EP0324394B1 - Process and agent for simultaneous vibratory grinding, cleaning and passivation of metallic workpieces - Google Patents

Process and agent for simultaneous vibratory grinding, cleaning and passivation of metallic workpieces Download PDF

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Publication number
EP0324394B1
EP0324394B1 EP89100227A EP89100227A EP0324394B1 EP 0324394 B1 EP0324394 B1 EP 0324394B1 EP 89100227 A EP89100227 A EP 89100227A EP 89100227 A EP89100227 A EP 89100227A EP 0324394 B1 EP0324394 B1 EP 0324394B1
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EP
European Patent Office
Prior art keywords
weight
acids
quantities
acid
cleaning
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EP89100227A
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German (de)
French (fr)
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EP0324394A3 (en
EP0324394A2 (en
Inventor
Jürgen Dr. Geke
Hermann Drosdziok
Herbert Wievelhoff
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to AT89100227T priority Critical patent/ATE96716T1/en
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Publication of EP0324394A3 publication Critical patent/EP0324394A3/en
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/73Chemical 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 characterised by the process
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B24GRINDING; POLISHING
    • B24BMACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B31/00Machines or devices designed for polishing or abrading surfaces on work by means of tumbling apparatus or other apparatus in which the work and/or the abrasive material is loose; Accessories therefor
    • B24B31/12Accessories; Protective equipment or safety devices; Installations for exhaustion of dust or for sound absorption specially adapted for machines covered by group B24B31/00
    • B24B31/14Abrading-bodies specially designed for tumbling apparatus, e.g. abrading-balls
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-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
    • C23F3/00Brightening metals by chemical means

Definitions

  • the invention relates to methods and means for simultaneous surface grinding, cleaning and passivating metallic workpieces.
  • Metal workpieces or molded parts can be processed either by manual mechanical deburring, grinding, sanding, brushing and polishing or by a mechanical-mechanical processing method.
  • the purely manual mechanical processing of large quantities of metallic parts, especially small metallic parts, is hardly acceptable today for reasons of economy.
  • the mechanical-chemical processing e.g. the so-called "slide grinding” is a process that is carried out in bell apparatus, drum apparatus, vibration machines or centrifugal machines.
  • the workpieces are brought into contact with natural (pebbles, dolomite, quartz, etc.) or synthetic (ceramic or plastic-bonded corundum, aluminum oxide, silicon carbide or boron carbide) grinding wheels of various shapes under spraying with water-based compositions specially developed for vibratory grinding.
  • the size and external shape (triangles, cylinders, stars, cones, spheres, etc.) and the roughness of the grinding wheels ("chips") ensure that the metal surfaces are abraded, possibly also polished.
  • Metallic workpieces and / or moldings can be descaled, deburred, ground, smoothed, polished and polished by such surface grinding.
  • the chemical treatment agents used in the course of the surface grinding are matched in their composition and their dosage to the metallic surfaces that are to be surface-finished, but must also take into account special features of the special vibratory finishing process.
  • the main tasks of such treatment agents are to ensure good cleaning, dispersing and dirt-carrying capacity, so that oil and grease contamination are emulsified and the abrasion of the abrasive bodies and the workpieces is completely removed and is not deposited on the workpieces.
  • the agents are intended to prevent corrosion of the metallic workpieces or molded parts and, moreover, to have a favorable influence on the grinding action and / or polishing action during slide grinding.
  • the agents do not coat the molded parts with a lubricating layer during grinding, which prevent the gloss effect when polishing the molded parts.
  • abrasives can act on the grinding action of the chips, thereby making it possible to deburr and pre-grind the workpieces with the same chips and, after changing the chemical treatment agent, to carry out a fine treatment and polishing.
  • the agents are usually packaged in such a way that they can be concentrated in liquid form or metered in prediluted by means of automated pumps.
  • abrasives react neutral to weakly alkaline in water and contain combinations of washing-active and corrosion-inhibiting substances.
  • US-A-3 071 456 describes a method for barrel finishing of metal parts with the aid of grinding wheels.
  • Aqueous formulations which contain phosphoric acid or phosphoric acid salts and / or nitro compounds or carboxylic acids, for example benzoic acid, toluic acid, gallic acid, acetic acid, citric acid or oxalic acid. These formulations result in the formation of a thin layer on the metal surfaces, which is rubbed off on the one hand by the mechanical treatment and on the other hand subsequently formed again.
  • the formulations can also contain wetting agents, for example petroleum sulfonate, and oxidation inhibitors.
  • FR-A-1 423 822 relates to a method for polishing stainless steel metal surfaces by mechanical treatment.
  • the formulations used here contain, in addition to grinding wheels, dilute acids, for example hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid or sulfonic acids, and surface-active substances.
  • the invention also relates to means for simultaneous surface grinding, cleaning and passivating metallic workpieces.
  • the method according to the invention and the means used in this method for simultaneous surface grinding, cleaning and passivating metallic workpieces can be applied to metallic workpieces and / or molded parts of the most varied composition. So it is possible in the course of the process workpieces or molded parts made of iron and all tendon alloys, for example steels of different compositions, cast iron, etc., copper and its alloys, for example brass, bronze etc., aluminum alloys, zinc or magnesium or other metals or Treat alloys.
  • the surprising thing about the present method is that not only the actual mechanical-chemical surface treatment of the surface grinding, which is usually carried out in drums or vibrators, can be carried out using these solutions.
  • the usually upstream step of cleaning the metallic workpieces or molded parts and passivating the respective metallic surface is carried out with the same solutions in the same process without the need for additional systems or treatment solutions.
  • the respective metallic surface is cleaned, descaled, passivated, deburred, ground, smoothed, polished and polished in one step.
  • the workpieces are brought into contact with aqueous solutions which have a pH in the range from 1 to 6. Solutions which have a pH in the range from 3.5 to 5 are preferably used.
  • aqueous solutions according to the invention are usually applied in the present process by spraying the workpieces or molded parts in the systems (drums, vibrators, etc.) in which they are moved together with the grinding wheels, with the aqueous solutions and these between the workpieces and run through the grinding wheels to the bottom of the respective system.
  • the solutions are in contact with the grinding wheel surfaces and metallic surfaces. They also remove the dirt detached in the cleaning process and the metal particles and / or abrasive particles detached in the tumble grinding process, are freed of such contaminants after exiting the system and brought back into contact with the workpieces and molded parts.
  • the workpieces and moldings are brought into contact with aqueous solutions which contain alkali metal salts and / or ammonium salts of orthophosphoric acid and / or pyrophosphoric acids as one of the essential components.
  • alkali metal salts are understood to mean all those compounds which have formed by condensation of several phosphate groups on one another.
  • the alkali metal salts are therefore the lithium salts, sodium salts, potassium salts, rubidium salts or cesium salts, of which the potassium salts and particularly the sodium salts are preferred because of their ready availability are.
  • ammonium salts both those with an NH4+ cation and also those ammonium salts which carry one or more organic substituents on the nitrogen atom can be used.
  • organoammonium compounds those which carry one or more alkyl radicals with a straight-chain or branched chain and 1 to 6 carbon atoms in the alkyl radical are particularly preferred.
  • the ammonium salts the NH4+ salts are particularly preferred and can advantageously be used as phosphate components in the aqueous solutions which are used in the process according to the invention.
  • the workpieces are brought into contact with acidic aqueous solutions which contain one or more of the phosphate components mentioned in amounts of 0.2 to 10% by weight.
  • the weight data are based on the finished application solution and indicate the active substance content which is used in such application solutions.
  • the inventive method for simultaneous surface grinding, cleaning and passivating metallic workpieces is further characterized in that the workpieces or molded parts are brought into contact with aqueous solutions which contain tartaric acid or citric acid or mixtures of these two carboxylic acids as a further essential component.
  • such aqueous solutions for simultaneous vibratory grinding, for cleaning and passivation of metallic workpieces which contain the carboxylic acid components mentioned in amounts of 0.01 to 1% by weight.
  • carboxylic acid components these is also based on the active substance content in the finished application solutions.
  • Another component of the aqueous solutions used in the process according to the invention are nonionic surfactants, it also being possible here for the aqueous solutions to contain one or more surfactants as surface-active components.
  • the total amounts of surfactants contained in the aqueous solutions used are in the range from 0.005 to 2% by weight, according to the process of the invention. This information also relates to the active substance content in the application solution.
  • the aqueous treatment solutions optionally contain one or more corrosion inhibitors.
  • Corrosion inhibitors of this type are to be matched to the metal from which the metallic workpieces or molded parts are made, which are to be cleaned, passivated and, at the same time, subjected to vibratory grinding according to the inventive method.
  • Aqueous solutions are preferably used in which one or more compounds from the group of alkali metal molybdates, preferably sodium molybdates, benzotriazole, tolyltriazole and benzothiazole, are used as corrosion inhibitor components.
  • Such corrosion inhibitors which, like the other components, can be used alone or in combination of several components acting in the same direction, are present in amounts of 0.001 to 0.02% by weight. As with the other components, this information is based on the active substance content in the application solution.
  • the process can be carried out using such acidic aqueous solutions which, in addition to the components described generally or in more detail above, also contain other active substances and / or auxiliaries which are customary per se.
  • active ingredients can be, for example, water hardness stabilizers. Their use is particularly advantageous if the treatment agents were mixed with water in the process, which contains large amounts of hardness formers, in particular alkaline earth metal carbonates.
  • Such water hardness stabilizers are, for example, phosphonic acids, such as, for example, hydroxyethane diphosphonic acid (HEDP) or phosphonobutane tricarboxylic acid (PBTC), or their water-soluble salts, but also ethylenediaminetetraacetic acid or its water-soluble salts, nitrilotriacetic acid and its water-soluble salts or else for such purposes from the Connections known in the art. If their co-use is desired, these are present in amounts of 0.01 to 0.2% by weight and allow the use of "hard" water in the process according to the invention.
  • phosphonic acids such as, for example, hydroxyethane diphosphonic acid (HEDP) or phosphonobutane tricarboxylic acid (PBTC)
  • HEDP hydroxyethane diphosphonic acid
  • PBTC phosphonobutane tricarboxylic acid
  • ethylenediaminetetraacetic acid or its water-soluble salts nitri
  • such aqueous solutions are usually brought into contact with the metallic workpieces or molded parts by dipping or spraying.
  • This is usually carried out at temperatures in the range from 20 to 60 ° C., but preferably at room temperature.
  • the treatment times depend very much on the degree of soiling, the thickness of the burrs or protrusions to be removed, the hardness, size and shape of the abrasive bodies and also on the properties of the aqueous treatment solutions. In preferred embodiments of the method, they are in the range between 10 and 60 minutes.
  • the surface treatment is followed only by a drying process.
  • This drying process can be carried out using conventional aids, such as, for example, maize meal, wood flour, etc., at room temperature using the drum method or using warm air. In special cases, however, a rinse can also be provided before the drying process. This essentially depends on the type of further treatment of the workpieces or molded parts treated according to the method according to the invention.
  • the invention also includes the means used in the method described in more detail above for simultaneous surface grinding, cleaning and passivating metallic workpieces or molded parts.
  • the agents can either be packaged in powder form and packaged as such and stirred into water at the application site with little effort, or they are prepared in the form of highly concentrated aqueous solutions and merely diluted at the application site.
  • the former has the advantage that only the pure substance is transported, thus avoiding unnecessary water transport.
  • the latter is more advantageous because liquid concentrates can be metered in automatically at the application site by means of metering pumps and thus make handling easier for the user.
  • the aqueous solutions which come on the market in the form of concentrates are homogeneous. Due to the components they contain, aqueous concentrates have a pH in the range from 1 to 6.
  • the pH value is preferably in the range from 3.5 to 5. However, if the pH value is not in this range due to the use of more alkaline components, it can optionally be added by adding non-corrosive acids, preferably for example phosphoric acids, phosphonic acids, phosphonocarboxylic acids or Carboxylic acids. However, a pH adjustment is usually not necessary.
  • the aqueous application solutions are usually used with an active substance content in the range from approximately 0.2 to approximately 14% by weight.
  • the agents according to the invention for simultaneous surface grinding, cleaning and passivating metallic workpieces contain, as phosphate components, alkali metal salts and / or ammonium salts of orthophosphoric acid and / or pyrophosphoric acids.
  • Preferred phosphate components in the agents according to the invention are acidic sodium phosphates and / or sodium pyrophosphates.
  • Other essential components of the agents according to the invention are tartaric acid and / or citric acid.
  • nonionic surfactants are nonionic surfactants. These can also be represented as individual compounds or in a mixture of several surfactants.
  • Such polyalkylene glycol ethers are known as weakly foaming nonionic surfactants, in some cases even as pronounced defoamers, and are therefore particularly suitable.
  • the agents according to the invention can optionally also contain one or more corrosion inhibitors. These are usually matched to the respective specific application problem and are thus geared towards the metallic surfaces that are to be cleaned, passivated and slip-treated. Suitable corrosion inhibitors can also be used with one another, which has the advantage that the agents according to the invention can thereby be used for a larger number of applications.
  • Compounds from the group alkali metal molybdates, preferably sodium molybdates, benzotriazole, tolyltriazole and benzothiazole, are preferably used as corrosion inhibitors.
  • the agents according to the invention can also contain other active substances and / or auxiliaries which are customary in cleaning, passivating and slide grinding agents.
  • additional active ingredients which are also used in preferred embodiments of the agents according to the invention, are water hardness stabilizers.
  • individual compounds or combinations from the group of the phosphonic acids such as, for example, hydroxyethyldiphosphonic acid, phosphonobutane tricarboxylic acid, or their water-soluble salts, ethylenediaminetetraacetic acid and their salts and nitrilotriacetic acid and their water-soluble salts can be used.
  • the agents according to the invention can be used as powder, i.e. as 100% active substance or as concentrates.
  • the application solutions have an active substance content in the range from approximately 0.2 to approximately 14% by weight.
  • the total amounts of the components specified above in detail are thus mixed with an amount of water which adds up to 100% by weight of the total amount of all components.
  • pH values are usually in the range from 1 to 6, preferably from 3.5 to 5. If, in the application solutions according to the invention, this pH value is not achieved solely by the specified components, further acids can optionally be added. However, these acids must not be corrosive and preferably come from the group of phosphoric acids, phosphonic acids, phosphonocarboxylic acids and carboxylic acids.
  • the invention is illustrated by the following example.
  • the metal parts were degreased, passivated and deburred at 20 ° C. for 20 minutes under the action of this solution, which had a pH of 3.5.
  • the result of this one-step process showed that very good degreasing and passivation had taken place and that the production-related metal burrs had been completely removed.
  • the steel parts showed a bluish-iridescent passivation layer.
  • the surfaces of the non-ferrous metals were, without exception, bare and smooth and showed no corrosion or contact points.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Physical Vapour Deposition (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

The invention relates to a process and agent for the simultaneous vibratory grinding, cleaning and passivation of metallic workpieces using acidic aqueous solutions which contain orthophosphoric acid and/or pyrophosphoric acids and/or water-soluble salts thereof, oligocarboxylic acids and, if required, also surfactants, corrosion inhibitors and other customary active ingredients and/or auxiliaries.

Description

Die Erfindung betrifft Verfahren und Mittel zum gleichzeitigen Gleitschleifen, Reinigen und Passivieren metallischer Werkstücke.The invention relates to methods and means for simultaneous surface grinding, cleaning and passivating metallic workpieces.

Metallische Werkstücke oder Gebrauchsgegenstände werden heute weitgehend im Wege der industriellen Massenfertigung in automatisierten Verfahren hergestellt. Die Oberflächen derartiger Metallteile, die aus Stahl, Gußeisen, Kupfer und seinen Legierungen, Aluminium und seinen Legierungen, Zink, Magnesium und anderen Metallen hergestellt sind, müssen meist noch einer Endbearbeitung unterworfen werden, bevor sie unmittelbar vertrieben, bestimmungsgemäß verwendet oder in bekannten Veredelungsverfahren weiterverarbeitet werden.Metallic workpieces or articles of daily use are now largely manufactured by means of industrial mass production in automated processes. The surfaces of such metal parts, which are made of steel, cast iron, copper and its alloys, aluminum and its alloys, zinc, magnesium and other metals, usually have to be subjected to a finishing process before they are sold directly, used as intended or further processed in known finishing processes will.

Durch Drehen, Fräsen, Gießen oder ähnliche, metallverarbeitende Verfahren hergestellte metallische Werkstücke haben häufig scharfe Schnittkanten oder Ecken oder auch rauhe oder mit Zunderschichten überzogene Oberflächen, so daß ein Entgraten und Abrunden der Schnittkanten und Ecken, häufig auch ein Glätten oder Polieren der gesamten Oberfläche, erforderlich ist. Gerade in Verfahren der Weiterverarbeitung ist die Qualität nachfolgend aufgebrachter Oberflächenschichten auf derartige Werkstücke in starkem Maße davon abhängig, wie gut die metallische Oberfläche für die Aufbringung derartiger zusätzlicher, veredelnder Schichten vorbereitet ist. Beispielsweise kann die galvanische Abscheidung von Metallen auf derartigen Oberflächen nur dann befriedigend verlaufen, wenn dem galvanischen Abscheidungsprozeß eine Reinigung, Entzunderung und schleifende Bearbeitung der Oberfläche vorausgegangen ist.Metallic workpieces produced by turning, milling, casting or similar, metal-processing methods often have sharp cut edges or corners or also rough or surfaces covered with scale layers, so that deburring and rounding of the cut edges and corners, often also smoothing or polishing of the entire surface, is required. Especially in processes of further processing, the quality of subsequently applied surface layers on such workpieces depends to a large extent on how good the metallic surface is for the application of such additional, refining agents Layers is prepared. For example, the galvanic deposition of metals on such surfaces can only proceed satisfactorily if the galvanic deposition process has been preceded by cleaning, descaling and grinding of the surface.

Die Bearbeitung metallischer Werkstücke oder Formteile kann entweder durch manuelles mechanisches Entgraten, Schleifen, Schmirgeln, Bürsten und Polieren oder durch ein mechanischchemisches Bearbeitungsverfahren erfolgen. Die rein manuellmechanische Bearbeitung von in großen Stückzahlen hergestellten metallischen Teilen, insbesondere von metallischen Kleinteilen, ist heute aus Wirtschaftlichkeitsgründen kaum noch vertretbar. Die mechanisch-chemische Bearbeitung, wie z.B. das sogenannte "Gleitschleifen" ist ein Verfahren, das in Glockenapparaten, Trommelapparaten, Vibrationsmaschinen oder Fliehkraftmaschinen vorgenommen wird. Die Werkstücke werden unter Besprühen mit speziell für das Gleitschleifen entwickelten Zusammensetzungen auf wäßriger Basis in eine gleitende Berührung mit natürlichen (Kieselsteine, Dolomit, Quarz usw.) oder synthetischen (keramisch- oder kunststoffgebundener Korund, Aluminiumoxid, Siliciumcarbid oder Borcarbid) Schleifkörpern unterschiedlichster Formen gebracht. Die Größe und äußere Form (Dreiecke, Zylinder, Sterne, Konusse, Kugeln usw.) und die Rauhigkeit der Schleifkörper ("Chips") sorgt für eine abschleifende, gegebenenfalls auch polierende Bearbeitung der Metalloberflächen. Durch ein derartiges Gleitschleifen können metallische Werkstücke und/ oder Formkörper entzundert, entgratet, geschliffen, geglättet, geglänzt und poliert werden.Metal workpieces or molded parts can be processed either by manual mechanical deburring, grinding, sanding, brushing and polishing or by a mechanical-mechanical processing method. The purely manual mechanical processing of large quantities of metallic parts, especially small metallic parts, is hardly acceptable today for reasons of economy. The mechanical-chemical processing, e.g. the so-called "slide grinding" is a process that is carried out in bell apparatus, drum apparatus, vibration machines or centrifugal machines. The workpieces are brought into contact with natural (pebbles, dolomite, quartz, etc.) or synthetic (ceramic or plastic-bonded corundum, aluminum oxide, silicon carbide or boron carbide) grinding wheels of various shapes under spraying with water-based compositions specially developed for vibratory grinding. The size and external shape (triangles, cylinders, stars, cones, spheres, etc.) and the roughness of the grinding wheels ("chips") ensure that the metal surfaces are abraded, possibly also polished. Metallic workpieces and / or moldings can be descaled, deburred, ground, smoothed, polished and polished by such surface grinding.

Die im Zuge des Gleitschleifens verwendeten chemischen Behandlungsmittel ("Compounds") werden in ihrer Zusammensetzung und ihrer Dosierung auf die metallischen Oberflächen abgestimmt, die gleitschleifend bearbeitet werden sollen, müssen jedoch auch Besonderheiten des speziellen Gleitschleifprozesses berücksichtigen. Die Hauptaufgaben derartiger Behandlungsmittel liegen darin, ein gutes Reinigungs-, Dispergier- und Schmutztragevermögen sicherzustellen, so daß Öl- und Fettverschmutzungen einemulgiert werden und der Abrieb der Schleifkörper und der Werkstücke vollständig entfernt und nicht auf den Werkstücken abgelagert wird. Zudem sollen die Mittel eine Korrosion der metallischen Werkstücke oder Formteile verhindern und zudem die Schleifwirkung und/oder Polierwirkung während des Gleitschleifens günstig beeinflussen. Dafür ist es erforderlich, daß die Mittel während des Schleifens die Formteile nicht mit einer Schmierschicht überziehen, die den Glanzeffekt beim Polieren der Formteile verhindern. Zudem können derartige Schleifmittel durch ihre Zusammensetzung auf die Schleifwirkung der Chips einwirken und es dadurch möglich machen, mit denselben Chips die Werkstücke zuerst zu entgraten und vorzuschleifen und, nach Wechsel des chemischen Behandlungsmittels, eine Feinbehandlung und Polierung anzuschließen.The chemical treatment agents ("compounds") used in the course of the surface grinding are matched in their composition and their dosage to the metallic surfaces that are to be surface-finished, but must also take into account special features of the special vibratory finishing process. The main tasks of such treatment agents are to ensure good cleaning, dispersing and dirt-carrying capacity, so that oil and grease contamination are emulsified and the abrasion of the abrasive bodies and the workpieces is completely removed and is not deposited on the workpieces. In addition, the agents are intended to prevent corrosion of the metallic workpieces or molded parts and, moreover, to have a favorable influence on the grinding action and / or polishing action during slide grinding. For this it is necessary that the agents do not coat the molded parts with a lubricating layer during grinding, which prevent the gloss effect when polishing the molded parts. In addition, due to their composition, such abrasives can act on the grinding action of the chips, thereby making it possible to deburr and pre-grind the workpieces with the same chips and, after changing the chemical treatment agent, to carry out a fine treatment and polishing.

Üblicherweise werden die Mittel so konfektioniert, daß sie in flüssiger Form konzentriert oder vorverdünnt mittels automatisierten Pumpen dosiert werden können. Üblicherweise reagieren derartige Gleitschleifmittel in Wasser neutral bis schwach alkalisch und enthalten Kombinationen waschaktiver und korrosionsinhibierender Substanzen.The agents are usually packaged in such a way that they can be concentrated in liquid form or metered in prediluted by means of automated pumps. Typically, such abrasives react neutral to weakly alkaline in water and contain combinations of washing-active and corrosion-inhibiting substances.

Nachteilig an den aus dem Stand der Technik bekannten und meist rein empirisch entwickelten Produkten ist es, daß für jeden Anwendungsfall, d.h. jedes metallische Material der Werkstücke bzw. Formteile, ein unterschiedlich eingestelltes Mittel verwendet werden mußte. Dies bedingte eine vollständige Umstellung des Gleitschleif-Vorgangs bei Wechsel der im Gleitschleif-Verfahren zu bearbeitenden Werkstücke. Nachteilig war es weiterhin, daß befriedigende Ergebnisse beim Gleitschleifen nur dann erzielt werden konnten, wenn die Oberflächen der metallischen Werkstücke oder Formteile vor dem Gleitschleifen sorgfältig gereinigt und passiviert worden waren. Dem eigentlichen Gleitschleifen vorgelagerte Bearbeitungsprozesse waren also erforderlich, um die Metalloberfläche in der gewünschten Form zu konditionieren. Abgesehen davon, daß diese vorgelagerten Bearbeitungsschritte getrennte Anlagen und Chemikalien erforderten, wurde die Wirkung der Gleitschleif-Mittel und damit auch der Erfolg des Gleitschleif-Verfahrens regelmäßig dadurch sehr nachteilig beeinflußt, daß die Reinigungsmittel und Passivierungsmittel in die Apparaturen zum Gleitschleifen eingeschleppt wurden. Dadurch konnten die Compounds beim Gleitschleifen nur in begrenztem Umfang ihre Wirkung entfalten.A disadvantage of the products known from the prior art and mostly developed purely empirically is that a differently adjusted agent had to be used for each application, ie each metallic material of the workpieces or molded parts. This necessitated a complete changeover of the vibratory finishing process when changing the workpieces to be machined using the vibratory finishing process. It was also disadvantageous that satisfactory results were only achieved with surface grinding could be achieved if the surfaces of the metallic workpieces or molded parts had been carefully cleaned and passivated before the surface grinding. Machining processes upstream of the actual vibratory grinding were therefore necessary in order to condition the metal surface in the desired shape. In addition to the fact that these upstream processing steps required separate systems and chemicals, the effect of the surface grinding agents and thus the success of the surface grinding method was regularly adversely affected by the fact that the cleaning agents and passivating agents were introduced into the equipment for surface grinding. As a result, the compounds were only able to develop their effects to a limited extent during surface grinding.

In der US-A-3 071 456 wird ein Verfahren zum Gleitschleifen (barrel finishing) von Metallteilen mit Hilfe von Schleifkörpern beschrieben. Hierbei werden wäßrige Formulierungen eingesetzt, die Phosphorsäure oder phosphorsaure Salze und/oder Nitroverbindungen oder Carbonsäuren, beispielsweise Benzoesäure, Toluylsäure, Gallussäure, Essigsäure, Citronensäure oder Oxalsäure, enthalten. Diese Formulierungen bedingen die Ausbildung einer dünnen Schicht auf den Metalloberflächen, die einerseits durch die mechanische Behandlung abgerieben und andererseits anschließend jeweils erneut ausgebildet wird. Die Formulierungen können ferner Netzmittel, beispielsweise Petroleumsulfonat, und Oxidationsinhibitoren enthalten.US-A-3 071 456 describes a method for barrel finishing of metal parts with the aid of grinding wheels. Aqueous formulations are used which contain phosphoric acid or phosphoric acid salts and / or nitro compounds or carboxylic acids, for example benzoic acid, toluic acid, gallic acid, acetic acid, citric acid or oxalic acid. These formulations result in the formation of a thin layer on the metal surfaces, which is rubbed off on the one hand by the mechanical treatment and on the other hand subsequently formed again. The formulations can also contain wetting agents, for example petroleum sulfonate, and oxidation inhibitors.

Ferner betrifft die FR-A-1 423 822 ein Verfahren zum Polieren von Metalloberflächen aus rostfreiem Stahl durch eine mechanische Behandlung. Die hierbei eingesetzten Formulierungen enthalten neben Schleifkörpern verdünnte Säuren, beispielsweise Salzsäure, Salpetersäure, Phosphorsäure, Schwefelsäure oder Sulfonsäuren, und oberflächenaktive Substanzen.Furthermore, FR-A-1 423 822 relates to a method for polishing stainless steel metal surfaces by mechanical treatment. The formulations used here contain, in addition to grinding wheels, dilute acids, for example hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid or sulfonic acids, and surface-active substances.

Überraschenderweise wurde nun gefunden, daß es bei Verwendung pulverförmiger oder flüssiger Mittel möglich ist, im Tauchverfahren oder Spritzverfahren die einzelnen Verfahrensschritte des Gleitschleifens, Reinigens und Passivierens in einem Verfahrensschritt zu vereinigen und dafür auch nur ein Mittel zu verwenden, das reinigend und passivierend wirkt und auch den Gleitschleifprozeß fördert. Damit ist es möglich geworden, die anwendungstechnischen Nachteile eines dreischrittigen Verfahrens unter Verwendung dreier unterschiedlich zusammengesetzter Lösungen zu vermeiden.Surprisingly, it has now been found that when powdery or liquid agents are used, it is possible to combine the individual process steps of surface grinding, cleaning and passivating in one process step by immersion or spraying process and to use only one agent for this which has a cleaning and passivating effect and also promotes the finishing process. This has made it possible to avoid the technical disadvantages of a three-step process using three differently composed solutions.

Die Erfindung betrifft ein Verfahren zum gleichzeitigen Gleitschleifen, Reinigen und Passivieren metallischer Werkstücke unter Verwendung saurer, wäßriger Lösungen, enthaltend Salze von Phosphorsäuren, Carbonsäuren und Netzmittel, welches dadurch gekennzeichnet ist, daß man die Werkstücke mit wäßrigen, einen pH-Wert im Bereich von 1 bis 6 aufweisenden Lösungen in Kontakt bringt, die die folgenden Komponenten enthalten:

  • (a) 0,2 bis 10 Gew.-% Alkalimetallsalze und/oder Ammoniumsalze der Orthophosphorsäure und/oder von Pyrophosphorsäuren,
  • (b) 0,01 bis 1 Gew.-% Weinsäure und/oder Citronensäure,
  • (c) 0,005 bis 2 Gew.-% eines oder mehrerer nichtionischer Tenside,
  • (d) gegebenenfalls 0,001 bis 0,02 Gew.-% eines oder mehrerer Korrosionsinhibitoren und
  • (e) gegebenenfalls 0,01 bis 0,2 Gew.-% weiterer, in Reinigungs-, Passivierungs- und Gleitschleifmitteln an sich üblicher Wirkstoffe und/oder Hilfsstoffe,
wobei die jeweils angegebenen Mengen auf den Aktivsubstanzgehalt in der Anwendungslösung bezogen sind.The invention relates to a method for simultaneous vibratory grinding, cleaning and passivation of metallic workpieces using acidic, aqueous solutions containing salts of phosphoric acids, carboxylic acids and wetting agents, which is characterized in that the workpieces with aqueous, a pH in the range of 1 up to 6 solutions that contain the following components:
  • (a) 0.2 to 10% by weight of alkali metal salts and / or ammonium salts of orthophosphoric acid and / or pyrophosphoric acids,
  • (b) 0.01 to 1% by weight of tartaric acid and / or citric acid,
  • (c) 0.005 to 2% by weight of one or more nonionic surfactants,
  • (d) optionally 0.001 to 0.02% by weight of one or more corrosion inhibitors and
  • (e) optionally from 0.01 to 0.2% by weight of further active substances and / or auxiliaries which are customary per se in cleaning, passivating and surface grinding agents,
where the amounts specified are based on the active substance content in the application solution.

Die Erfindung betrifft außerdem Mittel zum gleichzeitigen Gleitschleifen, Reinigen und Passivieren metallischer Werkstücke.The invention also relates to means for simultaneous surface grinding, cleaning and passivating metallic workpieces.

Das erfindungsgemäße Verfahren und die in diesem Verfahren verwendeten Mittel zum gleichzeitigen Gleitschleifen, Reinigen und Passivieren metallischer Werkstücke können auf metallische Werkstücke und/oder Formteile unterschiedlichster Zusammensetzung angewendet werden. So ist es möglich, im Zuge des Verfahrens Werkstücke oder Formteile aus Eisen und allen sehnen Legierungen, beispielsweise Stählen unterschiedlicher Zusammensetzung, Gußeisen usw., Kupfer und seinen Legierungen, beispielsweise Messing, Bronze usw., Aluminiumlegierungen, Zink oder Magnesium oder auch anderen Metallen oder Legierungen zu behandeln. Das Überraschende des vorliegenden Verfahrens liegt darin, daß nicht nur die eigentliche mechanisch-chemische Oberflächenbehandlung des Gleitschleifens, die üblicherweise in Trommeln oder Vibratoren durchgeführt wird, unter Verwendung dieser Lösungen durchgeführt werden kann. Vielmehr wird auch der üblicherweise vorgelagerte Schritt des Reinigens der metallischen Werkstücke oder Formteile und der Passivierung der jeweiligen metallischen Oberfläche mit denselben Lösungen im gleichen Verfahrensgang durchgeführt, ohne daß es dafür zusätzlicher Anlagen oder Behandlungslösungen bedürfte. So wird in einem Schritt die jeweilige metallische Oberfläche gereinigt, entzundert, passiviert, entgratet, geschliffen, geglättet, geglänzt und poliert.The method according to the invention and the means used in this method for simultaneous surface grinding, cleaning and passivating metallic workpieces can be applied to metallic workpieces and / or molded parts of the most varied composition. So it is possible in the course of the process workpieces or molded parts made of iron and all tendon alloys, for example steels of different compositions, cast iron, etc., copper and its alloys, for example brass, bronze etc., aluminum alloys, zinc or magnesium or other metals or Treat alloys. The surprising thing about the present method is that not only the actual mechanical-chemical surface treatment of the surface grinding, which is usually carried out in drums or vibrators, can be carried out using these solutions. Rather, the usually upstream step of cleaning the metallic workpieces or molded parts and passivating the respective metallic surface is carried out with the same solutions in the same process without the need for additional systems or treatment solutions. The respective metallic surface is cleaned, descaled, passivated, deburred, ground, smoothed, polished and polished in one step.

Dazu bringt man erfindungsgemäß die Werkstücke mit wäßrigen Lösungen in Kontakt, die einen pH-Wert im Bereich von 1 bis 6 aufweisen. Bevorzugt werden solche Lösungen verwendet, die einen pH-Wert im Bereich von 3,5 bis 5 aufweisen. Der Kontakt mit den Werkstücken oder Formteilen erfolgt - je nach Anlage - durch Eintauchen oder Besprühen. Üblicherweise werden die erfindungsgemäßen wäßrigen Lösungen in dem vorliegenden Verfahren dadurch aufgebracht, daß man die Werkstücke oder Formteile in den Anlagen (Trommeln, Vibratoren usw.), in denen sie zusammen mit den Schleifkörpern bewegt werden, mit den wäßrigen Lösungen besprüht und diese zwischen den Werkstücken und den Schleifkörpern hindurch zum Boden der jeweiligen Anlage laufen. Dabei sind die Lösungen in Kontakt mit den Schleifkörperoberflächen und metallischen Oberflächen. Sie tragen außerdem die im Reinigungsgang abgelösten Verschmutzungen sowie die im Gleitschleifgang abgelösten Metallpartikelchen und/oder Schleifkörperpartikelchen aus der Behandlungszone aus, werden nach Austritt aus der Anlage von derartigen Verunreinigungen befreit und erneut mit den Werkstücken und Formteilen in Kontakt gebracht.For this purpose, according to the invention, the workpieces are brought into contact with aqueous solutions which have a pH in the range from 1 to 6. Solutions which have a pH in the range from 3.5 to 5 are preferably used. Depending on the system, contact with the workpieces or molded parts takes place by immersion or spraying. The aqueous solutions according to the invention are usually applied in the present process by spraying the workpieces or molded parts in the systems (drums, vibrators, etc.) in which they are moved together with the grinding wheels, with the aqueous solutions and these between the workpieces and run through the grinding wheels to the bottom of the respective system. The solutions are in contact with the grinding wheel surfaces and metallic surfaces. They also remove the dirt detached in the cleaning process and the metal particles and / or abrasive particles detached in the tumble grinding process, are freed of such contaminants after exiting the system and brought back into contact with the workpieces and molded parts.

In dem erfindungsgemäßen Verfahren werden die Werkstücke und Formteile mit wäßrigen Lösungen in Kontakt gebracht, die Alkalimetallsalze und/oder Ammoniumsalze der Orthophosphorsäure und/oder von Pyrophosphorsäuren als eine der wesentlichen Komponenten enthalten. Dabei versteht man unter "Pyrophosphorsäuren" alle diejenigen Verbindungen, die durch Kondensation mehrerer Phosphatgruppen aneinander entstanden sind. Es kommen also als Alkalimetallsalze die Lithiumsalze, Natriumsalze, Kaliumsalze, Rubidiumsalze oder Cäsiumsalze in Betracht, von denen aufgrund ihrer leichten Verfügbarkeit die Kaliumsalze und besonders die Natriumsalze bevor-zugt sind. Als Ammoniumsalze können sowohl solche mit einem NH₄⁺-Kation als auch solche Ammoniumsalze verwendet werden, die einen oder mehrere organische Substituenten am Stickstoffatom tragen. Von derartigen Organoammoniumverbindungen sind besonders die bevorzugt, die einen oder mehrere Alkylreste mit geradkettiger oder verzweigter Kette und 1 bis 6 C-Atomen im Alkylrest tragen. Von den Ammoniumsalzen sind die NH₄⁺-Salze besonders bevorzugt und mit Vorteil als Phosphatkomponenten in den wäßrigen Lösungen verwendbar, die in dem erfindungsgemäßen Verfahren eingesetzt werden.In the process according to the invention, the workpieces and moldings are brought into contact with aqueous solutions which contain alkali metal salts and / or ammonium salts of orthophosphoric acid and / or pyrophosphoric acids as one of the essential components. "Pyrophosphoric acids" are understood to mean all those compounds which have formed by condensation of several phosphate groups on one another. The alkali metal salts are therefore the lithium salts, sodium salts, potassium salts, rubidium salts or cesium salts, of which the potassium salts and particularly the sodium salts are preferred because of their ready availability are. As ammonium salts, both those with an NH₄⁺ cation and also those ammonium salts which carry one or more organic substituents on the nitrogen atom can be used. Of such organoammonium compounds, those which carry one or more alkyl radicals with a straight-chain or branched chain and 1 to 6 carbon atoms in the alkyl radical are particularly preferred. Of the ammonium salts, the NH₄⁺ salts are particularly preferred and can advantageously be used as phosphate components in the aqueous solutions which are used in the process according to the invention.

In dem erfindungsgemäßen Verfahren werden die Werkstücke mit sauren wäßrigen Lösungen in Kontakt gebracht, die eine oder mehrere der genannten Phosphatkomponenten in Mengen von 0,2 bis 10 Gew.-% enthalten. Die Gewichtsangaben sind dabei bezogen auf die fertige Anwendungslösung und geben den Aktivsubstanz-Gehalt an, der in derartigen Anwendungslösungen zum Einsatz kommt.In the process according to the invention, the workpieces are brought into contact with acidic aqueous solutions which contain one or more of the phosphate components mentioned in amounts of 0.2 to 10% by weight. The weight data are based on the finished application solution and indicate the active substance content which is used in such application solutions.

Das erfindungsgemäße Verfahren zum gleichzeitigen Gleitschleifen, Reinigen und Passivieren metallischer Werkstücke ist weiterhin dadurch gekennzeichnet, daß man die Werkstücke oder Formteile mit wäßrigen Lösungen in Kontakt bringt, die als weitere essentielle Komponente Weinsäure oder Citronensäure oder Mischungen dieser beiden Carbonsäuren enthalten.The inventive method for simultaneous surface grinding, cleaning and passivating metallic workpieces is further characterized in that the workpieces or molded parts are brought into contact with aqueous solutions which contain tartaric acid or citric acid or mixtures of these two carboxylic acids as a further essential component.

Erfindungsgemäß werden solche wäßrige Lösungen zum gleichzeitigen Gleitschleifen, zur Reinigung und Passivierung metallischer Werkstücke eingesetzt, die die genannten Carbonsäurekomponenten in Mengen von 0,01 bis 1 Gew.-% enthalten. Dabei ist - wie auch im Falle der Phosphatkomponenten - auch diese Angabe bezogen auf den Aktivsubstanzgehalt in den fertigen Anwendungslösungen.According to the invention, such aqueous solutions for simultaneous vibratory grinding, for cleaning and passivation of metallic workpieces are used which contain the carboxylic acid components mentioned in amounts of 0.01 to 1% by weight. As in the case of the phosphate components, this is also based on the active substance content in the finished application solutions.

Eine weitere Komponente der in dem erfindungsgemäßen Verfahren angewendeten wäßrigen Lösungen sind nichtionische Tenside, wobei es auch hier möglich ist, daß die wäßrigen Lösungen ein Tensid oder auch mehrere Tenside als oberflächenaktive Komponenten enthalten. Die Gesamtmengen der Tenside, die in den verwendeten wäßrigen Lösungen enthalten sind, liegen dabei entsprechend dem erfindungsgemäßen Verfahren im Bereich von 0,005 bis 2 Gew.-%. Auch diese Angaben beziehen sich auf den Aktivsubstanzgehalt in der Anwendungslösung.Another component of the aqueous solutions used in the process according to the invention are nonionic surfactants, it also being possible here for the aqueous solutions to contain one or more surfactants as surface-active components. The total amounts of surfactants contained in the aqueous solutions used are in the range from 0.005 to 2% by weight, according to the process of the invention. This information also relates to the active substance content in the application solution.

Das Verfahren sieht außerdem vor, daß die wäßrigen Behandlungslösungen gegebenenfalls einen oder mehrere Korrosionsinhibitoren enthalten. Derartige Korrosionsinhibitoren sind jeweils auf das Metall abzustimmen, aus dem die metallischen Werkstücke oder Formteile bestehen, die gemäß dem erfindungsgemäßen Verfahren gereinigt, passiviert und gleichzeitig einer Gleitschleifung unterworfen werden sollen. Bevorzugterweise werden wäßrige Lösungen eingesetzt, in denen als Korrosionsinhibitor-Komponenten eine oder mehrere Verbindungen aus der Gruppe Alkalimetallmolybdate, bevorzugt Natriummolybdate, Benzotriazol, Tolyltriazol und Benzthiazol verwendet werden. Derartige Korrosionsinhibitoren, die, wie auch die anderen Komponenten, allein oder in Kombination mehrerer in gleicher Richtung wirkender Komponenten verwendet werden können, liegen in Mengen von 0,001 bis 0,02 Gew.-% vor. Wie auch bei den anderen Komponenten, so sind auch diese Angaben bezogen auf den Aktivsubstanzgehalt in der Anwendungslösung.The process also provides that the aqueous treatment solutions optionally contain one or more corrosion inhibitors. Corrosion inhibitors of this type are to be matched to the metal from which the metallic workpieces or molded parts are made, which are to be cleaned, passivated and, at the same time, subjected to vibratory grinding according to the inventive method. Aqueous solutions are preferably used in which one or more compounds from the group of alkali metal molybdates, preferably sodium molybdates, benzotriazole, tolyltriazole and benzothiazole, are used as corrosion inhibitor components. Such corrosion inhibitors, which, like the other components, can be used alone or in combination of several components acting in the same direction, are present in amounts of 0.001 to 0.02% by weight. As with the other components, this information is based on the active substance content in the application solution.

Das Verfahren kann unter Verwendung solcher saurer wäßriger Lösungen durchgeführt werden, die außer den oben allgemein oder im Detail auch näher beschriebenen Komponenten auch noch weitere an sich übliche Wirkstoffe und/oder Hilfsstoffe enthalten. Solche Wirkstoffe können beispielsweise Wasserhärte-Stabilisatoren sein. Deren Einsatz ist insbesondere dann von Vorteil, wenn in dem Verfahren die Behandlungsmittel mit Wasser angesetzt wurden, das größere Mengen an Härtebildnern, insbesondere Erdalkalimetallcarbonaten, aufweist. Derartige Wasserhärte-Stabilisatoren sind beispielsweise Phosphonsäuren, wie beispielsweise Hydroxyethandiphosphonsäure (HEDP) oder Phosphonobutantricarbonsäure (PBTC), oder deren wasserlösliche Salze, aber auch Ethylendiamintetraessigsäure bzw. ihre wasserlöslichen Salze, Nitrilotriessigsäure und ihre wasserlöslichen Salze oder auch andere, für derartige Zwecke aus dem Stand der Technik bekannte Verbindungen. Diese sind - sofern ihre Mitverwendung erwünscht wird - in Mengen von 0,01 bis 0,2 Gew.-% zugegen und erlauben in dem erfindungsgemäßen Verfahren die Verwendung auch "harter" Wässer.The process can be carried out using such acidic aqueous solutions which, in addition to the components described generally or in more detail above, also contain other active substances and / or auxiliaries which are customary per se. Such active ingredients can be, for example, water hardness stabilizers. Their use is particularly advantageous if the treatment agents were mixed with water in the process, which contains large amounts of hardness formers, in particular alkaline earth metal carbonates. Such water hardness stabilizers are, for example, phosphonic acids, such as, for example, hydroxyethane diphosphonic acid (HEDP) or phosphonobutane tricarboxylic acid (PBTC), or their water-soluble salts, but also ethylenediaminetetraacetic acid or its water-soluble salts, nitrilotriacetic acid and its water-soluble salts or else for such purposes from the Connections known in the art. If their co-use is desired, these are present in amounts of 0.01 to 0.2% by weight and allow the use of "hard" water in the process according to the invention.

Wie oben schon beschrieben, werden in dem erfindungsgemäßen Verfahren derartige wäßrige Lösungen üblicherweise im Tauchen oder Spritzen mit den metallischen Werkstücken oder Formteilen in Kontakt gebracht. Dabei erfolgt ein gleichzeitiges Gleitschleifen, Reinigen und Passivieren der Oberflächen der Werkstücke. Dieses wird üblicherweise bei Temperaturen im Bereich von 20 bis 60 °C, bevorzugt jedoch bei Raumtemperatur durchgeführt. Die Behandlungszeiten hängen sehr stark vom Verschmutzungsgrad, der Stärke der Grate bzw. Überstände, die entfernt werden sollen, von der Härte, Größe und Form der Schleifkörper sowie auch von den Eigenschaften der wäßrigen Behandlungslösungen ab. Sie liegen in bevorzugten Ausführungsformen des Verfahrens im Bereich zwischen 10 und 60 min. Üblicherweise wird der Oberflächenbehandlung lediglich ein Trocknungsprozeß nachgeschaltet. Dieser Trocknungsprozeß kann mittels üblicher Hilfsmittel, wie beispielsweise Maisschrot, Holzmehl usw., bei Raumtemperatur im Trommelverfahren oder mittels Warmluft erfolgen. In besonderen Fällen kann jedoch vor dem Trockenprozeß auch noch eine Spülung vorgesehen werden. Dies hängt im wesentlichen von der Art der Weiterbehandlung der entsprechend dem erfindungsgemäßen Verfahren behandelten Werkstücke oder Formteile ab.As already described above, in the process according to the invention, such aqueous solutions are usually brought into contact with the metallic workpieces or molded parts by dipping or spraying. This involves simultaneous surface grinding, cleaning and passivating the surfaces of the workpieces. This is usually carried out at temperatures in the range from 20 to 60 ° C., but preferably at room temperature. The treatment times depend very much on the degree of soiling, the thickness of the burrs or protrusions to be removed, the hardness, size and shape of the abrasive bodies and also on the properties of the aqueous treatment solutions. In preferred embodiments of the method, they are in the range between 10 and 60 minutes. Usually the surface treatment is followed only by a drying process. This drying process can be carried out using conventional aids, such as, for example, maize meal, wood flour, etc., at room temperature using the drum method or using warm air. In special cases, however, a rinse can also be provided before the drying process. This essentially depends on the type of further treatment of the workpieces or molded parts treated according to the method according to the invention.

Von der Erfindung umfaßt sind auch die in dem oben näher beschriebenen Verfahren verwendeten Mittel zum gleichzeitigen Gleitschleifen, Reinigen und Passivieren metallischer Werkstücke oder Formteile. Die Mittel können entweder in Pulverform konfektioniert und als solche verpackt und am Anwendungsort mit geringem Aufwand in Wasser eingerührt werden, oder sie werden in Form hochkonzentrierter wäßriger Lösungen konfektioniert und am Anwendungsort lediglich verdünnt. Ersteres hat den Vorteil, daß nur die reine Substanz transportiert und damit der unnötige Wassertransport vermieden wird. Letzteres ist jedoch deswegen vorteilhafter, weil flüssige Konzentrate mittels Dosierpumpen am Anwendungsort automatisch eindosiert werden können und damit die Handhabung für den Anwender erleichtern. Die in Form der Konzentrate in den Handel kommenden wäßrigen Lösungen sind homogen. Wäßrige Konzentrate weisen aufgrund der in ihnen enthaltenen Komponenten einen pH-Wert im Bereich von 1 bis 6 auf. Bevorzugt liegt der pH-Wert im Bereich von 3,5 bis 5. Sollte jedoch der pH-Wert durch Verwendung stärker alkalischer Komponenten nicht in diesem Bereich liegen, so kann er gegebenenfalls über die Zugabe nichtkorrosiver Säuren, bevorzugt beispielsweise Phosphorsäuren, Phosphonsäuren, Phosphonocarbonsäuren oder Carbonsäuren, eingestellt werden. Eine pH-Wert-Einstellung ist üblicherweise jedoch nicht erforderlich. Die wäßrigen Anwendungslösungen werden üblicherweise mit einem Aktivsubstanzgehalt im Bereich von ca. 0,2 bis ca. 14 Gew.-% eingesetzt.The invention also includes the means used in the method described in more detail above for simultaneous surface grinding, cleaning and passivating metallic workpieces or molded parts. The agents can either be packaged in powder form and packaged as such and stirred into water at the application site with little effort, or they are prepared in the form of highly concentrated aqueous solutions and merely diluted at the application site. The former has the advantage that only the pure substance is transported, thus avoiding unnecessary water transport. However, the latter is more advantageous because liquid concentrates can be metered in automatically at the application site by means of metering pumps and thus make handling easier for the user. The aqueous solutions which come on the market in the form of concentrates are homogeneous. Due to the components they contain, aqueous concentrates have a pH in the range from 1 to 6. The pH value is preferably in the range from 3.5 to 5. However, if the pH value is not in this range due to the use of more alkaline components, it can optionally be added by adding non-corrosive acids, preferably for example phosphoric acids, phosphonic acids, phosphonocarboxylic acids or Carboxylic acids. However, a pH adjustment is usually not necessary. The aqueous application solutions are usually used with an active substance content in the range from approximately 0.2 to approximately 14% by weight.

Die erfindungsgemäßen Mittel zum gleichzeitigen Gleitschleifen, Reinigen und Passivieren metallischer Werkstücke enthalten als Phosphatkomponenten Alkalimetallsalze und/oder Ammoniumsalze der Orthophosphorsäure und/oder von Pyrophosphorsäuren. Bevorzugte Phosphatkomponenten in den erfindungsgemäßen Mitteln sind saure Natriumphosphate und/oder Natriumpyrophosphate. Weitere essentiellen Komponenten der erfindungsgemäßen Mittel sind Weinsäure und/oder Citronensäure.The agents according to the invention for simultaneous surface grinding, cleaning and passivating metallic workpieces contain, as phosphate components, alkali metal salts and / or ammonium salts of orthophosphoric acid and / or pyrophosphoric acids. Preferred phosphate components in the agents according to the invention are acidic sodium phosphates and / or sodium pyrophosphates. Other essential components of the agents according to the invention are tartaric acid and / or citric acid.

Eine weitere Komponente der erfindungsgemäßen Mittel sind nichtionische Tenside. Auch diese können als Einzelverbindungen oder im Gemisch mehrerer Tenside vertreten sein.Another component of the agents according to the invention are nonionic surfactants. These can also be represented as individual compounds or in a mixture of several surfactants.

Als Tenside kommen für die erfindungsgemäßen Mittel eine Vielzahl von an sich aus dem Stand der Technik als Tenside bekannten Verbindungen in Frage. So werden u.a. als nichtionische Tenside Additionsprodukte von Ethylenoxid und/oder Propylenoyid an Fettalkohole oder Fettamine eingesetzt, also Alkohole und/oder Amine, die 6 bis 18 C-Atome im geradkettigen oder verzweigtkettigen Alkylrest tragen. Außerdem sind als nichtionische Tenside polyalkylenglykolether der nachfolgenden allgemeinen Formel geeignet



        R'-O-[(CH₂)m-O]n-R''



in der

R'
einen geradkettigen oder verzweigten Alkylrest mit 8 bis 18 C-Atomen,
R''
einen Alkylrest mit 4 bis 8 C-Atomen,
m
eine Zahl von 2 bis 4 und
n
eine Zahl von 7 bis 12 bedeuten.
A large number of compounds known per se from the prior art as surfactants are suitable as surfactants for the agents according to the invention. For example, addition products of ethylene oxide and / or propylene oxide to fatty alcohols or fatty amines, ie alcohols and / or, are used as nonionic surfactants Amines which carry 6 to 18 carbon atoms in the straight-chain or branched-chain alkyl radical. Polyalkylene glycol ethers of the following general formula are also suitable as nonionic surfactants



R'-O - [(CH₂) m -O] n -R ''



in the
R '
a straight-chain or branched alkyl radical having 8 to 18 carbon atoms,
R ''
an alkyl radical with 4 to 8 carbon atoms,
m
a number from 2 to 4 and
n
represent a number from 7 to 12.

Derartige polyalkylenglykolether sind als schwach schäumende nichtionische Tenside, z.T. sogar als ausgesprochene Entschäumer bekannt und damit besonders gut geeignet.Such polyalkylene glycol ethers are known as weakly foaming nonionic surfactants, in some cases even as pronounced defoamers, and are therefore particularly suitable.

Die erfindungsgemäßen Mittel können gegebenenfalls außerdem noch einen oder mehrere Korrosionsinhibitoren enthalten. Diese werden üblicherweise auf das jeweilige konkrete Anwendungsproblem abgestimmt und richten sich damit nach den metallischen Oberflächen, die gereinigt, passiviert und gleitschleifend behandelt werden sollen. Geeignete Korrosionsinhibitoren können auch miteinander verwendet werden, was den Vorteil hat, daß die erfindungsgemäßen Mittel dadurch für eine größere Zahl von Anwendungsfällen eingsetzt werden können. Als Korrosionsinhibitoren werden bevorzugt Verbindungen aus der Gruppe Alkalimetallmolybdate, bevorzugt Natriummolybdate, Benzotriazol, Tolyltriazol und Benzthiazol eingesetzt.The agents according to the invention can optionally also contain one or more corrosion inhibitors. These are usually matched to the respective specific application problem and are thus geared towards the metallic surfaces that are to be cleaned, passivated and slip-treated. Suitable corrosion inhibitors can also be used with one another, which has the advantage that the agents according to the invention can thereby be used for a larger number of applications. Compounds from the group alkali metal molybdates, preferably sodium molybdates, benzotriazole, tolyltriazole and benzothiazole, are preferably used as corrosion inhibitors.

Zusätzlich können die erfindungsgemäßen Mittel noch weitere, in Reinigungs-, Passiviervngs- und Gleitschleifmitteln an sich übliche Wirkstoffe und/oder Hilfsstoffe enthalten. Solche zusätzlichen Wirkstoffe, die in bevorzugten Ausführungsfornen der erfindungsgemäßen Mittel auch verwendet werden, sind Wasserhärtestabilisatoren. Als solche können Einzelverbindungen oder Kombinationen aus der Gruppe der Phosphonsäuren, wie beispielsweise Hydroxyethyldiphosphonsäure, Phosphonobutantricarbonsäure, oder deren wasserlösliche Salze, Ethylendiamintetraessigsäure und ihre Salze und Nitrilotriessigsäure und deren wasserlösliche Salze eingesetzt werden.In addition, the agents according to the invention can also contain other active substances and / or auxiliaries which are customary in cleaning, passivating and slide grinding agents. Such additional active ingredients, which are also used in preferred embodiments of the agents according to the invention, are water hardness stabilizers. As such, individual compounds or combinations from the group of the phosphonic acids, such as, for example, hydroxyethyldiphosphonic acid, phosphonobutane tricarboxylic acid, or their water-soluble salts, ethylenediaminetetraacetic acid and their salts and nitrilotriacetic acid and their water-soluble salts can be used.

Wie oben schon näher ausgeführt wurde, können die erfindungsgemäßen Mittel als Pulver, d.h. als 100 %ige Aktivsubstanz, oder auch als Konzentrate konfektioniert werden.As already explained in more detail above, the agents according to the invention can be used as powder, i.e. as 100% active substance or as concentrates.

In einer bevorzugten Ausführungsform der Erfindung liegen die Mittel gemäß der Erfindung als Pulver vor, enthaltend Salze von Phosphorsäuren, Carbonsäuren und Netzmittel, sowie:

  • (a) Alkalimetallsalze und/oder Ammoniumsalze der Orthophosphorsäure und/oder von Pyrophosphorsäuren in Mengen von 50 bis 98 Gew.-%,
  • (b) Weinsäure und/oder Citronensäure in Mengen von 1 bis 10 Gew.-%,
  • (c) ein oder mehrere nichtionische(s) Tensid(e) in Mengen von 0,1 bis 20 Gew.-%,
  • (d) gegebenenfalls einen oder mehrere Korrosionsinhibitor(en) in Mengen von 0,01 bis 0,5 Gew.-% und
  • (e) gegebenenfalls weitere, in Reinigungs-, Passivierungs- und Gleitschleifmitteln an sich übliche Wirkstoffe und/oder Hilfsstoffe in Mengen von 1 bis 20 Gew.-%.
In a preferred embodiment of the invention, the agents according to the invention are in the form of a powder containing salts of phosphoric acids, carboxylic acids and wetting agents, and also:
  • (a) alkali metal salts and / or ammonium salts of orthophosphoric acid and / or pyrophosphoric acids in amounts of 50 to 98% by weight,
  • (b) tartaric acid and / or citric acid in amounts of 1 to 10% by weight,
  • (c) one or more nonionic surfactant (s) in amounts of 0.1 to 20% by weight,
  • (d) optionally one or more corrosion inhibitor (s) in amounts of 0.01 to 0.5% by weight and
  • (e) if appropriate, further active ingredients and / or auxiliaries which are customary per se in cleaning, passivating and vibratory abrasives in amounts of 1 to 20% by weight.

In einer weiteren, gleichfalls bevorzugten Ausführungsform der Erfindung liegen die Mittel gemäß der Erfindung als wäßrige Konzentrate vor, d.h. daß derartige Konzentrate zu den Aktivsubstanzen auch noch Wasser enthalten, welches die Gesamtmenge aller Komponenten zu 100 Gew.-% addiert. Diese wäßrigen Konzentrate enthalten Salze von Phosphorsäuren, Carbonsäuren und Netzmittel, sowie:

  • (a) Alkalimetallsalze und/oder Ammoniumsalze der Orthophosphorsäure und/oder von Pyrophosphorsäuren in Mengen von 10 bis 50 Gew.-%,
  • (b) Weinsäure und/oder Citronensäure in Mengen von 0,5 bis 5 Gew.-%,
  • (c) ein oder mehrere nichtionische(s) Tensid(e) in Mengen von 0,2 bis 10 Gew.-%,
  • (d) gegebenenfalls einen oder mehrere Korrosionsinhibitor(en) in Mengen von 0,01 bis 0,1 Gew.-%,
  • (e) gegebenenfalls weitere, in Reinigungs-, Passivierungs- und Gleitschleifmitteln an sich übliche Wirkstoffe und/oder Hilfsstoffe in Mengen von 0,05 bis 1 Gew.-% und
  • (f) Wasser in Mengen, die die Gesamtmengen der Komponenten (a) bis (e) zu 100 Gew.-% aufsummieren.
In a further, likewise preferred embodiment of the invention, the compositions according to the invention are present as aqueous concentrates, ie that such concentrates also contain water to the active substances, which adds up to 100% by weight of the total amount of all components. These aqueous concentrates contain salts of phosphoric acids, carboxylic acids and wetting agents, as well as:
  • (a) alkali metal salts and / or ammonium salts of orthophosphoric acid and / or pyrophosphoric acids in amounts of 10 to 50% by weight,
  • (b) tartaric acid and / or citric acid in amounts of 0.5 to 5% by weight,
  • (c) one or more nonionic surfactant (s) in amounts of 0.2 to 10% by weight,
  • (d) optionally one or more corrosion inhibitor (s) in amounts of 0.01 to 0.1% by weight,
  • (e) optionally further active ingredients and / or auxiliaries which are customary per se in cleaning, passivating and vibratory abrasives in amounts of 0.05 to 1% by weight and
  • (f) water in amounts which add up to 100% by weight of the total amounts of components (a) to (e).

Derartige Konzentrate werden dann am Anwendungsort vom Anwender mit weiterem Wasser verdünnt beziehungsweise die pulverförmigen Produkte in Wasser gelöst. Dabei weisen die Anwendungslösungen - wie oben schon ausgeführt - einen Aktivsubstanzgehalt im Bereich von ca. 0,2 bis ca. 14 Gew.-% auf. Die Gesamtmengen der oben im einzelnen angegebenen Komponenten werden also mit einer solchen Wassermenge versetzt, die die Gesamtmenge aller Komponenten zu 100 Gew.-% aufsummiert. Dabei stellen sich üblicherweise - in Abhängigkeit von den verwendeten Einzelkomponenten - pH-Werte im Bereich von 1 bis 6, bevorzugt von 3,5 bis 5 ein. Sollte in den erfindungsgemäßen Anwendungslösungen dieser pH-Wert nicht allein durch die angegebenen Komponenten erreicht werden, so können gegebenenfalls noch weitere Säuren zugegeben werden. Diese Säuren dürfen jedoch nicht korrosiv sein und entstammen bevorzugt der Gruppe Phosphorsäuren, Phosphonsäuren, Phosphonocarbonsäuren und Carbonsäuren.Such concentrates are then diluted with additional water at the application site or the powdered products are dissolved in water. As already explained above, the application solutions have an active substance content in the range from approximately 0.2 to approximately 14% by weight. The total amounts of the components specified above in detail are thus mixed with an amount of water which adds up to 100% by weight of the total amount of all components. Depending on the individual components used, pH values are usually in the range from 1 to 6, preferably from 3.5 to 5. If, in the application solutions according to the invention, this pH value is not achieved solely by the specified components, further acids can optionally be added. However, these acids must not be corrosive and preferably come from the group of phosphoric acids, phosphonic acids, phosphonocarboxylic acids and carboxylic acids.

Die Erfindung wird durch das nachfolgende Beispiel näher erläutert.The invention is illustrated by the following example.

Werkstücke bzw. Formteile aus Eisen, Messing, Aluminiumlegierungen der Zusammensetzung AlSi₁₇Cu₄Mg (Silumin), Bronze, Kupfer, einer Magnesiumlegierung der Zusammensetzung MgMn₂ und Zink wurden unmittelbar aus der Produktion entnommen und in einer Vibrationsanlage unter Verwendung verschiedener Schleifkörper (Materialien Keramik, kunststoffgebundener Korund) unter Zugabe der nachfolgend in den Beispielen beschriebenen Testlösungen in einem Arbeitsgang gereinigt, oberflächenpassiviert und im Gleiten geschliffen. Nach der einstufigen Oberflächenbehandlung wurden die Werkstücke teilweise mit Leitungswasser (ca 15 °d) nachgespült und mit Maisschrot bzw. Warmluft (100 °C) getrocknet. Danach wurden die Oberflächen visuell beurteilt.Workpieces or molded parts made of iron, brass, aluminum alloys with the composition AlSi₁₇Cu₄Mg (silumin), bronze, copper, a magnesium alloy with the composition MgMn₂ and Zinc was taken directly from production and cleaned, surface passivated and ground in a single operation in a vibration system using various grinding media (ceramic, plastic-bonded corundum) with the addition of the test solutions described below in the examples. After the one-step surface treatment, the workpieces were partially rinsed with tap water (approx. 15 ° d) and dried with corn grist or warm air (100 ° C). The surfaces were then assessed visually.

Beispiel 1example 1

Verwendet wurde eine Anwendungslösung der folgenden Zusammensetzung:
98 % H₂O;
0,63 % Na₂H₂P₂O₇;
1,17 % NaH₂PO₄;
0,08 % Citronensäure;
0,06 % eines Additionsproduktes von 12 Mol Ethylenoxid (EO) an Kokosamin;
0,06 % eines C₁₂ bis C₁₈-Fettalkohol-9,1 EO-butylethers.
An application solution with the following composition was used:
98% H₂O;
0.63% Na₂H₂P₂O₇;
1.17% NaH₂PO₄;
0.08% citric acid;
0.06% of an adduct of 12 moles of ethylene oxide (EO) with coconut amine;
0.06% of a C₁₂ to C₁₈ fatty alcohol 9.1 EO-butyl ether.

Die Metallteile wurden 20 min bei 25 °C unter Einwirkung dieser Lösung, die einen pH-Wert von 3,5 aufwies, entfettet, passiviert und entgratet. Das Ergebnis dieses einstufigen Prozesses zeigte, daß eine sehr gute Entfettung und Passivierung erfolgt war und daß die produktionsbedingten Metallgrate völlig entfernt worden waren. Die Stahlteile zeigten eine bläulich-irisierende Passivierungsschicht. Die Oberflächen der Nichteisen-Metalle waren ausnahmslos blank und glatt und wiesen keine Korrosions- oder Anlaufstellen auf.The metal parts were degreased, passivated and deburred at 20 ° C. for 20 minutes under the action of this solution, which had a pH of 3.5. The result of this one-step process showed that very good degreasing and passivation had taken place and that the production-related metal burrs had been completely removed. The steel parts showed a bluish-iridescent passivation layer. The surfaces of the non-ferrous metals were, without exception, bare and smooth and showed no corrosion or contact points.

Auch nach mehrwöchiger Lagerung bei mittlerer Luftfeuchtigkeit konnte Korrosion auf den metallischen Oberflächen nicht festgestellt werden.Even after storage for several weeks in medium humidity, corrosion on the metallic surfaces could not be determined.

An dieser Stelle ist nochmals zu betonen, daß es sich bei dem vorliegenden Verfahren um ein einschrittiges Verfahren handelt, in dem in einer Praxisoperation sowohl entfettet als auch entoxidiert/passiviert als auch im Gleitschleifen entgratet werden kann.At this point, it should be emphasized again that the present process is a one-step process in which, in a practical operation, both degreased and deoxidized / passivated, as well as deburring in vibratory grinding, are possible.

Claims (10)

  1. A process for the simultaneous slide grinding, cleaning and passivation of metal workpieces using acidic aqueous solutions containing salts of phosphorus acids, carboxylic acids and wetting agents, characterized in that the workpieces are brought into contact with aqueous solutions which have a pH value in the range from 1 to 6 and which contain the following components:
    (a) 0.2 to 10% by weight alkali metal salts and/or ammonium salts of orthophosphoric acid and/or of pyrophosphoric acids,
    (b) 0.01 to 1% by weight tartaric acid and/or citric acid,
    (c) 0.005 to 2% by weight of one or more nonionic surfactants,
    (d) optionally 0. 001 to 0.02 by weight of one or more corrosion inhibitors and
    (e) optionally 0.01 to 0.2% by weight of other active substances and/or auxiliaries typically present in cleaning, passivating and slide grinding preparations,
    based in each case on the active substance content of the in-use solution.
  2. A process as claimed in claim 1, characterized in that the aqueous solutions have a pH value of 3.5 to 5.
  3. A process as claimed in claim 1 or 2, characterized in that acidic sodium phosphates and/or sodium pyrophosphates are used as the phosphate component (a).
  4. A process as claimed in one or more of claims 1 to 3, characterized in that one or more compounds selected from alkali metal molybdates, benzotriazole tolyl triazole and benthiazole is/are used as the corrosion inhibitor component (d).
  5. A process as claimed in one or more of claims 1 to 3, characterized in that water hardness stabilizers selected from phosphonic acids, ethylenediaminetetraacetic acid, nitrilotriacetic acid and water-soluble salts of these acids are used as additional active substance components (e).
  6. Powder-form compounds for the simultaneous slide grinding, cleaning and passivation of metal workpieces containing salts of phosphorus acids, carboxylic acids and wetting agents, characterized in that they contain the following components:
    (a) alkali metal salts and/or ammonium salts of orthophosphoric acid and/or of pyrophosphoric acids in quantities of 50 to 98% by weight,
    (b) tartaric acid and/or citric acid in quantities of 1 to 10% by weight,
    (c) one or more nonionic surfactant(s) in quantities of 0.1 to 20% by weight,
    (d) optionally one or more corrosion inhibitor(s) in quantities of 0.01 to 0.5% by weight and
    (e) optionally other active substances and/or auxiliaries known per se for slide grinding, cleaning and passivating compounds in quantities of 1 to 20% by weight.
  7. Liquid compounds for the simultaneous slide grinding, cleaning and passivation of metal workpieces containing salts of phosphorus acids, carboxylic acids and wetting agents, characterized in that they contain the following components:
    (a) alkali metal salts and/or ammonium salts of orthophosphoric acid and/or of pyrophosphoric acids in quantities of 10 to 50% by weight,
    (b) tartaric acid and/or citric acid in quantities of 0.5 to 5% by weight,
    (c) one or more nonionic surfactant(s) in quantities of 0.2 to 10% by weight,
    (d) optionally one or more corrosion inhibitor(s) in quantities of 0.01 to 0.1% by weight,
    (e) optionally other active substances and/or auxiliaries known per se for slide grinding, cleaning and passivating compounds in quantities of 0.05 to 1% by weight
    (f) water in quantities which balance the quantities of components (a) to (e) mentioned above to 100% by weight.
  8. Compounds as claimed in claim 6 or 7, characterized in that they contain acidic sodium phosphates and/or sodium pyrophosphates as the phosphate component (a).
  9. Compounds as claimed in claim 6 or 7, characterized in that they contain one or more compounds selected from alkali metal molybdates, benzotriazole, tolyl triazole and benzthiazole as the corrosion inhibitor component (d).
  10. Compounds as claimed in claim 6 to 7, characterized in that they contain water hardness stabilizers selected from phosphonic acids, ethylenediaminetetraacetic acid, nitrilotriacetic acid and water-soluble salts of these acids as additional active substance components (e).
EP89100227A 1988-01-14 1989-01-07 Process and agent for simultaneous vibratory grinding, cleaning and passivation of metallic workpieces Expired - Lifetime EP0324394B1 (en)

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DE3800834A DE3800834A1 (en) 1988-01-14 1988-01-14 METHOD AND MEANS FOR SIMULTANEOUS SLICING, CLEANING AND PASSIVATING OF METALLIC WORKSTUFFS

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US5047095A (en) 1991-09-10
EP0324394A3 (en) 1990-07-04
ES2046333T3 (en) 1994-02-01
DE58906058D1 (en) 1993-12-09
ATE96716T1 (en) 1993-11-15
EP0324394A2 (en) 1989-07-19
DE3800834A1 (en) 1989-07-27
DK734388D0 (en) 1988-12-30
DK734388A (en) 1989-07-15
TR25081A (en) 1992-09-23
JPH01219171A (en) 1989-09-01

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