EP1657320A1 - Fluid and its use to prepare iron and steel based mixtures - Google Patents

Fluid and its use to prepare iron and steel based mixtures Download PDF

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Publication number
EP1657320A1
EP1657320A1 EP05018859A EP05018859A EP1657320A1 EP 1657320 A1 EP1657320 A1 EP 1657320A1 EP 05018859 A EP05018859 A EP 05018859A EP 05018859 A EP05018859 A EP 05018859A EP 1657320 A1 EP1657320 A1 EP 1657320A1
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EP
European Patent Office
Prior art keywords
iron
liquid
stainless steel
inhibitor
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP05018859A
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German (de)
French (fr)
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EP1657320B1 (en
Inventor
Peter Dr. Quirmbach
Michael Dipl.-Ing. Hölzgen
Alfred Dipl.-Ing. Vuin
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Zschimmer and Schwarz GmbH and Co KG
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Zschimmer and Schwarz GmbH and Co KG
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0207—Using a mixture of prealloyed powders or a master alloy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/042—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling using a particular milling fluid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the invention relates to a liquid whose use for the preparation of powder mixtures based on iron or stainless steel and a process for the preparation of powder mixtures based on iron or stainless steel.
  • metal and especially iron or stainless steel based powder blends are used to make highly stressable parts therefrom.
  • suitable iron and stainless steel powder mixtures are first prepared, pressed into a molded part and the resulting molding (the green compact) is sintered to the finished part.
  • Powder mixtures based on iron or stainless steel for powder metallurgy are regularly composed of an iron powder, an alloy powder, such as a copper, graphite or iron phosphite powder and another substance which acts as a pressing aid.
  • Waxes or stearates for example zinc, aluminum, lead or, in particular, ethylene bis-stearate (EBS), are usually used for the substance acting as pressing assistant.
  • EBS ethylene bis-stearate
  • Powder mixtures of the aforementioned type tend to separate again. At the end of the treatment process or the mixing process is thus regularly no optimal homogeneous powder mixture before.
  • the molded articles produced from correspondingly inhomogeneous powder mixtures often have poor properties.
  • the powder mixtures prepared as above tend to "dust", since the Feinstkornanteil is not sufficiently involved in the powder mixture.
  • the invention has for its object to show a way how powder mixtures can be prepared on iron and / or stainless steel base, without the disadvantages described above.
  • the invention is based on the finding that the disadvantages described above in the preparation of powder mixtures based on iron or stainless steel can be prevented if the powder mixtures are not - as before - dry, but in the liquid according to the application prepared so particular mixed here.
  • the powder mixture based on iron or stainless steel is first mixed in the liquid according to the application and then dried.
  • the powder mixture may consist solely of an iron and / or stainless steel powder and an alloy powder; the addition of a pressing aid, such as a powdered stearate, may be dispensed with.
  • the liquid has at least one inhibitor in addition to water.
  • Inhibitors have the task to coat the components of the iron or stainless steel based powder mixture or to regulate the oxygen addition to the particles of the powder mixture such that they do not hydrolyze in the water or undergo any other reaction with the water.
  • Benzoates, ethanolaminic boric acid, phosphates and phosphonates and benzotriazoles, tolyltriazoles, sodium mercaptobenzotriazoles, amino-alkyl-benzimidazoles and mixtures thereof can be used as inhibitors, for example.
  • molybdate, nitrites, sebacates, silicates and mixtures thereof can be used as inhibitors.
  • the application according to the liquid may contain, for example, pressing aids.
  • the wax emulsion may be, for example, a wax emulsion based on paraffin, oxidized paraffin, polyethylene, polypropylene, stearates, amide waxes such as ethylene-bis-stearylamide, stearylamide or mixtures thereof.
  • wax or a stearate acts both as a pressing aid and as an inhibitor in a water-based liquid in which iron or stainless steel-based powder mixtures are to be mixed.
  • the wax or stearate can only be used if it is present as an emulsion in the liquid.
  • the addition of wax or a stearate in non-emulsified form would not lead to a distribution of the wax in the water. Accordingly, previous attempts to use water as a liquid for the treatment of iron-based powder mixtures failed because the non-emulsified waxes or stearates did not dissolve or disperse in the water.
  • the stabilizer regulates the viscosity of the liquid.
  • stabilizers are used, which increase the viscosity of the water, so that the decrease of the components of the powder mixture in the liquid is difficult and segregation is counteracted thereby.
  • Celluloses for example cellulose ethers, for example hydroxyethylcelluloses, hydroxypropylcelluloses, methylcelluloses, methylethylhydroxycelluloses, methylpropylhydroxycelluloses or mixtures thereof, can be used as stabilizers, for example.
  • cellulose ethers for example hydroxyethylcelluloses, hydroxypropylcelluloses, methylcelluloses, methylethylhydroxycelluloses, methylpropylhydroxycelluloses or mixtures thereof
  • stabilizers for example.
  • starch, starch ethers, guar, guar ether, xanthan or mixtures thereof can be used as stabilizers.
  • the liquid according to the application as an inhibitor may in particular also contain carboxylic acids and / or amines or their respective derivatives.
  • carboxylic acid derivatives prove to be particularly effective inhibitors in the amine neutralized state.
  • the carboxylic acids used may preferably be dicarboxylic acids and / or triazine derivatives.
  • dicarboxylic acids may be, in particular, 1,8-octanedicarboxylic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid (sebacic acid), 1,11-undecanedicarboxylic acid, 1,12-dodecanecarboxylic acid and so on up to and including 1,16-hexadecanedicarboxylic acid.
  • triazine derivatives in particular 1,3,5-triazine derivatives, in particular 1,3,5-triazine-2,4,6-triaminetricarboxylic acid, may be provided, for example.
  • the amines used can preferably be ethanolamines and / or imidazolines.
  • Ethanolamines may be, for example, in particular triethanolamine, diethanolamine, monoethanolamine and / or trishydroxymethylaminomethane.
  • polymers containing imidazole units may also be provided with non-polymeric imidazole derivatives, such as, for example, 2- (2-hepatadec-8-enyl-2-imidazolin-1-yl) ethanol. It is also possible for these latter to be provided with imidazole compounds, for example imidazoline derivatives, for example hydroxyethyl, aminoethyl and / or amidoethyl imidazole derivatives.
  • alkyl radicals may be present residues of oil and tall oil fatty acids to octanoic acid.
  • the abovementioned inhibitors are particularly effective if they are present in combination of amines and carboxylic acids, in each case in particular those of the abovementioned type.
  • the viscosity of the liquid can be regulated by all of the abovementioned inhibitors, in particular also the abovementioned carboxylic acids and amines, so that they can act as stabilizers. According to one embodiment, it is therefore intended to dispense with the addition of a separate stabilizer.
  • the inhibitors used simultaneously represent stabilizers in the sense of the application.
  • At least one of the further substances in the liquid can be, for example, a dispersant, for example polyacrylic acids.
  • a temporary binder may also be present in the liquid, for example a temporary binder based on polyacrylates, polyvinyl acetates, polyvinyl alcohols as well as cellulose and starch derivatives or mixtures thereof.
  • the preparation of powder mixtures based on iron or stainless steel is not only greatly improved, but also the properties of the sintered moldings produced from these mixtures are greatly improved compared to the molded parts according to the prior art.
  • the (sintered) molded parts produced from the powder mixtures which have been treated with the liquid according to the application have excellent properties, in particular high homogeneity and strength.
  • the powder mixture is first mixed in the liquid according to the application and then dried.
  • the homogenization of the powder mixture in the liquid according to the application can be carried out by known mixing units, for example attritors.
  • the mixing time in the liquid may be, for example, 1 to 3 hours.
  • the moist powder mixture is fed to a drying aggregate, for example a spray-drying plant.
  • the moist mixture is atomized to a granulate.
  • a powder mixture mixed in the liquid according to the application forms a characteristic granulate, which, in addition to proportions of granules, is characterized in particular by a proportion of hollow granules.
  • the dried granules Due to the regularly formed proportion of hollow granules, the dried granules can be very effectively formed into greenware in molds, usually in presses.
  • the wax emulsion in addition to its property as a pressing aid, also acts as an excellent inhibitor, whereby the homogeneity and green density of the pressed molded part at the same pressing pressure (compared to the pressing pressure or the properties of a molded part , which has been prepared according to the prior art) is increased or only a lower pressure is required to obtain the same properties in the molded article, which would be obtained without the use of a wax emulsion in the liquid according to the application.
  • the green body is finally subjected to a heat treatment and thereby sintered to iron or stainless steel product.
  • Wax emulsion can be present, for example, in proportions of 0.5-35% by weight, that is to say, for example, in proportions of 1-15% by weight or of 4-12% by weight in the liquid.
  • Carboxylic acid for example, in proportions of 0.1 to 5 wt .-%, that is, for example, in proportions of 0.5 to 4 wt .-% in the liquid.
  • Amines may, for example, in proportions of 0.1 to 7 wt .-%, that is, for example, in proportions of 0.5 to 5 wt .-% in the liquid.
  • Dispersant may, for example, in proportions of 0.01-33 wt .-%, that is, for example, in proportions of 0.05-6 wt .-% or 0.1-3 wt .-% in the liquid.
  • the liquid according to the application can be mixed, for example, with 3 to 7 times the amount of an iron or stainless steel-based powder mixture for moist mixing.
  • Example 3 the inhibitors simultaneously function as a stabilizer.

Abstract

Liquid (I), for the processing of powder mixtures based on iron- or high-grade steel, comprises water; inhibitor; and stabilizer. An independent claim is also included for a method for processing the powder mixtures based on iron- or high grade steel comprising mixing a powder mixture based on iron- or high grade steel first in (I) and subsequently drying.

Description

Die Erfindung betrifft eine Flüssigkeit, deren Verwendung zur Aufbereitung von Pulvermischungen auf Eisen- oder Edelstahlbasis sowie ein Verfahren zur Aufbereitung von Pulvermischungen auf Eisen- oder Edelstahlbasis.The invention relates to a liquid whose use for the preparation of powder mixtures based on iron or stainless steel and a process for the preparation of powder mixtures based on iron or stainless steel.

In der Pulvermetallurgie werden Metall- und insbesondere auf Eisen oder Edelstahl basierende Pulvermischungen verwendet, um hieraus hoch beanspruchbare Teile herzustellen.In powder metallurgy, metal and especially iron or stainless steel based powder blends are used to make highly stressable parts therefrom.

Hierzu werden zunächst geeignete Eisen- und Edelstahlpulver-Mischungen aufbereitet, zu einem Formteil gepresst und das dabei entstehende Formteil (der Grünling) zum fertigen Teil gesintert.For this purpose, suitable iron and stainless steel powder mixtures are first prepared, pressed into a molded part and the resulting molding (the green compact) is sintered to the finished part.

Pulvermischungen auf Eisen- oder Edelstahlbasis für die Pulvermetallurgie sind regelmäßig zusammengesetzt aus einem Eisenpulver, einem Legierungspulver, wie beispielsweise einem Kupfer-, Graphit- oder Eisenphosphitpulver sowie einem weiteren Stoff, der als Presshilfsmittel wirkt.Powder mixtures based on iron or stainless steel for powder metallurgy are regularly composed of an iron powder, an alloy powder, such as a copper, graphite or iron phosphite powder and another substance which acts as a pressing aid.

Für den als Presshilfsmittel wirkenden Stoff werden üblicherweise Wachse oder Stearate, beispielsweise Zink-, Aluminium-, Blei- oder insbesondere Ethylen-bis-stearat (EBS) eingesetzt.Waxes or stearates, for example zinc, aluminum, lead or, in particular, ethylene bis-stearate (EBS), are usually used for the substance acting as pressing assistant.

Pulvermischungen der vorgenannten Art neigen dazu, sich wieder zu entmischen. Am Ende des Aufbereitungsprozesses beziehungsweise des Mischvorgangs liegt dadurch regelmäßig keine optimal homogene Pulvermischung vor. Die aus entsprechend inhomogenen Pulvermischungen hergestellten Formkörper weisen häufig mangelhafte Eigenschaften auf.Powder mixtures of the aforementioned type tend to separate again. At the end of the treatment process or the mixing process is thus regularly no optimal homogeneous powder mixture before. The molded articles produced from correspondingly inhomogeneous powder mixtures often have poor properties.

Problematisch ist weiterhin, dass die Pulvermischungen, die wie vorstehend aufbereitet worden sind, nur eine mangelnde Grünfestigkeit aufweisen. Die Formgebung und anschließende Formerhaltung der Grünlinge ist dadurch sehr kompliziert. Die mangelnde Grünfestigkeit kann schließlich auch zu mangelhaften Eigenschaften des hieraus gesinterten Formkörpers führen.Another problem is that the powder mixtures, which have been prepared as described above, have only a lack of green strength. The shaping and subsequent preservation of shape of the green compacts is very complicated. The lack of green strength can eventually lead to poor properties of the sintered molded body.

Schließlich neigen die wie vorstehend aufbereiteten Pulvermischungen dazu, zu "stauben", da der Feinstkornanteil nicht ausreichend in die Pulvermischung eingebunden ist.Finally, the powder mixtures prepared as above tend to "dust", since the Feinstkornanteil is not sufficiently involved in the powder mixture.

Der Erfindung liegt die Aufgabe zugrunde, einen Weg aufzuzeigen, wie Pulvermischungen auf Eisen- und/oder Edelstahlbasis aufbereitet werden können, ohne dass die vorstehend beschriebenen Nachteile auftreten.The invention has for its object to show a way how powder mixtures can be prepared on iron and / or stainless steel base, without the disadvantages described above.

Erfindungsgemäß gelöst wird diese Aufgabe durch die zur Verfügungstellung einer Flüssigkeit zur Aufbereitung von Pulvermischungen auf Eisen- oder Edelstahlbasis, die

  • Wasser,
  • Inhibitor,
  • Stabilisator und
  • gegebenenfalls weitere Stoffe
    enthält.
This object is achieved according to the invention by the provision of a liquid for the preparation of powder mixtures based on iron or stainless steel, which
  • Water,
  • inhibitor,
  • Stabilizer and
  • optionally further substances
    contains.

Der Erfindung liegt die Erkenntnis zugrunde, dass die oben beschriebenen Nachteile bei der Aufbereitung von Pulvermischungen auf Eisen- oder Edelstahlbasis verhindert werden können, wenn die Pulvermischungen nicht - wie bisher - trocken, sondern in der anmeldungsgemäßen Flüssigkeit aufbereitet also insbesondere hierin gemischt werden.The invention is based on the finding that the disadvantages described above in the preparation of powder mixtures based on iron or stainless steel can be prevented if the powder mixtures are not - as before - dry, but in the liquid according to the application prepared so particular mixed here.

Dazu wird die Pulvermischung auf Eisen- oder Edelstahlbasis zunächst in der anmeldungsgemäßen Flüssigkeit gemischt und anschließend getrocknet.For this purpose, the powder mixture based on iron or stainless steel is first mixed in the liquid according to the application and then dried.

Die Pulvermischung kann allein aus einem Eisen- und/oder Edelstahlpulver sowie einem Legierungspulver bestehen; auf die Zugabe eines Presshilfsmittels, wie beispielsweise eines pulverförmigen Stearates, kann verzichtet werden.The powder mixture may consist solely of an iron and / or stainless steel powder and an alloy powder; the addition of a pressing aid, such as a powdered stearate, may be dispensed with.

Um eine Reaktion des Wassers mit dem Eisen- oder Edelstahlpulver, also insbesondere beispielsweise dessen Hydrolyse, zu verhindern, weist die Flüssigkeit neben Wasser mindestens einen Inhibitor auf.In order to prevent a reaction of the water with the iron or stainless steel powder, ie in particular, for example, its hydrolysis, the liquid has at least one inhibitor in addition to water.

Inhibitoren haben die Aufgabe, die Komponenten der auf Eisen oder Edelstahl basierenden Pulvermischung zu ummanteln beziehungsweise die Sauerstoffanlagerung an die Teilchen der Pulvermischung derart zu regulieren, dass diese im Wasser nicht hydrolysieren beziehungsweise eine sonstige Reaktion mit dem Wasser eingehen.Inhibitors have the task to coat the components of the iron or stainless steel based powder mixture or to regulate the oxygen addition to the particles of the powder mixture such that they do not hydrolyze in the water or undergo any other reaction with the water.

Frühere Versuche, Pulvermischungen auf Eisenbasis in Wasser zu mischen scheiterten regelmäßig daran, dass eine Reaktion der Eisenpartikel mit dem Wasser nicht verhindert werden konnte. Durch einen Inhibitor, insbesondere durch einen oder mehrere der nachfolgend genannten Inhibitoren, kann diese Reaktion nunmehr vollständig oder zumindest weitgehend unterbunden werden.Previous attempts to mix iron-based powder mixtures in water regularly failed because reaction of the iron particles with the water could not be prevented. By an inhibitor, in particular by one or more of the inhibitors mentioned below, this reaction can now be completely or at least largely suppressed.

Als Inhibitoren verwendet werden können beispielsweise Benzoate, ethanolaminische Borsäure, Phosphate und Phosphonate sowie Benzotriazole, Tolyltriazole, Natrium-Mercaptobenztriazole, Amino-Alkyl-Benzimidazole und Mischungen daraus. Alternativ oder kumulativ können als Inhibtor Molybdate, Nitrite, Sebazate, Silikate und Mischungen daraus eingesetzt werden.Benzoates, ethanolaminic boric acid, phosphates and phosphonates and benzotriazoles, tolyltriazoles, sodium mercaptobenzotriazoles, amino-alkyl-benzimidazoles and mixtures thereof can be used as inhibitors, for example. Alternatively or cumulatively, molybdate, nitrites, sebacates, silicates and mixtures thereof can be used as inhibitors.

Bisher war unbekannt, dass diese Substanzen als hervorragende Inhibitoren bei der flüssigen Aufbereitung von Pulvermischungen auf Eisen- oder Edelstahlbasis beziehungsweise dem Mischen von eisen- und edelstahlbasierten Pulvermischungen in Wasser wirken.It was previously unknown that these substances act as excellent inhibitors in the liquid preparation of powder mixtures based on iron or stainless steel or the mixing of iron- and stainless steel-based powder mixtures in water.

Als weiteren Stoff kann die anmeldungsgemäße Flüssigkeit beispielsweise Presshilfsmittel enthalten.As a further substance, the application according to the liquid may contain, for example, pressing aids.

Als Preßhilfsmittel können z.B. Wachsemulsionen eingesetzt werden. Die Wachsemulsion kann beispielsweise eine Wachsemulsion auf Basis von Paraffin, oxidiertem Paraffin, Polyethylen, Polypropylen, Stearate, Amidwachse wie zum Beispiel Ethylen-bis-stearylamid, Stearylamid oder Mischungen daraus sein.As pressing aids, e.g. Wax emulsions are used. The wax emulsion may be, for example, a wax emulsion based on paraffin, oxidized paraffin, polyethylene, polypropylene, stearates, amide waxes such as ethylene-bis-stearylamide, stearylamide or mixtures thereof.

Erfindungsgemäß wurde erkannt, dass Wachs beziehungsweise ein Stearat sowohl als Presshilfsmittel als auch als Inhibitor in einer Wasser basierenden Flüssigkeit, in der auf Eisen oder Edelstahl basierende Pulvermischungen gemischt werden sollen, wirkt. Das Wachs beziehungsweise Stearat kann jedoch nur dann eingesetzt werden kann, wenn dieses als Emulsion in der Flüssigkeit vorliegt. Die Zugabe von Wachs beziehungsweise einem Stearat in nicht-emulgierter Form würde zu keiner Verteilung des Wachses im Wasser führen. Entsprechend scheiterten frühere Versuche, Wasser als Flüssigkeit zur Aufbereitung von eisenbasierten Pulvermischungen zu verwenden, da sich die nicht-emulgierten Wachse beziehungsweise Stearate im Wasser nicht lösten beziehungsweise verteilten.According to the invention, it has been recognized that wax or a stearate acts both as a pressing aid and as an inhibitor in a water-based liquid in which iron or stainless steel-based powder mixtures are to be mixed. However, the wax or stearate can only be used if it is present as an emulsion in the liquid. The addition of wax or a stearate in non-emulsified form would not lead to a distribution of the wax in the water. Accordingly, previous attempts to use water as a liquid for the treatment of iron-based powder mixtures failed because the non-emulsified waxes or stearates did not dissolve or disperse in the water.

Durch den Stabilisator wird die Viskosität der Flüssigkeit reguliert. Insbesondere werden anmeldungsgemäß Stabilisatoren eingesetzt, die die Viskosität des Wassers erhöhen, so dass das Absinken der Komponenten der Pulvermischung in der Flüssigkeit erschwert wird und einer Entmischung dadurch entgegengetreten wird.The stabilizer regulates the viscosity of the liquid. In particular, according to the application stabilizers are used, which increase the viscosity of the water, so that the decrease of the components of the powder mixture in the liquid is difficult and segregation is counteracted thereby.

Als Stabilisatoren können beispielsweise Cellulosen eingesetzt werden, beispielsweise Celluloseether, beispielsweise Hydroxyethylcellulosen, Hydroxypropylcellulosen, Methylcellulosen, Methylethylhydroxycellulosen, Methylpropylhydroxycellulosen oder Mischungen daraus. Alternativ oder kumulativ können Alginate, Stärke, Stärkeether, Guar, Guarether, Xanthan oder Mischungen daraus als Stabilisatoren eingesetzt werden.Celluloses, for example cellulose ethers, for example hydroxyethylcelluloses, hydroxypropylcelluloses, methylcelluloses, methylethylhydroxycelluloses, methylpropylhydroxycelluloses or mixtures thereof, can be used as stabilizers, for example. Alternatively or cumulatively alginates, starch, starch ethers, guar, guar ether, xanthan or mixtures thereof can be used as stabilizers.

Kumulativ oder alternativ zu den vorgenannten Inhibitoren kann die anmeldungsgemäße Flüssigkeit als Inhibitor insbesondere auch Carbonsäuren und/oder Amine oder deren jeweilige Derivate enthalten. Insbesondere Carbonsäure-Derivate erweisen sich in dem mit Amin neutralisierten Zustand als besonders wirksame Inhibitoren.Cumulatively or alternatively to the abovementioned inhibitors, the liquid according to the application as an inhibitor may in particular also contain carboxylic acids and / or amines or their respective derivatives. In particular, carboxylic acid derivatives prove to be particularly effective inhibitors in the amine neutralized state.

Als Carbonsäuren können bevorzugt Dicarbonsäuren und/oder Triazinderivate eingesetzt werden. Dicarbonsäuren können beispielsweise insbesondere 1,8-Oktandicarbonsäure, 1,9-Nonandicarbonsäure, 1,10-Decandicarbonsäure (Sebacinsäure), 1,11-Undecandicarbonsäure, 1,12-Dodecancarbonsäure und so weiter bis einschließlich 1,16-Hexadecandicarbonsäure sein. Bezüglich der Triazinderivate können beispielsweise insbesondere 1,3,5-Triazinderivate, vor allem 1,3,5-Triazin-2,4,6-Triamintricarbonsäure vorgesehen sein.The carboxylic acids used may preferably be dicarboxylic acids and / or triazine derivatives. For example, dicarboxylic acids may be, in particular, 1,8-octanedicarboxylic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid (sebacic acid), 1,11-undecanedicarboxylic acid, 1,12-dodecanecarboxylic acid and so on up to and including 1,16-hexadecanedicarboxylic acid. With regard to the triazine derivatives, in particular 1,3,5-triazine derivatives, in particular 1,3,5-triazine-2,4,6-triaminetricarboxylic acid, may be provided, for example.

Als Amine können bevorzugt Ethanolamine und/oder Imidazoline eingesetzt werden. Ethanolamine können beispielsweise insbesondere Triethanolamin, Diethanolamin, Monoethanolamin und/oder Trishydroxymethylaminomethan sein. Bezüglich der Imidazoline können neben Polymere mitenthaltenden Imidazol-Einheiten auch nicht polymere Imidazol-Derivate, wie zum Beispiel 2-(2-Hepatadec-8-enyl-2-imidazolin-1-yl)ethanol vorgesehen sein. Es können auch diesen letzteren ähnliche Imidazolverbindungen vorgesehen sein, zum Beispiel Imidazolin-Derivate, wie zum Beispiel Hydroxyethyl-, Aminoethyl- und/oder Amidoethyl-Imdidazolderivate. Als Alkylreste können Reste von Öl- und Tallöl-Fettsäuren bis zur Octansäure vorhanden sein.The amines used can preferably be ethanolamines and / or imidazolines. Ethanolamines may be, for example, in particular triethanolamine, diethanolamine, monoethanolamine and / or trishydroxymethylaminomethane. With respect to the imidazolines, polymers containing imidazole units may also be provided with non-polymeric imidazole derivatives, such as, for example, 2- (2-hepatadec-8-enyl-2-imidazolin-1-yl) ethanol. It is also possible for these latter to be provided with imidazole compounds, for example imidazoline derivatives, for example hydroxyethyl, aminoethyl and / or amidoethyl imidazole derivatives. As alkyl radicals may be present residues of oil and tall oil fatty acids to octanoic acid.

Erfindungsgemäß wurde festgestellt, dass die vorgenannten Inhibitoren besonders effektiv sind, wenn diese in Kombination von Aminen und Carbonsäuren, jeweils insbesondere solchen der vorgenannten Art, vorliegen.According to the invention, it has been found that the abovementioned inhibitors are particularly effective if they are present in combination of amines and carboxylic acids, in each case in particular those of the abovementioned type.

Überraschenderweise wurde erfindungsgemäß ferner festgestellt, dass durch sämtliche der vorgenannten Inhibitoren, insbesondere auch die vorgenannten Carbonsäuren und Amine, die Viskosität der Flüssigkeit reguliert werden kann, diese also als Stabilisatoren wirken können. Nach einer Ausführungsform ist daher vorgesehen, auf die Zugabe eines separaten Stabilisators zu verzichten. In diesem Fall stellen die verwendeten Inhibitoren gleichzeitig Stabilisatoren im Sinne der Anmeldung dar.Surprisingly, it has also been found according to the invention that the viscosity of the liquid can be regulated by all of the abovementioned inhibitors, in particular also the abovementioned carboxylic acids and amines, so that they can act as stabilizers. According to one embodiment, it is therefore intended to dispense with the addition of a separate stabilizer. In this case, the inhibitors used simultaneously represent stabilizers in the sense of the application.

Wenigstens einer der weiteren Stoffe in der Flüssigkeit kann beispielsweise ein Dispergiermittel sein, beispielsweise Polyacrylsäuren.At least one of the further substances in the liquid can be, for example, a dispersant, for example polyacrylic acids.

Als weiterer Stoff kann aber auch ein temporärer Binder in der Flüssigkeit vorhanden sein, beispielsweise ein temporärer Binder auf Basis Polyacrylate, Polyvinylacetate, Polyvinylalkohole wie auch Cellulose- und Stärkederivate oder Mischungen daraus.As a further substance, however, a temporary binder may also be present in the liquid, for example a temporary binder based on polyacrylates, polyvinyl acetates, polyvinyl alcohols as well as cellulose and starch derivatives or mixtures thereof.

Durch die Verwendung der anmeldungsgemäßen Flüssigkeit wird die Aufbereitung von Pulvermischungen auf Eisen- oder Edelstahlbasis nicht nur stark verbessert, sondern auch die Eigenschaften der aus diesen Mischungen erstellten, gesinterten Formteile sind gegenüber den Formteilen nach dem Stand der Technik stark verbessert.By using the liquid according to the application, the preparation of powder mixtures based on iron or stainless steel is not only greatly improved, but also the properties of the sintered moldings produced from these mixtures are greatly improved compared to the molded parts according to the prior art.

So kann durch die Verwendung der anmeldungsgemäßen Flüssigkeit ein Stauben der Pulvermischungen praktisch vollständig verhindert werden. Auch kann die Grünfestigkeit der geformten Grünlinge stark erhöht werden.Thus, dusting of the powder mixtures can be virtually completely prevented by the use of the liquid according to the application. Also, the green strength of the molded green compacts can be greatly increased.

Die aus den Pulvermischungen, die mit der anmeldungsgemäßen Flüssigkeit aufbereitet worden sind, hergestellten (gesinterten) Formteile weisen sich durch hervorragende Eigenschaften, insbesondere eine hohe Homogenität und Festigkeit aus.The (sintered) molded parts produced from the powder mixtures which have been treated with the liquid according to the application have excellent properties, in particular high homogeneity and strength.

Zur Aufbereitung einer eisen- und/oder edelstahlbasierten Pulvermischung mit der anmeldungsgemäßen Flüssigkeit wird die Pulvermischung zunächst in der anmeldungsgemäßen Flüssigkeit gemischt und anschließend getrocknet.For the preparation of an iron- and / or stainless steel-based powder mixture with the liquid according to the application, the powder mixture is first mixed in the liquid according to the application and then dried.

Die Homogenisierung der Pulvermischung in der anmeldungsgemäßen Flüssigkeit kann durch bekannte Mischaggregate vorgenommen werden, beispielsweise Attritoren.The homogenization of the powder mixture in the liquid according to the application can be carried out by known mixing units, for example attritors.

Die Mischdauer in der Flüssigkeit kann beispielsweise 1 bis 3 Stunden betragen.The mixing time in the liquid may be, for example, 1 to 3 hours.

Nach der Mischung der Pulvermischung in der anmeldungsgemäßen Flüssigkeit wird die feuchte Pulvermischung einem Trocknungsaggregat, beispielsweise einer Sprühtrocknungsanlage, zugeführt.After mixing the powder mixture in the liquid according to the application, the moist powder mixture is fed to a drying aggregate, for example a spray-drying plant.

In der Trocknungsanlage, beispielsweise einer Sprühtrocknungsanlage, wird die feuchte Mischung zu einem Granulat verdüst.In the drying plant, for example a spray-drying plant, the moist mixture is atomized to a granulate.

Dabei bildet eine in der anmeldungsgemäßen Flüssigkeit gemischte Pulvermischung ein charakteristisches Granulat aus, das sich neben Anteilen an Vollgranulat insbesondere auch durch einen Anteil an Hohlgranulat auszeichnet.In this case, a powder mixture mixed in the liquid according to the application forms a characteristic granulate, which, in addition to proportions of granules, is characterized in particular by a proportion of hollow granules.

Aufgrund des regelmäßig gebildeten Anteils an Hohlgranulat kann das getrocknete Granulat in Formwerkzeugen, üblicherweise in Pressen, sehr effektiv zu Grünlingen geformt werden.Due to the regularly formed proportion of hollow granules, the dried granules can be very effectively formed into greenware in molds, usually in presses.

Eine Beschädigung des Formwerkzeugs, besonders der bewegten Teile eines ebensolchen, durch ein etwaiges Stauben des Granulats ist durch die Verwendung der anmeldungsgemäßen Flüssigkeit verhindert.Damage to the mold, especially the moving parts of a similar, by a possible dusting of the granules is prevented by the use of the liquid according to the application.

Wie oben bereits ausgeführt, wurde erfindungsgemäß festgestellt, dass die Wachsemulsion, neben ihrer Eigenschaft als Presshilfsmittel, gleichzeitig auch als hervorragender Inhibitor agiert, wodurch die Homogenität und Gründichte beziehungsweise -festigkeit des gepressten Formteils bei gleichem Pressdruck (im Vergleich zum Pressdruck beziehungsweise den Eigenschaften eines Formteils, das nach dem Stand der Technik aufbereitet wurde) erhöht ist beziehungsweise nur einer geringerer Pressdruck erforderlich ist, um beim Formteil die gleichen Eigenschaften zu erhalten, die es ohne die Verwendung einer Wachsemulsion in der anmeldungsgemäßen Flüssigkeit erhalten würde.As already stated above, it has been found according to the invention that the wax emulsion, in addition to its property as a pressing aid, also acts as an excellent inhibitor, whereby the homogeneity and green density of the pressed molded part at the same pressing pressure (compared to the pressing pressure or the properties of a molded part , which has been prepared according to the prior art) is increased or only a lower pressure is required to obtain the same properties in the molded article, which would be obtained without the use of a wax emulsion in the liquid according to the application.

Der Grünling wird schließlich einer Wärmebehandlung unterzogen und dabei zum Eisen- oder Edelstahlprodukt gesintert.The green body is finally subjected to a heat treatment and thereby sintered to iron or stainless steel product.

Die anmeldungsgemäße Flüssigkeit kann beispielsweise wie folgt zusammengesetzt sein (die nachfolgenden Angaben in Gewischts-%, soweit nicht anders angegeben, bezogen auf das Gesamtgewicht der Flüssigkeit):

  • Wasser: 25-99 Gew.-%, also beispielsweise auch 68-98 Gew.-% oder 82-93 Gew.-%;
  • Inhibitor: 0,02-50 Gew.-%, also beispielsweise auch 1-7 Gew.-% oder 1-4 Gew.-%;
  • Stabilisator: 0,005-7 Gew.-%, also beispielsweise auch 0,05-4 oder 0,1-1 Gew.-%;
  • Weitere Stoffe: 0-20 Gew.-%.
The liquid according to the application can be composed, for example, as follows (the following details in% by weight, unless stated otherwise, based on the total weight of the liquid):
  • Water: 25-99 wt .-%, that is, for example, 68-98 wt .-% or 82-93 wt .-%;
  • Inhibitor: 0.02-50 wt .-%, that is, for example, 1-7 wt .-% or 1-4 wt .-%;
  • Stabilizer: 0.005-7 wt .-%, that is, for example, 0.05-4 or 0.1-1 wt .-%;
  • Other substances: 0-20% by weight.

Wachsemulsion kann beispielsweise in Anteilen von 0,5-35 Gew.-%, also beispielsweise auch in Anteilen von 1-15 Gew.- oder von 4-12 Gew.-% in der Flüssigkeit vorliegen.Wax emulsion can be present, for example, in proportions of 0.5-35% by weight, that is to say, for example, in proportions of 1-15% by weight or of 4-12% by weight in the liquid.

Carbonsäure kann beispielsweise in Anteilen von 0,1 bis 5 Gew.-%, also beispielsweise auch in Anteilen von 0,5 bis 4 Gew.-% in der Flüssigkeit vorliegen.Carboxylic acid, for example, in proportions of 0.1 to 5 wt .-%, that is, for example, in proportions of 0.5 to 4 wt .-% in the liquid.

Amine können beispielsweise in Anteilen von 0,1 bis 7 Gew.-%, also beispielsweise auch in Anteilen von 0,5 bis 5 Gew.-% in der Flüssigkeit vorliegen.Amines may, for example, in proportions of 0.1 to 7 wt .-%, that is, for example, in proportions of 0.5 to 5 wt .-% in the liquid.

Dispergiermittel kann beispielsweise in Anteilen von 0,01-33 Gew.-%, also beispielsweise auch in Anteilen von 0,05-6 Gew.-% oder von 0,1-3 Gew.-% in der Flüssigkeit vorliegen.Dispersant may, for example, in proportions of 0.01-33 wt .-%, that is, for example, in proportions of 0.05-6 wt .-% or 0.1-3 wt .-% in the liquid.

Die anmeldungsgemäße Flüssigkeit kann beispielsweise mit der 3- bis 7-fachen Menge an einer eisen- oder edelstahlbasierten Pulvermischung zur feuchten Mischung gemischt werden.The liquid according to the application can be mixed, for example, with 3 to 7 times the amount of an iron or stainless steel-based powder mixture for moist mixing.

Nachfolgend werde zwei Beispiele für eine anmeldungsgemäße Flüssigkeit angegeben:

  • Beispiel 1:
    • Wasser: 88,2 Gew.-%;
    • Inhibitor in Form von Monoethanolaminborat: 2,2 Gew.-%;
    • Stabilisator in Form von Methylcellulose: 0,4 Gew.-%;
    • Wachsemulsion in Form einer 50%-igen Paraffinemulsion: 8,8 Gew.-%;
    • Dispergiermittel in Form von Polyammoniumacrylat: 0,4 Gew.-%.
  • Beispiel 2:
    • Wasser: 84,7 Gew.-%;
    • Inhibitor in Form von Monoethanolaminphosphat: 2,8 Gew.-%;
    • Stabilisator in Form von Methylhydroxypropylcellulose: 0,6 Gew.-%;
    • Wachsemulsion in Form einer 50%-igen Polypropylenemulsion: 11,3 Gew.-%;
    • Dispergiermittel in Form von Polyammoniumacrylat: 0,6 Gew.-%.
  • Beispiel 3:
    • Wasser: 88,2 Gew.-%;
    • Inhibitor in Form von 1,10-Decandicarbonsäure: 2,1 Gew.-%;
    • Inhibitor in Form von Triethanolamin: 2,1 Gew.-%;
    • Wachsemulsion in Form einer 50%-igen Paraffinemulsion: 7,6 Gew.-%.
Two examples of a liquid according to the application are given below:
  • Example 1:
    • Water: 88.2% by weight;
    • Inhibitor in the form of monoethanolamine borate: 2.2% by weight;
    • Stabilizer in the form of methylcellulose: 0.4% by weight;
    • Wax emulsion in the form of a 50% paraffin emulsion: 8.8% by weight;
    • Dispersant in the form of polyammonium acrylate: 0.4 wt .-%.
  • Example 2:
    • Water: 84.7% by weight;
    • Inhibitor in the form of monoethanolamine phosphate: 2.8% by weight;
    • Stabilizer in the form of methylhydroxypropylcellulose: 0.6% by weight;
    • Wax emulsion in the form of a 50% polypropylene emulsion: 11.3% by weight;
    • Dispersant in the form of polyammonium acrylate: 0.6 wt .-%.
  • Example 3:
    • Water: 88.2% by weight;
    • Inhibitor in the form of 1,10-decanedicarboxylic acid: 2.1% by weight;
    • Inhibitor in the form of triethanolamine: 2.1% by weight;
    • Wax emulsion in the form of a 50% paraffin emulsion: 7.6 wt .-%.

Bei Beispiel 3 nehmen die Inhibitoren gleichzeitig die Funktion als Stabilisator wahr.In Example 3, the inhibitors simultaneously function as a stabilizer.

In der feuchten Pulvermischung aus der anmeldungsgemäßen Flüssigkeit und der Eisen/Edelstahl-Pulvermischung können neben 100 Gew.-% Eisen/Edelstahl-Partikeln beispielsweise zusätzlich die folgenden Teile an den Komponenten der Flüssigkeit vorliegen:

  • 8-200 Gew.-% Wasser, also beispielsweise auch 12-70 oder 12-30 Gew.-% Wasser;
  • 0,05-10 Gew.-% Inhibitor, also beispielsweise auch 0,2-2 Gew.-% Inhibitor;
  • 0,01-5 Gew.-% Stabilisator, also beispielsweise auch 0,05-1 oder 0,05-0,5 Gew.-% Stabilisator.
In the moist powder mixture of the liquid according to the application and the iron / stainless steel powder mixture, in addition to 100% by weight of iron / stainless steel particles, for example, the following parts may additionally be present on the components of the liquid:
  • 8-200% by weight of water, for example also 12-70 or 12-30% by weight of water;
  • 0.05-10% by weight of inhibitor, that is to say for example also 0.2-2% by weight of inhibitor;
  • 0.01-5 wt .-% stabilizer, so for example, 0.05-1 or 0.05-0.5 wt .-% stabilizer.

Neben den 100 Gew.-% Eisen/Edelstahl-Partikeln und den vorgenannten Komponenten können in der feuchten Mischung beispielsweisel-5 Gew.-% Wachsemulsion, also beispielsweise auch 0,1-20 oder 0,5-4 Gew.-% Wachsemulsion und/oder 0,01-5 Gew.-% Dispergiermittel, also beispielsweise auch 0,05-1 Dispergiermittel vorliegen.In addition to the 100 wt .-% iron / stainless steel particles and the aforementioned components in the wet mixture beispielsweis-5 wt .-% wax emulsion, so for example, 0.1-20 or 0.5-4 wt .-% wax emulsion and / or 0.01-5 wt .-% dispersant, so for example, also present 0.05-1 dispersant.

Claims (13)

Flüssigkeit zur Aufbereitung von Pulvermischungen auf Eisen- oder Edelstahlbasis, enthaltend a) Wasser; b) Inhibitor; c) Stabilisator und d) gegebenenfalls weitere Stoffe. Liquid for the preparation of powder mixtures based on iron or stainless steel, containing a) water; b) inhibitor; c) stabilizer and d) optionally further substances. Flüssigkeit nach Anspruch 1, bei der der Inhibitor wenigstens einer der nachfolgenden Stoffe ist: Benzoate, ethanolaminische Borsäure, Phosphate und Phosphonate sowie Benzotriazole, Tolyltriazole, Natrium-Mercaptobenztriazole, Amino-Alkyl-Benzimidazole, Molybdate, Natriumnitrit, Sebazate oder Silikate.A fluid according to claim 1 wherein the inhibitor is at least one of the following: benzoates, ethanolaminic boric acid, phosphates and phosphonates and benzotriazoles, tolyltriazoles, sodium mercaptobenzotriazoles, amino-alkyl-benzimidazoles, molybdate, sodium nitrite, sebacates or silicates. Flüssigkeit nach Anspruch 1, bei der der Inhibitor wenigstens einer der nachfolgenden Stoffe ist: Carbonsäuren, Amine oder deren Derivate.A fluid according to claim 1, wherein the inhibitor is at least one of the following: carboxylic acids, amines or their derivatives. Flüssigkeit nach Anspruch 1, bei der der Stabilisator wenigstens einer der nachfolgenden Stoffe ist: Celluloseether, Alginat, Stärke, Stärkeether, Guar, Guarether oder Xanthan.A liquid according to claim 1, wherein the stabilizer is at least one of the following: cellulose ether, alginate, starch, starch ether, guar, guar ether or xanthan. Flüssigkeit nach Anspruch 1, bei der wenigstens einer der weiteren Stoffe eine Wachsemulsion ist.A fluid according to claim 1, wherein at least one of the further substances is a wax emulsion. Flüssigkeit nach Anspruch 5 mit einer Wachsemulsion auf Basis von wenigstens einem der folgenden Stoffe: Paraffin, oxidiertes Paraffin, Polyethylen, Polypropylen oder Amidwachs wie beispielsweise Ethylen-bis-stearylamid, Stearylamid oder Stearat.A liquid according to claim 5 comprising a wax emulsion based on at least one of paraffin, oxidized paraffin, polyethylene, polypropylene or amide wax such as ethylene-bis-stearylamide, stearylamide or stearate. Flüssigkeit nach Anspruch 1, bei der wenigstens einer der weiteren Stoffe ein Dispergiermittel ist.A fluid according to claim 1, wherein at least one of the further substances is a dispersant. Flüssigkeit nach Anspruch 7, bei der das Dispergiermittel eine Polyacrylsäure ist.A fluid according to claim 7, wherein the dispersant is a polyacrylic acid. Flüssigkeit nach Anspruch 1, bei der wenigstens einer der weiteren Stoffe ein temporärer Binder ist.A fluid according to claim 1, wherein at least one of the further substances is a temporary binder. Verwendung einer Flüssigkeit nach Anspruch 1 zur Aufbereitung von Pulvermischungen auf Eisen- oder Edelstahlbasis.Use of a liquid according to claim 1 for the preparation of powder mixtures based on iron or stainless steel. Verwendung einer Flüssigkeit nach Anspruch 10 als Mischflüssigkeit zur Aufbereitung von Pulvermischungen auf Eisen- oder Edelstahlbasis.Use of a liquid according to claim 10 as a mixed liquid for the preparation of powder mixtures based on iron or stainless steel. Verfahren zur Aufbereitung von Pulvermischungen auf Eisen- oder Edelstahlbasis, bei dem eine Pulvermischung auf Eisen- oder Edelstahlbasis zunächst in einer Flüssigkeit gemäß Anspruch 1 gemischt und anschließend getrocknet wird.Process for the preparation of powder mixtures based on iron or stainless steel, in which a powder mixture based on iron or stainless steel is first mixed in a liquid according to claim 1 and then dried. Verfahren nach Anspruch 12, bei dem die Trocknung in einer Sprühtrocknungsanlage erfolgt.Process according to Claim 12, in which the drying takes place in a spray-drying plant.
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