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
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
  • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
  • B21C9/00—Cooling, heating or lubricating drawing material
  • B21C9/005—Cold application of the lubricant
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
  • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
  • B21C9/00—Cooling, heating or lubricating drawing material
  • B21C9/02—Selection of compositions therefor
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
  • B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
  • B21J3/00—Lubricating during forging or pressing
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
  • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
  • C10M105/22—Carboxylic acids or their salts
  • C10M105/24—Carboxylic acids or their salts having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
• • 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
• • 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
  • C23C22/34—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 fluorides or complex fluorides

Definitions

• the present invention relates to a composition, often denoted hereinafter as a "bath" for brevity, for treating metal surfaces and to a film formation pro ⁇ cess, wherein said bath and process are applicable for the formation of lubricat- ing films prior to the cold working of metals and particularly of carbon steels, low alloy steels, stainless steels, steels plated with zinc or zinc alloy, titanium metal and alloys thereof, aluminiferous metals, and the like.
• Bath for brevity
• the formation of a lubricating film on metals prior to their cold working typically consists of the following two separate steps in the case of light cold working operations: the initial formation of a conversion film on the surface of the workpiece as a base layer treatment; the subsequent formation on this film of a lubricating film through the application of a lubricant.
• the complete lubrication treatment process comprises both a conversion step and a lubrica- tion step.
• Conversion treatment baths based on inorganic acid or low molecular weight organic acid (oxalic acid, etc.) are a technology already known as a use ⁇ ful point of departure for improving the lubrication carrier performance of the base layer films.
• Japanese Patent Application Laid Open [Kokai or Unexam- ined] Number Sho 62-174386 [174,386/1987] is an example of the addition of organic polymer to such conversion treatment baths in order to bring about an improvement in lubrication performance.
• an improvement in lubrication performance is obtained by improving the film's adherence through the addition of water soluble organic polymer (excluding proteins) to an oxalate based film forming agent.
• the water soluble organic polymers listed for addition in the ref ⁇ erenced patent are nonionic and have highly hydrophilic structures. In tests run by the present inventors, moderate improvements in the lubrication perform ⁇ ance were observed, but major performance improvements were not achieved. Examining this matter from the perspective of the essential nature of lubrication, films that contain these highly hydrophilic structures do bring about a reduction in contact between tool and workpiece basis metal, but they lack the high level lubricating property of simply reducing the friction coefficient that operates be ⁇ tween the film and tool surface. Disclosure of the Invention
• the present invention responds to the demands generated by the per ⁇ formance limits that characterize the prior art in the metal cold working sector.
• the present invention does this by providing both a bath and a process for treating metal surfaces for the formation thereon of composite films for the cold working of metal, wherein said bath and process provide major improvements in tool life, working degree or ratio, working speed, and the like.
• the present invention relates to a bath for treating metal sur ⁇ faces for the formation thereon of composite films for the cold working of metal, wherein said bath characteristically comprises a conversion treatment bath that contains organic cationic polymer having at least 1 cationic nitrogen atom per polymer molecule and having a molecular weight of 1,000 to 1,000,000 or that contains a salt of an aforesaid organic cationic polymer.
• the present invention also relates to a process for the formation of com ⁇ posite films for the cold working of metal, wherein said process is characterized by the formation of a composite film by treating the surface of a metal with a conversion treatment bath that contains organic cationic polymer having at least 1 cationic nitrogen atom per polymer molecule and having a molecular weight of 1 ,000 to 1 ,000,000 or that contains a salt of an aforesaid organic cationic polymer.
• the composite film that is the subject of the present invention consists of a film in which resin and inorganic crystals have formed a composite.
• the metal surface treatment bath used by the present invention com ⁇ prises a base conversion treatment bath in which organic cationic polymer (or salt thereof) is dissolved or stably dispersed.
• Said base conversion treatment bath is selected from the known phosphate treatment baths, oxalate treatment baths, and fluoride containing treatment baths, and should be selected as ap ⁇ intestinalte to the type of metal undergoing treatment.
• the treatment substrate is carbon steel, low alloy steel, steel plated with zinc or zinc alloy, or aluminum
• the bath can be selected as desired from the usual phos ⁇ phate treatment baths.
• the phosphate treatment baths are exemplified by zinc phosphate baths, zinc/calcium phosphate baths, and manganese phosphate baths.
• Oxalate treatment baths are used for stainless steels, and fluoride con ⁇ taining treatment baths are used for titanium metals and aluminum metals.
• fluoride containing treatment baths are made up from fluoride and an in ⁇ organic acid such as sulfuric acid or phosphoric acid, etc.
• the organic polymer present in the metal surface treatment bath of the present invention should contain at least 1 cationic nitrogen atom per polymer molecule and should have a molecular weight of 1 ,000 to 1,000,000. Preferably, with increasing preference in the order given, the molecular weight of the polymer does not exceed, 500,000, 250,000, 100,000, 50,000, 30,000, or 22,000. Although the chemical nature of the polymer, except for the requirement to contain cationic nitrogen, is not restricted, organic polymers defined as follows are particularly preferred: organic polymers that contain at least 1 type of resin skeleton selected from epoxy resins, urethane resins, poly- butadiene resins, acrylic resins, and maleic anhydride resins.
• Suitable salts of the organic cationic polymer encompass inorganic acid salts (e.g., phosphoric acid salts, nitric acid salts, sulfuric acid salts, etc.) and organic acid salts (e.g., propionic acid salts, gluconic acid salts, etc.) of the above described organic cationic polymers.
• organic cationic polymers and salts thereof can be used individually or in combinations of two or more.
• the improvement in lubrication performance is poor when the organic polymer has a molecular weight less than 1,000. When its molecular weight exceeds 1,000,000, it becomes highly problematic to obtain its solution or stable dispersion in the base conversion treatment bath. Still lower molecular weights as already noted above provide even more effective results.
• the metal surface treatment process in accordance with the present in ⁇ vention can be implemented by a spray or immersion conversion treatment or by electrolytic treatment, but the mechanical aspects of the treatment process using the treatment agent of the present invention are not specifically restricted.
• the above described conversion film is used in combination with an ov- erlayer or top layer of lubricant; however, the type of this lubricant is not specif ⁇ ically restricted. Operable in this regard are certainly the soap lubricants, oils, and mineral oil lubricants that are currently in the most widespread use for met ⁇ al cold working. Synthetic organic lubricants, etc., are also useable in this regard.
• micropowders of calcium soaps are typically used as lubri ⁇ cants in the wire drawing of steel wire.
• the organic polymer deposited in the grain boundaries of the conversion film crystals functions to promote a robust and continuing adherence by this lubricant to the surface of the steel wire. Due to this excellent carrier function, the lubricant under consideration is delivered in larger quantities to the die during wire drawing. This improvement in delivery efficiency results in a highly favorable lubrication performance. This in turn makes possible such effects as an improvement in die life, an increase in the wire drawing velocity, and an increase in the cross section reduction.
• an immersion treatment is generally carried out at ambient or elevated temperature using a water soluble sodium soap lub ⁇ ricant, oil (straight or emulsified), or mineral oil lubricant.
• the deposited organic polymer does not dissolve out, exfoliate, or delaminate even in these treatments and remains strongly adherent. This results in the development of excellent lubrication effects and avoids any restrictions on the lubricant's use conditions.
• an excellent lubrication, performance is again developed due to the same effects discussed above for wire drawing, pipe drawing, and forging.
• the lubricants used in this sector normally consist of oils that contain extreme pressure additives, as represented by the usual press oils.
• the organic polymer is generally added to the conversion treatment bath at 0.1 to 50 grams per liter (hereinafter often abbreviated "g/L") as solids.
• g/L grams per liter
• the amount of cationic polymer dis ⁇ solved and/or dispersed in the conversion treatment bath will be from 0.5 to 40, 1.0 to 27, 1.7 to 20, 2.5 to 11 , 3.0 to 8.7, 3.5 to 7.5, or 4.0 to 6.0, g/L as solids It has been found to be very difficult to obtain similar film deposition and formation of a composite film structure when an anionic or nonionic organic poly ⁇ mer is used in place of the organic cationic polymer as specified above.
• the mechanism underlying conversion film for ⁇ mation consists of the deposition of insoluble inorganic salts due to the increase in pH and the formation — and deposition — of insoluble salts formed between the eluted metal ion and components of the conversion treatment bath.
• the organic cationic polymer present in the conversion treatment bath in accordance with the present invention is dissolved or dispersed in the water in cationic form.
• the organic polymer participates in the formation of the composite film by precipitating in the form of solid resin in the grain boundaries of the conver ⁇ sion film crystals. This appears to induce an improvement in the adherence of the conversion film to the basis metal.
• a film is formed that apparently prevents metal/metal contact between the workpiece and tool and that thus functions like an extreme pressure film. This results in a major improvement in lubrication performance and particularly in resistance to seizure.
• the present invention is characterized by the use of a conversion treat ⁇ ment bath that contains organic cationic polymer or salt thereof.
• a conversion treat ⁇ ment bath that contains organic cationic polymer or salt thereof.
• the effects are minor when the surface of the metal workpiece is first treated with the base conversion treatment bath and then treated with a solu ⁇ tion that contains organic cationic polymer or salt thereof.
• a resin film is merely formed on top of the conversion film and formation of a compos ⁇ ite film does not occur, with the result that exfoliation of at least the polymer film during cold working becomes quite easy.
• the working examples provided hereinafter will confirm that the composite film in accordance with the present invention achieves a high level of lubrication performance.
• Carbon steel hard steel wire, SWRH62A, 2.05 mm in diameter
• Galvanized steel steel sheet hot-dip galvannealed on both sides (add-on for each side: 60 g/m 2 ), 0.8 mm thick Stainless steel: pipe, SUS304, 46 mm in diameter x 4 mm thick x 5000 mm long
• Table 1 reports the type of pretreatment and pretreatment conditions for the various test materials.
• Table 2 reports the type and conditions for the base conversion treatment.
• Table 3 reports the type and quantity of addition for the organic polymers that were added to the conversion treatment baths in both the invention examples and comparison examples.
• Table 4 reports the type of lubricant top layer used after the conversion treatment and the conditions for its application.
• Zn phosphate B PB-3300M 3 45 g/L 60 ° C, 8 seconds, immersion
• PALBONDTM 421 WDM a zinc phosphate conversion film forming agent (for carbon steel)
• PALBONDTM 3300M a zinc phosphate conversion film forming agent (for galvanized steel)
• the balance not shown for the Treatment Bath Compositions was water.
• a lubrication treatment was executed on the test materials by the pro ⁇ cess sequence given below.
• Process Sequence pretreatment ⁇ water wash (except for galvanized steel) ⁇ conversion treatment ⁇ water rinse ⁇ treatment with lubricant ⁇ drying.
• Punch size 50 mm diameter Punch shoulder: 5 mm radius Die size: 52 mm diameter Die shoulder: 5 mm radius Punch velocity: 30 mm/minute Temperature: 30 ° C
• Table 9 reports the results of the performance evaluations for the working and comparison examples. The results in this table demonstrate that the invention examples (numbers 1 to 12) gave a lubrication performance for the various materials that was superior to the lubrication performance afforded by the comparison examples (numbers 13 to 25).
• a major improvement in lubrication properties — and particularly in the seizure resistance — can be obtained by carrying out a lubrication treatment after the formation of a composite film on a metal surface using the metal sur ⁇ face treatment agent in accordance with the present invention.
• the invention makes possible in a single step an increase in such practical operat ⁇ ing limits in metal cold working as the working degree or ratio, working speed, tool life, and the like.
• the invention is therefore useful in terms of improving productivity, product stability, cost reduction, and the like.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Metallurgy (AREA)
• Materials Engineering (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Lubricants (AREA)
• Chemical Treatment Of Metals (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Metal Extraction Processes (AREA)

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• 1993
  • 1993-01-13 JP JP01941093A patent/JP3193798B2/ja not_active Expired - Fee Related
• 1994
  • 1994-01-11 CA CA002153331A patent/CA2153331A1/en not_active Abandoned
  • 1994-01-11 WO PCT/US1994/000212 patent/WO1994016119A1/en not_active Application Discontinuation
  • 1994-01-11 EP EP94906049A patent/EP0746637A1/en not_active Withdrawn
  • 1994-01-12 CN CN94100678A patent/CN1054892C/zh not_active Expired - Fee Related
  • 1994-01-13 KR KR1019940000490A patent/KR0144646B1/ko not_active IP Right Cessation

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