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EP0380067A1 - Méthode pour lubrifier du fer et de l'acier avant le façonnage à froid - Google Patents

Méthode pour lubrifier du fer et de l'acier avant le façonnage à froid Download PDF

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Publication number
EP0380067A1
EP0380067A1 EP90101350A EP90101350A EP0380067A1 EP 0380067 A1 EP0380067 A1 EP 0380067A1 EP 90101350 A EP90101350 A EP 90101350A EP 90101350 A EP90101350 A EP 90101350A EP 0380067 A1 EP0380067 A1 EP 0380067A1
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EP
European Patent Office
Prior art keywords
ions
process according
solution
lubricat
contact
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.)
Granted
Application number
EP90101350A
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German (de)
English (en)
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EP0380067B1 (fr
Inventor
Yoshio Nagae
Yoshihiko Sawasaki
Yasuo Okumura
Yasuo Tanizawa
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Henkel Corp
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Henkel Corp
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Publication of EP0380067A1 publication Critical patent/EP0380067A1/fr
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Publication of EP0380067B1 publication Critical patent/EP0380067B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • 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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • 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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/17—Orthophosphates containing zinc cations containing also organic acids

Definitions

  • This invention relates to a method for forming an im­proved lubricating layer optimized for cold plastic work­ing, e.g., drawing of tubing and wire, forging, header working, and the like, on the surface of objects made of iron and steel, e.g., low- and high-carbon steels, low al­loy steel, and the like.
  • the first major stage of the method is a phosphating treatment with an optimized compo­sition of phosphating solution.
  • cold work­ing When iron or steel is subjected to cold plastic-work­ing (generally denoted herein below simply as "cold work­ing"), the surface of the workpiece is usually first sub­jected to a lubrication treatment in order to reduce tool wear and seizure between the workpiece and tool.
  • this lubrication treatment conventionally consists of coating the surface of the article with an oil which contains an extreme-pressure additive or lubricity improver.
  • a widely practiced method consists of the formation of a zinc stearate lubri­cant layer over a zinc phosphate-based film and the addi­tional formation of a sodium stearate layer over this zinc stearate layer.
  • This may be achieved, for example, by dip­ping the article to be lubricated into a zinc phosphate based conversion treatment solution (containing sodium nitrite as accelerator) heated to 70 to 80 degrees Centi­grade, followed by, for example, dipping in a sodium stear­ate based metal soap solution (for example, Palube ® 235 from Nihon Parkerizing Company, Limited, Tokyo) heated to 70 to 75 degrees Centigrade.
  • a sodium stear­ate based metal soap solution for example, Palube ® 235 from Nihon Parkerizing Company, Limited, Tokyo
  • Japanese Patent Publication Number 60-20463 alternatively numbered 20,463/85.
  • the conversion treatment in the aforesaid in­vention is conducted at approximately 80 degrees Centigrade using a zinc and calcium phosphate based treatment solution with specified component concentrations.
  • the phos­phating solution for use in this invention should contain, in percentages by weight as are all percentages given here strictlyin unless other specified, 0.3 to 2.5 % of zinc ions, 0.01 to 2.0 % of ferrous ions, 0.5 to 5.0 % of phosphate ions, 0.7 to 12.0 % of nitrate ions, and 0.02 to 0.25 % of water soluble aromatic organic compounds that contain both nitro and sulfonic acid or sulfonate salt groups, with the fer­rous ion and zinc ion contents additionally being such that the weight ratio of ferrous ions to zinc ions in the phos­phating solution in within the range from 0.005 to 3.0.
  • the phosphating solution may also contain from 0.2 to 2.0 % of calcium ions, and when it does, the weight ration of calcium ions to zinc ions in the solution should also be in the range from 0.7 to 4.0.
  • the phosphating solution to be used for this invention may ad­ditionally contain a chelating agent for ferrous ions, chlorate ions, and heavy metal cations such as nickel, co­balt, manganese, or copper.
  • the phosphating solutions consist essentially of only water, the other con­stituents named above, and any necessary counter ions for the ionic constituents.
  • the iron or steel object to be treated is contacted with a phosphating solution as noted above for a time of from 3 to 20 minutes at a temperature of from 35 to 65 degrees Centigrade.
  • a final lubricating film is then formed by treating the phos­phate film thus formed by methods conventional in the art for treating zinc phosphate based films to produce lubri­cant films for cold working. Even though the methods used for forming the lubricating layer are conventional, the resulting layer gives superior lubrication, apparently as a result of favorable interactions with the phosphating layer deposited by a method according to this invention.
  • the phos­phating solution used comprises zinc ions and ferrous ions as its essential cationic components.
  • the zinc ion is to be present at 0.3 to 2.5 %, because the formation of a film suitable for cold working becomes problematical at a zinc ion concentration below 0.3 %; on the other hand, the con­version treatment is not improved with a zinc ion concen­tration in excess of 2.5 %, while bath management becomes difficult and the economics are also undesirable.
  • the ferrous ion content should be 0.01 to 2.0 %, and an additional restriction also applies: that the ferrous ion/zinc ion (Fe2+/Zn2+) weight ratio should fall within the range of 0.005 to 3.0.
  • the permis­sible ferrous ion based on the aforesaid weight ratio would calculate out to 0.00015 to 0.9 %.
  • the independent lower limit value for ferrous ion is 0.01 %, its content is in fact restricted to 0.01 to 0.9 %.
  • the ferrous ion content allowable under the con­straint of its ratio to zinc ions would be 0.0125 to 7.5 %, but in fact the ferrous ion content must be restricted to 0.0125 to 2.0 % because of the independent upper limit value for this ion.
  • the phos­phate film obtained performs unsatisfactorily as a lubrica­ tion base layer.
  • regulation of the iron concen­tration at such a low level in practice requires precipita­tion of iron by the frequent addition of an oxidant, such as NaNO2, H2O2, or the like, that at the temperature used can fairly rapidly oxidize ferrous ions to ferric ions, which are less soluble in these solutions. This increases sludge production.
  • Phosphate ion (PO43 ⁇ ) should be present at 0.5 to 5.0 %, with its optimal concentration being determined in part by the need to provide counter ions for the specified ca­tions present in the solution. Poor quality film formation is encountered at phosphate ion concentrations below 0.5 %. On the other hand, while the use of more than 5.0 % of phosphate is possible, this serves primarily to increase the cost without improving film formation.
  • Nitrate ion (NO3 ⁇ ) is to be present at 0.7 to 12.0 %. At less than 0.7 %, the film formation rate slows, length­ening the treatment time, and the film obtained is coarse and poorly adherent. Exceeding 12.0 % nitrate causes an increase in the Zn(NO3)2 concentration in the treatment solution, which causes a low Zn(H2PO4)2/Zn(NO3)2 ratio. This results in an unsatisfactory concentration of the Zn(H2PO4)2 required for good film formation and thus a re­duced conversion-coating capacity.
  • the phosphate treatment solution used in the present invention also contains, as an essential component, 0.02 to 0.25 % of water-soluble, nitro and sulfonic group containing aromatic compound(s).
  • these compounds are selected from the group of com­pounds containing a benzene, naphthalene, or anthracene nucleus with at least one each of a nitro and a sulfonic acid or sulfonate substituent on this nucleus.
  • the aromatic compounds are selected from the group consisting of nitrobenzene sulfonic acid, nitroaniline sul­fonic acid, nitrotoluene sulfonic acid, nitroxylene sulfon­ic acid, and the salts of these acids, with meta-nitroben­zene sulfonic acid or its salts most preferred. Any of these compounds will serve to lower the treatment tempera­ture for the iron-containing zinc phosphate treatment solu­tion while also functioning to give a fine, dense phosphate film with relatively small crystalline particles.
  • the treatment bath according to the present invention having the above described composition, although containing iron, nevertheless can produce a fine, dense phosphate film with relatively small crystalline particles on the surface of iron and steel, with preferred coat weights of 7 to 12 grams per square meter ("g/m2"), through immersion or other contact for 3 to 20 minutes at the relatively low tempera­tures of 35 to 65 degrees Centigrade.
  • This film forms a base layer adapted to severe cold-working operations.
  • an accelerator such as NO2 ⁇ or H2O2 is generally unnecessary, and preferably is not used in the phosphating solutions.
  • one effect is the relatively slight precipitation of sludge, such as FePO4 and/or Zn3(PO4)2, from the phosphating solutions used in a process according to the invention.
  • the phosphate treatment solution according to the invention may contain a chelating agent for iron to increase the rate of phosphate film formation.
  • a chelating agent for iron is used, it is preferably present in an amount of from 0.01 to 0.05 % of the phosphating solution and is preferably selected from the group consisting of oxalic acid, citric acid, glycerophosphoric acid, urea, polyvinyl alcohol, and poly(vinyl pyrrolidone).
  • the phosphate treatment solution used in the present inven­tion may contain chlorate ions from some constituent such as NaClO3 as additional oxidizer, simple and/or complex fluoride ions, and heavy metal ions such as nickel, cobalt, copper, and the like.
  • the method of the present inven­tion brings about the formation of a phosphate film on a clean iron or steel surface upon contact, preferably by immersion, for 3 to 20 minutes at 35 to 65 degrees Centi­grade in a phosphate treatment solution with the components as specified above.
  • This process according to the inven­tion also preferably includes a water rinse and drying step or a water rinse and neutralization step after phosphate film formation, and the process further includes another step of lubricant treatment after phosphating and preferab­ly after a water rinse and drying after phosphating.
  • the lubricant treatment may contain any conventional lubricant such as molybdenum disulfide, tungsten disulfide, graphite, highly fluorinated organic resin, or an oil lubricant which contains an extreme pressure additive. Most preferred, however, is the lubricating treatment comprising the forma­tion of a zinc/fatty acid film and an alkali metal/fatty acid film in layers over the phosphate film by immersion with heating to 70 to 75 degrees Centigrade in a weakly alkaline aqueous metal soap solution based on the alkali metal salts of C16 to C18 saturated and/or unsaturated fat­ty acids, most preferably sodium stearate.
  • any conventional lubricant such as molybdenum disulfide, tungsten disulfide, graphite, highly fluorinated organic resin, or an oil lubricant which contains an extreme pressure additive.
  • the lubricating treatment comprising the forma­tion of a zinc/fatty acid film and an alkali metal/fatty acid
  • the final step in a method according to the invention generally is that of drying the lubricant film.
  • the film formed by phosphating contains mainly phosphophyllite ⁇ Zn2Fe(PO4)2 ⁇ 4H2O ⁇ crystals.
  • the treatment solution contains cal­cium ions in the quantity specified above, a uniform, mic­roparticulate film is formed in which the main component is scholzite ⁇ Zn2ca(PO4)2 ⁇ 2H2O ⁇ but also contains some phosphophyllite and hopeite ⁇ Zn3(PO4)2 ⁇ 4H2O ⁇ with the same approximate size as the scholzite crystals.
  • concentrations of zinc and ferrous ions for phos­phating solutions with calcium according to the invention are preferred to be within the same ranges as for solutions without calcium, although in some cases the adverse conse­quences of concentrations outside the preferred ranges are different in the presence of calcium.
  • concentrations less than 0.3 %, relatively soft monetite tends to coprecipitate in the conversion film.
  • coprecipitated crystals of hopeite ⁇ Zn3(PO4)2 ⁇ 4H2O ⁇ and phosphophyllite tend to be dispersed in the aforementioned scholzite crystals, readi­ly leading to heterogeneity in the crystalline structure of the film.
  • the film obtained tends to be unsatis­factory as a lubrication base layer adapted to severe cold-­working operations.
  • the ferrous ion concentration exceeds 2.0 % or when Fe2+/Zn2+ exceeds 3.0, there is a decline in the zinc and calcium content in the phosphate films due to the excess iron fraction in the treatment solution, causing a poor coating formation or the formation of a coarse film of Fe-Hureaulith ⁇ Fe5H2(PO4)4 ⁇ 4H2O ⁇ -containing scholzite crystals.
  • the critical punch depth for the development of seizure was determined using backward punch extrusion as reported by Danno, et al. (of the Toyota Central Research Laboratory) in Sosei to Kako [Journal of the Japan Society for the Technology of Plasticity], Vol­ume 24, Number 265. This method is briefly described below.
  • a 200 ton cold-forging crank press made by Fukui Kikai Kabushiki Kaisha was used at a rate of 30 strokes per minute.
  • Workpieces to be tested were made of type SKD11 steel, which is described in detail in Table 2 Weight of Produced Coating and Quantity of Metal Soap No. weight of phosphate film quantity of metal soap g/m2 g/m2 examples 1 9.4 3.7 2 8.2 3.5 3 9.1 2.6 4 8.0 2.2 comparison examples 1 4.0 1.5 2 7.5 1.9 3 15.0 1.7 4 6.8 1.5 Japanese Industrial Standard G - 4404.
  • the test method may be further appre­ciated with the aid of Figures 2 and 3.
  • Figure 2 shows a cross section of part of the test machinery with a test in progress.
  • a load cell 1 applies pres­sure through a punch holder 2 to the punch 3.
  • the punch 3 forces a workpiece 6 to deform as it forms a hollow space in the originally solid cylindrical work­piece while pushing it through a cylindrical hole in the die 4 that has a diameter slightly smaller than that of original workpiece.
  • a strain gauge 7 monitors the mechanical force being used in the defor­mation.
  • the shape of the punch is shown in greater detail in Figure 3a.
  • the main shaft of the punch has a diam­eter of 20.8 millimeters ("mm"), but the leading edge has a diameter of 21.2 mm and is rounded as shown in the Figure, with a radius of curvature of not less than 0.5 mm at any point and a very smooth finish (meeting the standards described in Japanese Indus­trial Standard BO6O1 for marking with the symbol of four equilateral triangles with adjacent bases) on all parts of the punch which come into contact with the workpiece during the testing process.
  • the workpiece initially has a height (dimension H in Figure 3b) of from 18 - 40 mm and has a diameter (dimension D in Figure 3b) of 30 mm.
  • the lubrication treatment method of the present invention achieves the following benefits:
  • An efficient treatment with an immersion treatment time of 3 to 20 minutes can be used at a relatively low temperature of 35 to 65 degrees Centigrade.
  • a dense, fine phosphate coating with a coating weight of 7 to 12 g/m2 is formed and provides an optimal base layer for severe cold-working.
  • the treatment solution develops only a small quantity of sludge.
  • the lubricant film obtained by implementing the pres­ent invention has excellent cold-working properties.
  • the coating obtained has very good properties when a metal soap film layer is formed on the phosphate coating using a lubricant treatment solution comprising an aqueous treatment solution based on the alkali metal salt of saturated or unsaturated C16 to C18 fatty acid, particu­larly sodium stearate.
  • Table 4 Bowden Test Conditions pressure element SUJ-2, 5 mm ⁇ load 5 kg sliding width 10 mm sliding velocity 10 mm/sec sliding temperature 25°C Table 5 No.

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  • 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)
  • Chemical Treatment Of Metals (AREA)
  • Lubricants (AREA)
EP90101350A 1989-01-26 1990-01-24 Méthode pour lubrifier du fer et de l'acier avant le façonnage à froid Expired - Lifetime EP0380067B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP15128/89 1989-01-26
JP1015128A JP2636919B2 (ja) 1989-01-26 1989-01-26 鉄鋼の冷間塑性加工用潤滑処理方法

Publications (2)

Publication Number Publication Date
EP0380067A1 true EP0380067A1 (fr) 1990-08-01
EP0380067B1 EP0380067B1 (fr) 1993-05-26

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EP90101350A Expired - Lifetime EP0380067B1 (fr) 1989-01-26 1990-01-24 Méthode pour lubrifier du fer et de l'acier avant le façonnage à froid

Country Status (11)

Country Link
EP (1) EP0380067B1 (fr)
JP (1) JP2636919B2 (fr)
AR (1) AR244117A1 (fr)
AT (1) ATE89875T1 (fr)
AU (1) AU621977B2 (fr)
BR (1) BR9000328A (fr)
CA (1) CA2008551A1 (fr)
DE (1) DE69001680T2 (fr)
DK (1) DK0380067T3 (fr)
ES (1) ES2042082T3 (fr)
ZA (1) ZA90305B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995007370A1 (fr) * 1993-09-06 1995-03-16 Henkel Kommanditgesellschaft Auf Aktien Procedes de phosphatage sans nickel
CN115980111A (zh) * 2022-12-23 2023-04-18 首钢集团有限公司 一种磷化膜膜重的检测方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4622078A (en) * 1984-03-01 1986-11-11 Gerhard Collardin Gmbh Process for the zinc/calcium phosphatizing of metal surfaces at low treatment temperatures
EP0287133A1 (fr) * 1987-04-11 1988-10-19 Metallgesellschaft Ag Procédé de phosphatation avant la peinture électrophorétique par immersion

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6020463B2 (ja) * 1982-06-04 1985-05-22 日本パ−カライジング株式会社 鉄鋼材の冷間加工潤滑処理方法
DE3408577A1 (de) * 1984-03-09 1985-09-12 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen
AU592671B2 (en) * 1986-09-26 1990-01-18 Ppg Industries Ohio, Inc. Phosphate coating composition and method of applying a zinc-nickel phosphate coating

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4622078A (en) * 1984-03-01 1986-11-11 Gerhard Collardin Gmbh Process for the zinc/calcium phosphatizing of metal surfaces at low treatment temperatures
EP0287133A1 (fr) * 1987-04-11 1988-10-19 Metallgesellschaft Ag Procédé de phosphatation avant la peinture électrophorétique par immersion

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995007370A1 (fr) * 1993-09-06 1995-03-16 Henkel Kommanditgesellschaft Auf Aktien Procedes de phosphatage sans nickel
AU678284B2 (en) * 1993-09-06 1997-05-22 Henkel Kommanditgesellschaft Auf Aktien Nickel-free phosphatization process
US5792283A (en) * 1993-09-06 1998-08-11 Henkel Kommanditgesellschaft Auf Aktien Nickel-free phosphating process
CN115980111A (zh) * 2022-12-23 2023-04-18 首钢集团有限公司 一种磷化膜膜重的检测方法

Also Published As

Publication number Publication date
ES2042082T3 (es) 1993-12-01
CA2008551A1 (fr) 1990-07-26
JPH02197581A (ja) 1990-08-06
AU621977B2 (en) 1992-03-26
BR9000328A (pt) 1990-11-27
AU4873690A (en) 1990-08-02
DE69001680D1 (de) 1993-07-01
DK0380067T3 (da) 1993-06-21
JP2636919B2 (ja) 1997-08-06
ATE89875T1 (de) 1993-06-15
AR244117A1 (es) 1993-10-29
EP0380067B1 (fr) 1993-05-26
DE69001680T2 (de) 1993-09-30
ZA90305B (en) 1991-03-27

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