EP1913181B1 - Electropolishing method - Google Patents
Electropolishing method Download PDFInfo
- Publication number
- EP1913181B1 EP1913181B1 EP06776534.7A EP06776534A EP1913181B1 EP 1913181 B1 EP1913181 B1 EP 1913181B1 EP 06776534 A EP06776534 A EP 06776534A EP 1913181 B1 EP1913181 B1 EP 1913181B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrolyte
- phosphoric acid
- rinsing
- acid
- electropolishing
- 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.)
- Not-in-force
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- 238000000034 method Methods 0.000 title claims description 47
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 55
- 239000003792 electrolyte Substances 0.000 claims description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 28
- 229910000831 Steel Inorganic materials 0.000 claims description 21
- 239000010959 steel Substances 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 238000005498 polishing Methods 0.000 claims description 7
- -1 iron ions Chemical class 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 239000008237 rinsing water Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 2
- 150000007522 mineralic acids Chemical class 0.000 claims 1
- 239000012487 rinsing solution Substances 0.000 claims 1
- 229960004838 phosphoric acid Drugs 0.000 description 20
- 235000011007 phosphoric acid Nutrition 0.000 description 20
- 239000002253 acid Substances 0.000 description 8
- 238000007792 addition Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910001315 Tool steel Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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 the electrochemical polishing of 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.
- 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.
- the objects to be electropolished which are suspended from corresponding support elements or arranged in baskets or the like, are immersed in an electrolyte, the polishing bath, and lifted out of the latter 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.
- chromic acid ie an oxo acid of hexavalent chromium (chromate)
- chromate hexavalent chromium
- 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.
- chromic acid also represents a significant cost factor that further restricts the economics of the electropolishing process.
- 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 article increases the corrosive effect 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.
- the DE 808 519 B describes a process for polishing and deburring high or low carbon and low alloy steels electrolytically.
- 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.
- the AT 190 769 B describes a method 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 DE 808 519 C describes a process for polishing and deburring high or low carbon and low alloy steels electrolytically.
- the GB 835 594 A relates to a method of treating wires.
- the GB 601 980 A describes an electrolytic process using sulfuric acid and phosphoric acid.
- 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 with phosphoric acid-containing solution following the actual electropolishing step with a solution having a phosphoric acid content of at least 50% by weight , is carried out.
- 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 significant, 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 commercial degreasing solution can be used.
- the workpieces are usually rinsed with water and then immersed in the electropolishing and anodized.
- An undesirable chemical attack on the surfaces of the electropolishing article may be inhibited 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 ° C, preferably 60 ° C to 90 ° 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 withdrawn used electrolyte must either be returned to an authorized location for destruction or made ready for use 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 (II) sulfate falls which, in turn, can be further used industrially as a reducing agent.
- a set of tools hardened tool steel (material no. 1.3343) was in an electrolyte consisting of 50 parts by weight of phosphoric acid and 50 parts by weight of sulfuric acid having a specific gravity of 1.75 kg / l and an iron content of 4.5 wt .% at an electrolyte temperature of 80 ° C, a current density of 40 A / dm 2 and a voltage of 12 V for a period of 6 min electropolished and then pre-rinsed in concentrated phosphoric acid (85 wt.%) at room temperature, rinsed in water, then dipped in water at a temperature of 60 ° 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 ° C, a current density of 40 A / dm 2 and a voltage of 11 V eiektropoliert 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.
Landscapes
- 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)
Description
Die vorliegende Erfindung beschreibt ein Verfahren zum elektrochemischen Polieren von 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.The present invention describes a method for the electrochemical polishing of 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 entsprechenden 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 Elektropolierverfahren haben insbesondere für Stähle mit einem Chromgehalt über 12%, die gemeinhin als nicht rostende Stähle, Edelstähle 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.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 suspended from corresponding support elements or arranged in baskets or the like, are immersed in an electrolyte, the polishing bath, and lifted out of the latter 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 electropolishing methods 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 Edelstählen eingesetzten Verfahren jedoch nicht mit ausreichender Qualität elektropoliert werden. Die Ursache hierfür liegt in der geringen Säurebeständigkeit 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.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.
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
Ohne Chromsäure werden verschiedene Stähle, Aluminium, Nickel und deren Legierungen gemäß
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 Gegenstands 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 article increases the corrosive effect 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 Edelstählen 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 comparable to the process for the machining of stainless steels in terms of cost and potential for electropolishing low alloyed steels, in which this chemical attack of the diluted acid can be avoided without the addition of expensive and umweit- and harmful substances, of considerable advantage ,
Die
Die
Die
Aus der
Die
Die
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, 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 sonstiger 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 with phosphoric acid-containing solution following the actual electropolishing step with a solution having a phosphoric acid content of at least 50% by weight , is carried out. 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 significant, 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 handelsübliche 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. For this purpose, any commercial degreasing solution can be used. Then the workpieces are usually rinsed with water and then immersed in the electropolishing and anodized. An undesirable chemical attack on the surfaces of the electropolishing article may be inhibited 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 chemische Aktivität zu erreichen, sollte die Temperatur des Elektrolyten über 50 °C, bevorzugt 60 °C bis 90 °C, 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. To a sufficient for an economic process chemical To achieve activity, the temperature of the electrolyte should be above 50 ° C, preferably 60 ° C to 90 ° C.
Das Problem des chemischen Angriffs 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-1,4-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 rinsing water in the last rinsing step in order to prevent subsequent corrosion in the course of drying.
Es zeigt sich, dass die Anreicherung der Phösphorsäure 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 accumulation of the phos- phoric 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 Vernichtung abzugeben oder durch Regeneration wieder gebrauchsfähig zu machen. Zur Regeneration 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-(II)-sulfat an, das seinerseits etwa als Reduktionsmittel industriell weiter verwendet werden kann.The withdrawn used electrolyte must either be returned to an authorized location for destruction or made ready for use 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 (II) sulfate falls which, in turn, can be further used industrially as a reducing agent.
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 Ausführungsformen 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 limited to the conditions listed here.
Ein Satz Schneidwerkzeuge aus gehärtetem Werkzeugstahl (Werkstoff Nr. 1.3343) wurde in einem Elektrolyten bestehend aus 50 Gew.-Teilen Phosphorsäure und 50 Gew.-Teilen Schwefelsäure mit einem spezifischen Gewicht von 1,75 kg/l und einem Eisengehalt von 4,5 Gew.% bei einer Elektrolyttemperatur von 80°C, 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 60°C getaucht, dem ein handelsüblicher Korrosionsinhibitor in einer Konzentration von 2 Gew.% zugesetzt war, und an Luft getrocknet.A set of tools hardened tool steel (material no. 1.3343) was in an electrolyte consisting of 50 parts by weight of phosphoric acid and 50 parts by weight of sulfuric acid having a specific gravity of 1.75 kg / l and an iron content of 4.5 wt .% at an electrolyte temperature of 80 ° C, a current density of 40 A / dm 2 and a voltage of 12 V for a period of 6 min electropolished and then pre-rinsed in concentrated phosphoric acid (85 wt.%) at room temperature, rinsed in water, then dipped in water at a temperature of 60 ° 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 50°C, einer Stromdichte von 40 A/dm2 und einer Spannung von 11 V für eine Dauer von 6 min eiektropoliert. 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 ° C, a current density of 40 A / dm 2 and a voltage of 11 V eiektropoliert 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.The result of the electropolishing was equivalent in both methods with respect to leveling of the surfaces and smoothing of the cutting edges.
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 (10)
- A method of electrochemical polishing of low-alloy steels using an electrolyte containing 100 to 30 wt.% phosphoric acid and 0 to 70 wt.% sulfuric acid and in which the electrolyte is rinsed off, characterized in that a solution containing phosphoric acid is used for the rinsing, where the phosphoric acid content of the rinsing solution is at least 50 wt.%.
- The method as claimed in claim 1, characterized in that concentrated phosphoric acid is used for the rinsing.
- The method as claimed in one of the preceding claims, characterized in that the electrolyte is substantially chromium-free.
- The method as claimed in one of the preceding claims, characterized in that the electrolyte has a water content of max. 20 wt.%.
- The method as claimed in one of the preceding claims, characterized in that the electrolyte contains 80-50 wt.% phosphoric acid and 20-50 wt.% sulfuric acid.
- The method as claimed in one of the preceding claims, characterized in that the electrolyte contains iron ions in an amount of at least 1 wt.%.
- The method as claimed in claim 6, characterized in that the electrolyte has more than 2.0 wt.%, though at most approx. 8% iron ions.
- The method as claimed in one of the preceding claims, characterized in that the electrochemically polished steel is rinsed with water following the rinsing with solution containing phosphoric acid.
- The method as claimed in claim 8, characterized in that the inorganic acids contained in the rinsing water are recovered.
- The method as claimed in one of the preceding claims, characterized in that the electrolyte is supplemented at least partially with the electrolyte-enriched phosphoric acid from the first rinsing stage and optionally with phosphoric acid recovered from at least one other water-based rinsing stage.
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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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EP1913181B1 true EP1913181B1 (en) | 2017-10-04 |
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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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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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- 2006-07-31 EP EP06776534.7A patent/EP1913181B1/en not_active Not-in-force
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