mason jar closed and the climate load as described in Example 1, carried out.
  • the reference system is therefore only for VCI corrosion protection conditionally determined by Cu base materials, while the inventive Substance combination, as the example shows, opposite the usual utility metals even under the extreme Moist air conditions unfold reliable VCI properties.
  • 35% by mass of this mixture was at 65% by mass of a conventional LD-PE mixed and processed to a VCI masterbatch.
  • an extruder Rheocord 90 (HAAKE) with opposite Twin screw used. With the screw speed from 65 to 80 rpm was at cylinder temperatures around 150 ° C and a nozzle temperature extruded from 158 ° C and by cold cut granulated.
  • This granulated VCI masterbatch was made by Blasextrusion processed to VCI films, including the extruder was to equip with single screw and ring nozzle.
  • VCI film VCI (3) thus produced using a combination of substances according to the invention was processed into bags (cutting and welding of the superimposed side seams).
  • Sheet metals Carbon Steel C25, cold rolled, (90 x 50 x 1) mm 3 (Q-Panel, Q-Panel Lab Products, Cleveland, Ohio 44145 USA), and Zn-plated hot-dip galvanized steel ( ZnSt ) (EKO steel GmbH, D-15872 Eisendazzlingnstadt) were each positioned inside spacer frames in ⁇ -arrangement and welded into a prefabricated bag.
  • the reference system (R3) was a commercially available VCI film Use which according to chemical analysis dicyclohexylamine nitrite, Sodium molybdate and sodium benzoate contained, in total about the double amount compared to the VCI components of the invention Fabric combination, and a layer thickness of 110 had ⁇ m.
  • VCI LDPE film
  • test sheets with film wrapping could after each cycle through the transparent film material be inspected
  • VCI film VCI (4) prepared was partially cut to surface or processed into bags (cutting and welding the superimposed side seams) and these for the packaging used by electronic circuit boards. there these were 50.8 x 50.8 mm boards, in the stack of 5 pieces each with an intermediate layer VCI film were to be welded into a VCI bag. Every circuit board had a layer system consisting of galvanic Cu (25 microns) / chemically Ni (5 microns) / Sud Au (0, 3 microns), its bondability to ensure storage and transport processes was.
  • the reference VCI packaging material was a commercial one VCI film (R4) for use as VCI components cyclohexylamine caprylate and benzotriazole emitted and 100 microns Layer thickness possessed.
  • packaging of the printed circuit board stack made with LDPE film 100 ⁇ m.
  • Bondability was deemed to exist when the averages the tearing force was> 10 cN and the microscopic detected crack had occurred at the bond site.
  • the intermediate storage time from unpacking to Bonding test from 2 to at least 8 h to be extended by the 20 and 25 cycles were at least 45 more samples or 37% stable bonding. All samples in VCI film R4 had been subjected to more than 25 cycles however, are classified as no longer bondable.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Wrappers (AREA)
  • Gas Separation By Absorption (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
EP02013016A 2001-07-30 2002-06-12 Dampfphasen-Korrosionsinhibitoren und Verfahren zu deren Zubereitung Expired - Lifetime EP1281790B1 (de)

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DE10137130 2001-07-30
DE10137130A DE10137130C1 (de) 2001-07-30 2001-07-30 Dampfphasen-Korrosionsinhibitoren, Verfahren zu deren Zubereitung und Verwendung

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EP1281790A1 EP1281790A1 (de) 2003-02-05
EP1281790B1 true EP1281790B1 (de) 2004-08-18

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US (1) US6752934B2 (zh)
EP (1) EP1281790B1 (zh)
JP (1) JP4226288B2 (zh)
CN (1) CN1306066C (zh)
AT (1) ATE274074T1 (zh)
BR (1) BR0202966A (zh)
CZ (1) CZ299386B6 (zh)
DE (2) DE10137130C1 (zh)
DK (1) DK1281790T3 (zh)
ES (1) ES2227361T3 (zh)
PT (1) PT1281790E (zh)
RU (1) RU2287616C2 (zh)
TW (1) TW581825B (zh)
WO (1) WO2003012170A1 (zh)

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WO2007088155A1 (de) 2006-01-31 2007-08-09 Corpac Deutschland Gmbh & Co. Kg Haube oder deckel, insbesondere für behälter für korrosionsempfindliche ladung

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US7261839B2 (en) * 2002-01-22 2007-08-28 Northern Technologies International Corp. Tarnish inhibiting composition and article containing it
US8008373B2 (en) * 2002-01-22 2011-08-30 Northern Technologies International Corp. Biodegradable polymer masterbatch, and a composition derived therefrom having improved physical properties
US20030220436A1 (en) * 2002-01-22 2003-11-27 Gencer Mehmet A. Biodegradable polymers containing one or more inhibitors and methods for producing same
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US7361391B2 (en) * 2002-10-02 2008-04-22 Milprint, Inc. Metalized film laminates with anticorrosion agents
DE102006005666A1 (de) * 2006-01-31 2007-08-09 Corpac Deutschland Gmbh & Co.Kg Folie sowie hieraus hergestellte Haube
KR100825277B1 (ko) 2006-06-07 2008-04-28 (주)알티아이엔지니어링 기화성 방청제 및 그 제조 방법
NO20063247L (no) * 2006-07-12 2008-01-14 Norsk Hydro As Beskyttelse av prosessutstyr som har et vesentlig damptrykk ved a tilsette en fordampende komponent til gassen som er i kontakt med det nevnte utstyret
DE102008017654A1 (de) * 2007-04-12 2008-10-30 Robert Bosch Gmbh Bauteilanordnung
DE102007059726B4 (de) * 2007-12-12 2010-01-07 Excor Korrosionsforschung Gmbh Dampfphasen-Korrosionsinhibitoren, Verfahren zu deren Herstellung und deren Verwendung
DE102010006099A1 (de) * 2010-01-28 2011-08-18 EXCOR Korrosionsforschung GmbH, 01067 Zusammensetzungen von Dampfphasen-Korrosionsinhibitoren, Verfahren zu deren Herstellung und deren Verwendung für den temporären Korrosionsschutz
CN101798687A (zh) * 2010-04-21 2010-08-11 陕西电力科学研究院 直接空冷系统用环保型气相缓蚀剂
RU2468303C1 (ru) * 2011-06-01 2012-11-27 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Национальный исследовательский университет "МЭИ" Теплообменник системы вентиляции
RU2515871C2 (ru) * 2012-03-30 2014-05-20 Общество с ограниченной ответственностью "Научно-производственная фирма "ТРАВЕРС" (ООО "НПФ ТРАВЕРС") Ингибитор углекислотной коррозии для парогенерирующих установок низкого и среднего давления аминат пк-1
RU2516176C2 (ru) * 2012-03-30 2014-05-20 Общество с ограниченной ответственностью "Научно-производственная фирма "ТРАВЕРС" (ООО "НПФ ТРАВЕРС") Ингибитор углекислотной коррозии для паровых котлов среднего и высокого давления аминат пк-2
RU2500835C1 (ru) * 2012-03-30 2013-12-10 Общество с ограниченной ответственностью "Научно-производственная фирма "ТРАВЕРС" (ООО "НПФ ТРАВЕРС") Ингибитор углекислотной коррозии для паро-конденсатных установок аминат пк-3
CN104099649B (zh) * 2014-06-25 2016-08-24 武汉钢铁(集团)公司 用于电镀锡板的钝化剂
RU2588615C1 (ru) * 2015-05-19 2016-07-10 Общество с ограниченной ответственностью "Научно-производственное объединение ЕВРОХИМ" Ингибитор для защиты от коррозии реакционного оборудования
DE102015003654A1 (de) * 2015-06-11 2016-12-15 Zoran Jevtic Vorrichtung zum Schutz vorwiegend für Formen, Werkzeuge und Vorrichtungen
CN105140595B (zh) * 2015-09-06 2018-01-09 河南科技大学 一种电解液缓蚀剂、铝空气电池用电解液及铝空气电池
CN105926358A (zh) * 2016-05-06 2016-09-07 安徽马钢和菱实业有限公司 一种新型防锈纸用气相缓蚀剂
RU2669137C1 (ru) * 2017-08-17 2018-10-08 Федеральное государственное бюджетное образовательное учреждение высшего образования " Юго-Западный государственный университет" (ЮЗГУ) Ингибитор коррозии нефтяных труб и способ его получения
DE102017122483B3 (de) 2017-09-27 2018-10-25 Excor Korrosionsforschung Gmbh Zusammensetzungen von Dampfphasen-Korrosionsinhibitoren und deren Verwendung sowie Verfahren zu deren Herstellung
DE102019100123B4 (de) 2019-01-04 2021-02-04 Excor Korrosionsforschung Gmbh Zusammensetzungen und Verfahren zur Vorbehandlung von Substraten für die nachfolgende Fixierung von Dampfphasen-Korrosionsinhibitoren
DE102019112436A1 (de) 2019-05-13 2020-11-19 Excor Korrosionsforschung Gmbh Zusammensetzungen und Verfahren zur Freisetzung von Dampfphasen-Korrosionsinhibitoren
CN114364740B (zh) * 2019-07-03 2024-04-30 北方技术国际公司 可生物降解的vci包装组合物
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CN114574866A (zh) * 2020-11-30 2022-06-03 中国石油天然气股份有限公司 金属缓蚀剂化合物及其制备方法、缓蚀剂组合物及其应用
CN114806694A (zh) * 2022-05-28 2022-07-29 王雪峰 一种防锈耐腐蚀切削液及其加工工艺

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RU2287616C2 (ru) 2006-11-20
RU2004102800A (ru) 2005-06-10
CN1537179A (zh) 2004-10-13
ES2227361T3 (es) 2005-04-01
JP2003113483A (ja) 2003-04-18
JP4226288B2 (ja) 2009-02-18
CZ299386B6 (cs) 2008-07-09
EP1281790A1 (de) 2003-02-05
CN1306066C (zh) 2007-03-21
TW581825B (en) 2004-04-01
WO2003012170A1 (de) 2003-02-13
US20030031583A1 (en) 2003-02-13
CZ20022615A3 (cs) 2003-03-12
US6752934B2 (en) 2004-06-22
PT1281790E (pt) 2004-12-31
ATE274074T1 (de) 2004-09-15
DK1281790T3 (da) 2004-12-06
DE50200845D1 (de) 2004-09-23
BR0202966A (pt) 2003-06-03
DE10137130C1 (de) 2003-03-13

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