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EP0366941A1 - Procédé de revêtement par électrodéposition de surfaces métalliques aptes au chromatage - Google Patents

Procédé de revêtement par électrodéposition de surfaces métalliques aptes au chromatage Download PDF

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Publication number
EP0366941A1
EP0366941A1 EP89118116A EP89118116A EP0366941A1 EP 0366941 A1 EP0366941 A1 EP 0366941A1 EP 89118116 A EP89118116 A EP 89118116A EP 89118116 A EP89118116 A EP 89118116A EP 0366941 A1 EP0366941 A1 EP 0366941A1
Authority
EP
European Patent Office
Prior art keywords
chromating
solution
chromated
metal surfaces
dip coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP89118116A
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German (de)
English (en)
Other versions
EP0366941B1 (fr
Inventor
Rainer Professor Dr. Huss
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sep Gesellschaft fur Technische Studien Entwicklung Planung MbH
Original Assignee
Sep Gesellschaft fur Technische Studien Entwicklung Planung MbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sep Gesellschaft fur Technische Studien Entwicklung Planung MbH filed Critical Sep Gesellschaft fur Technische Studien Entwicklung Planung MbH
Publication of EP0366941A1 publication Critical patent/EP0366941A1/fr
Application granted granted Critical
Publication of EP0366941B1 publication Critical patent/EP0366941B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment

Definitions

  • the invention relates to a method for electrophoretic dip coating of chromatable metal surfaces.
  • Chromatable metal surfaces are primarily surfaces of the metals zinc, cadmium, aluminum, magnesium, and their chromatable alloys.
  • the method is therefore also suitable for the electrophoretic dip coating of iron and steel surfaces which are coated with such metals or their alloys, for example for coating galvanized iron or steel surfaces.
  • Metal surfaces are not only painted for decorative purposes, often - especially when painting iron and steel parts - the focus is on corrosion protection. A very good corrosion protection is achieved by painting iron and steel parts as long as the paint forms a complete coating. If the varnish layer has pores, holes, cracks or similar defects due to injuries, aging processes or due to incorrect manufacture of the varnish layer, these defects lead to rapid rust formation and a cauliflower-like lifting of the varnish layer infiltrated by corrosion processes ("cauliflower" -Corrosion and filiform corrosion). The corrosion damage is therefore not limited to the location of the defect in the paint layer, but spreads quickly.
  • Corrosion protection which is retained even in the event of minor damage to the protective layer, can be provided by galvanizing. Due to the thick zinc layer of typically 50 to 200 ⁇ m, hot galvanizing of steel parts together with the iron-zinc alloy as a transition layer of zinc on the surface to the base material steel provides excellent corrosion protection.
  • galvanizing zinc layers are much less thick.
  • galvanized steel sheets have no brittle intermediate layers made of iron-zinc alloys.
  • Galvanizing is the only low-cost process a cathodic corrosion protection of the steel, which means that even in the case of scratches up to a width of approx. 0.7 mm, the corrosion of the steel is electrochemically suppressed by the zinc layer.
  • the zinc coating as the sole protection for steel is only a completely inadequate corrosion protection due to the small layer thicknesses that are applied in galvanic processes (average 10 ⁇ m). This applies in particular to shiny, smooth layers. These are not even close to hand.
  • the corrosion protection found in the salt spray test according to DIN 50021 is only minimal; after about 6 to 8 hours the zinc layer is corroded away and brown rust appears.
  • a significant improvement in corrosion protection can be achieved by chromating or phosphating the zinc surface.
  • chromating or phosphating the zinc surface In the salt spray test, it is customary for blue chromating to take 24 hours, and for yellow chromating to about 200 hours before the first white rust appears.
  • Phosphating on galvanic zinc layers also increases corrosion protection. However, these surfaces are rough and, if damaged, do not show the self-healing mechanism that is known from chromating. Therefore, phosphating is only used as a primer for subsequent painting. In the salt spray test, these layers are corrosion-resistant up to a test duration of around 150 hours.
  • the protective effect of chromating can be increased by dipping freshly chromated parts in special aqueous so-called sealing solutions, which has a significant effect in the salt spray test.
  • galvanized metal parts are chromated, rinsed and then rinsed wet in a dispersion of Dipped plastics, whereby an elastic, intimately interlocking composite layer of uneven thickness of chromating and plastic is obtained, which provides good protection against corrosion.
  • DE-AS 15 21 656 describes the chromating of zinc and zinc alloys. After rinsing and subsequent air drying, the chromated metal surfaces can be given a siccative coating based on so-called drying oils (unsaturated fatty acids), which crosslink with the absorption of oxygen from the air.
  • drying oils unsaturated fatty acids
  • Electrocoating is particularly suitable since this process produces layers of uniform thickness, so that high demands on the dimensional accuracy of the painted parts can be met.
  • critical cavities such as blind holes or inner pipe walls are also continuously painted. These inaccessible areas are usually well protected against injuries from external influences. Electrophoretic dip painting of galvanized steel parts can therefore lead to a significant improvement in corrosion protection.
  • the adhesion between zinc and the organically structured paints is very problematic. It has been shown that the paint flakes off within a short time under exposure to weather and / or mechanical stresses. Adhesion mediation is therefore required for the paint application. Adhesion mediation is also necessary in any case if metals with similar properties to zinc, for example cadmium or aluminum, are to be painted. An adhesion promoter is also frequently used for steel.
  • the adhesion imparting usually consists of phosphating.
  • the phosphating process has some serious disadvantages: -The entire process for promoting adhesion using phosphating is quite extensive: -Activate (inoculate with TiO2 particles in order to obtain fine-grained, even phosphating layers) -Phosphating; do the washing up -Cromic acid diving; Do the washing up.
  • phosphating solution must be filtered continuously to remove any precipitated, insoluble tertiary phosphate; this would interfere with the phosphating process.
  • concentration of the phosphating solution is very high with 100 to 200 g / l phosphating salt; this requires a considerable amount of rinsing after phosphating. Both the filtration and the rinsing lead to a considerable amount of phosphate-containing sludge; This must be disposed of as special waste due to the heavy metal content.
  • analysis of the phosphating solution is complex and difficult to automate; however, the process should be automated to ensure consistent quality in continuous operation.
  • the object of the invention is to provide a method by means of which electro-dipping lacquers can be deposited on chromatable metal surfaces with much better adhesion than corresponds to the state of the art and by which the disadvantages of phosphating for promoting adhesion can be avoided.
  • This object is achieved according to the invention by a process for electrophoretic dip coating of chromatable metal surfaces, which is characterized in that the metal surfaces are pretreated by chromating and the chromated metal surfaces are kept wet from chromating to introduction into the bath for electrophoretic dip coating.
  • the metal surfaces are pretreated by chromating and the chromated metal surfaces are kept wet from chromating to introduction into the bath for electrophoretic dip coating.
  • chromating layers can be used as adhesion promoters for electrocoat materials, provided that these are kept wet after production until electrocoating.
  • freshly produced, still wet chromating layers have a hydrophilic surface which is suitable for electrocoating. This suitability is maintained if the freshly prepared chromate layers are kept wet or stored in a moist state until electro-coating.
  • electro-dipping paints can only be deposited with poor adhesion. It has also been found that after drying, once again wetting the once dried chromating layer with water does not lead to an improvement in the adhesion of coating compositions applied by electrocoating. This applies in the same way to all chromate layers applied by customary procedures.
  • chromating is applied as an adhesive base before electrocoating.
  • such chromating has a smooth, shiny surface.
  • the chromated surface is kept wet according to the invention, the surface has such a high surface tension that when wetted with water at the interface, that is, at the edge of the water drop, a contact angle of the order of 0 degrees results. If drying takes place, this contact angle is greatly increased, for example to 20 to 50 degrees, which results in poor wettability.
  • the high-quality deposition of the electrocoating material on the chromating layer can be ensured in that the lacquer is deposited directly after the chromating without intermediate drying.
  • the high-quality deposition of the electrocoating material on the chromating layer can also be ensured by keeping the chromating layers permanently moist until the beginning of the lacquer deposition by spraying with water or by storing in air with a high relative humidity. Spraying with water is particularly suitable if the entire surface can be sprayed.
  • a high relative humidity is to be understood as a humidity which is required so that no water can evaporate from the chromated surface and drying out is prevented. It depends on the length of time that must be bridged before the paint deposition begins. In general, for example, a relative humidity of> 90% can be assumed; with long storage it can be up to 100%.
  • the method according to the invention can improve the adhesion of coatings deposited by electrophoretic dip coating on surfaces of chromatable metals.
  • chromatable metals are, for example, zinc, cadmium, aluminum, magnesium and their chromatable alloys.
  • the method according to the invention is thus suitable, for example, for iron or steel surfaces, such as sheets, which are coated with such chromatable metals, such as zinc.
  • chromating of the metal surfaces is carried out in the usual manner known to the person skilled in the art. Any known chromating process can be used, as described, for example, in the book T.W. Jelinek, "Galvanic galvanizing", Leuze Verlag 1982, is described.
  • the chromating is preferably carried out using a chromating solution which consists only of inorganic components.
  • a chromating solution has, for example, a concentration of 1 to 10 g / l chromic acid (H2CrO4), in particular about 4g / l chromic acid at a pH of 0 to 3, preferably from 2.3 to 2.7. It is cheap, but not necessary, if the chromating solution contains one or more salts of the metal to be chromated. Examples of such salts are chlorides, nitrates and / or fluorides.
  • the concentration of such salts which may be present is, for example, 0.001 to 0.1 mol / l, preferably 0.05 mol / l.
  • the pH of a freshly prepared chromating solution can be adjusted, for example, with an oxide or hydroxide of the metal to be chromated. It can be checked during operation by measurement, for example with a glass electrode or by conductivity measurement, and set again to the desired value by adding acid, oxide or hydroxide.
  • chromations represent the last layer, the so-called "finish" for chromatable metals and are optimized for this purpose; ie they offer some protection against corrosion (zinc: yellow and olive chromate) or improve the appearance (zinc: blue and black chromate).
  • finish for chromatable metals and are optimized for this purpose; ie they offer some protection against corrosion (zinc: yellow and olive chromate) or improve the appearance (zinc: blue and black chromate).
  • other aspects such as environmental friendliness, long service life, regenerability etc., which do not directly affect the quality of the chromating layer, are currently hardly considered.
  • chromating solutions that contain only inorganic components are particularly suitable, since they can be regenerated by the process known from DE-PS 31 38 503.
  • disruptive degradation products are removed from the chromating solutions with the aid of ion exchangers, electrodialysis, electrolysis or chemical oxidation, the pH or the conductivity are measured during operation, the Cr6+ - and Cr3+- Concentrations are determined photometrically and supplementary solutions are added in accordance with these analysis values and the flow through the ion exchangers or the separation, exchange or reaction devices are regulated in such a way that the composition of the chromating solution is kept in a predetermined concentration range.
  • Very low-concentration chromating solutions are sufficient to promote adhesion between galvanically deposited zinc and electrocoat. Because the chromate solution is carried away with the chromated metal parts, undesired degradation products in the chromate solutions cannot be concentrated to disturbing values. On removal of the unwanted degradation products, as described in DE-PS 31 38 503 e.g. provided with the help of ion exchangers can therefore be dispensed with; it is sufficient to supplement the compensation of the chromate solution that has been carried out.
  • the known chromating processes can also be used which work without hexavalent chromium, that is to say without chromate.
  • These methods are also familiar to the person skilled in the art and are described, for example, in the above-mentioned book by TW Jelinek.
  • Such Chromating is badly suited for corrosion protection purposes, but it gives good adhesion and has the advantage that the baths used are environmentally friendly because they do not contain hexavalent chromium.
  • Such baths contain chromium (III) salts, such as potassium chromium sulfate; they can contain acids such as nitric acid and salts such as fluorides, for example ammonium hydrogen fluoride.
  • layer thicknesses of up to 0.01 ⁇ m with a layer weight of 0.03 mg / dm2 are used for colorless chromating, and layer thicknesses of up to 0.08 ⁇ m for a layer weight for blue chromating from 0.5 to 5 mg / dm2, with yellow chromating layer thicknesses of up to 1 ⁇ m with layer weights of 5 to 20 mg / dm2 and with olive chromating layer thicknesses of up to 1.25 ⁇ m with a layer weight of 20 mg / dm2.
  • Rinsing with water can be beneficial to remove excess chromating solution immediately after chromating. Whether such a rinsing process is carried out depends on the concentrations of the chemical compounds and ions used in the chromating solution and on the procedure. With electrophoretic paint deposition, as few ions as possible should be carried into the paint bath. If the chromated metal parts are to be introduced into the electrodeposition bath without delay, a rinsing process can be carried out before the, regardless of the composition of the chromating solution used Electrodeposition can be particularly cheap. If, on the other hand, the chromated metal parts are kept wet by spraying with water until they are introduced into the electrodeposition bath, an additional rinsing process can be dispensed with if the chromating solution is suitably composed.
  • the metal surfaces pretreated according to the invention by chromating and wet holding can be coated or painted by conventional electrophoretic dip coating.
  • All customary coating compositions or electrophoretic dip coating processes which are familiar to the person skilled in the art are suitable. There is no restriction with regard to the coating agents that can be used or electrophoretic dip coating processes.
  • electrophoretic dip painting anaphoresis and cataphoresis, cataphoresis, i.e. cataphoretic dip coating is particularly preferred.
  • anodic deposition anaphoresis is also suitable.
  • lacquer layers produced in the manner according to the invention are shiny, smooth and non-porous and provide excellent protection against corrosion.
  • These lacquer layers can serve, for example, as primers, on which conventional further processing with, for example, fillers and topcoats can take place.
  • a steel sheet was treated according to the following process steps: - degreasing (with solvent or aqueous alkaline); do the washing up - pickling (with mixed acid or sulfuric acid); do the washing up - electrolytic degreasing; do the washing up - galvanizing (cyanide, alkaline or acidic); rinsing - Brightening (10 s; 3g / l HNO3); rinsing can be omitted - chromating (1-3 min), rinsing; do not dry; - cataphoretic dip painting with a commercially available electrodeposition paint; Rinse with water - drying, baking
  • the chromating bath has the following composition: 1 - 5g / l H2CrO4 2 - 10 g / l Zn (NO3) 2 pH about 2.5; adjusted with ZnO or NaOH
  • the chromating layer is almost transparent and leads to very good adhesion of the lacquer layer.
  • the paint layer is shiny, smooth, even, non-porous and provides good protection against corrosion.
  • the chromating solution shows no self-decomposition.
  • dissolution of zinc (and iron in the non-galvanized areas) during the chromating process is very low, degradation products do not accumulate to a disruptive concentration; there is no need to clean the solution using a cation exchanger.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
EP89118116A 1988-09-29 1989-09-29 Procédé de revêtement par électrodéposition de surfaces métalliques aptes au chromatage Expired - Lifetime EP0366941B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3833119 1988-09-29
DE3833119A DE3833119A1 (de) 1988-09-29 1988-09-29 Verfahren zur chromatierung und lackierung von metalloberflaechen mit wasserverduennbaren lacken

Publications (2)

Publication Number Publication Date
EP0366941A1 true EP0366941A1 (fr) 1990-05-09
EP0366941B1 EP0366941B1 (fr) 1996-01-31

Family

ID=6364004

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89118116A Expired - Lifetime EP0366941B1 (fr) 1988-09-29 1989-09-29 Procédé de revêtement par électrodéposition de surfaces métalliques aptes au chromatage

Country Status (8)

Country Link
US (1) US5707505A (fr)
EP (1) EP0366941B1 (fr)
AT (1) ATE133723T1 (fr)
BR (1) BR8904920A (fr)
CA (1) CA1339915C (fr)
DE (2) DE3833119A1 (fr)
ES (1) ES2093611T3 (fr)
MX (1) MX173144B (fr)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
DE10025643A1 (de) * 2000-05-24 2001-12-06 Ozf Oberflaechenbeschichtungsz Aluminium- und Magnesium-Druckgusskörper mit einer eingebrannten kataphoretischen Tauchlackierungsschicht und Verfahren zu deren Herstellung

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WO2001076811A1 (fr) * 2000-04-07 2001-10-18 Whyco Technologies, Inc. Procede de masquage de revetements et objet resultant
US7291252B2 (en) * 2001-12-07 2007-11-06 United States Steel Corporation Electrocoating chrome-plated steel
DE102005019700A1 (de) * 2005-04-22 2006-12-21 Eisenmann Maschinenbau Gmbh & Co. Kg Oberflächenbehandlungsanlage
DE102008000919B4 (de) * 2008-04-01 2014-01-09 Siegenia-Aubi Kg Verfahren zur Aufbringung eines zusätzlichen Korrosionsschutzes auf ein metallisches Bauteil und nach dem Verfahren hergestellter verzinkter Beschlag
EP2405031A1 (fr) 2010-07-07 2012-01-11 Mattthias Koch Procédé de revêtement d'objets profilés et objet ainsi obtenu
EP2985363A1 (fr) 2014-08-13 2016-02-17 Matthias Koch Substrat revêtu
DE202014009707U1 (de) 2014-12-10 2015-02-05 Slk Spezial-Lackierung Koch Gmbh Beschichtete Substrate
PT3117907T (pt) 2015-07-13 2018-01-31 Hec High End Coating Gmbh Processo para produção de substratos revestidos
EP3225717A1 (fr) 2016-03-30 2017-10-04 HEC High End Coating GmbH Procede de fabrication de substrat revetu, substrat revetu et son utilisation
EP3498883A1 (fr) 2017-12-13 2019-06-19 HEC High End Coating GmbH Procédé de fabrication de substrat revêtu, substrat revêtu et son utilisation

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10025643A1 (de) * 2000-05-24 2001-12-06 Ozf Oberflaechenbeschichtungsz Aluminium- und Magnesium-Druckgusskörper mit einer eingebrannten kataphoretischen Tauchlackierungsschicht und Verfahren zu deren Herstellung
DE10025643B4 (de) * 2000-05-24 2007-02-01 OZF Oberflächenbeschichtungszentrum GmbH+Co. Verfahren zum Beschichten von Aluminium- und Magnesium-Druckgusskörpern mit einer kataphoretischen Elektrotauchlackierungsschicht und mit diesem Verfahren hergestellte Aluminium- und Magnesium-Druckgusskörper

Also Published As

Publication number Publication date
EP0366941B1 (fr) 1996-01-31
ATE133723T1 (de) 1996-02-15
ES2093611T3 (es) 1997-01-01
CA1339915C (fr) 1998-06-16
US5707505A (en) 1998-01-13
DE58909586D1 (de) 1996-03-14
DE3833119A1 (de) 1990-04-12
DE3833119C2 (fr) 1990-09-27
BR8904920A (pt) 1990-05-08
MX173144B (es) 1994-02-02

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