WO1995031588A1 - Fabrication d'activateurs phosphates destines a la phosphatation par micro-ondes - Google Patents

Fabrication d'activateurs phosphates destines a la phosphatation par micro-ondes Download PDF

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Publication number
WO1995031588A1
WO1995031588A1 PCT/EP1995/001654 EP9501654W WO9531588A1 WO 1995031588 A1 WO1995031588 A1 WO 1995031588A1 EP 9501654 W EP9501654 W EP 9501654W WO 9531588 A1 WO9531588 A1 WO 9531588A1
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Prior art keywords
titanium
reaction mixture
phosphate
acids
activating
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PCT/EP1995/001654
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German (de)
English (en)
Inventor
Karl Dieter Brands
Bernd Mayer
Sandra Witt
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Henkel Kommanditgesellschaft Auf Aktien
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Priority to DE59503273T priority Critical patent/DE59503273D1/de
Priority to EP95919995A priority patent/EP0759097B1/fr
Priority to JP7529314A priority patent/JPH10500175A/ja
Publication of WO1995031588A1 publication Critical patent/WO1995031588A1/fr

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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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated

Definitions

  • the invention is in the field of phosphating metal surfaces made of steel, zinc, aluminum or their alloys.
  • the metal substrates can consist entirely of these metals or alloys, but they can also be multi-layered and have a coating of a metallic material that differs from the base metal. Examples of this are steels which are coated with zinc, aluminum or with alloys, the main component of which is zinc or aluminum. Examples of this are coatings of zinc-aluminum alloys, zinc-iron alloys, zinc-nickel alloys on a steel substrate. Another example is galvanized aluminum.
  • the invention relates to a new production process for phosphate-containing activating agents which are brought into contact with the said metal surfaces in the form of a dilute aqueous solution or suspension before the actual phosphating of the said metal surfaces.
  • the new manufacturing process is distinguished by the fact that it is carried out using microwaves.
  • the method can be used for activators based on polymeric titanium phosphates, but also on a titanium-free basis.
  • Corrosion-inhibiting phosphating of such surfaces is common not only in automobile construction, but also in the manufacture of household appliances such as washing machines or refrigerators. For the latter area of application, but also increasingly for applications in building construction and automotive engineering, material is being used with increasing tendency which has already been phosphated as a strip material in the steelworks and optionally also coated organically.
  • the workpieces are cleaned, rinsed and activated in order to achieve a thin and uniform phosphate layer during phosphating, which is known to form a prerequisite for good corrosion protection.
  • high zinc phosphating processes that had been common for a long time, it was possible to remove adhering oils, fats and other impurities, also from mechanical processing, from the metal surface in one process step and at the same time for the subsequent step of zinc phosphating to activate.
  • the treatment baths generally contain one or two additional cations of divalent metals, such as nickel, manganese, calcium, magnesium or barium.
  • a “trication-phosphating process” in which manganese and nickel ions are used in addition to zinc ions is described, for example, in DE-A-3918136.
  • a process which uses manganese and magnesium in addition to zinc has been published in WO90 / 15889.
  • Zinc-barium phosphating was known from DE-A-3906898.
  • DE-A-40 13483 describes a phosphating process in which, in addition to the concentrations of zinc and manganese customary for low-zinc phosphating, copper ions in the ppm range are used.
  • the mentioned methods lead in connection with the usually following one Electrocoating for significantly improved corrosion protection.
  • these processes react much more sensitively to changes in the process parameters and to impurities which are introduced into the phosphating bath with the metal sheets to be coated.
  • the step of activating the metal surface is thus of much greater importance than before. It has proven to be particularly advantageous to connect the activation after the cleaning and degreasing step in a separate process step. This is particularly true if the phosphating by the low-zinc process takes place in one dipping process, but is also equally important for the zinc phosphating by a spray or combined spray-immersion process and immersion-spraying process.
  • the activation of the metal surface has the following goals:
  • Reduction of the minimum phosphating time i.e. the time until the metal surface is completely covered with a closed zinc phosphating layer.
  • Titanium (IV) phosphates generally form during the reaction of aqueous Ti (IV) salt solutions with soluble phosphates or phosphoric acid. Products with activating properties are, however, only obtained under special manufacturing conditions, which are described in more detail, among other things, in the above-mentioned documents by Jernstedt.
  • the main production parameters are:
  • titanium yl sulfate, potassium hexafluorotitanate, titanium tetrachloride, titanium dioxide, potassium titanium oxide oxalate or titanium disulfate as titanium components
  • EP-A-307839 describes a process for the preparation of activating agents containing polymeric titanium phosphates, in which the reaction of the titanium components with the phosphate components in an aqueous medium under hydrothermal conditions, here at temperatures between 100 and 160 ° C. under which pressure is performed.
  • EP-B-339452 teaches that titanium phosphate-containing.
  • Activating agent with extended bath life can produce if a complexing agent is present in a sub-stoichiometric amount with respect to titanium during the reaction of the titanium with the phosphate components in an aqueous medium at a temperature between 75 and 120 ° C.
  • the quality of activation baths containing titanium phosphate is improved if they continue to contain pyrophosphate and water-soluble, anionic copolymers of unsaturated carboxylic acids with acrylic acid ester, acrylic acid amide, acrylonitrile, isobutylene, and / or styrene or water-soluble, anionic condensation products Contain naphthalenesulfonic acid and formaldehyde.
  • US Pat. No. 3,864,139 describes activating agents or activating baths which contain, in addition to polymeric titanium phosphates, additional “stabilizing agents”. Examples of such stabilizing agents are: alkali metal conduction rates and aminopolycarboxylates.
  • Activates containing phosphates are also known, in which the use of titanium compounds is dispensed with.
  • EP-A-340530 teaches that activating phosphates are obtained if a phosphate component with complexing agents is selected from the group of 1,1-diphosphonic acids and poly (aldehydocarboxylic acids) in suitable amounts. Conditions.
  • Phosphate-containing activating agents have hitherto generally been marketed in the form of powders which are introduced into the aqueous activating bath at the point of use, if appropriate after predispersion. This is disadvantageous for the application, since dust problems can occur when the powders are used and since the addition of the powders to the aqueous activation baths is difficult to automate.
  • the activating agents as storage-stable, pumpable, concentrated aqueous suspensions or solutions which have to be diluted with the appropriate amount of water for use.
  • Such a "liquid activating agent” is described, for example, in EP-A-554179, wherein a powdery activating agent containing titanium phosphate is first prepared in a conventional manner. The powder is introduced into water to form a two to twenty percent by weight suspension, the viscosity of which is suitably adjusted to prevent the suspension from settling during storage with a thickener based on a polysaccharide.
  • This activating agent can be sold in powder form, but also in the form of an aqueous concentrate stabilized by thickening and having a water content of 50 to 90%.
  • aqueous activating agent concentrates described above have in common that the activating component is prepared in an aqueous slurry, then dried to a powder and then suspended in thickened water. Due to the previously necessary intermediate drying of the activating product, such a procedure is energy-intensive.
  • the object of the present invention was to provide a new process for the production of titanium-containing or titanium-free activating agents based on phosphate, which provides activation products with short reaction times and which is conventionally processed into powder, but advantageously without an intermediate drying directly in Form of a stabilized aqueous concentrate can be used.
  • the object is achieved by a process for the preparation of phosphate-containing activating agents for the activation of metal surfaces made of steel, zinc, aluminum or their alloys prior to phosphating, characterized in that an aqueous solution or slurry of one or more alkali metal phosphates, oligophosphates and / or polyphosphates together with a second reaction component selected from titanium compounds, complexing agents or combinations thereof is subjected to radiation with microwaves.
  • Phosphate components suitable for the production of phosphate-containing activating agents for phosphating are known in the prior art, for example from EP-B-339452. They can be summarized under the general formulas (I) to (III), mixtures of different phosphate components generally being used, for example sodium dihydrogen phosphate together with disodium hydrogen phosphate or mixtures of orthophosphates of the general formula (I) with metaphosphates of all ⁇ general formula (III): M m H3-mP ⁇ 4 (D
  • M represents an alkali metal and m 0, 1, 2 or 3, n 2, 3 or 4,
  • P 0, 1, 2 ..., n + 2 and q 0 or 1 and r are an integer from 2 to 20
  • aqueous slurry of the reaction components Treatment of the aqueous slurry of the reaction components with microwaves leads to a reaction mixture with activating properties only in a technically attractive time, for example less than 30 minutes, if the solids content of the aqueous reaction mixture is between 40 and 80% by weight . Particularly short reaction times of less than 5 to about 15 minutes are required if the aqueous reaction mixture has a solids content of between 55 and 75% by weight.
  • the pH of the reaction mixture is, as is customary in the production of phosphate-containing activating agents, from 6 to 12 and is preferably in the range from 7 to 11. This can be achieved, for example, by appropriate mixing of primary and secondary alkali metal phosphates.
  • the pH can be adjusted to the required range, for example by adding sodium hydroxide solution.
  • the irradiation time should be selected so that the total energy input by the microwaves is preferably at least 10 kJ per kilogram of reaction mixture.
  • the energy input can be varied by varying the energy of the individual pulse with a constant pulse sequence or by varying the temporal pulse sequence when the pulse energy is constant.
  • the reaction mixture itself is heated up by the microwave radiation, it is advisable to preheat the reaction mixture before the microwave radiation.
  • the temperature of the reaction mixture should be between 80 and 150 ° C, for example between 95 and 140 ° C. Temperatures above the boiling point of the reaction mixture naturally assume that the reaction takes place in a suitable, microwave-permeable autoclave. Teflon autoclaves, for example, are suitable for this. If one works at a temperature which is 1 to 10 ° below the boiling temperature of the reaction mixture, the reaction can take place without pressure. This is preferred from a process engineering point of view, since open reaction vessels can be used here. It may be necessary to compensate for the water loss that occurs during the microwave radiation by adding water.
  • the reaction mixture can be dried to a powder product in a conventional manner after the end of the microwave radiation. This can be done, for example, by evaporating so much water from the reaction mixture by heating and / or applying a vacuum that a solid, millable solid remains, which can be ground to a free-flowing powder. This procedure leads to a conventional powdery activating agent, but the required reaction time is significantly reduced by the microwave radiation.
  • the reaction mixture can also be diluted directly to the use concentration of 0.01 to 2% by weight after the microwave irradiation. If the solids content is above 30% by weight, either the storage stability is no longer guaranteed or the suspension has to be thickened to such an extent that it is no longer pumpable and thus loses its application advantage.
  • the reaction mixture is preferably diluted with water to a solids content of between 10 and 25% by weight and, in order to increase the storage stability, the viscosity of the suspension or solution is adjusted such that it is in the range between 15 and 25, preferably from 18 to 21 DIN seconds.
  • the viscosity is measured here according to DIN 53211-4 as the run-out time from a flow cup at a temperature of 20 ° C.
  • the thickener can already be mixed with the water used to dilute the reaction mixture or can only be added after the dilution has taken place.
  • Suitable thickeners are known from the prior art via phosphate-containing activating agents.
  • EP-A-454211 lists, for example: polymers of natural origin, for example polypeptides such as gelatin or polysaccharides such as starch, xanthan or dextrins. According to the teaching of EP-A-554 179, polysaccharides can also be used.
  • These thickeners are also suitable in the context of the present invention. Good storage stability of the suspension without a negative influence on the activating effect was obtained when polysaccharides were used as thickeners. If a longer storage period is envisaged, an addition of a fungicide may be necessary to avoid mold formation.
  • titanium-containing or titanium-free reaction partners can be reacted with the phosphate components listed above.
  • the use of titanium-containing reaction partners is preferred.
  • Suitable titanium compounds as reaction components are listed in the above-mentioned prior art, for example in EP-B-339452. Examples include: various modifications of titanium dioxide or their digestion products with alkali, in particular with a melt or an aqueous solution of sodium hydroxide, titanium tetrahalides such as in particular titanium tetrachloride, alkali metal He- xafluorotitanates such as especially dipotassium hexafluorotitanate, titanium acetyl acetonate and / or titanyl sulfate.
  • titanium phosphate-containing activating agents are only formed if the titanium component is reacted with a large molar excess of the phosphate components. It is therefore also preferred for the present invention that the molar ratio of titanium to phosphorus in the reaction under microwave irradiation is preferably in the range 1:20 to 1:60, in particular in the range 1:25 to 1:40.
  • EP-B-339452 can be applied analogously to the present invention. From this document it is known that the addition of special complexing agents in a small amount during the reaction leading to polymeric titanium phosphate - the molar ratio of complexing agent to titanium being below 1.0 - leads to activated products with significantly improved application properties.
  • the increased effectiveness of the activating agents produced according to the invention is particularly evident in a bath capacity which is significantly increased in comparison to standard products and which permits an extended service life of the activating baths.
  • R for an unsubstituted or a para position with halogen, amino, hydroxy or C ⁇ _4 alkyl groups, preferably substituted with Cl or NH 2 , phenyl radical, a straight-chain or branched-chain or cyclic, saturated or mono- or polyunsaturated alkyl radical with 1 to 10 Carbon atoms,
  • X represents hydrogen, hydroxy, halogen or amino
  • Mj and M 2 each independently represent hydrogen and / or the equivalent of an alkali metal ion.
  • the poly (aldehydocarboxylic acids) and the 1,1-diphosphonic acids are preferably used as sodium salts, so that M in the general formula (IV) is sodium.
  • a preferred embodiment of the present invention is that the complexing agent is used in an amount of 0.05 to 0.7 mol per mol of titanium .
  • the complexing agent is used in an amount of 0.1 to 0.6 mol per mol of titanium.
  • the poly (aldehydocarboxylic acids) used according to the invention are commercially available and are available from Degussa AG, Frankfurt, for example under the names POC OS 20, POC HS 0010, POC HS 2020, P0C HS 5060, POC HS 65120 and POC AS 0010, POC AS 2020, POC AS 5060 or POC AS 65120 sold.
  • the designation HS relates to the acid form and the designation AS to the sodium salt form of the poly (aldehydocarboxylic acids).
  • acrolein can be produced according to a special process developed by Degussa, the "oxidative polymerization" of acrolein.
  • acrolein is treated alone or as a mixture with acrylic acid in aqueous solution with hydrogen peroxide.
  • the H 2 0 2 acts here as an initiator of the polymerization and as a molecular weight regulator.
  • some of the aldehyde groups of acrolein are oxidized to carboxyl groups by hydrogen peroxide. This gives rise to polymers with pendant aldehyde and carboxyl groups, namely the poly (aldehydocarboxylic acids), the preparation of which is described in DE-C-2357036.
  • Complexing agents which can further be used are those which, according to EP-A-201 841, improve the effectiveness of titanium-containing phosphating agents.
  • Water-soluble anionic copolymers of unsaturated carboxylic acids with acrylic acid esters, amides, nitriles, isobutylene and / or styrene and water-soluble anionic condensation products of naphthalenesulfonic acid and formaldehyde are mentioned here.
  • suitable complexing agents can be selected from the group of phosphonocarboxylic acids and hydroxycarboxylic acids and aminopolycarboxylic acids.
  • the stabilizing effect of citrate or aminopolycarboxylate on the activating titanium phosphate colloids is known from US Pat. No. 3,864,139.
  • the complexing agents Depending on the molar ratio of complexing agent to titanium and after adding At the time of the reaction mixture, the complexing agents have different effects on the properties of the products obtained.
  • a substoichiometric ratio that is to say in a molar ratio of complexing agents (in the case of polymers with respect to the monomer unit) to titanium of less than 1 and when added before the beginning, but at the latest before the end of the microwave irradiation, the complexing agents affect the particle size of the titanium phosphate formed -Colloids off.
  • the teaching of EP-B-339452 shows that activating agents with particularly favorable activating properties are obtained in this way.
  • the complexing agents stabilize the ready-to-use activation baths prepared from the activating agent concentrates against premature loss of activity the influence of water hardness.
  • US-A-3,864,139 and EP-A-180523 are also preferably used as a complexing agent in the context of the present invention.
  • the molar ratio between complexing agents (in the case of polymers based on the Molar mass of the monomer units) and titanium compound is between 0.05 and 3.
  • it is advantageous to add the complexing agent to the reaction mixture before the end of the microwave irradiation, while for molar ratios between 1 and 3 at least the proportion of the complexing agent exceeding the molar ratio 1 also after the microwave irradiation has ended can be added. If the total amount of complexing agent is added before the microwave irradiation begins, this has a favorable effect on the viscosity of the reaction mixture.
  • the activating effect of colloidal titanium phosphates can be increased by adding ions of metals that are more noble than the substrates to be activated. continue to improve. As described in EP-A-454211, the presence of copper ions is particularly favorable.
  • the Cu: Ti weight ratio should be between 100: 1 and 1:60.
  • reaction mixture additionally contain calcium ions in a Ca: Ti molar ratio between 2: 1 and 5: 1.
  • EP-A-340530 discloses the production of titanium-free phosphate-containing activating agents for phosphating, with suitable complexing agents being reacted with a phosphate component. According to the present invention, this method can also be carried out using microwaves.
  • the same components or mixtures which were mentioned above for the reaction with titanium compounds and which can be described by the general formulas (I), (II) and (III) can be used as phosphate components.
  • the above-described poly (aldehydocarboxylic acids) or their alkali metal salts and / or 1,1-diphosphonic acids of the general formula (IV) are suitable as complexing agents.
  • the weight ratio of complexing agent to alkali metal phosphate is in the range from 0.01: 1 to 0.1: 1, preferably in the range from 0.02: 1 to 0.05: 1.
  • the titanium-containing or titanium-free, phosphate-containing activating agents produced under the action of microwaves are used for activating metal surfaces made of steel, zinc, aluminum or their alloys prior to phosphating, preferably zinc phosphating and in particular low-zinc phosphating, the activating agents in Form aqueous dispersions or solutions are used, the solids content of activating agent is 0.01 to 2, preferably 0.05 to 1 wt .-%.
  • the pH value of the ready-to-use activating solution or activating suspension lies in the technically customary range, such as that in the EP-A-454211 states: 7 to 11, preferably 7.5 to 10.
  • the ready-to-use activating bath can contain further auxiliaries which are known in the prior art (EP-A-454211), for example condensed phosphates in amounts of up to 1.2 g / 1 (calculated as P 2 0s), silicates in amounts up to 0.5 g / 1 (calculated as Si0 2 ), complexing agents in amounts up to 1 g / 1, water-soluble organic polymer in amounts up to 0, 1 g / 1, thickeners in amounts up to 0.1 g / 1 and surfactants in amounts up to 0.3 g / 1.
  • condensed phosphates in amounts of up to 1.2 g / 1 (calculated as P 2 0s)
  • silicates in amounts up to 0.5 g / 1 (calculated as Si0 2 )
  • the reaction mixtures were adjusted to a total solids content of 13% by weight of water and, using the thickening agent Kelzan K5C151 (polysaccharide of the xanthan type, from Kelco Corp.), to a viscosity between 18 and 21 DIN Seconds, determined as the flow time from a flow cup according to DIN 53211-4, thickened.
  • Kelzan K5C151 polysaccharide of the xanthan type, from Kelco Corp.
  • Example 9 In the case of Example 9, irradiation was carried out in a Teflon autoclave, with no water being able to evaporate due to the closed reaction vessel.
  • a reaction mixture according to Example 3 was irradiated with microwaves (700 W) in a Teflon autoclave provided with a manometer for 10 minutes.
  • the pressure in the autoclave rose to 3.5 bar, corresponding to a water temperature of approximately 140 ° C.
  • Activating agents produced by the process according to the invention were tested in connection with phosphating processes on steel sheets (St 1405) and on both sides electrolytically galvanized steel sheets (ZE), as are used in automobile construction.
  • the following process step (spray process) customary in body production was carried out:
  • the free acid score is the consumption in ml of 0.1 normal sodium hydroxide solution to titrate 10 ml bath solution up to a pH of 3.6. Similarly, the total acid score indicates consumption in ml up to a pH of 8.2.
  • the mass per unit area (“layer weight”) was determined by dissolving it in 5% chromic acid solution in accordance with DIN 50942. Table 2 contains the results. In all cases, optically perfect slice images were obtained.
  • Example 4 The influence of the irradiation time at 700 watts on the activatability of the products obtained was checked using a batch mixture according to Example 4. It was found that under the conditions of Example 4, a sufficient activation effect is not achieved if the irradiation time is less than 4 minutes. A good activation effect is observed with irradiation times between 5 and 15 minutes. Longer exposure times are possible, but do not bring any advantage.
  • Table 3 In order to check the influence of the microwave power in watts on the activating effect of the products obtained at a given irradiation time, tests were carried out in accordance with Table 3. A just acceptable activation effect was achieved with a microwave power of 240 watts with a layer weight of the phosphate layer of 2.9 g / m 2 . Higher microwave outputs yielded optimal activation results with layer weights of 1.2 to 1.6 g / m. Microwave powers over 800 watts are therefore not necessary under the chosen conditions for batch size and irradiation time.

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  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Treatment Of Metals (AREA)

Abstract

L'invention concerne un procédé de fabrication d'activateurs phosphatés destinés à l'activation de surfaces métalliques en acier, zinc, aluminium ou leurs alliages avant phosphatation. Ce procédé se caractérise en ce que l'on irradie au moyen de micro-ondes une solution aqueuse ou une suspension d'un ou de plusieurs phosphates, oligophosphates et/ou de polyphosphates de métaux alcalins avec un second réactif, celui-ci étant constitué par des dérivés du titane ou des agents complexants du groupe des acides phosphoniques et des acides poly(aldéhydocarboxyliques). Les activateurs sont de préférence formulés sous forme de concentré aqueux avec une teneur en matières solides comprise entre 5 et 30 % en poids.
PCT/EP1995/001654 1994-05-11 1995-05-02 Fabrication d'activateurs phosphates destines a la phosphatation par micro-ondes WO1995031588A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE59503273T DE59503273D1 (de) 1994-05-11 1995-05-02 Herstellung phosphathaltiger aktiviermittel für die phosphatierung unter einsatz von mikrowellen
EP95919995A EP0759097B1 (fr) 1994-05-11 1995-05-02 Fabrication d'activateurs a base de phosphates pour la phosphatation assistee par micro-ondes
JP7529314A JPH10500175A (ja) 1994-05-11 1995-05-02 マイクロ波を用いるリン酸塩処理用のリン酸塩含有活性化剤の製造

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4416619A DE4416619A1 (de) 1994-05-11 1994-05-11 Herstellung phosphathaltiger Aktiviermittel für die Phosphatierung unter Einsatz von Mikrowellen
DEP4416619.2 1994-05-11

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DE102019134298A1 (de) * 2019-12-13 2021-06-17 Thyssenkrupp Steel Europe Ag Verfahren zum Herstellen eines Stahlflachprodukts mit einer metallischen Schutzschicht auf Basis von Zink und einer auf einer Oberfläche der metallischen Schutzschicht erzeugten Phosphatierschicht und derartiges Stahlflachprodukt

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD111938A1 (fr) * 1974-06-27 1975-03-12
EP0201841A2 (fr) * 1985-05-10 1986-11-20 Nihon Parkerizing Co., Ltd. Procédé de phosphatation de surfaces métalliques
EP0340530A1 (fr) * 1988-04-28 1989-11-08 Henkel Kommanditgesellschaft auf Aktien Agents d'activation ne contenant pas de titane, procédé pour leur préparation et leur utilisation pour activer des surfaces métalliques avant la phosphatation au zinc
EP0454211A1 (fr) * 1990-04-21 1991-10-30 METALLGESELLSCHAFT Aktiengesellschaft Procédé pour appliquer des couches de phosphates sur des surfaces métalliques
EP0454212A1 (fr) * 1990-04-21 1991-10-30 METALLGESELLSCHAFT Aktiengesellschaft Procédé pour préparer des agents activateurs pour la phosphatation au zinc et leur utilisation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD111938A1 (fr) * 1974-06-27 1975-03-12
EP0201841A2 (fr) * 1985-05-10 1986-11-20 Nihon Parkerizing Co., Ltd. Procédé de phosphatation de surfaces métalliques
EP0340530A1 (fr) * 1988-04-28 1989-11-08 Henkel Kommanditgesellschaft auf Aktien Agents d'activation ne contenant pas de titane, procédé pour leur préparation et leur utilisation pour activer des surfaces métalliques avant la phosphatation au zinc
EP0454211A1 (fr) * 1990-04-21 1991-10-30 METALLGESELLSCHAFT Aktiengesellschaft Procédé pour appliquer des couches de phosphates sur des surfaces métalliques
EP0454212A1 (fr) * 1990-04-21 1991-10-30 METALLGESELLSCHAFT Aktiengesellschaft Procédé pour préparer des agents activateurs pour la phosphatation au zinc et leur utilisation

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DE59503273D1 (de) 1998-09-24
EP0759097A1 (fr) 1997-02-26
DE4416619A1 (de) 1995-11-16
JPH10500175A (ja) 1998-01-06
EP0759097B1 (fr) 1998-08-19

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