EP3186417B1 - Electrolyte for polishing of high-grade steels, comprising a pyridine carboxylic acid - Google Patents
Electrolyte for polishing of high-grade steels, comprising a pyridine carboxylic acid Download PDFInfo
- Publication number
- EP3186417B1 EP3186417B1 EP15757232.2A EP15757232A EP3186417B1 EP 3186417 B1 EP3186417 B1 EP 3186417B1 EP 15757232 A EP15757232 A EP 15757232A EP 3186417 B1 EP3186417 B1 EP 3186417B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- electrolyte
- electropolishing
- polishing
- pyridinecarboxylic
- 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.)
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- 239000003792 electrolyte Substances 0.000 title claims description 38
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 title claims description 15
- 238000005498 polishing Methods 0.000 title description 13
- 229910000831 Steel Inorganic materials 0.000 title description 2
- 239000010959 steel Substances 0.000 title description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 20
- 150000001412 amines Chemical class 0.000 claims description 15
- 229910001220 stainless steel Inorganic materials 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229960003512 nicotinic acid Drugs 0.000 claims description 10
- 235000001968 nicotinic acid Nutrition 0.000 claims description 10
- 239000011664 nicotinic acid Substances 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- 125000005270 trialkylamine group Chemical group 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims 1
- 238000007792 addition Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 7
- 239000002184 metal Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 description 2
- 229910000734 martensite Inorganic materials 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- QYSXJUFSXHHAJI-XFEUOLMDSA-N Vitamin D3 Natural products C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C/C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-XFEUOLMDSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229940000635 beta-alanine Drugs 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 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 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- QYSXJUFSXHHAJI-YRZJJWOYSA-N vitamin D3 Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-YRZJJWOYSA-N 0.000 description 1
- 235000005282 vitamin D3 Nutrition 0.000 description 1
- 239000011647 vitamin D3 Substances 0.000 description 1
- 229940021056 vitamin d3 Drugs 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
Definitions
- the present invention relates to the use of certain additives to an electrolyte suitable for electropolishing stainless steels in order to reduce the processing time of materials until a certain polishing quality is achieved and / or to reduce the minimum current density to obtain a polishing effect.
- Electropolishing is a widely used technique in the art for surface treatment of stainless steels. This is done not only to give the surfaces gloss and smoothness for decorative reasons, but predominantly to improve technical-functional properties of the surfaces. These properties include corrosion resistance, cleanability, metallic cleanliness, biocompatibility, resistance to fatigue cracking, reflection and absorption, among others.
- Stainless steels are increasingly being used in a wide variety of technical areas, where not only the surface properties but also strength, toughness, corrosion resistance and last but not least the price are of importance.
- the industry is rapidly developing new grades of stainless steel that are very different in alloy and microstructure.
- electropolishing is also required as a surface treatment for these materials.
- Prior art stainless steel electropolishing processes are based on mixtures of phosphoric acid in the concentration range of 50% to 80% and sulfuric acid in the concentration range of 50% to 20%. Common is the addition of brighteners to support the polishing effect. Modern electrolytes after the State of the art contain a combination of amines such. B.Tributylamin or dimethylamine and phosphonic according to EP 0 249 650 B1 ,
- Essential criteria for the selection of electrolytes in industrial applications are suitability for different grades of stainless steel, required current density and voltage to achieve the desired polishing effect, the limit of metal uptake up to the still a polishing effect.
- this electrolyte contains significant amounts of water (regularly up to 50 wt .-% water). A polishing effect in the context of the present invention can not be achieved with such a bath.
- this electrolyte uses certain aminoalkanoic acids, in particular glycine, beta-alanine or aminoproprionate, which can not be understood as amines or alkanolamines in the context of the present invention.
- US 3,342,711 discloses electrolyte compositions for electropolishing.
- the invention relates to the use of an electrolyte which is equally suitable for electropolishing all stainless steel grades with good results, preferably within a shorter time and with less consumption of energy and chemicals. Another object is that the electrolyte of the invention contains no additional hazardous substances and is suitable to be used in existing electropolishing.
- pyridinecarboxylic acids such as picolinic acid, isonicotinic acid, quinolinic acid and, in particular, nicotinic acid
- Nicotinic acid is known as vitamin D3 and as an additive to food and feed. In this respect, there are no safety concerns against the use of nicotinic acid.
- Nicotinic acid is compatible with all electrolytes for electropolishing stainless steels based on mixtures of phosphoric acid and sulfuric acid. These electrolytes may also contain additions of amines or phosphonic acids.
- the electrolytes show after the addition of a significantly improved leveling behavior, so that is usually the processing time to achieve a defined quality depending on the initial quality of the electrolytes by 40% to 70% shorter. At the same time, the minimum current density to achieve a polishing effect drops by 40% to 60% depending on the material and microstructure.
- the invention relates to the uses of claims 1 and 2.
- An electrolyte having the composition specified in claims 1 and 2 is disclosed in US 5,234,347 EP 0 832 315 A1 mentioned in a process for demetallizing high-acid baths using this method in the electropolishing of stainless steel surfaces.
- the specified electrolyte composition was merely an experimental composition (electrolyte 3). Special properties or effects were not observed with this electrolyte.
- An electrolyte used according to the invention regularly consists of a phosphoric acid / sulfuric acid mixture, wherein - as customary in the prior art - the phosphoric acid in a concentration range of 50 to 80 wt .-% and the sulfuric acid in a concentration range of 50 to 20 wt .-% is used.
- pyridinecarboxylic acid is taken to mean a heteroaromatic compound which consists of a pyridine ring which may be substituted by at least one but also by two carboxy groups.
- the preferred pyridine carboxylic acid is nicotinic acid.
- the pyridinecarboxylic acid is used in an amount of 0.1 to 5.0 wt .-%, preferably 0.8 to 1.5 wt .-%.
- the electrolyte used according to the invention may additionally contain an amine or else combinations of amines (inter alia tributylamine or dimethylamine).
- an alkanolamine can be used, such as a dialkanolamine (including diethanolamine and diisopropanolamine and the like).
- these amines or alkanolamines are used in an amount of 0.2 to 1.0 wt .-%.
- the weight ratio of pyridinecarboxylic acid to amine or alkanolamine in the electrolytes according to the invention is regularly 4: 1 to 1: 1.
- the amine / alkanolamine is a C 1 -C 4 di- or trialkylamine or a C 1 -C 4 di- or trialkanolamine.
- Electropolishing in the sense of the present invention means that the rough values of the treated surface are improved by the electropolishing. That is, with regard to the roughness values, the average roughness Ra regularly is less than 0.5 ⁇ m and the roughness depth Rz is less than 2 ⁇ m. It was observed that, according to the method of the invention, starting from a mean roughness value of about 1.0 ⁇ m according to the method of the invention, an average roughness Ra of less than 0.5 ⁇ m was obtained. A parameter for the method according to the invention is thus a polishing effect in which the average roughness value is lowered by at least 0.5 ⁇ m.
- An automatic electropolishing system for processing sheet metal parts was operated with an electrolyte which consisted of equal parts of phosphoric acid and sulfuric acid with additions of amines.
- the plant operated in two-shift operation with polishing times of 15 to 20 minutes, depending on the geometry of the parts and current densities of 15 A / dm 2 .
- the polishing time for the sheet metal parts used dropped to 8 minutes at 8 A / dm 2 current density.
- the parts had a much higher gloss level and were uniformly polished over the entire surface.
- Hardened martensitic steel medical parts (X7Cr14) were previously treated in an electrolyte of 60% phosphoric acid, 30% sulfuric acid and 10%
- Chromic acid electropolished at current densities of 30 A / dm 2 electropolished An equivalent result could be achieved in an electrolyte with 50% phosphoric acid, 50% sulfuric acid and additions of amines and 1% nicotinic acid within the same processing time at a current density of 15A / dm 2 .
- the same electrolyte without nicotinic acid caused an etching attack on the metal and destroyed the part.
- the sheet was electropolished in the electrolyte according to the invention with a current density of 8 A / dm 2 and a polishing time of 12 minutes. Subsequently, the surface was rinsed with water and dried in air. The electropolished surface was uniformly glossy and had a roughness value of Ra 0.4 ⁇ m.
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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)
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
- Pyridine Compounds (AREA)
Description
Die vorliegende Erfindung betrifft die Verwendung bestimmter Zusätze zu einem Elektrolyten, der zum Elektropolieren von Edelstählen geeignet ist, um die Bearbeitungszeit von Werkstoffen bis zum Erreichen einer bestimmten Polierqualität zu vermindern und/oder die Mindeststromdichte zur Erzielung eines Poliereffektes zu reduzieren.The present invention relates to the use of certain additives to an electrolyte suitable for electropolishing stainless steels in order to reduce the processing time of materials until a certain polishing quality is achieved and / or to reduce the minimum current density to obtain a polishing effect.
Elektropolieren ist ein in der Technik auf breiter Basis angewandtes Verfahren zur Oberflächenbehandlung von Edelstählen. Dies geschieht nicht nur, um den Oberflächen aus dekorativen Gründen Glanz und Glätte zu, verleihen, sondern überwiegend, um technisch-funktionelle Eigenschaften der Oberflächen zu verbessern. Zu diesen Eigenschaften zählen unter anderen Korrosionsbeständigkeit, Reinigungsfähigkeit, metallische Sauberkeit, Biokompatibilität, Beständigkeit gegen Ermüdungsbrüche, Reflexion und Absorption.Electropolishing is a widely used technique in the art for surface treatment of stainless steels. This is done not only to give the surfaces gloss and smoothness for decorative reasons, but predominantly to improve technical-functional properties of the surfaces. These properties include corrosion resistance, cleanability, metallic cleanliness, biocompatibility, resistance to fatigue cracking, reflection and absorption, among others.
Edelstähle werden zunehmend in verschiedensten technischen Bereichen eingesetzt, in denen neben den Oberflächeneigenschaften auch Festigkeit, Zähigkeit, Korrosionsbeständigkeit und nicht zuletzt der Preis von Bedeutung sind. Um diesen Forderungen zu genügen entwickelt die Industrie in rascher Folge neue Edelstahlqualitäten, die in Legierung und Gefüge stark unterschiedlich sind. Gegenwärtig werden etwa 200 verschiedene Werkstoffqualitäten angeboten. Hinsichtlich Gefüge umfassen diese Austenit, Superaustenit, Duplex, Lean Duplex, Ferrit und Martensit. Die Palette der Legierungen ist weit gestreut.Stainless steels are increasingly being used in a wide variety of technical areas, where not only the surface properties but also strength, toughness, corrosion resistance and last but not least the price are of importance. In order to meet these requirements, the industry is rapidly developing new grades of stainless steel that are very different in alloy and microstructure. Currently about 200 different material qualities are offered. In terms of microstructure, these include austenite, super austenite, duplex, lean duplex, ferrite and martensite. The range of alloys is widely spread.
Auch für diese Werkstoffe wird in der Regel Elektropolieren als Oberflächenbehandlung gefordert.As a rule, electropolishing is also required as a surface treatment for these materials.
Elektropolierverfahren für Edelstahl nach dem Stand der Technik beruhen auf Gemischen von Phosphorsäure im Konzentrationsbereich von 50% bis 80% und Schwefelsäure im Konzentrationsbereich von 50% bis 20%. Üblich ist der Zusatz von Glanzbildnern zur Unterstützung des Poliereffekts. Moderne Elektrolyte nach dem Stand der Technik enthalten eine Kombination von Aminen wie z. B.Tributylamin oder Dimethylamin sowie Phosphonsäuren gemäß
Wesentliche Kriterien zur Auswahl von Elektrolyten in der industriellen Anwendung sind Eignung für verschiedene Edelstahlqualitäten, erforderliche Stromdichte und Spannung, um den gewünschten Poliereffekt zu erzielen, die Grenze der Metallaufnahme bis zu der noch ein Poliereffekt eintritt.Essential criteria for the selection of electrolytes in industrial applications are suitability for different grades of stainless steel, required current density and voltage to achieve the desired polishing effect, the limit of metal uptake up to the still a polishing effect.
Keiner der gegenwärtig verfügbaren Elektrolyte deckt die gesamte Breite der Edelstahlqualitäten hinsichtlich Legierung und Gefüge ab. Bei Vorliegen verschiedener Qualitäten sind in der Regel zwei oder mehrere Elektrolyte erforderlich. Schwierigkeiten treten besonders dann auf, wenn innerhalb eines Bauteils mehrere Edelstahlqualitäten verarbeitet sind.None of the currently available electrolytes covers the entire width of the stainless steel grades in terms of alloy and microstructure. In the presence of different qualities usually two or more electrolytes are required. Difficulties occur especially when several stainless steel grades are processed within a component.
Aus der
Darüber hinaus enthält dieser Elektrolyt erhebliche Mengen Wasser (regelmäßig bis zu 50 Gew.-% Wasser). Eine Polierwirkung im Sinne der vorliegenden Erfindung kann man mit einem solchen Bad nicht erreichen.In addition, this electrolyte contains significant amounts of water (regularly up to 50 wt .-% water). A polishing effect in the context of the present invention can not be achieved with such a bath.
Darüber hinaus setzt dieser Elektrolyt bestimmte Aminoalkansäuren ein, insbesondere Glycin, Beta-Alanin oder Aminoproprionat, welche nicht als Amine oder Alkanolamine im Sinne der vorliegenden Erfindung aufgefasst werden können.
Die Erfindung betrifft die Verwendung eines Elektrolyten, der gleichermaßen geeignet ist alle Edelstahlqualitäten mit gutem Ergebnis zu elektropolieren, möglichst innerhalb kürzerer Zeit und mit geringerem Verbrauch an Energie und Chemikalien. Ein weiteres Ziel besteht darin, dass der erfindungsgemäße Elektrolyt keine zusätzlichen Gefahrstoffe enthält und geeignet ist in bestehenden Elektropolieranlagen eingesetzt zu werden.The invention relates to the use of an electrolyte which is equally suitable for electropolishing all stainless steel grades with good results, preferably within a shorter time and with less consumption of energy and chemicals. Another object is that the electrolyte of the invention contains no additional hazardous substances and is suitable to be used in existing electropolishing.
Überraschend hat sich ergeben, dass eine Zugabe von Pyridincarbonsäuren, wie Picolinsäure, Isonicotinsäure, Chinolinsäure und insbesondere Nicotinsäure, die gewünschte Wirkung zeigt. Nicotinsäure ist bekannt als Vitamin D3 und als Zusatz zu Lebens- und Futtermitteln. Insofern bestehen keine Sicherheitsbedenken gegen die Verwendung von Nicotinsäure.Surprisingly, it has been found that addition of pyridinecarboxylic acids, such as picolinic acid, isonicotinic acid, quinolinic acid and, in particular, nicotinic acid, has the desired effect. Nicotinic acid is known as vitamin D3 and as an additive to food and feed. In this respect, there are no safety concerns against the use of nicotinic acid.
Nicotinsäure ist kompatibel mit allen Elektrolyten zum Elektropolieren von Edelstählen, die auf Gemischen von Phosphorsäure und Schwefelsäure basieren. Diese Elektrolyte können auch Zusätze von Aminen oder Phosphonsäuren enthalten.Nicotinic acid is compatible with all electrolytes for electropolishing stainless steels based on mixtures of phosphoric acid and sulfuric acid. These electrolytes may also contain additions of amines or phosphonic acids.
Überraschend hat sich gezeigt, dass nach dem Zusatz von 0,1% bis 5,0%, bevorzugt von 0,8% bis 1,5% zu Elektrolyten aus Gemischen von Phosphorsäure und Schwefelsäure mit Zusätzen von Aminen, diese Elektrolyte geeignet sind alle Qualitäten von Edelstählen in guter bis sehr guter Qualität zu elektropolieren.Surprisingly, it has been shown that after the addition of 0.1% to 5.0%, preferably from 0.8% to 1.5%, to electrolytes from mixtures of phosphoric acid and sulfuric acid with additions of amines, these electrolytes are suitable for all qualities of stainless steels in good to very good quality to electropolish.
Die Elektrolyte zeigen nach dem Zusatz ein deutlich verbessertes Einebnungsverhalten, so dass in der Regel die Bearbeitungszeit zur Erreichung einer definierten Qualität je nach Ausgangsqualität der Elektrolyte um 40% bis 70% kürzer ist. Gleichzeitig sinkt die Mindeststromdichte zur Erzielung eines Poliereffektes je nach Werkstoff und Gefüge um 40% bis 60%.The electrolytes show after the addition of a significantly improved leveling behavior, so that is usually the processing time to achieve a defined quality depending on the initial quality of the electrolytes by 40% to 70% shorter. At the same time, the minimum current density to achieve a polishing effect drops by 40% to 60% depending on the material and microstructure.
Zusätze von Nicotinsäure verbessern die Fähigkeit zur Metallaufnahme um 20% bis 40%. In der Folge sind Elektrolyte, deren Grenze im Metallgehalt bei 5 Gew.% lag einsetzbar bis ca. 7 Gew.%.Additions of nicotinic acid improve the metal uptake capacity by 20% to 40%. As a result, electrolytes whose limit in the metal content at 5 wt.% Was used to about 7 wt.%.
Gegenstand der Erfindung sind die Verwendungen der Ansprüche 1 und 2. Ein Elektrolyt mit der in den Ansprüchen 1 und 2 angegebenen Zusammensetzung wird in der
Ein erfindungsgemäß verwendeter Elektrolyt besteht regelmäßig aus einem Phosphorsäure/Schwefelsäure-Gemisch, wobei - wie im Stand der Technik üblich - die Phosphorsäure in einem Konzentrationsbereich von 50 bis 80 Gew.-% und die Schwefelsäure in einem Konzentrationsbereich von 50 bis 20 Gew.-% eingesetzt wird.An electrolyte used according to the invention regularly consists of a phosphoric acid / sulfuric acid mixture, wherein - as customary in the prior art - the phosphoric acid in a concentration range of 50 to 80 wt .-% and the sulfuric acid in a concentration range of 50 to 20 wt .-% is used.
Als Pyridincarbonsäure im Sinne der vorliegenden Erfindung wird ein Heteroaromat angesehen, der aus einem Pyridinring besteht, der mit mindestens einer, aber auch mit zwei Carboxygruppen substituiert sein kann. Die bevorzugte Pyridincarbonsäure ist die Nicotinsäure.For the purposes of the present invention, pyridinecarboxylic acid is taken to mean a heteroaromatic compound which consists of a pyridine ring which may be substituted by at least one but also by two carboxy groups. The preferred pyridine carboxylic acid is nicotinic acid.
Die Pyridincarbonsäure wird in einer Menge von 0,1 bis 5,0 Gew.-%, vorzugsweise 0,8 bis 1,5 Gew.-% eingesetzt.The pyridinecarboxylic acid is used in an amount of 0.1 to 5.0 wt .-%, preferably 0.8 to 1.5 wt .-%.
Der erfindungsgemäß verwendete Elektrolyt kann zusätzlich ein Amin oder auch Kombinationen von Aminen enthalten (u.a. Tributylamin oder Dimethylamin). Statt des Amins kann aber auch ein Alkanolamin eingesetzt werden, wie beispielsweise ein Dialkanolamin (u.a. Diethanolamin und Diisopropanolamin und dergleichen). Wie im Stand der Technik üblich, werden diese Amine bzw. Alkanolamine in einer Menge von 0,2 bis 1,0 Gew.-% eingesetzt.The electrolyte used according to the invention may additionally contain an amine or else combinations of amines (inter alia tributylamine or dimethylamine). Instead of the amine but also an alkanolamine can be used, such as a dialkanolamine (including diethanolamine and diisopropanolamine and the like). As in the state of Technique usual, these amines or alkanolamines are used in an amount of 0.2 to 1.0 wt .-%.
Das Gewichtsverhältnis Pyridincarbonsäure zu Amin oder Alkanolamin in den erfindungsgemäßen Elektrolyten beträgt regelmäßig 4:1 bis 1:1. Vorzugsweise ist das Amin/Alkanolamin ein C1-C4 Di-oder Trialkylamin bzw. ein C1-C4 Di-oder Trialkanolamin.The weight ratio of pyridinecarboxylic acid to amine or alkanolamine in the electrolytes according to the invention is regularly 4: 1 to 1: 1. Preferably, the amine / alkanolamine is a C 1 -C 4 di- or trialkylamine or a C 1 -C 4 di- or trialkanolamine.
Elektropolieren im Sinne der vorliegenden Erfindung bedeutet, dass die Rauwerte der behandelten Oberfläche durch das Elektropolieren verbessert werden. Das heißt bezüglich der Rauigkeitswerte, dass der Mittenrauwert Ra regelmäßig kleiner als 0,5 µm und die Rautiefe Rz weniger als 2 µm ausmacht. Es wurde beobachtet, dass nach dem erfindungsgemäßen Verfahren ausgehend von einem Mittenrauwert von etwa 1,0 µm nach dem erfindungsgemäßen Verfahren ein Mittenrauwert Ra von weniger als 0,5 µm erhalten wurde. Eine Kenngröße für das erfindungsgemäße Verfahren ist somit eine Polierwirkung bei der der Mittenrauwert um mindestens 0,5 µm abgesenkt wird.Electropolishing in the sense of the present invention means that the rough values of the treated surface are improved by the electropolishing. That is, with regard to the roughness values, the average roughness Ra regularly is less than 0.5 μm and the roughness depth Rz is less than 2 μm. It was observed that, according to the method of the invention, starting from a mean roughness value of about 1.0 μm according to the method of the invention, an average roughness Ra of less than 0.5 μm was obtained. A parameter for the method according to the invention is thus a polishing effect in which the average roughness value is lowered by at least 0.5 μm.
Eine automatische Elektropolieranlage zur Bearbeitung von Blechteilen wurde mit einem Elektrolyten betrieben, der zu gleichen Teilen aus Phosphorsäure und Schwefelsäure mit Zusätzen von Aminen bestand. Die Anlage arbeitete im Zweischichtbetrieb mit Polierzeiten von 15 bis 20 Minuten je nach Geometrie der Teile und Stromdichten von 15 A/dm2. Nach Zugabe von 1,0 Gew.% Nicotinsäure sank die Polierzeit bei den eingesetzten Blechteilen auf 8 Minuten bei 8 A/dm2 Stromdichte. Die Teile wiesen einen deutlich höheren Glanzgrad auf und waren auf der gesamten Oberfläche gleichmäßig poliert.An automatic electropolishing system for processing sheet metal parts was operated with an electrolyte which consisted of equal parts of phosphoric acid and sulfuric acid with additions of amines. The plant operated in two-shift operation with polishing times of 15 to 20 minutes, depending on the geometry of the parts and current densities of 15 A / dm 2 . After addition of 1.0% by weight of nicotinic acid, the polishing time for the sheet metal parts used dropped to 8 minutes at 8 A / dm 2 current density. The parts had a much higher gloss level and were uniformly polished over the entire surface.
In der laufenden Produktion konnte festgestellt werden, dass die Leistung der Elektropolieranlage um 100% erhöht werden konnte ohne den Verbrauch an Chemikalien und Energie wesentlich zu erhöhen. Die Einsparung an Arbeitszeit, Energie und Chemikalien hat zur Folge, dass heute die doppelte Leistung ohne höhere Kosten gegenüber dem vorherigen Zustand erzielt wird.In the current production it could be determined that the power of the electropolishing plant could be increased by 100% without substantially increasing the consumption of chemicals and energy. The savings in working time, energy and chemicals mean that today twice the performance is achieved without incurring higher costs compared to the previous state.
Teile für die Medizintechnik aus gehärtetem martensitischen Stahl (X7Cr14) wurden zuvor in einem Elektrolyten aus 60% Phosphorsäure, 30% Schwefelsäure und 10%Hardened martensitic steel medical parts (X7Cr14) were previously treated in an electrolyte of 60% phosphoric acid, 30% sulfuric acid and 10%
Chromsäure elektropoliert bei Stromdichten von 30 A/dm2 elektropoliert. Ein gleichwertiges Ergebnis konnte in einem Elektrolyten mit 50% Phosphorsäure, 50% Schwefelsäure und Zusätzen von Aminen und 1% Nicotinsäure innerhalb gleicher Bearbeitungszeit bei einer Stromdichte von 15A/dm2 erzielt werden. Derselbe Elektrolyt ohne Nicotinsäure führte zu einem Ätzangriff auf das Metall und zerstörte das Teil.Chromic acid electropolished at current densities of 30 A / dm 2 electropolished. An equivalent result could be achieved in an electrolyte with 50% phosphoric acid, 50% sulfuric acid and additions of amines and 1% nicotinic acid within the same processing time at a current density of 15A / dm 2 . The same electrolyte without nicotinic acid caused an etching attack on the metal and destroyed the part.
Ein Blech aus Werkstoff 1.4462 mit Duplex Gefüge in der Größe DIN A4 und 2,0 mm Dicke, die Oberfläche geschliffen mit Korn 180, wies im Ausgangszustand einen Rauigkeitswert von Ra 1,0 µm auf. Das Blech wurde in dem erfindungsgemäßen Elektrolyten elektropoliert mit einer Stromdichte von 8 A/dm2 und einer Polierdauer von 12 Minuten. Anschließend wurde die Oberfläche mit Wasser gespült und an Luft getrocknet. Die elektropolierte Oberfläche war gleichmäßig glänzend und wies einen Rauigkeitswert von Ra 0,4µm auf.A sheet of material 1.4462 with duplex structure in size A4 and 2.0 mm thickness, the surface ground with grain 180, had in the initial state a roughness value of Ra 1.0 microns. The sheet was electropolished in the electrolyte according to the invention with a current density of 8 A / dm 2 and a polishing time of 12 minutes. Subsequently, the surface was rinsed with water and dried in air. The electropolished surface was uniformly glossy and had a roughness value of Ra 0.4 μm.
Claims (6)
- A use of an additive of pyridinecarboxylic acid in an electrolyte based on a phosphoric acid/sulfuric acid mixture for electropolishing stainless steels in order to shorten the processing time during electropolishing, wherein the electrolyte comprises50 - 80 wt% phosphoric acid,20 - 15 wt% sulfuric acid,0.1 - 5.0 wt% pyridinecarboxylic acid.
- The use of an additive of pyridinecarboxylic acid in an electrolyte based on a phosphoric acid/sulfuric acid mixture for electropolishing stainless steels in order to reduce the minimum current density during electropolishing, wherein the electrolyte comprises50 - 80 wt% phosphoric acid,20 - 15 wt% sulfuric acid,0.1 - 5.0 wt% pyridinecarboxylic acid.
- The use as set forth in claim 1 or 2, wherein the electrolyte contains 0.8 to 1.5 wt% of pyridinecarboxylic acid.
- The use as set forth in any one of the preceding claims, wherein the pyridinecarboxylic acid is nicotinic acid.
- The use as set forth in any one of the preceding claims, wherein the electrolyte contains 0.2 - 1.0 wt% of amines or alkanolamines and the weight ratio of pyridinecarboxylic acid to amine or alkanolamine is 4:1 to 1:1.
- The use as set forth in any one of the preceding claims, wherein the amine is a C1-C4 alkylamine or trialkylamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL15757232T PL3186417T3 (en) | 2014-08-29 | 2015-08-28 | Electrolyte for polishing of high-grade steels, comprising a pyridine carboxylic acid |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP14002999 | 2014-08-29 | ||
| PCT/EP2015/069744 WO2016030506A1 (en) | 2014-08-29 | 2015-08-28 | Electrolyte for polishing stainless steels, containing a pyridinecarboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3186417A1 EP3186417A1 (en) | 2017-07-05 |
| EP3186417B1 true EP3186417B1 (en) | 2018-08-15 |
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ID=51454521
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP15757232.2A Not-in-force EP3186417B1 (en) | 2014-08-29 | 2015-08-28 | Electrolyte for polishing of high-grade steels, comprising a pyridine carboxylic acid |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP3186417B1 (en) |
| HU (1) | HUE040386T2 (en) |
| PL (1) | PL3186417T3 (en) |
| WO (1) | WO2016030506A1 (en) |
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| KR20210137130A (en) * | 2019-03-08 | 2021-11-17 | 스트라우만 홀딩 에이쥐 | Dental drill surface treatment |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1070190A (en) * | 1963-11-14 | 1967-06-01 | Kyowa Hakko Kogyo Kk | Electrolytic polishing of metals |
| JPS4812612B1 (en) | 1964-02-27 | 1973-04-21 | ||
| EP0249650B1 (en) | 1986-06-20 | 1989-12-13 | Poligrat Gmbh | Electrolyte for electrochemically polishing metal surfaces |
| DE19521132C1 (en) * | 1995-06-09 | 1996-10-17 | Poligrat Holding Gmbh | Demetallising used, highly acidic electropolishing baths |
-
2015
- 2015-08-28 HU HUE15757232A patent/HUE040386T2/en unknown
- 2015-08-28 EP EP15757232.2A patent/EP3186417B1/en not_active Not-in-force
- 2015-08-28 PL PL15757232T patent/PL3186417T3/en unknown
- 2015-08-28 WO PCT/EP2015/069744 patent/WO2016030506A1/en active Application Filing
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Also Published As
| Publication number | Publication date |
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| HUE040386T2 (en) | 2019-03-28 |
| WO2016030506A1 (en) | 2016-03-03 |
| PL3186417T3 (en) | 2018-11-30 |
| EP3186417A1 (en) | 2017-07-05 |
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