EP2357266B1 - Zusammensetzungen von Dampfphasen-Korrosionsinhibitoren, Verfahren zu deren Herstellung und deren Verwendung für den temporären Korrosionsschutz - Google Patents

Zusammensetzungen von Dampfphasen-Korrosionsinhibitoren, Verfahren zu deren Herstellung und deren Verwendung für den temporären Korrosionsschutz Download PDF

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Publication number
EP2357266B1
EP2357266B1 EP11000332A EP11000332A EP2357266B1 EP 2357266 B1 EP2357266 B1 EP 2357266B1 EP 11000332 A EP11000332 A EP 11000332A EP 11000332 A EP11000332 A EP 11000332A EP 2357266 B1 EP2357266 B1 EP 2357266B1
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Prior art keywords
corrosion
vci
inhibiting substance
substance combination
oil
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Not-in-force
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EP11000332A
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German (de)
English (en)
French (fr)
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EP2357266A1 (de
Inventor
Georg Reinhard
Peter Neitzel
Gerhard Hahn
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Excor Korrosionsforschung GmbH
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Excor Korrosionsforschung GmbH
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Publication of EP2357266A1 publication Critical patent/EP2357266A1/de
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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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/10—Amides of carbonic or haloformic acids
    • C10M2215/102—Ureas; Semicarbazides; Allophanates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives

Definitions

  • the present invention relates to combinations of substances as vapor-phase corrosion inhibitors (vapor phase inhibitors VPCI, volatile corrosion inhibitors, VCI) for the protection of conventional utility metals, such as iron, chromium, nickel, tin, zinc, aluminum, copper, magnesium and their alloys against corrosion in humid climates.
  • vapor phase inhibitors VPCI volatile corrosion inhibitors
  • VCI volatile corrosion inhibitors
  • These corrosion inhibitors are usually selected according to the type of metal to be protected and are used as powders, packaged in bags of a material which is permeable to the vaporous VCIs (cf., for example: E. Vuorinen, E. Kalman, W. Focke, Introduction to vapor phase corrosion inhibitors in metal packaging, Surface Eng. 29 (2004) 281 pp. ; US 6,752,934 B2 ).
  • VCI contains modern packaging materials for corrosion protection either as powders or tablets within gas-permeable containers (eg paper bags, plastic capsules), coatings on paper, cardboard, foams or textile fleece or directly incorporated within polymeric carrier materials.
  • gas-permeable containers eg paper bags, plastic capsules
  • coatings on paper, cardboard, foams or textile fleece or directly incorporated within polymeric carrier materials.
  • VCI-containing packaging materials by dissolving the VCI components in a suitable solvent and applying them to a suitable carrier material is particularly obvious and has long been practiced. Methods of this kind with various active ingredients and solvents are, for example, in JP 61,227,188 . JP 62,063,686 . JP 63,028,888 . JP 63,183,182 . JP 63,210,285 . US 3,887,481 and US 5,958,115 described.
  • VCI oils are for example in the patents GB 919,778 . GB 1,224,500 . US 3,398,095 . US 3,785,975 and JP 07145490 A described.
  • these VCI oils are significantly different from preservative oils, whose anticorrosive properties have been enhanced by incorporation of nonvolatile and therefore only direct contact corrosion inhibitors.
  • Such corrosion protection oils are, for example, in the patents US 5,681,506 and US Pat. No. 7,014,694 B1 described.
  • a group of substances used for this purpose are oxidizing agents that can act as passivators. With such passivators it can be achieved that the POL is emulated spontaneously as an oxide covering layer on metal surfaces when it has been destroyed by partial chemical dissolution or local mechanical abrasion (abrasion, erosion) (cf., for example: E. Vuorinen, et al. loc cit and US 6,752,934 B2 ).
  • the nitrites have proven to be versatile as salts of nitrous acid in practical corrosion protection. Therefore, they have long been used as VCI.
  • the relatively volatile dicyclohexylammonium nitrite has been used as VCI for more than 60 years (see, for example, Vuorinen et al., Loc.cit.) And is mentioned as constituent of VCI compositions in numerous patents (for example: US 2,419,327 . US 2,432,840 . US 2,534,201 . US 4,290,912 . JP 62109987 . JP 63210285 A and US. 6,752,934 B2 ).
  • the subject carboxylates are known to form pH buffer systems of higher buffer capacity in aqueous media or condensation films on metal surfaces with or without the simultaneous presence of an amine, depending on the particular carboxylic acid / salt system present, and thus usually hinder the reducibility of oxidants.
  • the passivation effect can then be achieved only if the concentration of the relevant oxidant is comparatively much higher than the proportions of the other active ingredients.
  • VCI combinations in mineral oils or synthetic oils, oxidizing agents, such as nitrites, are in any case unsuitable because they would cause a relatively rapid oxidative decomposition of the relevant base oil.
  • VCI salts of conventional aliphatic and aromatic carboxylic acids are not sufficiently soluble in oils. Therefore, the known formulations of VCI oils have hitherto been limited mainly to the use of amines as VCI components (cf., for example: GB 919,778 . GB 1,224,500 . US 3,398,095 . US 3,785,975 and JP 07145490 A ).
  • VCI oils from which only amines are emitted in the temperature range of interest up to 80 ° C, are exclusively suitable for the VCI corrosion protection of iron-based materials.
  • zinc and aluminum they are known to cause, together with condensed water, usually too high an alkalisation of the surfaces, as a result of which strong Corrosion begins to form zincates or aluminates, before finally the hydroxides and basic carbonates arise, for which the term white rust is common.
  • copper materials frequently undergo corrosion under the action of amines to form Cu-amine complexes.
  • VCI-treated oils for coping with the temporary corrosion protection of ferrous and non-ferrous metals with design-related small cavities
  • amine- and oxidant-free VCI systems are required.
  • preparations of interest which process not only to one VCI oil, but also to VCI donors (mixtures of VCI components in bags, capsules) and to coated VCI packaging materials (eg papers, boards, foams) are of particular interest to let.
  • VCI products which each contain similar active ingredients and thus are fully compatible with each other, particularly effective VCI corrosion protection packaging, which has been identified as having a long service life, could be produced, eg. B.
  • VCI- ⁇ 1 engine blocks in lidded trays, in which additionally VCI-emitting bags, capsules or VCI-coated paper or foam blanks are introduced, even for long-term storage always for saturation of the gas space of the relevant Tray's with the VCI components as a prerequisite for the maintenance of VCI corrosion protection.
  • the object of the invention is to provide, in contrast to the above-mentioned disadvantages of conventional volatile, acting on the vapor phase corrosion inhibitors improved evaporation or sublimation corrosion inhibiting substances and combinations of substances, both as a powder mixture and incorporated in coatings and in particular in oils under the practically interesting climatic conditions within technical packaging and analogous closed spaces with sufficient speed from the corresponding depot, eg a bag containing the VCI components, a coating containing the VCI components on a support such as paper, cardboard or foam or an oil containing the VCI components evaporate or sublimate and after adsorption and / or condensation on the surface of located in this space metals there provide conditions under which the usual utility metals are reliably protected from atmospheric corrosion.
  • the object of the invention is also to specify methods for producing or processing such substances and substance combinations for the production of improved VCI packaging materials.
  • the corrosion-inhibiting substance combination according to the invention preferably contains a further component (4), namely a benzotriazole, preferably a benzotriazole substituted on the benzene ring.
  • This component is particularly advantageous for the protection of copper and copper alloys, but also offers advantages in the protection of other utility metals.
  • components (1) to (4) are in the corrosion-inhibiting combination of substances 0.1 to 5 wt .-% component (1), 0.2 to 12 wt .-% component (2), 1 to 15% by weight of component (3) and 0.4 to 10% by weight of component (4).
  • polysubstituted pyrimidine examples include 2,4-dihydroxy-5-methylpyrimidine (thymine), 2-amino-4-methyl-pyrimidine, 2-amino-4-methoxy-6-methyl-pyrimidine, 2- Amino-4,6-dimethyl-pyrimidine (cytosine) or a mixture thereof.
  • suitable pyrimidines can easily be determined by routine experimentation by a person skilled in the art.
  • the term "polysubstituted" as used herein includes two or more substitutions.
  • the monoalkylurea are N-butylurea, N-hexylurea, N-benzylurea, N-cyclohexylurea or a mixture thereof.
  • the term "monoalkyl urea” as used herein also includes cycloalkyl and aralkyl monosubstituted ureas. In contrast to the monoalkylurea used according to the invention, however, the use of an unsubstituted or di-substituted urea leads to significantly poorer results and no satisfactory VCI corrosion protection.
  • C 3 to C 5 aminoalkyl diol are 2-amino-2-methyl-1,3-propanediol, 2-amino-3-methyl-1,4-butanediol, 2-amino-2 -methylbutanediol-1,4, or a mixture thereof.
  • Further suitable aminoalkyldiols can easily be determined by routine experiments by a person skilled in the art.
  • benzotriazole are unsubstituted benzotriazole, a benzene ring-alkylated, especially methylated, benzotriazole, preferably 5-methylbenzotriazole, or a mixture of methylbenzotriazoles (referred to herein as tosyltriazole).
  • components (1) to (3) or (1) to (4) may be mixed together or dispersed in water or pre-mixed in a solubilizer which is miscible with mineral oils and synthetic oils in any ratio.
  • This solubilizer is preferably a phenylalkyl alcohol and / or an alkylphenol, in which the components are present in dissolved or dispersed form.
  • phenylalkyl alcohol examples include a benzyl alcohol, 2-phenylethanol, Methylphenylcarbinol, 3-phenylpropanol or a mixture thereof.
  • alkylphenol examples include di-tert-butyl-4-methyl-phenol, 2,6-di-tert-butyl-4-ethyl-phenol, 2,6-di-tert. Butyl-4-methoxy-phenol, 2,6-di-octadecyl-4-methyl-phenol, 2,4,6-tri-tert-butyl-phenol or a mixture thereof.
  • the corrosion-inhibiting substance combinations according to the invention may additionally contain substances already introduced as vapor-phase corrosion inhibitors, individually or as a mixture thereof.
  • a combination of substances according to the invention can be prepared, for example, by mixing components (1) to (3) or (1) to (4) together in the desired proportions (plus any additional components).
  • the corrosion-inhibiting components (1) to (3) or (1) to (4) are first mixed together and then in water or one with mineral oils and synthetic oils in any ratio miscible solubilizers dissolved or dispersed.
  • composition of the corrosion-inhibiting substance combinations according to the invention is preferably adjusted so that in the temperature range up to 70 ° C at rel.
  • these combinations of substances are used directly in the form of appropriate mixtures or incorporated according to methods known per se in the production of VCI packaging materials and oil preparations, so that these packaging materials or oils act as VCI depot and the anti-corrosion properties of the inventive substance combinations particularly advantageous Unfolding can come.
  • the corrosion inhibiting substance combinations are used as a volatile corrosion inhibitor (VPCI, VCI) in the form of finely powdered mixtures in the packaging, storage or transport of metallic materials.
  • VPCI volatile corrosion inhibitor
  • the corrosion-inhibiting substance combinations can also be incorporated into coating materials or coating solutions, preferably in an aqueous / organic medium, and / or colloidal composite materials, in order to support materials such as paper, cardboard, foams, textile fabrics, textile non-wovens and similar fabrics within the scope of production of VCI-emitting packaging coating and then apply it during packaging, storage and transport operations.
  • the corrosion inhibiting fabric combinations are used to make VCI anticorrosion oil from which vapor phase corrosion inhibitors (VPCI, VCI) are emitted.
  • such a VCI corrosion protection oil comprises a mineral oil or synthetic oil and 2 to 10 wt .-%, based on the oil phase, of a corrosion inhibiting combination of substances according to the invention in a solubilizer, and the composition is adjusted so that from the VCI oil in the temperature range to 70 ° C at rel. Humidity (RH) ⁇ 98% evaporate or sublime all corrosion inhibitor components with sufficient quantity and speed for the vapor space corrosion protection.
  • the corrosion-inhibiting substance combinations according to the invention or VCI corrosion protection oils containing them can advantageously be used for the corrosion protection of conventional use metals such as iron, chromium, nickel, tin, zinc, aluminum, magnesium and copper and their alloys.
  • the invented fabric combinations and VCI oils containing them are primarily used to treat the wide range of common working metals, including iron, chromium, nickel, tin, zinc, aluminum, magnesium and copper and their alloys, in packaging, during transportation and during use the storage in analogous closed rooms to protect against atmospheric corrosion.
  • the metal parts to be protected with the respective combination of substances or the oil advantageously need not be directly coated.
  • the substance combinations according to the invention are nitrite- and cycloalkylamine-free and advantageously consist exclusively of substances which can be processed easily and safely by methods known per se and are classified as nontoxic and harmless to the environment in the proportions to be used. They are therefore particularly suitable for the production of anti-corrosive packaging materials, which are applicable on a large scale cost and without risk potential.
  • the type, proportion of the individual components in the mixture according to the invention and the proportion of the mixture in the respective VCI depot only depend on the production conditions of the VCI-emitting product concerned and not on the type of metal to be protected against corrosion.
  • the mason jars with the metal samples, the deionized water and the combination of substances according to the invention were sealed, for which purpose a lid with a sealing ring and a clamping bracket were used. After 16 h of waiting at room temperature, the so-called build-up phase of the VCI components within the vessel could be considered as complete.
  • VCI (1) In reference to the substance mixture VCI (1) according to the invention, 5 g portions of a commercial VCI powder were tested in the same way.
  • This reference VCI powder (R1) consisted of: 54.0% by mass Monoethanolaminbenzoat 23.0% by mass 1H-Benzotriazole 23.0% by mass Filler (silica gel)
  • test specimens which had been used together with the substance mixture VCI (1) according to the invention had at all 4 parallel batches after 40 cycles an unchanged appearance.
  • the GGG25 test specimens showed first point-shaped rust spots after 8 to 10 cycles, which increased rapidly as the tests continued. On the steel rings edge rust could be observed after 11 to 12 cycles.
  • test specimens made of galvanized steel showed clear signs of white rust after 42 cycles both in the edge areas and on the surfaces.
  • the FTIR microscopy PerkinElmer FTIR measuring station Spectrum One FTIR with auto-image microscope system in combination with a diamond cell) was used as basic Zinc carbonate (2 ZnCO 3 x 3 Zn (OH) 2 ) could be identified.
  • the reference system R1 is therefore suitable only for VCI corrosion protection of Cu base materials.
  • the VCI effect of the substance combination VCI (1) according to the invention compared to the usual use metals is shown to advantage in a very advantageous manner from the example described.
  • VCI paper VCI (2) With this preparation, paper webs (kraft paper 70 g / m 2 ) were coated, whereby a wet application of 15 g / m 2 was realized.
  • VCI paper VCI (2) according to the invention thus prepared in air, it was tested for its anti-corrosive effect in comparison to a commercial corrosion protection paper serving as reference system (R2).
  • the reference system (R2) contained by chemical analysis, the active ingredients ethanolamine benzoate, sodium benzoate / benzoic acid, benzotriazole and urea, the total content was about twice as high as the combination of substances of the invention.
  • Test specimens of low-alloyed steel 100Cr6, cast iron GGG25, fine-grained galvanized steel with zinc coating 17 ⁇ m and E-Cu were again used as in Example 1, and the test ritual was analogous to that described in Example 1.
  • the only difference was that instead of the VCI powder mixtures, the individual mason jars were now lined with the VCI paper, each with a circular cut of ⁇ 8 cm at the bottom, a coat of 13 x 28 cm and a circular cut with ⁇ again 9 cm for the lid. Then the test specimen rack and the beaker were placed with the demineralized water, the mason jar closed and the climate load as described in Example 1, performed.
  • test specimens from GGG25 showed first point-shaped rust spots after 10 cycles during the inspection, which rapidly increased as the tests continued. On the steel rings edge rust could be observed after 15 cycles.
  • test specimens made of galvanized steel had after 15 cycles at the edges first approaches of white rust, which increased significantly under further load, so that the test specimens were completely covered after 42 cycles.
  • the test specimens made of Cu-SF were coated after 42 cycles with a light dark gray colored, non-wipeable tarnish film.
  • the reference system R2 is conditionally suitable only for the VCI corrosion protection of Cu base materials, while the VCI paper VCI (2) produced on the basis of the combination of substances according to the invention, as the example shows, is reliable with respect to the usual use metals even under the extreme humid air conditions under long-term stress VCI properties unfolded.
  • test specimens made from low-alloy steel 100Cr6, cast iron GGG25, fine-grain galvanized steel with zinc coating 17 ⁇ m and E-Cu were again used analogously to Example 1, and the test ritual was analogous to that described in Example 1.
  • test specimens made of PMMA were now each equipped with 3 pieces of one and the same test specimen while the test sheet positioned in the middle was covered on both sides with the VCI oil according to the invention, while the specimens were arranged laterally at a distance of about 1 cm Test specimens were used without oil. It was thus possible to determine the extent to which the oil film applied to the centrally positioned test specimen is capable of preventing both the directly contacted metal substrate and the emission of the VCI components via the vapor phase within the closed mason jar the two specimens not coated with an oil film from corrosion to protect.
  • VCI oil R3 which was also formulated on the basis of a mineral oil, contained the active substances after chemical analysis: 11.5 g / kg dicyclohexylamine 15.0 g / kg Diethylamino-ethanol 35.5 g / kg 3.5 trimethylhexanoic acid.
  • test specimen was coated with this reference VCI oil R3 and placed in a mason jar with 2 similar, but non-oiled specimens within a test specimen rack.
  • VCI oil VCI (3) consequently ensured good corrosion protection for the respective metal substrates in direct contact as well as for the specimens not exposed to the oil due to the VCI components emitted via the vapor phase.
  • test specimens made from the low-alloy steel 100C also showed in both the oiled and the non-oiled state 40 cycles no signs of corrosion.
  • the test specimens made from GGG25 on the other hand, remained free of rust only in the oiled state during the 40 cycles, whereas the non-oiled surfaces of the test specimens, especially on the side facing away from the oiled, centrally positioned test specimen, increasingly showed rusting effects.
  • the punctiform rust spots observed here after 10 cycles increased significantly in number and extent in continuation of the tests.
  • test specimens of E-Cu oiled with the reference oil R3 were free of visually detectable changes after 40 cycles, while the non-oiled specimens were coated relatively evenly with a dark gray colored, non-wipeable run-on film.
  • the reference system R3 is only suitable for VCI corrosion protection of steel, while the VCI oil VCI (3) according to the invention, as shown in the example, exhibits reliable VCI properties in the long-term test, even in the extreme humid air conditions, compared with all conventional utility metals.
  • Example 3 The effectiveness was tested analogously to Example 3 again with test specimens made of low-alloy steel 100Cr6, cast iron GGG25, feinkornverzinktem steel with zinc coating 17 microns and E-Cu according to the same test ritual as described in Example 3.
  • VCI oil VCI (4) a commercially available VCI oil of about the same mean viscosity was again tested in an analogous manner. This was also formulated on the basis of a mineral oil, but contained after chemical analysis but the active ingredients: 96.0 g / kg morpholine 15.0 g / kg Diethylamino-ethanol 65.0 g / kg oleic acid 23.0 g / kg benzotriazole
  • VCI- ⁇ 1 VCI (4) according to the invention ensured, as did the VCI- ⁇ 1 VCI (3) according to the invention, of good quality for the respective metal substrates in direct contact as well as for the specimens not exposed to the oil due to the VCI components emitted via the vapor phase corrosion protection.
  • test specimens made of the low-alloyed steel 100C and the gray cast iron GGG25 likewise showed no signs of corrosion after 40 cycles either in the oiled or un-oiled state.
  • E-Cu Oils Lubricated with Reference Oil R4 were free of visually detectable changes after 40 cycles, while E-Cu non-oiled specimens were again relatively evenly coated with a dark colored, non-wipeable tarnish.
  • test specimens made of fine-grain galvanized steel with a zinc coating of 17 ⁇ m significantly changed their appearance during wet-air application.
  • Both the oiled and the non-ooze sheets had flat appearances of white rust after only 10 cycles, which after 40 cycles was a relatively uniform white layer.
  • the reference system R4 is therefore suitable only for VCI corrosion protection of iron-based materials, while the VCI- ⁇ 1 VCI (4) according to the invention, as the example shows, ensures a pronounced multi-metal protection in that it is compared to all common utility metals even under the extreme humid conditions in the long-term experiment reliable VCI Properties unfolded.
  • This coating solution was used to coat a 3 mm thick non-woven material of cotton fibers (so-called suction cardboard), whereby a wet application of 50 g / m 2 was achieved.
  • the reference system (R5) used was a commercially available VCI chip material which consisted of 3 mm thick cotton cellulose and, according to chemical analysis, the active ingredients: 10.7 g / kg sodium nitrite 16.5 g / kg Ethanolamine (2-aminoethanol) 66.1 g / kg Caprylic acid (n-octanoic acid) 32.6 g / kg urea contained in total about a more than six times higher amount of active ingredient compared to the VCI components in the substance combination VCI according to the invention (5).
  • VCI chip Metarials (R5) similar packaging as with the inventive VCI cotton fleece VCI (5) were prepared by again the named metal combinations arranged in spacer frames and on both sides with a likewise (30 x 30 x 3) mm 3 large cut of the chip material (R5) provided in bags made of PE-LD film, 100 microns, were welded.
  • similar packagings were prepared in which no VCI emitting nonwoven material was positioned in order to detect separately the proportion of the anti-corrosive effect attributable to the barrier effect of the PE-LD film at 100 ⁇ m.
  • the surfaces of the foil-wrapped test panels were inspected through the transparent sheet material after each cycle (within the stable 25 ° C phase). As soon as visible corrosion phenomena could be detected on individual test panels, the number of cycles that had elapsed until then was registered, and thereafter the climate load was continued, until all test panels of a model package were affected, or the extent of corrosion of individual test panels could no longer be assessed by visual inspection through the foil walls. After the end of the tests, the packaging material was removed and the surface condition of each test panel was finally evaluated.
  • Table 1 Results of the wet-air temperature cycling of model packaging (averages of number of cycles from 3 parallel samples each) packagings Number of cycles according to DIN EN 60068-2-30 Surface condition of the test panels R5 ' 6 DC03, first rust spots in edge areas; 9 ZnSt, spots white rust in the edge area; 12 Al 7075, small white dots on surfaces; 18 Termination of the climate load, as corrosion on all sheets clearer VCI (5) finished after 40 All test panels are still free from visible changes R5 12 ZnSt, first white rust on edges; 18 Al 7075, small white dots 26 DC03, selective rust, to ZnSt White rust distributed over the surfaces: Cancellation of the climate load, as further advances in corrosion on test panels can no longer be assessed with certainty

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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)
  • Paints Or Removers (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Lubricants (AREA)
EP11000332A 2010-01-28 2011-01-17 Zusammensetzungen von Dampfphasen-Korrosionsinhibitoren, Verfahren zu deren Herstellung und deren Verwendung für den temporären Korrosionsschutz Not-in-force EP2357266B1 (de)

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DE102010006099A DE102010006099A1 (de) 2010-01-28 2010-01-28 Zusammensetzungen von Dampfphasen-Korrosionsinhibitoren, Verfahren zu deren Herstellung und deren Verwendung für den temporären Korrosionsschutz

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EP2357266A1 EP2357266A1 (de) 2011-08-17
EP2357266B1 true EP2357266B1 (de) 2012-05-09

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US (1) US8906267B2 (ja)
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JP (1) JP5745872B2 (ja)
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JP7154498B2 (ja) * 2018-10-09 2022-10-18 地方独立行政法人大阪産業技術研究所 鉄系部材の製造方法
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ATE557112T1 (de) 2012-05-15
MX2011000792A (es) 2011-07-27
US20110198540A1 (en) 2011-08-18
CN102168271B (zh) 2015-09-09
DE102010006099A1 (de) 2011-08-18
US8906267B2 (en) 2014-12-09
CN102168271A (zh) 2011-08-31

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