EP3461931A1 - Compositions des inhibiteurs de corrosion à phase vapeur et leur utilisation ainsi que leur procédé de production - Google Patents

Compositions des inhibiteurs de corrosion à phase vapeur et leur utilisation ainsi que leur procédé de production Download PDF

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Publication number
EP3461931A1
EP3461931A1 EP18156539.1A EP18156539A EP3461931A1 EP 3461931 A1 EP3461931 A1 EP 3461931A1 EP 18156539 A EP18156539 A EP 18156539A EP 3461931 A1 EP3461931 A1 EP 3461931A1
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Prior art keywords
corrosion
vci
mass
component
substituted
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German (de)
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EP3461931B1 (fr
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Prof. Dr. Georg REINHARD
Dr. Peter NEITZEL
Dr. Frank FAßBENDER
Gerhard Hahn
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Excor Korrosionsforschung GmbH
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Excor Korrosionsforschung GmbH
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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
    • 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
    • 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
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/12—Oxygen-containing compounds
    • C23F11/122—Alcohols; Aldehydes; Ketones
    • 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
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/145—Amides; N-substituted amides
    • 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
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom

Definitions

  • the present invention relates to combinations of substances as vapor-phase corrosion inhibitors (vapor phase inhibitors VpCl, volatile corrosion inhibitors, VCI) and methods of their application for the protection of conventional utility metals, such as iron, chromium, nickel, aluminum, copper and their Alloys and galvanized steels against corrosion in humid air climates.
  • vapor phase inhibitors VpCl volatile corrosion inhibitors
  • VCI volatile corrosion inhibitors
  • vapor phase corrosion inhibitors are basically of the type of metal to be protected select (see eg: US 4,374,174 . US 6,464,899 . US 6,752,934 B2 . US 7,824,482 B2 and US 8,906,267 B2 ).
  • VpCI / VCI volatile corrosion inhibitors
  • conditioning or incubation time during which the conditions for the VCl corrosion protection set after the container / the packaging has been sealed, may be more susceptible to corrosion
  • metal surfaces should not be too large, since otherwise the corrosion process is already started before the VCI molecules have come close to the metal surface.
  • VpCl / VCI components Depending on the nature of the metals to be protected and the surface states present, it is therefore not only necessary to use a suitable combination of VpCl / VCI components, but also to apply them in such a way that the so-called build-up phase necessary for the development of their effect is adapted to the respective requirements.
  • VpCl / VCI in the form of finely dispersed powders, packaged in bags of a material which is permeable to the vaporous active substances (eg paper bag, porous polymer film, perforated capsule), have therefore long been commercially available. To expose them within a closed package next to the metal parts to be protected is the simplest form of practical application of VpCI / VCI (see eg: E. Vuorinen, E. Kalman, W.
  • VpCI / VCI are usually already integrated so that their technical application can be simple and automated. Papers, cardboards, foams or textile nonwoven material with a VCl-containing coating are just as familiar as polymeric carrier materials into which the relevant VCI active ingredients have been incorporated in such a way that their emission from them remains possible. So z. B. in the patents US 3,836,077 . US 3,967,926 . US 4,124,549 . US 4,290,912 . US 5,209,869 . US 5,332,525 . US 5,393,457 . US 6,752,934 B2 . US 7,824,482 . US 8,906,267 B2 . JP 4,124,549 .
  • VpCl / VCI With the incorporation of VpCl / VCI into a coating composition, experience has shown that it is relatively easy today to produce coatings on sheet-like packaging materials (papers, cardboards, foams, textile nonwoven material, etc.) from which the respective VpCl / VCI are released at emission rates suitable for the VCI corrosion protection guarantee comparatively short construction phases.
  • VpCl / VCI in polymeric carrier materials, preferably in polyolefins (PO), such as polyethylene (PE) and polypropylene (PP), and the provision of VpCl / VCI emitting films and other PO products (granules, trays, etc.), as they are z. B.
  • PO polyolefins
  • PP polypropylene
  • VpCl / VCI emitting films and other PO products granules, trays, etc.
  • EP 1 218 567 A1 and EP 1641960 B1 is proposed in US 4,124,549 . US 4,290,912 , US 5,139,700, US Pat. No. 6,464,899 B1 . US 6,752,934 B2 . US 6,787,065 B1 . US 7,824,482 .
  • EP 1 218 567 A1 and EP 1641960 B1 Experience has shown that is practiced to a particularly high degree, if only because these products can be applied advantageously for the automation
  • VpCl / VCI products generally have the disadvantage that the VpCl / VCI incorporated in the course of the extrusion via the polymer melt are relatively firmly enclosed within the polymer matrix in powder form or in coatings, in contrast to the VpCl / VCI depots described above and their emission is only comparatively difficult.
  • VpCI / VCI films which are usually used today with layer thicknesses d in the range of 60 .mu.m.ltoreq.d.ltoreq.150 .mu.m, it is also possible to accommodate by far not so high specific active ingredient concentrations as, for example, in VpCl / VCI coatings.
  • Another approximately similar way consists in the entry of single or multiple VpCI / VCI components in a suitable adhesive in order to subsequently coat the inside of polymer films according to the requirements (cf., for example: EP 2 347 897 A1 . EP 2 730 696 A1 . EP 2 752 290 A1 and US 2015/0018461 A1 ). Indeed, if an adhesive is selected that is compatible with the incorporated VpCl / VCI components and cures as a porous layer, one actually achieves higher emission rates of these components than from films in which the VpCl / VCI components were integrated during extrusion.
  • VpCI / VCI system as finely dispersed powder directly in the film used as packaging material (cf., for example: US 8,603,603 ), as highly filled compacts (so-called premix, cf. US 6,787,065 B1 ) to place in addition to the metal parts to be protected, or to introduce it in the form of small granules in a flat, porous foam, on the other side of a thin polyolefin film was laminated (see, eg: US 5,393,457 and US 9,435,037 B2 ), further possibilities within a foil outer packaging to present a low-resistance, subliming VpCl / VCI system with a relatively high proportion.
  • VpCl / VCI-containing oils As is well known, these include the VpCl / VCI-containing oils, and there is still a growing demand for those products which are suitable for the VCI corrosion protection of components composed of different metals and processing states.
  • VpCl / VCI-containing oil is known to not only the relevant metal substrate on which it was applied as a thin film, but also surface areas of the same component or adjacent metal objects, the Because of their geometry (eg holes, narrow notches folded sheet metal layers) could not be coated with an oil film, protect against corrosion.
  • VpCl / VCI components now emitted from the oil as the carrier material should not be allowed to flow through the vapor phase within closed spaces (eg packaging, containers, cavities) reach the oil-covered surface areas of metal parts and form there a corrosion-protective adsorption film.
  • VpCl / VCI oils are for example in the patents US 919,778 . US 3,398,095 . US 3,785,975 . US 8,906,267 . US 1,224,500 and JP 07145490 A described.
  • these VpCl / VCI oils are significantly different from preservative oils whose anticorrosive properties are enhanced by incorporation of non-volatile and therefore only direct-contact corrosion inhibitors were.
  • Such corrosion protection oils are, for example, in the patents US 5,681,506 . US Pat. No. 7,014,694 B1 and WO 2016/022406 A1 described.
  • VpCI / VCI oils were only profiled for the VCI corrosion protection of ferrous materials. They usually contain higher proportions of one or more amines, so that their migration within the oil phase and its emission therefrom into the atmosphere of a closed package can result in a relatively high concentration gradient. Correspondingly short is then also necessary for the development of their VCI-effect build-up phase.
  • the amine which has reached the metal surface to be protected via the gas phase, in the water condensed there from humid air, ensures an alkaline surface pH value at which the POL of conventional iron materials is resistant (cf., for example, E. Kunze (ed. loc cit).
  • Amines which already have a vapor or sublimation pressure under normal conditions to be used as VCI / VpCl have been practiced for many years and are described in numerous patents (see, for example: E. Vuorinen, et.al, loc.cit US 8,906,267 B2 ).
  • the preferred secondary amines previously preferred for use such as diethanolamine, morpholine, piperidine, u.a.m. hardly technically applied, after it became known that these are nitrosiert already in air under normal conditions easily to carcinogenic N-Nitrosaminen.
  • cyclic amines and amino alcohols are liquid under normal conditions, they must first be converted into the solid state by salt formation for the abovementioned applications (for example for powder-containing emitters or incorporation into polymeric support materials).
  • the relevant amine carbonates, nitrites, nitrates, molybdate and carboxylates, the latter predominantly the amine benzoates and caprylates, are today among the most commonly used for the corrosion protection of iron materials VCI / VpCl (see, for example: EP 0 990 676 B1 . US 4,124,549 . US 5,137,700 . US 393,457 . US Pat. No. 6,464,899 A1 . US 8,603,603 B2 . US 9,435,037 . US 9,518,328 B2 and JP 2016-117920 A ).
  • both the amine component and the associated carboxylic acid are volatile and thereby both pass through the vapor phase to the metal surface to be protected.
  • the resulting there in the presence of water vapor surface pH is then usually in the neutral range, whereby the corrosion protection effect against non-ferrous metals is usually favorably influenced.
  • amines alone lead to higher, alkaline alkaline surface pH values, which lead to corrosion phenomena, especially with aluminum base materials and galvanized steels.
  • VCI / VpCl preparations with amine carboxylates are, at best, suitable for the relatively short-term corrosion protection of iron materials, but are not suitable for the protection of mixed metal components.
  • nitrites acting as passivators With these salts of nitrous acid it can be achieved that the POL of iron materials is spontaneously reproduced if 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 ). Therefore, you can find application for quite some time as VCI / VpCI.
  • the relatively volatile salt dicyclohexylammonium nitrite (DICHAN) has been used for more than 70 years as a VCI for the protection of iron materials (see, for example, Vuorinen et al, loc. Cit.).
  • VpCI / VCI packaging materials that are applicable not only to the protection of ferrous materials, but also at least to galvanized steels and aluminum materials
  • various amine-free VpCl / VCI systems have been proposed in which a salt of nitrous acid ( Ammonium or Alkalinalitrit) is combined with other substances capable of sublimation, such as various saturated or unsaturated carboxylic acids or their alkali metal salts, a multiply substituted phenol and / or an aliphatic ester of a hydroxy-benzoic acid (cf., for example: US 4,290,912 . US Pat. No. 6,464,899 B1 . US 6,752,934 . US 6,787,065 B1 . EP 1 641 960 B1 and KR 1020160011874 A ).
  • VpCI / VCI combination consisting of an aminoalkyldiol with C 3 to C 5 , a monoalkylurea, a preferably multiply substituted pyrimidine and benzotriazole, could be achieved in several metals and surface states existing objects a good VCI corrosion protection, without an admixture of as carriers of acting substances.
  • VpCl / VCI oils have therefore been formulated in the past mainly by using amines as VCI components (cf., for example: US 919,778 . US 1,224,500 . US 3,398,095 . US 3,785,975 and JP 07145490 A ), sometimes supplemented by further volatile additives, such as C 6 to C 12 alkylcarboxylic acids and esters of unsaturated fatty acids (cf. US 3,398,095 ).
  • VpCl / VCI oils are therefore suitable exclusively 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 alkalization of the surfaces, as a result of which severe corrosion occurs with the formation of zincates or aluminates, before finally giving rise to the hydroxides and basic carbonates for which the term white rust is customary.
  • copper materials frequently undergo corrosion under the action of amines to form Cu-amine complexes.
  • VpCl / VCI combination of an aminoalkyldiol with C 3 to C 5 , a monoalkylurea, a preferably multiply substituted pyrimidine and benzotriazole can be added via a solubilizer so in a mineral oil or synthetic oil that a VpCl / VCI oil is formed with which can be a good VCI corrosion protection for a wide range of common commodity metals.
  • a solubilizer so in a mineral oil or synthetic oil that a VpCl / VCI oil is formed with which can be a good VCI corrosion protection for a wide range of common commodity metals.
  • VpCl / VCI oil it has proven to be disadvantageous that only relatively small proportions of the VpCl / VCI components can be added so that the very good VCI effect of fresh preparations decreases more and more during longer-term applications. The same could be observed when such VpCl / VCI oil was diluted with a common mineral oil.
  • VpCl / VCI treated oils for coping with the temporary corrosion protection of ferrous and non-ferrous metals with constructive small cavities
  • novel VpCl / VCI systems are therefore required, the application of which in practice does not have the disadvantages described connected is.
  • preparations which are not only of interest for a VpCl / VCI oil but also at least for VpCl / VCI donors (mixtures of pulverulent VpCl / VCI components in pouches, capsules, etc.) and coated VpCl / VCI packaging agents ( eg paper, cardboard, foam).
  • VpCI / VCI which are fully compatible with each other, especially effective VCI corrosion protection packages identified by long service life could be produced for the mentioned applications, eg preserving packages of VpCI / VCI oil treated engine blocks in containers sealed with a lid, in which additionally VCI-emitting bags, capsules or VCI-coated paper or foam blanks were placed, even for long-term storage always for saturation of the gas space of the containers with the VpCI / VCI components as a prerequisite for the maintenance of VCI corrosion protection to care.
  • the object of the invention is to provide over 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 into coatings and oils under the practically interesting climatic conditions within from technical packaging and analogous closed containers with sufficient speed from the corresponding depot, eg a VpCI / VCI components containing bag containing a VpCI / VCI components coating on a support such as paper, cardboard or foam, or a VpCI / VCI components containing oil or sublimate after adsorption and / or Condensation on the surface of located in this space metal parts there provide conditions under which the usual utility metals are reliably protected from atmospheric corrosion.
  • the corrosion-inhibiting substance combination comprises 1 to 30% by weight of component (1), 5 to 40% by weight of component (2), 2 to 20% by weight of component (3) and 0.5 to 10% by weight -% component (4), in each case based on the total amount of the combination of substances contained.
  • the substituted 1,4-benzoquinone is preferably selected from the group consisting of tetramethyl-1,4-benzoquinone (duroquinone), trimethyl-1,4-benzoquinone, 2,6-dimethoxy-1,4-benzoquinone (DMBQ), 2,5-dimethoxy-1,4-benzoquinone, 2-methoxy-6-methyl-1,4-benzoquinone, and similarly structured, especially alkyl or alkoxy substituted, substituted 1,4-benzoquinones and combinations thereof.
  • duroquinone tetramethyl-1,4-benzoquinone
  • DMBQ 2,6-dimethoxy-1,4-benzoquinone
  • 2-methoxy-6-methyl-1,4-benzoquinone 2-methoxy-6-methyl-1,4-benzoquinone
  • the aromatic or alicyclic substituted carbamate is preferably selected from the group comprising benzyl carbamate, phenyl carbamate, cyclohexyl carbamate, p-tolyl carbamate and similarly structured substituted carbamates and combinations thereof.
  • the polysubstituted phenol is preferably selected from the group consisting of 5-methyl-2- (1-methylethyl) phenol (thymol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol) , 2-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 2,6-dimethoxyphenol (syringol) and similarly structured polysubstituted phenols and combinations thereof.
  • the monosubstituted pyrimidine is preferably selected from the group consisting of 2-aminopyrimidine, 4-aminopyrimidine, 2-methylpyrimidine, 4-methylpyrimidine, 5-methoxypyrimidine, 5-ethoxypyrimidine, 4-phenylpyrimidine, 2-phenoxypyrimidine, 4- (N, N- Dimethylamino) pyrimidine and similarly structured monosubstituted pyrimidines and combinations thereof.
  • the components (1) to (4) can be mixed together, for example, or dispersed in water or premixed in a solubilizer which is miscible with mineral oils and synthetic oils.
  • This solubilizer is preferably an arylalkyl ether alcohol customary for oil preparations, for example phenoxyethanol (Protectol PE), in which the components are present in dissolved or dispersed form.
  • arylalkyl ether alcohol customary for oil preparations, for example phenoxyethanol (Protectol PE), in which the components are present in dissolved or dispersed form.
  • 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.
  • composition of the corrosion-inhibiting substance combinations according to the invention is preferably adjusted so that in the temperature range up to +80 ° C at rel.
  • Humidity (RH) ⁇ 98% evaporate or sublime all components with sufficient volume and speed for steam room corrosion protection.
  • 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 VpCl / VCI packaging materials and oil preparations, so that these packaging materials or oils act as a VCI depot and the anti-corrosion properties of the inventive substance combinations particularly can be advantageous to unfold.
  • the corrosion-inhibiting substance combinations are used as a volatile corrosion inhibitor (VPCI, VCI) in the form of finely powdered mixtures or pellets (pellets) produced therefrom in the packaging, storage or transport of metallic materials.
  • VPCI volatile corrosion inhibitor
  • VCI 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 to coat VCI-emitting packaging 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 anticorrosion oil comprises a mineral oil or synthetic oil and 0.5 to 5% by mass, more preferably 0.8 to 3% by mass, based on the oil phase, of a corrosion inhibiting substance combination according to the invention, optionally in a solubilizer, and the composition is adjusted so that from the VCI oil in the temperature range up to 80 ° C at rel.
  • Humidity (RH) ⁇ 98% evaporate or sublime all corrosion inhibitor components with sufficient volume and speed for steam room corrosion protection.
  • the substance combinations according to the invention are nitrite- and amine-free and advantageously consist exclusively of substances which can be easily and safely processed by methods known per se and in the applicable proportions are classified as non-toxic and the environment is not hazardous. They are therefore particularly suitable for the production of corrosion-protective packaging materials that are applicable on a large scale cost and without significant hazard potential.
  • compositions according to the invention are preferably formulated within the following proportions by weight: Component (1): 1 to 30% Component (2): 5 to 40% Component (3): 2 to 20% Component (4): 0.5 to 10%.
  • the type, proportion of the individual components in the mixture according to the invention and the proportion of mixture in the respective VpCI / VCI depot only depend on the conditions of production of the relevant VpCl / VCI emitting product and the necessary processing aids, but not on the type of from corrosion to metal to be protected.
  • VCI (1) was prepared using the anhydrous components of the combination of substances according to the invention and further anhydrous substances serving as processing aids: 10.0 mass% Tetramethyl-1,4-benzoquinone (Duroquinone) 8.0% by mass benzyl 6.0% by mass 5-methyl-2- (1-methylethyl) phenol (thymol), 6.0% by mass 5-Ethoxy, 20.0 mass% Silica gel (SiO 2 ) 10.0 mass% Sodium benzoate, (micronized, d 95 ⁇ 10 ⁇ m) 8.0% by mass 1-H benzotriazole 1.0% by mass 2- (2H-Benzotriazol-2-yl) -p-cresol (Tinuvin P, CIBA) 30.0 mass% non-polar PE wax (CWF 201, ALROKO) 1.0% by mass Calcium stearate (d 95 ⁇ 8 ⁇ m)
  • test plates 90 x 50 xd
  • test plates 90 x 50 xd
  • test plate 1 test plate made of DC 03 steel, cold-rolled, low-carbon, material no.
  • the mason jars with the test plates, the deionized water and the combination of substances according to the invention were sealed, for which purpose a cover with a sealing ring and three clamping clamps 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, 0.5 g portions of a commercially available VCI powder were tested in the same way.
  • This reference VCI powder (R1) consisted of 28.8% by mass Dicyclohexylaminbenzoat 67.1 mass% cyclohexylamine 1.5% by mass 1-H benzotriazole 2.6% by mass Silica gel (SiO 2 )
  • test panels of the 4 different metals which were used together with the composition of the invention VCI (1), had in all 4 parallel batches after 35 cycles an unchanged appearance.
  • the commercial reference system R1 is therefore suitable only for VCI corrosion protection of iron-based 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.
  • a coating composition VCI (2) of the following composition was prepared: 1.0% by mass 2,6-dimethoxy-1,4-benzoquinone (DMBQ) 1.0% by mass benzyl 1.5% by mass thymol 2.5% by mass 2-aminopyrimidine 55.0 mass% PLEXTOL BV 411 6.0% by mass methyl ethyl ketone 16.0% by mass deionized water 10.0 mass% Sodium benzoate, (micronized, d 95 ⁇ 10 ⁇ m) 6.0% by mass Polymer thickener (Rheovis VP 1231.
  • the commercially available reference system (R2) with a grammage of 66 g / m 2 contained the following active substances after chemical analysis: 6.2 mass% Triethanolamincaprylat 3.4% by mass Monoethanolamincaprinat 1.4% by mass benzotriazole 6.7% by mass sodium benzoate
  • the test ritual again corresponded to that described in Example 1. The only difference was that, instead of the VCI powder mixture specified in a Tyvek bag, the individual mason jars were now lined with the VCI paper.
  • a waiting time of 16 h at room temperature was specified as the so-called build-up phase of the VCI components within the closed vessel.
  • the exposure of the individual mason jars was again for 16 h in a heating cabinet according to DIN 50011-12 at 40 ° C, then for 8 h at room temperature.
  • the reference system R2 is only suitable for VCI corrosion protection of iron base materials, while in the case of Cu base materials, the active substances emitted from the reference system R2 are adsorbed in such different specific concentrations that defects in the VCI corrosion protection effect result.
  • the VCI paper VCI (2) produced on the basis of the combination of substances according to the invention has, as the example shows, exhibited reliable VCI properties over the usual service metals even under the extreme moist air conditions with long-term stress.
  • a corrosion protection oil VCI (3) of the following composition was prepared: 0.6% by mass duroquinone 0.1% by mass benzyl 0.2% by mass thymol 0.2% by mass 4-phenylpyrimidine 92.7 mass% ( Mineral oil with thixotropic agent normal wax (BANTLEON base oil LV 16-050-2) 6.0% by mass phenoxyethanol 0.2% by mass Tolyltriazole (TTA, COFERMIN)
  • VCI oil VCI (3) according to the invention resulted as an optically clear fluid, characterized by an average kinematic viscosity of 25 ⁇ 3 mm 2 / s (20 ° C).
  • VCI oil VCI (3) In reference to the VCI oil VCI (3) according to the invention, a commercially available VCI oil of approximately the same mean kinetic viscosity was tested in an analogous manner.
  • the test ritual again corresponded to that described in Example 1.
  • a waiting time of 16 h at room temperature was specified as the so-called build-up phase of the VCI components within the closed vessel.
  • the exposure of the individual mason jars was again for 16 h in a heating cabinet according to DIN 50011-12 at 40 ° C, then for 8 h at room temperature.
  • VCI oil VCI (3) according to the invention consequently ensured good corrosion protection both for the metal substrates in direct contact in question and for the test sheets inside the sealed mason jar with the VCI components not emitted by the oil.
  • test plates made of the low alloyed steel DC 03 also exhibited no signs of corrosion after 35 cycles either in the oiled or in the non-oiled state.
  • test plates made of Al 99.5, Cu-ETP and galvanized steel on the other hand, this was only the case when oiled.
  • brown start-up film After the non-oiled Cu-ETP test plates, dark gray to black-looking spots were observed after only 7 cycles at the upper edge regions, from which after 35 cycles in most cases relatively uniform, non-wipeable start-up films were formed.
  • the reference system R3 can only be used in direct contact with the corrosion protection compared to the usual use metals.
  • the active substances that are emitted into the gas phase are only suitable for VCI corrosion protection of iron-based materials.
  • the VCI oil VCI (3) according to the invention ensures a pronounced multimetal protection in that it develops reliable VCI properties in the long-term test, even under the extreme humid air conditions, in comparison with the usual utility metals.

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  • 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)
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RU2759710C1 (ru) * 2021-04-01 2021-11-17 Федеральное государственное бюджетное учреждение науки Институт физической химии и электрохимии им. А.Н. Фрумкина Российской академии наук (ИФХЭ РАН) Таблетированный летучий ингибитор коррозии

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US20190093236A1 (en) 2019-03-28
CN109554712A (zh) 2019-04-02
CN109554712B (zh) 2021-02-09
PL3461931T3 (pl) 2020-08-24
ES2793506T3 (es) 2020-11-16
EP3461931B1 (fr) 2020-03-25
RU2703747C1 (ru) 2019-10-22
JP6688849B2 (ja) 2020-04-28
JP2019077947A (ja) 2019-05-23
US10753000B2 (en) 2020-08-25
DE102017122483B3 (de) 2018-10-25

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