EP1913181A1 - Electropolishing method - Google Patents

Electropolishing method

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Publication number
EP1913181A1
EP1913181A1 EP06776534A EP06776534A EP1913181A1 EP 1913181 A1 EP1913181 A1 EP 1913181A1 EP 06776534 A EP06776534 A EP 06776534A EP 06776534 A EP06776534 A EP 06776534A EP 1913181 A1 EP1913181 A1 EP 1913181A1
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EP
European Patent Office
Prior art keywords
electrolyte
phosphoric acid
acid
electropolishing
rinsing
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Granted
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EP06776534A
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German (de)
French (fr)
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EP1913181B1 (en
Inventor
Siegfried Piesslinger-Schweiger
Olaf BÖHME
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Poligrat GmbH
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Poligrat GmbH
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/16—Polishing
    • C25F3/22—Polishing of heavy metals
    • C25F3/24—Polishing of heavy metals of iron or steel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F7/00—Constructional parts, or assemblies thereof, of cells for electrolytic removal of material from objects; Servicing or operating
    • C25F7/02—Regeneration of process liquids

Definitions

  • the present invention describes a method for electrochemical polishing
  • Electrochemical polishing is a process that is used to deburr, smooth and shine metal surfaces. Due to the higher current density of fine scratches and other unevenness, the metal ionizes and dissolves faster at these points than at the smooth areas of a metal workpiece, thereby compensating its unevenness. For this purpose, the objects to be electropolished, which are at corresponding
  • Carrying elements hang or are arranged in baskets or the like, immersed in an electrolyte, the polishing bath, and lifted out of this after a certain time. After draining the bath liquid from the polished surfaces, the articles are immersed in rinsing baths to completely remove the electrolyte.
  • These electropol- ogy processes have found broad industrial application, in particular for steels with a chromium content above 12%, commonly referred to as stainless steels, stainless steels or acid-resistant steels. In this case, predominantly electrolytes based on mixtures of phosphoric acid and sulfuric acid are used, to which brighteners and inhibitors can be added to further improve the effect.
  • chromic acid ie an oxo acid of hexavalent chromium (chromate)
  • chromate hexavalent chromium
  • the patent JP-A 5 163 600 describes the addition of ascorbic acid or salts of ascorbic acid as a way to reduce the hexavalent chromate to chromium (III) ions, which are less toxic.
  • chromic acid is also a significant cost factor, which further restricts the economics of the electro polishing process.
  • Electrolyte contains 5 to 60 wt .-% sulfuric acid and 30 to 80 wt .-% phosphoric acid.
  • the electrolyte bath may additionally contain a trivalent dissolved metal, such as iron.
  • AT 190 769 B describes a process and an electrolyte for the electrolytic cleaning of metal objects.
  • the electrolyte consists of hydrochloric acid and after the electrolysis is rinsed, the phosphoric acid in the ratio of about 0.05% to 3% can be added to the rinse water.
  • This phosphoric acid additive serves the purpose of preventing the formation of oxides on the metal of the treated article.
  • the invention presented here is based on an electropolishing method which, like the electropolishing method for stainless steel, is based on mixtures of phosphoric acid and sulfuric acid, the first rinsing step following the actual electropolishing step with phosphoric acid-containing solution, preferably with a solution having a phosphoric acid content of at least 50% by weight. has performed.
  • the use of concentrated phosphoric acid, which contains a proportion of 85 wt.% H 3 PO 4 is suitable here as a starting solution. This process does not require the addition of chromic acid or other inhibitors and therefore offers considerable, not only economic benefits.
  • the articles to be electro-polished are degreased in an optional step to avoid contamination of the electrolyte and to make the surfaces of the workpieces completely accessible to the electrolyte.
  • Any commercially available degreasing solution can be used for this purpose.
  • the workpieces are usually rinsed with water and then immersed in the electropolishing and anodized.
  • An undesirably strong chemical attack on the surfaces of the electropolishing article may be prevented during the electropolishing step by keeping the water content of the electrolytes low. Therefore, almost exclusively highly concentrated acids such as sulfuric acid, phosphoric acid and mixtures of sulfuric acid and phosphoric acid are used for the electropolishing of steels and steel alloys. Particularly good effect show thereby electrolytes, which have a water content of at most 20 wt.%.
  • the temperature of the electrolyte should be above 50 0 C, preferably 60 0 C to 90 0 C.
  • the iron ions removed from the workpiece surface during the electropolishing process dissolve in the electrolyte and are enriched there. Beyond a critical concentration of about 8% by weight, corresponding to about 140 grams per liter of iron in the electrolyte, the effectiveness of the electrolyte decreases markedly. This requires a reduction of the iron content by partial exchange with fresh electrolyte.
  • the removal of the spent electrolyte can be done both directly, as well as by extraction in the rinsing process.
  • the removed, consumed electrolyte is either delivered to an approved site for Ver ⁇ tion or to make it usable again by regeneration.
  • the electrolytic precipitation of the iron in the form of Fe (II) sulfate from the concentrated electrolyte is outstandingly suitable.
  • waste from the electropolishing process ultimately only the removed iron in the form of iron (I ⁇ ) sulfate, which in turn can be used industrially as a reducing agent, for example.
  • a set of hardened tool steel cutting tools (material no. 1.3343) was prepared in an electrolyte consisting of 50% by weight of phosphoric acid and 50% by weight of sulfuric acid having a specific gravity of 1.75 kg / l and an iron content of 4.5% by weight. Electropolished at a electrolyte temperature of 80 0 C, a current density of 40 A / dm 2 and a voltage of 12 V for a period of 6 min and then pre-rinsed in concentrated phosphoric acid (85 wt.%) at room temperature, rinsed in water, then in Water immersed at a temperature of 6O 0 C, to which a commercial corrosion inhibitor in a concentration of 2 wt.% Was added, and dried in air.
  • a second set was placed in an electrolyte containing 70 wt% phosphoric acid, 2.5 wt% sulfuric acid and 9 wt% chromic acid having a specific gravity of 1.740 kg / l and an iron content of 2.5 wt% at an electrolyte temperature of 50 0 C, a current density of 40 A / dm 2 and a voltage of 11 V electropolished for a period of 6 min.
  • the parts were then rinsed with water and dried.
  • the result of the electropolishing was equivalent in both methods with respect to leveling of the surfaces and smoothing of the cutting edges.
  • Heat-treated steel plates were electropolished in the cured and uncured state in electrolytes according to Example 1.
  • the current density was 25 A / dm 2 at 14 V and an electropolishing time of 60 min.
  • the rinsing process was carried out as described in Example 1, as well as drying in air.
  • the results obtained on the cured and uncured plates were equivalent in terms of material removal, gloss and leveling in both processes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

The invention relates to an inexpensive and environmentally friendly method for electrochemically polishing steel, especially low-alloy steels. The method is characterized in that the workpieces, after electropolishing, are rinsed in a phosphoric acid/sulfuric acid bath containing little water in a first rinsing step, thereby preventing the freshly polished surfaces from chemical attacks without using inhibitors such as chromata which are environmentally harmful and injurious to health. Recirculation of the acids and rinse solutions allows to recover them, thereby creating a waste water-free process.

Description

Elektropolierverfahren Electropolishing process
Die vorliegende Erfindung beschreibt ein Verfahren zum elektrochemischen Polieren vonThe present invention describes a method for electrochemical polishing
Werkstücken aus Stahl, bei dem eine Verätzung der Oberfläche beim Spülvorgang auch ohne den Einsatz kostspieliger und umweltschädlicher Inhibitoren vermieden werden kann. Dieses Verfahren eignet sich insbesondere auch für Werkstücke aus niedrig legierten Stählen, die für einen chemischen Angriff besonders anfällig sind.Workpieces made of steel, in which an etching of the surface during the flushing process can be avoided without the use of costly and environmentally harmful inhibitors. This method is particularly suitable for workpieces made of low-alloyed steels, which are particularly vulnerable to chemical attack.
Das elektrochemische Polieren ist ein Verfahren, dass dem Entgraten, Glätten und Glänzen von Metalloberflächen dient. Aufgrund der höheren Stromdichte an feinen Kratzern und anderen Unebenheiten ionisiert und löst sich das Metall an diesen Stellen schneller als an den glatten Bereichen eines Metallwerkstücks, wodurch dessen Unebenheiten ausgeglichen werden. Hierzu werden die zu elektropolierenden Gegenstände, die an entsprechendenElectrochemical polishing is a process that is used to deburr, smooth and shine metal surfaces. Due to the higher current density of fine scratches and other unevenness, the metal ionizes and dissolves faster at these points than at the smooth areas of a metal workpiece, thereby compensating its unevenness. For this purpose, the objects to be electropolished, which are at corresponding
Trageelementen hängen oder in Körben oder dergleichen angeordnet sind, in einen Elektrolyten, das Polierbad, eingetaucht und nach einer gewissen Zeit aus diesem herausgehoben. Nach dem Abfließen der Badflüssigkeit von den polierten Oberflächen werden die Gegenstände in Spülbäder getaucht, um den Elektrolyten vollständig zu entfernen. Diese Elektropo- lierverfahren haben insbesondere für Stähle mit einem Chromgehalt über 12%, die gemeinhin als nicht rostende Stähle, Edelstahle oder säurebeständige Stähle bezeichnet werden, breite industrielle Anwendung gefunden. Hierbei werden überwiegend Elektrolyte auf der Basis von Gemischen aus Phosphorsäure und Schwefelsäure eingesetzt, denen zur weiteren Verbesserung der Wirkung Glanzbildner und Inhibitoren zugesetzt werden können.Carrying elements hang or are arranged in baskets or the like, immersed in an electrolyte, the polishing bath, and lifted out of this after a certain time. After draining the bath liquid from the polished surfaces, the articles are immersed in rinsing baths to completely remove the electrolyte. These electropol- ogy processes have found broad industrial application, in particular for steels with a chromium content above 12%, commonly referred to as stainless steels, stainless steels or acid-resistant steels. In this case, predominantly electrolytes based on mixtures of phosphoric acid and sulfuric acid are used, to which brighteners and inhibitors can be added to further improve the effect.
Stähle mit einem Chromgehalt unter 12%, d.h. niedrig legierte Stähle wie Baustähle und Werkzeugstähle, welche den Großteil der eingesetzten Stahlqualitäten bilden, können mit den für die Bearbeitung von Edelstahlen eingesetzten Verfahren jedoch nicht mit ausreichender Qualität elektropoliert werden. Die Ursache hierfür liegt in der geringen Säurebe- ständigkeit dieser Stähle, die dazu führt, dass die Elektrolyte beim Elektropolierprozess die Oberflächen unkontrollierbar chemisch angreifen und verätzen.Steels with a chromium content below 12%, i. However, low-alloyed steels such as structural steels and tool steels, which make up the majority of the steel grades used, can not be electropolished with sufficient quality using the processes used to process stainless steels. The reason for this lies in the low acid resistance of these steels, which leads to the electrolytes chemically attacking and etching the surfaces during the electropolishing process in an uncontrollable manner.
Um niedrig legierte Stähle mit Elektrolyten auf der Basis von Phosphorsäure und Schwefelsäure erfolgreich elektropolieren zu können, wird den Elektrolyten meist in nennenswerter Konzentration Chromsäure, d.h. eine Oxosäure des sechswertigen Chroms (Chromat) als Inhibitor zugesetzt, der den chemischen Angriff auf die Oberflächen des zu bearbeitenden Werkstücks während des Elektropolierens verhindert. Chromate sind hoch toxisch, fruchtschädigend und krebserregend, weshalb ihr Einsatz in der Industrie zunehmend eingeschränkt wird und hohen Sicherheitsauflagen hinsichtlich Arbeitsschutz und Umweltschutz unterliegt. Das Patent JP-A 5 163 600 beschreibt den Zusatz von Ascorbinsäure oder Salzen der Ascorbinsäure als Möglichkeit, das sechswertige Chromat zu Chrom-(III)-Ionen, die weniger giftig sind, zu reduzieren. Die Verwendung von Chromsäure stellt jedoch auch einen erheblichen Kostenfaktor dar, der die Wirtschaftlichkeit des Elektro- polierverfahrens weiter einschränkt.In order to successfully electropolish low-alloyed steels with electrolytes based on phosphoric acid and sulfuric acid, chromic acid, ie an oxo acid of hexavalent chromium (chromate), is added to the electrolyte in an appreciable concentration, which inhibits the chemical attack on the surfaces of the material Workpiece during the electropolishing prevents. Chromates are highly toxic, teratogenic and carcinogenic, which is why their use in the industry is increasingly limited and subject to high safety standards in terms of occupational safety and environmental protection. The patent JP-A 5 163 600 describes the addition of ascorbic acid or salts of ascorbic acid as a way to reduce the hexavalent chromate to chromium (III) ions, which are less toxic. However, the use of chromic acid is also a significant cost factor, which further restricts the economics of the electro polishing process.
Ohne Chromsäure werden verschiedene Stähle, Aluminium, Nickel und deren Legierungen gemäß US-A 2,773,821 in Lösungen aus Schwefel- und Phosphorsäure elektropoliert, wobei jedoch der Zusatz von Hydroxyessigsäure, Benzolsulfonsäure und Toluolsulfonsäure benötigt wird. Die organischen Zusätze machen bis zu 40% der Elektropolierlösung aus. EP-A 0 249 650 verwendet zum chromfreien elektrochemischen Polieren von Gegenständen aus Stahl, Edelstahl, Nickellegierungen, Aluminium und Aluminiumlegierungen einen Chelatbildner auf der Basis von Phosphonsäure. EP-A 1 443 129 beschreibt den Zusatz von bis zu 50% Alkoholen und weiteren oberflächenaktiven Substanzen zur Elektropolierlösung, bevor die elekt- ropolierten Gegenstände lackiert werden. All diese Zusätze stellen einen nicht unerheblichen Kostenfaktor dar.Without chromic acid, various steels, aluminum, nickel and their alloys according to US-A 2,773,821 are electropolished in solutions of sulfuric and phosphoric acid, but the addition of hydroxyacetic acid, benzenesulfonic acid and toluenesulfonic acid is needed. The organic additives account for up to 40% of the electropolishing solution. EP-A 0 249 650 uses a chelating agent based on phosphonic acid for chromium-free electrochemical polishing of articles made of steel, stainless steel, nickel alloys, aluminum and aluminum alloys. EP-A 1 443 129 describes the addition of up to 50% of alcohols and other surface-active substances to the electropolishing solution before the electropolished objects are painted. All these additions represent a not inconsiderable cost factor.
Entscheidende Bedeutung für den Glanz und die Glattheit des bearbeiteten Gegenstands kommt dem auf den Elektropolierschritt folgenden Spülprozess zu, durch den die Oberflächen von dem anhaftenden Elektrolyten gereinigt werden sollen. Die dabei auftretende Verringerung der Konzentration der Säure an der Oberfläche des elektropolierten Gegens- tands erhöht die korrosive Wirkung des Elektrolyten. Dieser Effekt soll durch den Zusatz von Inhibitoren wie Chromsäure unterdrückt werden. Ohne diese Zusätze werden die frisch polierten Metalloberflächen dabei wieder verätzt, wodurch der durch das Elektropolieren erzielte Effekt glatterer und glänzenderer Oberflächen in erheblichem Maße verloren geht.Decisive for the gloss and smoothness of the machined article is the flushing process following the electropolishing step, which is intended to clean the surfaces of the adhering electrolyte. The resulting reduction in the concentration of the acid on the surface of the electropolished object increases the corrosive action of the electrolyte. This effect is to be suppressed by the addition of inhibitors such as chromic acid. Without these additions, the freshly polished metal surfaces are again etched, whereby the effect achieved by the electropolishing of smoother and glossier surfaces is lost to a considerable extent.
Für die Industrie wäre daher ein den Verfahren für die Bearbeitung von Edelstahlen hinsichtlich Kosten und Gefährdungspotential vergleichbares Elektropolierverfahren für niedrig legierte Stähle, bei dem dieser chemische Angriff der verdünnten Säure auch ohne den Zusatz kostspieliger sowie umweit- und gesundheitsschädlicher Substanzen vermieden werden kann, von erheblichem Vorteil.For the industry would therefore be a method for machining stainless steel in terms of cost and hazard potential comparable electropolishing for low alloy steels, in which this chemical attack of the dilute acid can be avoided without the addition of expensive and umweit- and harmful substances of considerable advantage ,
Die DE 808 519 B beschreibt ein Verfahren zum Polieren und Entgraten von hoch oder niedrig kohlenstoffhaltigen und von schwach legierten Stählen auf elektrolytischem Wege. Der Elektrolyt enthält 5 bis 60 Gew.-% Schwefelsäure und 30 bis 80 Gew.-% Phosphorsäure. Das Elektrolytbad kann zusätzlich ein dreiwertiges gelöstes Metall, wie u.a. Eisen, enthalten.DE 808 519 B describes a method for polishing and deburring of high or low carbon and low alloy steels by electrolytic means. Of the Electrolyte contains 5 to 60 wt .-% sulfuric acid and 30 to 80 wt .-% phosphoric acid. The electrolyte bath may additionally contain a trivalent dissolved metal, such as iron.
Die AT 190 769 B beschreibt ein Verfahren und einen Elektrolyten zur elektrolytischen Reini- gung von Metallgegenständen. Der Elektrolyt besteht aus Salzsäure und im Anschluss an die Elektrolyse wird gespült, wobei dem Spülwasser Phosphorsäure im Verhältnis von etwa 0,05% bis 3% zugegeben werden kann. Dieser Phosphorsäure-Zusatz dient dem Zweck, die Bildung von Oxiden auf dem Metall des behandelten Gegenstandes zu verhindern.AT 190 769 B describes a process and an electrolyte for the electrolytic cleaning of metal objects. The electrolyte consists of hydrochloric acid and after the electrolysis is rinsed, the phosphoric acid in the ratio of about 0.05% to 3% can be added to the rinse water. This phosphoric acid additive serves the purpose of preventing the formation of oxides on the metal of the treated article.
Detaillierte Beschreibung der ErfindungDetailed description of the invention
Der hier vorgestellten Erfindung liegt ein Elektropolierverfahren zu Grunde, das wie die Elektropolierverfahren für Edelstahl auf Gemischen von Phosphorsäure und Schwefelsäure beruht, wobei der auf den eigentlichen Elektropolierschritt folgende erste Spülschritt mit phosphorsäurehaltiger Lösung, bevorzugt mit einer Lösung die einen Phosphorsäuregehalt von mindestens 50 Gew.% aufweist, durchgeführt wird. Insbesondere die Verwendung von konzentrierter Phosphorsäure, die einen Anteil von 85 Gew.% H3PO4 enthält, eignet sich hier als Ausgangslösung. Dieses Verfahren kommt ohne den Zusatz von Chromsäure oder sonsti- ger Inhibitoren aus und bietet daher erhebliche, nicht nur wirtschaftliche Vorteile.The invention presented here is based on an electropolishing method which, like the electropolishing method for stainless steel, is based on mixtures of phosphoric acid and sulfuric acid, the first rinsing step following the actual electropolishing step with phosphoric acid-containing solution, preferably with a solution having a phosphoric acid content of at least 50% by weight. has performed. In particular, the use of concentrated phosphoric acid, which contains a proportion of 85 wt.% H 3 PO 4 , is suitable here as a starting solution. This process does not require the addition of chromic acid or other inhibitors and therefore offers considerable, not only economic benefits.
Zunächst werden die zu elektropolierenden Gegenstände in einem optionalen Schritt entfettet, um eine Verunreinigung des Elektrolyten zu vermeiden und die Oberflächen der Werkstücke vollständig für den Elektrolyten zugänglich zu machen. Hierzu kann jede han- delsübliche Entfettungslösung verwendet werden. Daraufhin werden die Werkstücke üblicherweise mit Wasser abgespült und im Anschluss daran ins Elektropolierbad getaucht und anodisch geschaltet. Ein unerwünscht starker chemischer Angriff auf die Oberflächen des zu elektropolierenden Gegenstands kann während des Elektropolierschritts dadurch unterbunden werden, dass der Wassergehalt der Elektrolyte niedrig gehalten wird. Daher werde zum Elektropolieren von Stählen und Stahllegierungen fast ausschließlich hochkonzentrierte Säuren, wie Schwefelsäure, Phosphorsäure und Gemische aus Schwefelsäure und Phosphorsäure verwendet. Besonders gute Wirkung zeigen dabei Elektrolyte, die einen Wassergehalt von maximal 20 Gew.% aufweisen.First, the articles to be electro-polished are degreased in an optional step to avoid contamination of the electrolyte and to make the surfaces of the workpieces completely accessible to the electrolyte. Any commercially available degreasing solution can be used for this purpose. Then the workpieces are usually rinsed with water and then immersed in the electropolishing and anodized. An undesirably strong chemical attack on the surfaces of the electropolishing article may be prevented during the electropolishing step by keeping the water content of the electrolytes low. Therefore, almost exclusively highly concentrated acids such as sulfuric acid, phosphoric acid and mixtures of sulfuric acid and phosphoric acid are used for the electropolishing of steels and steel alloys. Particularly good effect show thereby electrolytes, which have a water content of at most 20 wt.%.
Zudem erweist es sich als vorteilhaft, wenn der Elektrolyt bereits von Beginn an Eisen-(III)- Ionen in einer Konzentration von mindestens 1 Gew.%, bevorzugt in einer Konzentration über 2,0 Gew.%, enthält. Um eine für einen wirtschaftlichen Prozess ausreichende chemi- sche Aktivität zu erreichen, sollte die Temperatur des Elektrolyten über 50 0C, bevorzugt 60 0C bis 90 0C, betragen.In addition, it proves to be advantageous if the electrolyte from the beginning of iron (III) - ions in a concentration of at least 1 wt.%, Preferably in a concentration above 2.0 wt.% Contains. In order to obtain a chemical process sufficient for an economic To reach cal activity, the temperature of the electrolyte should be above 50 0 C, preferably 60 0 C to 90 0 C.
Das Problem des chemischen Angriffe bei der Verringerung der Säurekonzentration im Zuge des Spülprozesses ohne die Verwendung von Inhibitoren konnte in dem erfindungsgemäßen Verfahren dadurch gelöst werden, dass in der ersten Stufe des Spülprozesses nicht mit Wasser, sondern mit konzentrierter, wasserarmer Phosphorsäure bei Raumtemperatur gespült wird. Überraschend zeigt sich, dass die Oberflächen anschließend an diesen ersten Spülschritt problemlos mit Wasser fertig gespült werden können, ohne dass ein chemischer Angriff der verdünnten Säure beobachtet werden kann. Dabei ist es von Vorteil, dem Spülwasser im letzten Spülschritt einen gewissen Anteil an handelsüblichen Korrosionsinhibitoren wie etwa KORANTIN BH (2-Butin-l,4-diol) zuzusetzen, um eine nachträgliche Korrosion im Verlauf der Trocknung zu verhindern.The problem of chemical attack in reducing the acid concentration in the course of the rinsing process without the use of inhibitors could be solved in the inventive method that is rinsed in the first stage of the rinsing process not with water, but with concentrated, low-water phosphoric acid at room temperature. Surprisingly, it turns out that the surfaces can be readily rinsed with water after this first rinsing step, without any chemical attack of the dilute acid being observed. It is advantageous to add a certain amount of commercially available corrosion inhibitors such as KORANTIN BH (2-butyne-1,4-diol) to the rinse water in the last rinsing step in order to prevent subsequent corrosion in the course of drying.
Es zeigt sich, dass die Anreicherung der Phosphorsäure mit Elektrolyt in der ersten Spülstufe bis zu einem Gehalt an Schwefelsäure von ca. 20 Gew.% die Ergebnisse nicht beeinträchtigt. Dies eröffnet die Möglichkeit, die mit Schwefelsäureelektrolyt angereicherte Phosphorsäure ihrerseits als Grundstoff für die Herstellung von neuem Elektrolyten zu verwenden. Auch die Rückgewinnung der in den weiteren Spülprozess verschleppten Phosphorsäure aus dem Spülwasser ist ohne Qualitätsverlust möglich. Dies macht die Rückgewinnung der Mineralsäuren, verbunden mit einer Kreislaufführung des Spülwassers über einen Verdampfer äußerst wirtschaftlich. Auf diese Weise kann der Elektropolierprozess quasi abwasserfrei gestaltet werden.It turns out that the enrichment of the phosphoric acid with electrolyte in the first rinsing stage up to a sulfuric acid content of about 20% by weight does not affect the results. This opens up the possibility of using the phosphoric acid enriched with sulfuric acid electrolyte as a raw material for the production of new electrolyte. Also, the recovery of the depleted in the further rinsing process phosphoric acid from the rinse water is possible without loss of quality. This makes the recovery of the mineral acids, combined with a circulation of the rinse water via an evaporator extremely economical. In this way, the electropolishing process can be designed virtually wastewater-free.
Die während des Elektropolierens von der Werkstückoberfläche abgetragenen Eisenionen gehen im Elektrolyt in Lösung und werden dort angereichert. Jenseits einer kritischen Konzentration von ca. 8 Gew.%, entsprechend ca. 140 Gramm pro Liter Eisen im Elektrolyten, vermindert sich die Wirksamkeit des Elektrolyten deutlich. Dies macht eine Verringerung des Eisengehaltes durch Teilaustausch mit frischem Elektrolyten erforderlich. Die Entnahme des verbrauchten Elektrolyten kann sowohl direkt, als auch durch Ausschleppung in den Spülprozess erfolgen.The iron ions removed from the workpiece surface during the electropolishing process dissolve in the electrolyte and are enriched there. Beyond a critical concentration of about 8% by weight, corresponding to about 140 grams per liter of iron in the electrolyte, the effectiveness of the electrolyte decreases markedly. This requires a reduction of the iron content by partial exchange with fresh electrolyte. The removal of the spent electrolyte can be done both directly, as well as by extraction in the rinsing process.
Der entnommene, verbrauchte Elektrolyt ist entweder an eine zugelassene Stelle zur Ver¬ nichtung abzugeben oder durch Regeneration wieder gebrauchsfähig zu machen. Zur Rege- neration des verbrauchten Elektrolyten eignet sich hervorragend das elektrolytische Fällen des Eisens in Form von Fe(II)-Sulfat aus dem konzentriertem Elektrolyten. Somit fällt als Abfall aus dem Elektropolierprozess letztlich nur das abgetragene Eisen in Form von Eisen- (IΙ)-sulfat an, das seinerseits etwa als Reduktionsmittel industriell weiter verwendet werden kann.The removed, consumed electrolyte is either delivered to an approved site for Ver ¬ tion or to make it usable again by regeneration. For the regeneration of the spent electrolyte, the electrolytic precipitation of the iron in the form of Fe (II) sulfate from the concentrated electrolyte is outstandingly suitable. Thus, as waste from the electropolishing process, ultimately only the removed iron in the form of iron (IΙ) sulfate, which in turn can be used industrially as a reducing agent, for example.
Durch Verwendung des erfindungsgemäßen Verfahrens können somit auch niedrig legierte Stähle genauso effizient und kostengünstig wie Edelstahl elektropoliert werden. Zudem stellt dieses Verfahren auch eine erheblich umweltschonendere und die Gesundheit weniger gefährdende Methode des Elektropolierens dar.By using the method according to the invention, even low-alloyed steels can thus be electropolished just as efficiently and cost-effectively as stainless steel. In addition, this method also represents a much more environmentally friendly and health less hazardous method of electropolishing.
Die Erfindung wird in den folgenden Beispielen näher erläutert. Die Beispiele stellen nur mögliche Ausfϋhrungsformen des hier beschriebenen Elektropolierverfahrens dar, es soll keineswegs eine Beschränkung auf die hier aufgeführten Bedingungen impliziert werden.The invention is explained in more detail in the following examples. The examples represent only possible embodiments of the electropolishing method described here, it is by no means intended to be restricted to the conditions listed here.
BeispieleExamples
Beispiel 1:Example 1:
Ein Satz Schneidwerkzeuge aus gehärtetem Werkzeugstahl (Werkstoff Nr. 1.3343) wurde in einem Elektrolyten bestehend aus 50 Gew.% Phosphorsäure und 50 Gew.% Schwefelsäure mit einem spezifischen Gewicht von 1,75 kg/l und einem Eisengehalt von 4,5 Gew.% bei einer Elektrolyttemperatur von 800C, einer Stromdichte von 40 A/dm2 und einer Spannung von 12 V für eine Dauer von 6 min elektropoliert und anschließend in konzentrierter Phosphorsäure (85 Gew.%) bei Raumtemperatur vorgespült, in Wasser endgespült, anschließend in Wasser einer Temperatur von 6O0C getaucht, dem ein handelsüblicher Korrosionsinhibitor in einer Konzentration von 2 Gew.% zugesetzt war, und an Luft getrocknet.A set of hardened tool steel cutting tools (material no. 1.3343) was prepared in an electrolyte consisting of 50% by weight of phosphoric acid and 50% by weight of sulfuric acid having a specific gravity of 1.75 kg / l and an iron content of 4.5% by weight. Electropolished at a electrolyte temperature of 80 0 C, a current density of 40 A / dm 2 and a voltage of 12 V for a period of 6 min and then pre-rinsed in concentrated phosphoric acid (85 wt.%) at room temperature, rinsed in water, then in Water immersed at a temperature of 6O 0 C, to which a commercial corrosion inhibitor in a concentration of 2 wt.% Was added, and dried in air.
Ein zweiter Satz wurde in einem Elektrolyten mit 70 Gew.% Phosphorsäure, 2,5 Gew.% Schwefelsäure und 9 Gew.% Chromsäure mit einem spezifischen Gewicht von 1,740 kg/l und einem Eisengehalt von 2,5 Gew.% bei einer Elektrolyttemperatur von 500C, einer Stromdichte von 40 A/dm2 und einer Spannung von 11 V für eine Dauer von 6 min elektropoliert. Die Teile wurden anschließend mit Wasser gespült und getrocknet.A second set was placed in an electrolyte containing 70 wt% phosphoric acid, 2.5 wt% sulfuric acid and 9 wt% chromic acid having a specific gravity of 1.740 kg / l and an iron content of 2.5 wt% at an electrolyte temperature of 50 0 C, a current density of 40 A / dm 2 and a voltage of 11 V electropolished for a period of 6 min. The parts were then rinsed with water and dried.
Das Ergebnis der Elektropolitur war bei beiden Verfahren gleichwertig hinsichtlich Einebnung der Oberflächen und Glättung der Schneidkanten. 83The result of the electropolishing was equivalent in both methods with respect to leveling of the surfaces and smoothing of the cutting edges. 83
- 6 -- 6 -
Beispie! 2:Step Example! 2:
Platten aus Vergütungsstahl wurden in gehärtetem und ungehärtetem Zustand in Elektrolyten gemäß Bespiel 1 elektropoliert. Die Stromdichte betrug 25 A/dm2 bei 14 V und einer Elektropolierdauer von 60 min. Der Spülprozess erfolgte wie in Beispiel 1 beschrieben, ebenso das Trocknen an Luft. Die erzielten Ergebnisse an den gehärteten und den ungehärteten Platten waren bei beiden Verfahren gleichwertig hinsichtlich Werkstoffabtrag, Glanz und Einebnung. Heat-treated steel plates were electropolished in the cured and uncured state in electrolytes according to Example 1. The current density was 25 A / dm 2 at 14 V and an electropolishing time of 60 min. The rinsing process was carried out as described in Example 1, as well as drying in air. The results obtained on the cured and uncured plates were equivalent in terms of material removal, gloss and leveling in both processes.

Claims

83- 7 -Patentansprüche 83-7 patent claims
1. Verfahren zum elektrochemischen Polieren von niedrig legierten Stählen unter Verwendung eines Elektrolyten, der 100 bis 30 Gew.-% Phosphor-A method of electrochemically polishing low alloy steels using an electrolyte containing 100 to 30 wt% phosphorus
5 säure und 0 bis 70 Gew.-% Schwefelsäure enthält und bei dem der Elektrolyt abgespült wird, dadurch gekennzeichnet, dass eine phosphorsäurehaltige Lösung zur Spülung eingesetzt wird.5 acid and 0 to 70 wt .-% sulfuric acid and in which the electrolyte is rinsed, characterized in that a phosphoric acid-containing solution is used for rinsing.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass der Phosphor- lo Säuregehalt der Spüllösung mindestens 50 Gew.-% beträgt.2. The method according to claim 1, characterized in that the Phosphor lo acid content of the rinse solution is at least 50 wt .-%.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass zur Spülung konzentrierte Phosphorsäure eingesetzt wird.3. The method according to claim 2, characterized in that for rinsing concentrated phosphoric acid is used.
i5 4. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der Elektrolyt im wesentlichen chromfrei ist.i5 4. The method according to any one of the preceding claims, characterized in that the electrolyte is substantially free of chromium.
5. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der Elektrolyt einen Wassergehalt von maximal 20 Gew.-% auf- 0 weist.5. The method according to any one of the preceding claims, characterized in that the electrolyte has a water content of at most 20 wt .-% to 0 has.
6. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der Elektrolyt 80-50 Gew.-% Phosphorsäure und 20-50 Gew.-% Schwefelsäure enthält. 56. The method according to any one of the preceding claims, characterized in that the electrolyte contains 80-50 wt .-% phosphoric acid and 20-50 wt .-% sulfuric acid. 5
7. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeich¬ net, dass der Elektrolyt Eisenionen in einer Menge enthält, die den chemischen Angriff auf die Oberfläche des Stahls inhibiert.7. The method according to any one of the preceding claims, characterized in ¬ net, that the electrolyte contains iron ions in an amount which inhibits the chemical attack on the surface of the steel.
0 8. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der Elektrolyt Eisenionen in einer Menge von mindestens 1 Gew.- % enthält.8. The method according to any one of the preceding claims, characterized in that the electrolyte contains iron ions in an amount of at least 1% by weight.
9. Verfahren nach Ansprüchen 1-7, dadurch gekennzeichnet, dass der Elekt- 5 rolyt über 2,0 Gew.-%, jedoch maximal ca. 8% Eisenionen aufweist. 6 0075839. The method according to claims 1-7, characterized in that the Ele- 5 rolyt over 2.0 wt .-%, but not more than about 8% iron ions. 6 007583
- 8 -- 8th -
10. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der elektrochemisch polierte Stahl im Anschluss an die Spülung mit phosphorsäurehaltiger Lösung mit Wasser gespült wird.10. The method according to any one of the preceding claims, characterized in that the electrochemically polished steel is rinsed after the rinse with phosphoric acid solution with water.
11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass die im Spülwasser enthaltenen Mineralsäuren zurückgewonnen werden.11. The method according to claim 10, characterized in that the mineral acids contained in the rinse water are recovered.
12. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der Elektrolyt zumindest zum Teil durch die mit Elektrolyt ange- reicherte Phosphorsäure aus der ersten Spülstufe und gegebenenfalls durch aus mindestens einer weiteren, wässrigen Spülstufe zurückgewonnener Phosphorsäure ergänzt wird. 12. The method according to any one of the preceding claims, characterized in that the electrolyte is at least partially supplemented by the phosphoric acid enriched with electrolyte from the first rinsing step and optionally by at least one further, aqueous rinsing step recovered phosphoric acid.
EP06776534.7A 2005-08-09 2006-07-31 Electropolishing method Not-in-force EP1913181B1 (en)

Applications Claiming Priority (2)

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DE102005037563A DE102005037563B3 (en) 2005-08-09 2005-08-09 Process for electrochemical polishing of alloy steels useful for for electropolishing of steel, especially stainless steel involves using chromium-free electrolyte containing phosphoric acid and sulfuric acids
PCT/EP2006/007583 WO2007017156A1 (en) 2005-08-09 2006-07-31 Electropolishing method

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DE102007011632B3 (en) * 2007-03-09 2008-06-26 Poligrat Gmbh Method for electropolishing and/or electrochemical deburring of surfaces made from titanium or titanium-containing alloys comprises using an electrolyte made from methane sulfonic acid or one or more alkane diphosphonic acids
DE102012104707A1 (en) * 2012-05-31 2013-12-05 Benteler Automobiltechnik Gmbh Method for producing an exhaust gas heat exchanger
US9504554B2 (en) * 2013-01-16 2016-11-29 Biotronik Ag Microstructured absorbable implant
US9163322B2 (en) * 2013-07-01 2015-10-20 General Electric Company Method and apparatus for refurbishing turbine components
US10557212B2 (en) 2016-03-08 2020-02-11 Chemeon Surface Technology, Llc Electropolishing method and product

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Publication number Priority date Publication date Assignee Title
GB601980A (en) * 1944-04-20 1948-05-18 Westinghouse Electric Int Co Improved process for removing burrs, slivers and fine metal particles from ferrous laminations
BE494931A (en) * 1949-04-07
US2740755A (en) * 1953-04-01 1956-04-03 Dwight E Couch Electropolishing with phosphorous acid
US2773821A (en) * 1956-06-12 1956-12-11 Electro Gleam Inc Composition for use in electropolishing
GB835594A (en) * 1957-03-15 1960-05-25 Samuel Fox And Company Ltd Improved method and means for the treatment of wire
US4306946A (en) * 1980-08-18 1981-12-22 General Electric Company Process for acid recovery from waste water
DE3667505D1 (en) * 1986-06-20 1990-01-18 Poligrat Gmbh ELECTROLYT FOR ELECTROCHEMICAL POLISHING OF METAL SURFACES.
EP1443129A1 (en) * 2003-01-30 2004-08-04 Mir-Chem GmbH Method for treating a metallic workpiece

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Title
See references of WO2007017156A1 *

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HUE037490T2 (en) 2018-08-28
EP1913181B1 (en) 2017-10-04

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