EP0974682A1 - Procédé et dispositif pour le traitement chimique des surfaces métalliques - Google Patents

Procédé et dispositif pour le traitement chimique des surfaces métalliques Download PDF

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Publication number
EP0974682A1
EP0974682A1 EP99113319A EP99113319A EP0974682A1 EP 0974682 A1 EP0974682 A1 EP 0974682A1 EP 99113319 A EP99113319 A EP 99113319A EP 99113319 A EP99113319 A EP 99113319A EP 0974682 A1 EP0974682 A1 EP 0974682A1
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EP
European Patent Office
Prior art keywords
line
solution
process bath
added
bath
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.)
Withdrawn
Application number
EP99113319A
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German (de)
English (en)
Inventor
Matthias Hamacher
Bernhard Kotschy
Peter Dr. Kuhm
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.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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
Priority claimed from DE19858035A external-priority patent/DE19858035A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0974682A1 publication Critical patent/EP0974682A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/106—Other heavy metals refractory metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel

Definitions

  • the invention relates to a method for the chemical treatment of metal surfaces, especially for phosphating or pickling, in which the Metal surfaces in contact with a solution of a process bath which contains several components in aqueous solution, the Composition of the process bath by adding solutions or gases, especially air, in a predetermined range.
  • phosphating metal sheets When phosphating metal sheets, they are so-called phosphating solutions by immersion in a process bath or by spraying brought into contact with the solution. It can be very hard on the metal surface thin phosphate layer are created, which on the one hand protect against corrosion and on the other hand to improve the liability of what is subsequently applied Varnish is used. Thicker layers of phosphate are produced when these are Forming aid to facilitate forming processes.
  • Phosphoric acid contains the solution mainly zinc, so that the metal surface is covered with a zinc phosphate layer.
  • Phosphating solution still other components e.g. B.
  • other metal ions such Manganese ions, and so-called accelerators, are used for uniform Ensure formation of the phosphate layer on the metal surface.
  • phosphate layers that act as sliding layers are based on the Usually on manganese phosphate.
  • the usual phosphating solutions are in the Usually acidic, with a pH of around 1.5 to 4.5. If the phosphating solution acid sensitive components such as accelerators contains, which must decompose quickly in the acid phosphating solution these components are replenished particularly frequently.
  • acid-sensitive components are in one alkaline solution before and with this solution in the acidic Phosphating solution metered. The disadvantage at the dripping point is resulting local increase in pH to more than 4, which leads to a Precipitation of zinc ions as zinc phosphate leads, so that subsequently also zinc or zinc phosphate must be added.
  • the free acid alkaline solutions or dispersions e.g. Sodium hydroxide solution or sodium carbonate solution, hydroxylamine, zinc carbonate
  • these alkaline solutions greatly increase the pH at the point of addition, zinc phosphate precipitates more and more as sludge.
  • Zinc phosphate sludge formation increases the free acid again, so again must be blunted.
  • the valuable zinc phosphate If phosphating solution is lost, this valuable substance must be replenished become. This increases the operating costs of the process.
  • the Sludge hinder the phosphating process, so that it from the phosphating bath must be separated and disposed of.
  • the composition of the phosphating solution does not only change by reducing the content of your components. It continues to be so undesirable if the iron ion content increases too much. It is known to ventilate the bath to reduce the iron content. This is done with compressed air introduced over fine-pored membranes arranged in the process bath, so that the Oxygen in the air oxidizes the iron ions, which then precipitate and form Lower the bottom of the bath container.
  • the fine-pored membranes with a pore size of about 20 ⁇ m produce very fine air bubbles that work well in the process bath to solve.
  • the consumption of the compressed air used for ventilation which one represents a clear cost factor, can be achieved by using this fine-pored Keep membranes low.
  • the invention is therefore based on the object, the economy of significantly improve the methods mentioned at the beginning.
  • Another job of The invention is to increase the process reliability, since when replenishing individual components the proportion of the other components did not change shall be.
  • a process for the chemical treatment of metal surfaces in which the metal surfaces are brought into contact with a solution of a process bath (1) which contains several components in aqueous solution, the composition of the process bath (1) being added of solutions or gases, especially air, in a predetermined range, characterized by that one circulates the solution of the process bath (1) via a first line (2) and a circulation pump (3) and feeds the solution and / or the gas to be added into the first line (2) or into the process bath at a point where due to the end of the line (2) a strong mixing occurs, the end of the line (2) can be in the process bath or above the surface (10) of the process bath.
  • the end of the line (2) can be above the surface (10) of the process bath. You choose the distance of the end of the Line (2) from the process bath surface (10) so that no process bath solution in the line (2) can be drawn back. For example, this distance range from about 10 to about 50 cm.
  • the process bath solution circulated through line (2) onto the surface (10) of the process bath (1) sprayed on, producing a strong turbulence mixed with the remaining process bath solution.
  • the solution to be added is then fed in at that point in the process bath, where this strong turbulence prevails.
  • this point is with the Reference numerals (11) indicated.
  • the solution to be added can be fed in done, for example, by having a line for the solution to be added ends above the surface (10) of the process bath, so that at the point (11) the solution to be added freely on the surface of the Process bath can leak. Because of the great turbulence at this point the solution to be added quickly mixes with a large amount of the Process bath solution. Accordingly, one embodiment of the method is thereby characterized in that the solution to be added to the process bath at a Point feeds where a strong due to the end of the line (2) Mixing occurs and the end of the line (2) above the Surface (10) of the process bath is.
  • the solution to be added is preferably a basic solution (for example an aqueous solution of sodium hydroxide, sodium carbonate or an alkaline amine solution, for example a solution of hydroxylamine) which mixed with the phosphating bath solution to blunt the free acid shall be.
  • a basic solution for example an aqueous solution of sodium hydroxide, sodium carbonate or an alkaline amine solution, for example a solution of hydroxylamine
  • the function of the first line (2) can be from the line of the heating circuit and the function of the circulation pump (3) from the pump of the heating circuit be taken over.
  • the pump is the heating circuit the process bath is constantly active during plant operation and rolls the Process bath solution constantly via a heat exchanger (12) (Fig. 3), pumps for the spraying system in spraying systems or circulation pumps in diving tanks can be switched off during breaks or long interruptions.
  • the heat cycle can Design so that the process bath solution heated in the heat exchanger (12) not, as was previously the case, below the surface (10) of the process bath in the Process bath is fed, but that the line used for this (2) like described above the surface (10) of the process bath ends.
  • the method according to the invention is thereby characterized in that the first line (2) is a heating line for the process bath represents, via which the solution of the process bath via a heat exchanger (12) in the process bath is returned.
  • a branch line (9) (Fig. 3) is provided, through which a partial flow of the bath solution circulated in the heating circuit is fed in below the surface of the process bath and only a further partial flow through the end of the line (2) above the process bath surface (10) ) to be led.
  • the volume fraction of the process bath solution circulated per unit of time, which is introduced directly into the process bath through the branch line (9), can be most easily determined by the cross-sectional ratios of the branch line (9) and the part of the circulation line (2) that continues after branching off this branch line (9) ) to adjust.
  • the cross-sectional ratios can be selected such that a bath volume of approximately 1 to approximately 10 m 3 / h is applied to the process bath surface from the end of the line (2) above the process bath surface (10).
  • the nozzle can be narrowed at the end of the pipe (2) Flow rate of the pumped process bath solution at the entry point in the bathroom can also be increased. This increases the desired Mixing effect when adding the solution to be added. Accordingly an embodiment of the method according to the invention characterized in that the end lying above the process bath surface the first line (2) constricted in a nozzle shape and the solution to be added to the Process bath gives up at a point where due to the end of the line (2) strong mixing occurs.
  • a second line (6) (Fig. 3) open, through which gas, in particular air, is sucked into the first line (2)
  • gas in particular air
  • the gas sucked in is dispersed in the Line (2) circulated process bath solution and is with this in the process bath mixed in.
  • a controllable valve preferably in connection with a flow meter, be provided as shown in Fig. 1 and 2.
  • the first line (2) is provided with a suction pump (4).
  • a suction pump (4) can in the solution to be added and / or the gas to be added the line (2) are fed, the solution to be added or the Gas to be added already inside the suction pump and in the subsequent one Section of the line (2) mixed with the process solution.
  • the process bath is to be aerated, the costly use of Compressed air and membranes, as the ambient air is drawn in via the suction pump can be, which then mixes in the line with the circulated solution.
  • the end of the line immersed in the process bath does not require a gas distributor and can therefore be an open pipe end. Even if the bubble diameter considerably larger than that emerging from the membranes Is compressed air bubbles, this can be done by adding a larger one at no additional cost Compensate for air flow and / or a longer ventilation period.
  • the method according to the invention can be applied to process baths with phosphating solutions.
  • the phosphating solutions can serve different technical purposes.
  • they can represent so-called low-zinc phosphating solutions, as are described, for example, in EP-A-228 151.
  • These have a zinc content of between about 0.3 and about 2 g / l and produce zinc phosphate or zinc iron phosphate layers on the substrate, which can be doped with other metals such as manganese and which have area-related masses ( Layer weights ") in the range from about 1 to about 3 g / m 2.
  • Such phosphating solutions are preferably used to produce phosphate layers which serve as a corrosion-protecting adhesive base for a subsequent coating, such as, for example, a cathodic dip coating in vehicle construction
  • the phosphating solution does not contain any heavy metal ions that are built into the phosphate layer up to 1.2 g / m 2.
  • phosphating solutions are known which, compared to the low zinc phosphating solutions, have much higher contents of zinc (more than 3 g / l) and possibly other divalent metals, which produce crystalline phospha Layering with a layer weight significantly above 3 g / m 2 . These serve as such or, after covering with oils or soaps, as forming aids for forming processes by cold flow such as, for example, pipe or wire drawing.
  • Acid manganese phosphate solutions are used to produce sliding layers for moving machine parts such as cylinders.
  • Phosphating solutions usually contain so-called accelerators contribute to the rapid and uniform formation of the phosphating layer. These are usually substances with an oxidizing effect, for example Nitrate, nitrite, chlorate and / or hydrogen peroxide. Sometimes these are what For example, for nitrite and hydrogen peroxide, acidic Phosphating solution is not stable, so it is not concentrated in a phosphating bath can be incorporated. Rather, they have to make it ready for use Phosphating bath are added continuously or discontinuously. For this The process according to the invention is particularly suitable for addition.
  • the method according to the invention enables the oxidation of especially divalent iron in a phosphating solution to the trivalent stage to perform effectively.
  • the process according to the invention can be used not only in phosphating baths, but also in other process baths.
  • Cooling lubricant tanks are an example and called lacquer coagulation baths.
  • lacquer coagulation baths There is an inexpensive one Aeration is beneficial to limit the growth of anaerobic bacteria or kill these bacteria.
  • the invention can be used for the same purpose Use ventilation also for neutral cleaning baths.
  • the method can also advantageously be used to add oxidizing substances use in a pickling solution, for example for pickling stainless steel and / or of titanium or its alloys. This will make it for the Pickling and / or passivation step required reduction-oxidation potential discontinued or maintained.
  • the method is suitable Reduction-oxidation potential of a pickling solution, as described in EP-B-505 606 is described to increase or maintain.
  • a solution Oxidizing agent such as hydrogen peroxide in particular.
  • the oxidizer has the task of the iron (II) and / or formed during the pickling step Oxidize titanium (III) to the next higher oxidation state. Because of the strong Turbulence in the suction pump and especially in one, preferably the Subsequent to the submersible static mixer, this oxidation reaction takes place very quickly.
  • a suction pump is preferably used, which works according to the Venturi principle works and is driven by the recirculated solution. A separate drive the pump is therefore not required.
  • the invention behind the suction pump a static mixer.
  • the suction pump working according to the Venturi principle requires the static one Mixer no separate drive. Also the investment costs for one Mixers are very small, and this mixer can as well at no additional cost the suction pump must be resistant to chemicals.
  • the one to be added is carried out Solution or the gas to be added to the suction pump via a second one Line to, in which a valve and a flow meter are arranged, so that a controlled and metered addition of gas and solution is possible.
  • the valve can also be timed to maintain running to facilitate the desired composition of the process bath. It is also possible and advantageous to integrate the valve in a control loop, which sensors for detecting the component concentrations in the process bath contains. This is a fully automatic monitoring and replenishment possible.
  • the solution of the process bath is preferably left at a throughput of 0.1 to 5 m 3 / h, in particular from 0.5 to 1 m 3 / h, through the first line (2) and, if present, through the Flow suction pump.
  • the circulation line which in this case branches off to the third line.
  • the one you want Throughput through the first line can be selected by an appropriate choice Reach line diameter and / or through a throttle valve.
  • the solution and / or gas can also be metered in independently of a bath circulation.
  • the solution and / or gas to be added can also be metered in independently of a bath circulation.
  • the works on the Venturi principle and driven by a fresh water supply is, the solution to be added or the gas to be added with the Fresh water mixes.
  • the invention also relates to a plant for carrying out the invention Process, with a container for the process bath and a first line with a circulation pump with which the process bath can be circulated.
  • the above tasks are performed in one embodiment solved according to the invention in that one after the Venturi principle working suction pump is provided, at whose suction inlet a second line for a solution to be added and / or a gas to be added connected.
  • the first line it is preferably downstream behind the Suction pump arranged a static mixer.
  • valve in the second line, one, in particular controllable, valve and a flow meter are provided.
  • the valve can be controlled by a timer or part of a control loop be if additional measuring devices for detecting the concentrations in the Process bath and control electronics are provided.
  • a circulation of the process bath is already provided in some known systems, however, the flow through the circulation line is often considerably higher than the flow rate desired for the operation of the suction pump. In this case it is favorable if one branches off a third line from the circulation pump, the is designed so that the largest part of the circulated solution through this third line flows. The smaller part of the circulated solution then flows through the suction pump.
  • the invention relates to a system for Performing the method according to one or more of claims 2 to 6, with a container for the process bath (1) and a first line (2) with a Circulation pump (3) and a heat exchanger (12) with which the solution of the Process bath can be circulated, characterized in that the end of the line (2) is above the process bath.
  • This embodiment differs of known systems, such as those used for layer-forming or non-layer-forming phosphating of metal surfaces are used, characterized in that the line (2) leading over the heat exchanger is not below the surface (10) of the process bath ends, but above.
  • a third line (9) through which a partial flow of the circulated solution of the process bath in the Process bath below whose bath surface is returned.
  • first line (2) and the third line (9) can be specified which proportion of the heat exchanger circulated process bath solution through the branch line (9) or through the Branch of the branch line (9) continuing part of the line (2) on the Surface of the process bath is applied.
  • process bath 1 is aerated.
  • the process bath with a volume of about 50 to 200 m 3 is circulated without interruption via a first line 2 and a circulating pump 3, the circulated liquid flow being 0.6 m 3 / h.
  • a suction pump 4 working according to the Venturi principle
  • z. B a water jet pump
  • a static mixer 5 is arranged.
  • a second line 6 is connected through which air is supplied via a valve 7 and a flow meter 8 can.
  • the solution of the process bath 1 is circulated by means of the circulation pump 3 via a third line 9 with a throughput of 10 m 3 / h and more.
  • a part of the circulated solution namely 0.6 m 3 / h, reaches a first branch 2 via a branch point, in which the suction pump 4 and the static mixer 5 are arranged.
  • this example corresponds to the example according to FIG. 1.
  • the mixing in of liquids e.g. B. concentrates for replenishing individual components is provided here.
  • liquids can also be fed to the process bath 1 by means of the second line 6.
  • the first line (2) represents the circulation line of the Heating circuit.
  • a pump (3) which is shown in Fig. 3 for example in Flow direction is in front of the heat exchanger (12), but also behind it Heat exchanger could be, part of the process bath solution (1) on the Pumped heat exchanger (12) and heated in the process.
  • At least part of the pumped process bath solution flows through the end of the circulation line (2), that ends above the surface (10) of the process bath solution (1).
  • a branch line (9) can be provided through which a partial flow through the Line (2) circulated process bath solution below the bath surface in the Process bath is returned.
  • the reference number (6) is an optional Line indicated through which a gas in the line (2) above its end can be sucked into the circulated process bath solution, if desired via a control valve and / or a flow meter. If you do this Provides suction line (6), they are preferably arranged so that their open Comes to lie above the process bath surface. If by a Malfunction process bath solution rises back into the gas line (6) this arrangement ensured that this process bath solution in the process bath runs back without causing any damage.
  • With the reference number (11) is that Marked location where by the impact of the circulated process bath solution the surface (10) of the process bath is particularly turbulent and where in one of the embodiments of the invention solution to be added.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
EP99113319A 1998-07-18 1999-07-09 Procédé et dispositif pour le traitement chimique des surfaces métalliques Withdrawn EP0974682A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19832424 1998-07-18
DE19832424 1998-07-18
DE19858035A DE19858035A1 (de) 1998-07-18 1998-12-16 Verfahren zur chemischen Behandlung von Metalloberflächen und dazu geeignete Anlage
DE19858035 1998-12-16

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EP0974682A1 true EP0974682A1 (fr) 2000-01-26

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EP (1) EP0974682A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012004907A1 (de) 2012-03-02 2013-09-05 Sms Siemag Ag Verfahren zum Beizen von Standard Stählen
WO2015165600A1 (fr) * 2014-04-30 2015-11-05 Rio Verwaltungs Ag Dispositif et procédé de traitement pour décaper et phosphater des pièces métalliques
CN108368611A (zh) * 2015-11-05 2018-08-03 雷托马克斯有限公司 用于对线或线部件酸洗和磷化的处理设备和用于对线或线部件覆层的处理方法以及处理设施

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US6695931B1 (en) 1999-05-24 2004-02-24 Birchwood Laboratories, Inc. Composition and method for metal coloring process
US6576346B1 (en) * 1999-05-24 2003-06-10 Birchwood Laboratories, Inc. Composition and method for metal coloring process
US6652977B2 (en) 2001-09-10 2003-11-25 Johnson Diversey, Inc. Primer composition
US6899956B2 (en) 2002-05-03 2005-05-31 Birchwood Laboratories, Inc. Metal coloring process and solutions therefor
US7964044B1 (en) 2003-10-29 2011-06-21 Birchwood Laboratories, Inc. Ferrous metal magnetite coating processes and reagents
US7144599B2 (en) 2004-07-15 2006-12-05 Birchwood Laboratories, Inc. Hybrid metal oxide/organometallic conversion coating for ferrous metals
CN103173756B (zh) * 2012-10-19 2016-01-20 湖南吉利汽车部件有限公司 增强磷化槽内磷化液表面循环的气动装置
US10745812B2 (en) * 2017-08-24 2020-08-18 The Boeing Company Methods, systems and apparatuses for copper removal from aluminum desmutting solutions

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JPS5947386A (ja) * 1982-09-08 1984-03-17 Nisshin Steel Co Ltd メツキ鋼板のクロメ−ト処理方法
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EP0267166A2 (fr) * 1986-09-11 1988-05-11 Eka Nobel Aktiebolag Procédé pour diminuer l'émission d'oxydes d'azote à partir de liquides contenant de l'acide nitrique
EP0505606A1 (fr) * 1991-03-29 1992-09-30 Itb S.R.L. Procédé de décapage et de passivation de l'acier inoxydable sans utilisation de l'acide nitrique
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DE19755350A1 (de) * 1997-12-12 1999-06-17 Henkel Kgaa Verfahren zum Beizen und Passivieren von Edelstahl

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JPS5947386A (ja) * 1982-09-08 1984-03-17 Nisshin Steel Co Ltd メツキ鋼板のクロメ−ト処理方法
EP0228151A1 (fr) * 1985-08-27 1987-07-08 HENKEL CORPORATION (a Delaware Corp.) Solutions aqueuses acides de phosphatation pour leur utilisation dans un procédé de phosphatation de surfaces métalliques
EP0267166A2 (fr) * 1986-09-11 1988-05-11 Eka Nobel Aktiebolag Procédé pour diminuer l'émission d'oxydes d'azote à partir de liquides contenant de l'acide nitrique
EP0505606A1 (fr) * 1991-03-29 1992-09-30 Itb S.R.L. Procédé de décapage et de passivation de l'acier inoxydable sans utilisation de l'acide nitrique
EP0776993A1 (fr) * 1995-11-28 1997-06-04 Eka Chemicals AB Procédé de décapage d'acier
EP0885985A1 (fr) * 1997-05-05 1998-12-23 Akzo Nobel N.V. Procédé de traitement d'un métal
DE19755350A1 (de) * 1997-12-12 1999-06-17 Henkel Kgaa Verfahren zum Beizen und Passivieren von Edelstahl

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012004907A1 (de) 2012-03-02 2013-09-05 Sms Siemag Ag Verfahren zum Beizen von Standard Stählen
WO2015165600A1 (fr) * 2014-04-30 2015-11-05 Rio Verwaltungs Ag Dispositif et procédé de traitement pour décaper et phosphater des pièces métalliques
RU2691443C2 (ru) * 2014-04-30 2019-06-13 Рио Фервальтунгс Аг Обрабатывающее устройство и способ обработки для травления и фосфатирования металлических деталей
US10513784B2 (en) 2014-04-30 2019-12-24 Rio Verwaltungs Ag Treatment device and treatment method for pickling and phosphating metal parts
CN108368611A (zh) * 2015-11-05 2018-08-03 雷托马克斯有限公司 用于对线或线部件酸洗和磷化的处理设备和用于对线或线部件覆层的处理方法以及处理设施
CN108368611B (zh) * 2015-11-05 2020-12-29 雷托马克斯有限公司 用于对线或线部件酸洗和磷化的处理设备和用于对线或线部件覆层的处理方法以及处理设施

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