EP0232929B1 - Procédé facilitant la déformation à froid d'acier inoxydable - Google Patents

Procédé facilitant la déformation à froid d'acier inoxydable Download PDF

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Publication number
EP0232929B1
EP0232929B1 EP87200060A EP87200060A EP0232929B1 EP 0232929 B1 EP0232929 B1 EP 0232929B1 EP 87200060 A EP87200060 A EP 87200060A EP 87200060 A EP87200060 A EP 87200060A EP 0232929 B1 EP0232929 B1 EP 0232929B1
Authority
EP
European Patent Office
Prior art keywords
water
stainless steel
oxalate
oxalate coating
coating
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
EP87200060A
Other languages
German (de)
English (en)
Other versions
EP0232929A1 (fr
Inventor
Sakae Sonoda
Morio Iwamoto
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.)
Nihon Parkerizing Co Ltd
Original Assignee
Nihon Parkerizing Co Ltd
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 Nihon Parkerizing Co Ltd filed Critical Nihon Parkerizing Co Ltd
Priority to AT87200060T priority Critical patent/ATE51423T1/de
Publication of EP0232929A1 publication Critical patent/EP0232929A1/fr
Application granted granted Critical
Publication of EP0232929B1 publication Critical patent/EP0232929B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C23C22/05—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 using aqueous solutions
    • C23C22/06—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 using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/46—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates

Definitions

  • the invention relates to a method for facilitating the cold forming of stainless steel by applying an oxalate coating and then a lubricant.
  • the oxalation solutions used to produce the oxalate coating contain, as the main constituent, oxalic acid, additives such as fluoride or chloride, which cause the pickling attack, and sodium thiosulfate or the like, which act as accelerators in the formation of crystals in the layer.
  • an oxalate coating of a suitable layer weight can be produced, to which a lubricating layer is applied in a next operation using a metal soap solution or dispersion.
  • a layer system is currently the best form of preparation of stainless steels for cold forming, provided that conventional degrees of deformation are intended.
  • the high-quality and highly corrosion-resistant stainless steels behave disadvantageously with regard to the formation of oxalate coatings, since the layer formation reaction is severely hindered when using conventional oxalation solutions.
  • the content of the bath components causing the pickling attack such as fluoride or chloride, has been increased, but this has the consequence that the treatment time takes longer and the coating formation is unsatisfactory.
  • the object of the invention is to provide a method for facilitating the cold forming of stainless steels, with which in particular the problems mentioned above can be remedied and which also leads to adhesive coatings in the case of highly corrosion-resistant stainless steels, so that even in the case of heavy cold forming, seizure or cold welding is avoided.
  • Particularly suitable water-soluble polymers are polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol; Polyacrylic acid, casein, glue and the like. Polyvinyl alcohol and polyvinyl pyrrolidone are preferred.
  • the concentrations of the active constituents of the oxalation solution are significant in that than with oxalic acid below 20 g / l there is no sufficient reaction with the stainless steel and above 100 g / l no further increase in reactivity can be achieved.
  • the oxide film does not dissolve sufficiently from the stainless steel surface at a concentration below 5 g / l, so that the formation of the coating proceeds with difficulty. At concentrations above 50 g / l there is practically no additional effect.
  • water-soluble polymer do not lead to an improvement in the coating adhesion at concentrations below the lower limit, and the maximum adhesion is reached at concentrations at the upper limit.
  • Metal soaps are particularly suitable as lubricants for application to the oxalate coating.
  • iron soaps are formed by reaction with the oxalate coating and the soap solution.
  • Calcium, barium, zinc soaps and the like dispersed in water give rise to layers of lubricant of the corresponding soaps on the workpiece surface.
  • the oxalate coating is applied by contact with an oxalating solution which has a temperature of 70 to 100 ° C., preferably 85 to 95 ° C.
  • hydroxylammonium sulfate in combination with oxalic acid is able to quickly and easily bring about complete removal of the oxide film and also to accelerate the formation of the oxalate coating.
  • oxalation solutions which additionally contain fluoride and / or chloride can also be used in the process according to the invention.
  • the water-soluble polymer contained in the oxalation solution is firmly incorporated into the oxalate coating during the formation of the coating, so that it is not removed even by water rinsing. As a result of the installation, a high binding and adhesive effect is also achieved.
  • Sodium thiosulfate is used primarily for nucleation and is therefore particularly responsible for the fineness of the oxalate coating produced.
  • lubricant was applied by treatment with a sodium stearate solution (70 g / l; 75'C; 3 min) before the hot air drying.
  • the wire rods treated and weighed with the individual oxalation solutions - as indicated above - were placed in a 5% by weight aqueous solution of chromic acid at 80 ° C. for a period of 15 min. submerged. Then the wire rods were withdrawn and the layer weights converted into g / m 2 .
  • the adhesion or abrasion resistance of the respective oxalate coatings was tested - also with wire rod.
  • the individual wire rods were tested in a reproducible manner and for a certain time that was identical for all samples using an Amsler testing machine (brake pad against wheel principle).
  • the friction body KIMWIPE® from Jujo Kimberly K.K.
  • the weight of the remaining oxalate coating was then determined using the aforementioned method.
  • the pulling speed was 17.8 m / min.
  • the oxalation solutions used in the process according to the invention led in all cases to residual coating weights of more than 2 g / m 2 in the adhesion test, as a result of which superior adhesion to conventional oxatation solutions tested according to comparison is demonstrated.
  • Tube specimens made of Incolloy 800 (20 Cr, 32 Ni) were used as test objects.
  • Example 1 The treatment was carried out according to the procedure of Example 1 (without soaping). The layer weights were then determined, as indicated in Example 1.
  • test results show that proper oxalate coatings were formed using the oxalation process used in the invention. Although they differed somewhat in terms of layer weight, they possessed the properties necessary for cold forming to a sufficient extent.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Metal Extraction Processes (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Lubricants (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Sheet Steel (AREA)

Claims (5)

1. Procédé pour faciliter le formage à froid d'un acier fin par application d'un revêtement d'oxalate et ensuite d'un lubrifiant, caractérisé en ce que l'on applique le revêtement d'oxalate par contact avec une solution de formation d'oxalate comprenant :
20 à 100 g/l d'acide oxalique
5 à 50 g/I de sulfate d'hydroxylamine
0,3 à 3 g/I d'un polymère hydrosoluble et
0,1 à 10 g/I de thiosulfate de sodium, éventuellement des fluorure(s) et/ou chlorure(s) en supplément ainsi que des composants passant en solution à partir de l'acier fin traité et les contaminants habituels, le reste étant de l'eau.
2. Procédé selon la revendication 1, caractérisé en ce que l'on applique le revêtement d'oxalate par contact avec une solution de formation d'oxalate, qui contient comme polymère hydrosoluble un alcool polyvinylique et/ou une polyvinylpyrolidone.
3. Procédé selon la revendication 1, caractérisé en ce que l'on applique le revêtement d'oxalate par contact avec une solution de formation d'oxalate, qui contient comme polymère hydrosoluble un polyéthylèneglycol, un acide polyacrylique, de la caséine et/ou de la colle.
4. Procédé selon la revendication 1, 2 ou 3, caractérisé en ce que l'on applique le revêtement d'oxalate par contact avec une solution de formation d'oxalate, qui présente une température de 70 à 100 °C.
5. Procédé selon la revendication 4, caractérisé en ce que l'on applique le revêtement d'oxalate par contact avec une solution de formation d'oxalate, qui présente une température de 85 à 95 'C.
EP87200060A 1986-01-21 1987-01-16 Procédé facilitant la déformation à froid d'acier inoxydable Expired - Lifetime EP0232929B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87200060T ATE51423T1 (de) 1986-01-21 1987-01-16 Verfahren zur erleichterung der kaltumformung von edelstahl.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP61010752A JPS62170484A (ja) 1986-01-21 1986-01-21 ステンレス鋼の冷間加工用潤滑処理方法
JP10752/86 1986-01-21

Publications (2)

Publication Number Publication Date
EP0232929A1 EP0232929A1 (fr) 1987-08-19
EP0232929B1 true EP0232929B1 (fr) 1990-03-28

Family

ID=11759045

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87200060A Expired - Lifetime EP0232929B1 (fr) 1986-01-21 1987-01-16 Procédé facilitant la déformation à froid d'acier inoxydable

Country Status (4)

Country Link
EP (1) EP0232929B1 (fr)
JP (1) JPS62170484A (fr)
AT (1) ATE51423T1 (fr)
DE (2) DE3700933A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002088387A (ja) * 2000-09-14 2002-03-27 Sakai Chem Ind Co Ltd 非塩素系潤滑油組成物を使用する金属加工
ITMN20060021A1 (it) * 2006-03-23 2007-09-24 Gilcotubi S R L Sistema di produzione di strutture tubolari inossidabili e saldabili con alta resistenza meccanica e relativo prodotto ottenuto
US11607929B2 (en) 2018-08-09 2023-03-21 Hanon Systems Thermal cycle resistant fastening system for refrigerant fitting
US20220119730A1 (en) * 2019-02-14 2022-04-21 Chemetall Gmbh Simplified method for pretreating metal substrates for cold forming and reactive lubricant therefor
BR112022016684A2 (pt) 2020-02-25 2022-10-11 Chemetall Gmbh Método para pré-tratamento de um substrato metálico, substrato metálico pré-tratado, processo de conformação a frio de um substrato metálico, composição lubrificante aquosa, e, mistura padrão
MX2022010395A (es) 2020-02-25 2022-09-07 Chemetall Gmbh Metodo de pretratamiento de una etapa de sustratos metalicos para el conformado en frio de metales.
CN111500955B (zh) * 2020-04-17 2021-08-24 抚顺特殊钢股份有限公司 一种核电蒸发器用n06625合金异型材制造工艺
BR112023019649A2 (pt) 2021-04-01 2023-10-31 Chemetall Gmbh Método de pré-tratamento de um substrato metálico, substrato metálico pré-tratado, processo de conformação a frio, e, composição lubrificante aquosa

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2759862A (en) * 1952-03-11 1956-08-21 Devex Corp Coating compositions and method of treating ferrous surfaces therewith
CA930651A (en) * 1971-01-12 1973-07-24 Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Energy, Mines, And Resources Forming oxalate conversion coatings on iron or steel
JPS524255B2 (fr) * 1972-08-26 1977-02-02
DE2424382A1 (de) * 1974-05-20 1975-12-04 Metallgesellschaft Ag Verfahren zur vorbereitung von metallischen werkstuecken fuer die spanlose kaltumformung

Also Published As

Publication number Publication date
JPS62170484A (ja) 1987-07-27
DE3762053D1 (de) 1990-05-03
DE3700933A1 (de) 1987-07-30
JPH0129872B2 (fr) 1989-06-14
EP0232929A1 (fr) 1987-08-19
ATE51423T1 (de) 1990-04-15

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