EP0987350B1 - Verfahren und Vorrichtung zum Aufbringen eines Phosphatüberzuges auf Werkstücke - Google Patents

Verfahren und Vorrichtung zum Aufbringen eines Phosphatüberzuges auf Werkstücke Download PDF

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Publication number
EP0987350B1
EP0987350B1 EP99890263A EP99890263A EP0987350B1 EP 0987350 B1 EP0987350 B1 EP 0987350B1 EP 99890263 A EP99890263 A EP 99890263A EP 99890263 A EP99890263 A EP 99890263A EP 0987350 B1 EP0987350 B1 EP 0987350B1
Authority
EP
European Patent Office
Prior art keywords
wire
phosphating
bath
unit
pickling
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.)
Expired - Lifetime
Application number
EP99890263A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0987350A3 (de
EP0987350A2 (de
Inventor
Heinz Dipl.-Ing. Stockner
Heinz Fischer
Josef Hönecke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Voestalpine Wire Rod Austria GmbH
Original Assignee
Voestalpine Wire Rod Austria GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Voestalpine Wire Rod Austria GmbH filed Critical Voestalpine Wire Rod Austria GmbH
Priority to AT99890263T priority Critical patent/ATE331825T1/de
Priority to SI9930917T priority patent/SI0987350T1/sl
Publication of EP0987350A2 publication Critical patent/EP0987350A2/de
Publication of EP0987350A3 publication Critical patent/EP0987350A3/de
Application granted granted Critical
Publication of EP0987350B1 publication Critical patent/EP0987350B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/36—Phosphatising

Definitions

  • the invention relates to a method for applying a phosphate coating with controlled layer thickness as an aid in a non-cutting cold forming of low-alloy or non-alloyed steels in the form of wires or rods with the use of electric current.
  • the invention comprises a device for applying a phosphate coating with controlled layer thickness as an aid for a non-cutting cold forming of low-alloyed or unalloyed wires or rods made of steel, consisting of at least the components: electrolytically operable phosphating unit, drying device, supply, supply and Discharge devices for the wire or rod.
  • phosphate coatings For a chemical surface treatment of workpieces, in particular of iron-based alloys, as a temporary corrosion protection and sliding aid in a chipless shaping or the like cold forming or as a preparation and part of a surface refinement, an application of phosphate coatings has long been proven and is state of the art.
  • a phosphating of the workpieces is carried out in a treatment bath containing as main components phosphates, usually alkali or zinc phosphate and reaction accelerating oxidizing agent in aqueous solution.
  • Optimum film formation conditions can be achieved by precise tuning of the phosphate concentration, the type and amount of the accelerating agents added, and the temperature and pH in the bath.
  • process conditions are to be selected, in which the loosely lying layer part is formed as small as possible.
  • the process conditions determine the structure of the phosphate coating, which structure is to a great extent the Adhesion of a lubricant on the surface affected.
  • the surface of the workpiece both over its circumference and over its longitudinal extent has a high adhesive strength, a uniformly formed, required thickness and a finely crystalline surface structure of the phosphate layer.
  • the correct phosphate layer thickness is of particular importance because excessive layers, if necessary, significantly increase the friction, in particular during the first method step or during the first pull.
  • phosphations which are too thin or uneven over the circumference of the workpiece tend to rupture the layer in the course of drawing, which can lead to inferior surface qualities of the product and lower durability of the drawing dies of the last draws.
  • DE 25 05 836 A1 discloses that the surfaces are treated cathodically in an acidic phosphating solution containing a chelate compound.
  • zinc is first deposited by the electric current onto the surface of the stainless steel, and then a lubricating film is formed in a phosphating step.
  • US-2,812,296 discloses a method for treating the surface of steel sheet to increase corrosion resistance and improve the adhesion of a lacquer layer to make this sheet usable as a substitute for tinplate in the manufacture of cans for packaging purposes.
  • the invention has for its object to overcome the shortcomings of the previously known phosphatizing treatments and to provide an economical method with which a firmly adhering, fine crystalline phosphate coating with a constant in cross-section and selectable thickness and with the same over the length basis weight on workpieces of iron-based alloys, especially on low-alloy steel wires, can be applied.
  • a consistency of the coating should be achievable even with different treatment times and different ion concentrations in the treatment bath.
  • the object is achieved in a generic method in that the wire or rod moves in the longitudinal direction relative to the device and thereby successively brought at least its near-surface region to an elevated temperature between 45 ° C and 120 ° C, passed through at least one treatment bath and during the passage through a phosphating unit with a lead time between 1.5 and 19 seconds, the surface is cathodically phosphated under the influence of electrical current such that when phosphating perpendicular to the longitudinal extent of the wire circumferentially a same potential course in the treatment bath by a substantially tubular order the wire arranged anode takes place and the electrical parameters are adjusted so that the current density on the wire of 0.5 to 20 A / dm 2 reaches and the thereby applied layer dried after the removal of the wire from the bath or allowed to dry.
  • the advantages provided by the invention are to be seen essentially in that at short treatment times, so with high efficiency, a fine crystalline, well-adhering phosphate coating, which is variable in its layer thickness by the electrical values in the cathodic electrolysis, is applied with high quality.
  • This makes it possible to form desired phosphate layer thicknesses on the workpiece surface by adjusting the cathode current density largely independent of fluctuations in the phosphate concentration in the proportion of the lower-dose accelerating oxidizing agent, the temperature and the pH of the bath.
  • the advantageous phosphate layer formation on the workpiece can be assisted, if this is brought to a temperature between 45 ° C and 120 ° C and the treatment bath is maintained at one between 45 ° C and the boiling point thereof, preferably with the proviso that the bath temperature is equal to or lower than the workpiece surface temperature is set.
  • anode is further advantageously formed in the phosphating bath in such a way that its current density is kept at a value of 0.1 to 0.6, in particular about 0.3 times the current density at the workpiece surface, electrolysis parameters which are easily controllable can be achieved particularly effectively become.
  • the workpiece is moved through the treatment bath at a speed of 5 to 500 m / min, preferably of 30 to 100 m / min, and on the surface of which a phosphate coating of 1 to 50 g / m 2 , preferably from 5 to 15 g / m 2 is applied.
  • a phosphate coating of 1 to 50 g / m 2 , preferably from 5 to 15 g / m 2 is applied.
  • Both the quality and the uniformity of the phosphating can be increased if the electrical values in the cathodic electrolysis are controlled as a function of the cation concentration in and of the respective throughput time of the workpiece by the phosphating with the proviso that the coating thickness over the workpiece length in the is kept substantially constant and that at an interruption of the continuous movement, the workpiece dug out of the treatment bath or the bath level is lowered below the workpiece level.
  • This also makes it possible to largely eliminate a negative effect of the same on the product quality in the event of plant malfunctions.
  • a particular advantage with regard to a continuous, highly economical phosphating can be achieved if the workpiece is pickled in its direction of passage before a supported by the action of electric current, in particular a cathodic phosphating. It has proved to be useful when anodic pickling in the run with a current density on the workpiece between 20 and 100 A / dm 2 , preferably between 40 and 80 A / dm 2 carried out and the pickling bath at a temperature between 45 ° C. and 95 ° C is maintained.
  • the electrical power supply of the device can be simplified and their controllability can be effectively obtained if the electrolytic pickling and the like phosphating be electrically connected in series and supplied with regulated DC voltage.
  • the material flow can be improved and the quality assurance of the coating can be increased if the workpiece with a cross-sectional area of 0.003 to 700 mm 2 descaled immediately after removal from the supply and / or linearly.
  • the further object of the invention is achieved in a device of the type mentioned above in that the individual components of the device each have such an embodiment and arrangement that the wire or rod in the longitudinal direction through this Wegbewegbar and is machinable therein and that the phosphating unit at least one heating device for a moving wire or rod is arranged upstream, wherein the electroluminescent electrolysis unit for phosphating comprises at least one tubular electrode surrounding the wire and has a supply and on - and outlet side an overflow device for the phosphating.
  • the advantages that are achieved by this embodiment of the device according to the invention result essentially from the fact that in an economically operable continuous system by means of an upstream heating device for the wire or rod best conditions for a fine crystalline phosphating with control of the phosphate layer thickness are created. It is also important that the electrolysis unit has a substantially concentric surrounding the workpiece electrode so that circumferentially the same potential variation or a same cathode case of the voltage is reached to the workpiece surface and favorable conditions for phosphating with constant layer thickness are given. In this context, a movement in the phosphating or a supply of unused Reactant on the workpiece surface important, which according to the invention by overflow devices, which prevent shyness and erosion, can be achieved.
  • the phosphating unit which can be supplied with electric current, in the phosphating bath area and / or in its supply or discharge area has a device for rapidly lowering the bath level below the level of the workpiece.
  • the electrolytically operable phosphating unit at least one, preferably substantially identically constructed pickling unit, preferably immediately upstream, a particularly economical and safe phosphating with high product quality can be achieved.
  • the course of the coating can be promoted in terms of design and formation of the phosphate coating on the workpiece when the phosphating unit and the pickling unit and / or the supply means for the liquid phosphating and pickling media have controllable heating means for these.
  • the electrical power line and contact training can be provided in a favorable manner that the tube electrode of the pickling unit and the tube electrode of the phosphating unit with the negative and positive pole of a controllable DC voltage source can be connected and that the workpiece can be formed without connection in each case as the anode and cathode ,
  • the substantially concentrically arranged around the wire tubular electrode of the phosphating and / or the pickling unit, seen in the axial direction formed by at least two shell segments and at least a portion of Shell segments can be raised or swung out.
  • the heating device is designed as an induction or conductively acting system and at least after the heating device, preferably before and / or after the pickling unit of the phosphating unit and optionally the drying device, a temperature measuring device for detecting and / or regulating the workpiece temperature is arranged, and when all measuring devices of the device are connected to a central measuring and / or regulating and / or documentation unit, a fully automatic operation of the device for applying a phosphate coating and highest quality of the coating can be achieved.
  • FIG. 1 shows a device according to the invention for applying a phosphate coating to wire, which is subsequently deformed in a drawing device.
  • the individual components of the device are created and arranged for a passage of the wire.
  • a pickled wire rod 11 From a drum or a collar 1, a pickled wire rod 11, axially directed by a for example Bie concertstrom, and introduced into a controllable heating device 3.
  • a regulation of the particular inductively or conductively acting on the wire heat plant can be done by a downstream temperature measuring T 1 .
  • a downstream in the passage direction Z of the wire 11 phosphating unit 5 has a container for a phosphating medium 50 and has at least one feed 52 for this. Inlet and outlet sides, the container in each case has an overflow device 53,54, through which the wire 11 can be spent largely frictionless through the phosphating. For faults or for an insertion of the wire 11, the phosphatizing bath level can be lowered by means of a device 55.
  • a tubular electrode 51 in the container which may be made in segmental form, is substantially concentrically positionable about the wire 11 and has a connection to the PLUS pole of a controllable DC source 8 with its MINUS pole connected to a contact roller 51 '.
  • a heater (not shown) for the phosphating medium 50 may be disposed in the container or in a supply vessel.
  • temperature detection means T 3 T 4 T 5 the measured values are preferably supplied to control device, the surface temperatures of the wire and those of the bath are detectable.
  • the phosphating unit 5 is arranged downstream of the washing means 11, not shown in FIG. 1, for the wire 11, which wire subsequently passes through a drying device 6 and optionally a soaping device and is deformed in a drawing bench 7.
  • the pickling unit 4 has basically the same structure as the phosphating unit 5, but may have a different structure. It is important that, because a pickling in the same line as applying a Phosphatierüberzuges, the pickling parameters are tuned with concentration of pickling liquid, temperature of the pickling medium and the wire, electrolysis conditions and pickling time and the like on the wire speed. Particularly advantageous is a current flow through the tube electrode 51 in the phosphating medium 50 via the wire 11 and via the tube electrode 41 in the pickling liquid 40 at a connection of the electrodes to a controllable Gieichsiromttle. 8

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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)
  • Chemical Treatment Of Metals (AREA)
  • Metal Extraction Processes (AREA)
  • Electroplating Methods And Accessories (AREA)
EP99890263A 1998-08-06 1999-08-05 Verfahren und Vorrichtung zum Aufbringen eines Phosphatüberzuges auf Werkstücke Expired - Lifetime EP0987350B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AT99890263T ATE331825T1 (de) 1998-08-06 1999-08-05 Verfahren und vorrichtung zum aufbringen eines phosphatüberzuges auf werkstücke
SI9930917T SI0987350T1 (sl) 1998-08-06 1999-08-05 Postopek in naprava za nanasanje fosfatne prevleke na obdelovance

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT136398 1998-08-06
AT0136398A AT405947B (de) 1998-08-06 1998-08-06 Verfahren und vorrichtung zum aufbringen eines phosphatüberzuges auf werkstücke

Publications (3)

Publication Number Publication Date
EP0987350A2 EP0987350A2 (de) 2000-03-22
EP0987350A3 EP0987350A3 (de) 2004-03-24
EP0987350B1 true EP0987350B1 (de) 2006-06-28

Family

ID=3512272

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99890263A Expired - Lifetime EP0987350B1 (de) 1998-08-06 1999-08-05 Verfahren und Vorrichtung zum Aufbringen eines Phosphatüberzuges auf Werkstücke

Country Status (5)

Country Link
EP (1) EP0987350B1 (cs)
AT (1) AT405947B (cs)
CZ (1) CZ295733B6 (cs)
DE (1) DE59913624D1 (cs)
ES (1) ES2268846T3 (cs)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015121349A1 (de) * 2015-12-08 2017-06-08 Staku Anlagenbau Gmbh Vorrichtung zur Oberflächenbehandlung eines Endlosmaterials sowie deren Verwendung
CN110863229A (zh) * 2019-12-09 2020-03-06 嘉兴东恒机械设备有限公司 新型金属材料无酸电解磷化工艺

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010028385A1 (de) * 2010-04-29 2011-11-03 Endress + Hauser Gmbh + Co. Kg Verfahren und Vorrichtung zur Durchführung mindestens eines oberflächenmodifizierenden Prozesses an metallischen Werkstücken
CN102277612A (zh) * 2011-08-02 2011-12-14 威海银兴预应力线材有限公司 钢绞线拉丝在线磷化、皂化装置
CN102586839B (zh) * 2012-03-26 2014-12-10 南通高罕金属设备科技有限公司 折叠式开坯在线磷化处理装置
CN103741195B (zh) * 2013-12-23 2016-06-15 南通恒新金属工艺科技有限公司 钢丝电解磷化处理装置
CN108360042A (zh) * 2018-04-02 2018-08-03 江阴海瑞德机电科技有限公司 单丝过电轮装置
CN112226755B (zh) * 2020-09-23 2023-06-23 山东大业股份有限公司 一种金属线材表面处理用磷化方法及装置

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1080914A (fr) * 1953-06-16 1954-12-14 United States Steel Corp Procédé électrochimique de revêtement des surfaces en acier, produits destinés à sa mise en oeuvre et produits en résultant
GB1165014A (en) * 1966-08-22 1969-09-24 Herbert Kenmore Apparatus for Treating Wire and Rods.
JPS5837391B2 (ja) * 1980-02-21 1983-08-16 新日本製鐵株式会社 燐酸塩処理性に優れた冷延鋼板の製造方法
JPS58100902A (ja) * 1981-12-09 1983-06-15 Hitachi Ltd 広幅鋼帯の分割処理法
US5087342A (en) * 1988-04-07 1992-02-11 Seneca Wire And Manufacturing Company Continuous steel strand electrolytic processing
JPH0436498A (ja) * 1990-06-01 1992-02-06 Nippon Parkerizing Co Ltd 鉄鋼線材の表面処理方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015121349A1 (de) * 2015-12-08 2017-06-08 Staku Anlagenbau Gmbh Vorrichtung zur Oberflächenbehandlung eines Endlosmaterials sowie deren Verwendung
CN110863229A (zh) * 2019-12-09 2020-03-06 嘉兴东恒机械设备有限公司 新型金属材料无酸电解磷化工艺

Also Published As

Publication number Publication date
AT405947B (de) 1999-12-27
CZ295733B6 (cs) 2005-10-12
EP0987350A3 (de) 2004-03-24
EP0987350A2 (de) 2000-03-22
DE59913624D1 (de) 2006-08-10
ES2268846T3 (es) 2007-03-16
CZ271099A3 (cs) 2000-03-15
ATA136398A (de) 1999-05-15

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