EP2006420A1 - Mikroporöse Schicht zur Minderung der Reibung bei Metallverformungsprozessen - Google Patents

Mikroporöse Schicht zur Minderung der Reibung bei Metallverformungsprozessen Download PDF

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Publication number
EP2006420A1
EP2006420A1 EP07388045A EP07388045A EP2006420A1 EP 2006420 A1 EP2006420 A1 EP 2006420A1 EP 07388045 A EP07388045 A EP 07388045A EP 07388045 A EP07388045 A EP 07388045A EP 2006420 A1 EP2006420 A1 EP 2006420A1
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EP
European Patent Office
Prior art keywords
layer
friction
metal forming
microporous layer
substrate
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Withdrawn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
EP07388045A
Other languages
English (en)
French (fr)
Inventor
Peter Torben Tang
Mogens Arentoft
Niels Bay
Morten Jerne Borrild
Io Mizushima
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.)
Danmarks Tekniskie Universitet
Original Assignee
Danmarks Tekniskie Universitet
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 Danmarks Tekniskie Universitet filed Critical Danmarks Tekniskie Universitet
Priority to EP07388045A priority Critical patent/EP2006420A1/de
Priority to PCT/DK2008/000233 priority patent/WO2008154925A1/en
Priority to US12/452,118 priority patent/US20100137171A1/en
Priority to EP08758242.5A priority patent/EP2176447B1/de
Priority to DK08758242.5T priority patent/DK2176447T3/en
Priority to JP2010512520A priority patent/JP5602013B2/ja
Publication of EP2006420A1 publication Critical patent/EP2006420A1/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/30—Acidic compositions for etching other metallic material
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/10—Bearings
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin

Definitions

  • the present invention relates to a microporous layer to be used in low friction metal forming.
  • the invention further relates to a process for producing said microporous layer and the use of the layer as a lubrication carrier for cold forming of metals, particularly for micro-scale components.
  • the main objectives of lubrication are to reduce friction and to avoid galling, the latter resulting from i.a. breakdown of the lubricant film, metal-to-metal contact between tool and workpiece and pick-up of workpiece material on the tool surface.
  • a thorough lubrication is essential in metal forming in order to obtain products of satisfactory quality.
  • a conversion coating is typically used in order to lower friction and avoid metal-to-metal contact and subsequent galling.
  • the function of the conversion coating is dual, i.e. a mechanical function and a chemical function. Due to its topographic nature - with crystal grains of varying orientation and tilt angle - a large surface area is created, said surface area with pockets being suitable for entrapment of lubricant.
  • the conversion coating normally breaks up into separate islands due to surface expansion during the forming operation, and excess lubricant flows into the cracks between these islands, thus preventing metal-to-metal contact between the tool and workpiece surfaces.
  • many of the lubricants are chosen so as to ensure a chemical reaction with the conversion coating, thus establishing a chemical bonding of the lubricant film to the workpiece surface.
  • Lubrication systems for cold forging of steel can be summarized as follows: Table 1 Process Deformation Lubrication Upsetting light none Mi + EP + FA severe Ph + SP Ironing and open-die extrusion light Ph + Mi + EP + FA severe Ph + SP Extrusion light Ph + Mi + EP + FA severe Ph + SP Ph + MoS 2 Ph + MoS 2 + SP MI: mineral oil SP: soap EP: extreme pressure additive Ph: phosphate coating FA: fatty additives
  • the operational sequence for phosphate coating and soap lubrication is cleaning of the workpiece (comprising mechanical cleaning, degreasing, rinsing with cold water, pickling, further rinsing with cold water and subsequent rinsing with warm water containing activators), phosphating, rinsing with cold water, neutralizing, lubrication with soap, MoS 2 etc. and finally drying.
  • This crystalline deposit must subsequently be removed from the surface.
  • the conversion coatings are conventionally selected among zinc phosphate, calcium aluminate and aluminium fluoride coatings.
  • the lubricants are selected among sodium stearate, zinc stearate and MoS 2 .
  • the choice of lubricant system for cold forging of aluminium alloys depends on the hardness and the surface expansion of the aluminium alloy.
  • a process for producing a solid lubricant co-deposited metal film of a self-supplying type is described in US patent No. 3.787.294 .
  • a metallic layer which is deposited by electroplating, is used to reduce friction.
  • particles of graphite fluoride are trapped in the layer. The presence of these particles will reduce friction.
  • the invention provides lower friction and improved resistance against galling. This fact allows for several benefits such as increased production speed, reduced pick-up and reduced wear on tools implying fewer production stops. Further the invention allows for products with closer tolerances. All these benefits will reduce costs and/or increase the quality of the products.
  • the invention ensures a lubricant film thickness of significantly smaller size than those normally applied, thereby allowing forming of a wide variety of products ranging from micro-scale products to much larger products with closer tolerances.
  • the aspect of the invention is a novel type of conversion layer in the form of a thin, porous metallic film, which is electrochemically deposited on the workpiece surface.
  • the alloying elements in the film are carefully selected to ensure that a deposit is formed, which consists of fine grains of (two or more) pure metals rather than a solid solution.
  • one of the metals is selectively removed by chemical etching, thereby leaving a micro- or even nanoporous layer on the surface of the workpiece.
  • a lubricating film subsequently is applied to said surface, the lubricant will be trapped in the pores, whereby an ideal surface for lowering friction by enhancing lubricant entrapment during one or more subsequent metal forming process steps is created.
  • the invention concerns a microporous layer for metal forming, said layer being (a) a thin metallic film, which has been electrochemically deposited on the surface of a metal substrate, and (b) due to subsequent etching, whereby micro- or nanopores are created in the layer, being capable of capturing a lubricant in these pores, thereby providing an ideal surface for lowering friction in metal forming processes.
  • the invention concerns a layer in the form of a thin, porous metallic film, which is electrochemically deposited on a workpiece surface. Further, the invention concerns a process for producing a microporous layer for lowering friction in metal forming processes on such a metal substrate, wherein the following steps are carried out:
  • the electrochemically deposited alloy is selected among Feln, SnZn, AgCo, AgBi, AgFe, AgNi, InZn, BiCo, BiCu, BiSn, BiZn, PdCu, PdCo, CoCu, AgCu, AuCu and AuCo.
  • the electrochemically deposited alloy is SnZn.
  • the chemical etching is carried out by means of a solution dissolving a selected metallic phase, said solution being a concentrated or diluted inorganic acid, organic acid, inorganic base, organic base or mixtures thereof.
  • the etching is carried out with diluted hydrochloric acid, especially when the electrochemically deposited alloy is SnZn.
  • the invention may be used not only for the treatment of workpieces in macro-scale, but also as a lubrication carrier for cold forming of micro-scale components, such as potentiometer axles for hearing aids.
  • the conventional solid film lubrication with phosphate coating and soap lubrication often is inappropriate due to (a) packing of dies with excess lubricant and (b) inability to obtain close tolerances, as film thickness of lubricant is of the same order of magnitude as component detailed being formed.
  • Liquid lubricants are preferred, but because galling problems can be expected, a combination of an ultra-thin, porous metallic film and a liquid lubricant is used to overcome these problems.
  • This example describes the electroplating and etching of a copper substrate.
  • the copper substrate (a Cu-plate) was degreased cathodically in an alkaline solution and activated (pickled) in a commercial acidic solution. Then the SnZn alloy was electrodeposited on the copper plate at an applied current density of 1A/dm 2 at a bath temperature of 40 °C with stirring at 400 - 500 rpm in a commercial electrolyte for 12 minutes.
  • the commercial electrolyte had the following composition: 0.6 l/l SLOTOLOY ZSN 21; 0.013 l/l FS 20; 0.04 l/l SLOTOLOY ZSN 22; 0.0015 l/l SLOTOLOY ZSN 23; 70 g/l ZnCl 2 ; 45 g/l KCI, and 30 g/l H 3 BO 3 .
  • the thickness of the electrodeposit was 5 ⁇ m, and the Zn content in the deposit may vary from 10 to 40 at.% depending on the agitation.
  • a selective etching of the zinc in the SnZn alloy deposit was carried out with a 10% (v/v) HCl solution in deionised water for 0.5; 1; 4 and 24 hours, respectively.
  • the etching time may be accelerated by increasing the acid concentration or by using electrochemical etching.
  • the geometry of the porous coating of the etched SnZn alloy depends on the composition and the etching conditions. Increasing the temperature will also increase the etching rate. The number and size of holes in the etched SnZn alloy increases with the Zn content. A Zn content of about 10 at.% in the alloy deposit is too low for fabricating a porous coating.
  • This example presents results obtained by using a friction test known as the ring compression test.
  • the Zn content decreases with increasing agitation speed in the cell, as shown in the table 2 below.
  • the composition varies depending on the position of the sample. Also the geometry of the sample may give rise to this problem.
  • Table 2 Zn content for various positions (up, down, right, left) of samples Up Right Down Left 600 rpm 1.7 4.9 14.6 16.0 500 rpm 2.3 1.8 13.5 1.2 400 rpm 22.1 21.6 46.0 31.4 300 rpm 38.5 25.2 53.5 39.2
  • a 1 I beaker was used as electrochemical cell as shown in Fig. 1 .
  • Providing the test specimens, i.e. the copper rings, with said coating has significant impact on the friction between anvils and plane surfaces of test specimens, as it appears from table 3.
  • the copper ring was located in the centre between two tin anodes. Agitation was conducted by means of a magnetic stirrer.
  • Table 3 shows the combinations and a qualification of friction between anvils and plane sides of test specimens, ranked with lower friction being preferable.
  • Table 3 Coating Lubricant Ranked results Friction none (reference) applied worst highest coated not applied better lower coated applied best lowest
  • the problem of heterogeneous composition could be improved with this system compared to conventional systems.
  • the Zn contents of the deposits appeared to be much lower (from 1.6 ⁇ 0.2 to 3.7 ⁇ 0.8 at.%), regardless of the agitation speed.
  • the amount of tin concentrate FS 20 was decreased, while the amount of ZnCl 2 was increased.
  • the electrolyte had the following composition: 0.6 I/I SLOTOLOY ZSN 21; 0.009 I/I FS 20; 0.04 I/I SLOTOLOY ZSN 22; 0.0015 I/I SLOTOLOY ZSN 23; 98 g/l ZnCl 2 ; 45 g/l KCI, and 30 g/l H 3 BO 3 .
  • the current density was 1 A/dm 2 and the temperature 40 °C.
  • compositions of the deposits for the modified electrolyte were analyzed, both at the top and at the bottom of the samples.
  • the composition distribution was homogeneous.
  • Table 4 Zn content (at.%) in deposits for modified electrolyte 1 (top) 2 (top) 3 (bottom) 4 (bottom) 800 rpm 30.9 30.2 27.2 31.1 500 rpm 35.0 34.8 34.0 36.7 400 rpm 36.0 35.3 300 rpm 49.5 43.3 44.2 44.9
  • the geometry of the porous coating of the etched SnZn alloy is different from one deposited from the previous system: It is like a three-dimensional network (and may affect the friction).
  • the measurement of the friction is based on the fact that because the difference in length between h 1 and h 2 is larger, the sample has a higher friction, as shown in Fig. 6 .
  • porous surface geometry of an etched SnZn alloy deposit is determined by the composition of the alloy. About 40 at.% Zn appears to be reasonable. Further, it is possible to control the composition by changing the agitation in the cell (but it is difficult to obtain identical and reproducible compositions). The friction is improved with a porous coating of etched SnZn alloy with 40 at.% Zn.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • ing And Chemical Polishing (AREA)
  • Forging (AREA)
EP07388045A 2007-06-21 2007-06-22 Mikroporöse Schicht zur Minderung der Reibung bei Metallverformungsprozessen Withdrawn EP2006420A1 (de)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP07388045A EP2006420A1 (de) 2007-06-22 2007-06-22 Mikroporöse Schicht zur Minderung der Reibung bei Metallverformungsprozessen
PCT/DK2008/000233 WO2008154925A1 (en) 2007-06-21 2008-06-20 A microporous layer for lowering friction in metal-forming processes
US12/452,118 US20100137171A1 (en) 2007-06-21 2008-06-20 microporous layer for lowering friction in metal-forming processes
EP08758242.5A EP2176447B1 (de) 2007-06-21 2008-06-20 Mikroporöse schicht zur verminderung von reibung bei metallumformungsverfahren
DK08758242.5T DK2176447T3 (en) 2007-06-21 2008-06-20 Microporous layer to decrease the friction in metal forming processes
JP2010512520A JP5602013B2 (ja) 2007-06-21 2008-06-20 金属成形プロセスにおける摩擦を低減するためのマイクロ多孔性層

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP07388045A EP2006420A1 (de) 2007-06-22 2007-06-22 Mikroporöse Schicht zur Minderung der Reibung bei Metallverformungsprozessen

Publications (1)

Publication Number Publication Date
EP2006420A1 true EP2006420A1 (de) 2008-12-24

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EP07388045A Withdrawn EP2006420A1 (de) 2007-06-21 2007-06-22 Mikroporöse Schicht zur Minderung der Reibung bei Metallverformungsprozessen
EP08758242.5A Not-in-force EP2176447B1 (de) 2007-06-21 2008-06-20 Mikroporöse schicht zur verminderung von reibung bei metallumformungsverfahren

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP08758242.5A Not-in-force EP2176447B1 (de) 2007-06-21 2008-06-20 Mikroporöse schicht zur verminderung von reibung bei metallumformungsverfahren

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US (1) US20100137171A1 (de)
EP (2) EP2006420A1 (de)
JP (1) JP5602013B2 (de)
DK (1) DK2176447T3 (de)
WO (1) WO2008154925A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014005941A1 (de) * 2014-04-24 2015-11-12 Te Connectivity Germany Gmbh Verfahren zum Herstellen eines elektrischen Kontaktelements zur Vermeidung von Zinnwhiskerbildung, und Kontaktelement
CN109988932B (zh) * 2017-12-29 2021-01-26 清华大学 纳米多孔铜的制备方法
JP7053411B2 (ja) * 2018-08-31 2022-04-12 株式会社アイシン 金属部品の製造方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2450339A (en) * 1943-09-17 1948-09-28 Mallory & Co Inc P R Method of making porous metal filters
US3438789A (en) * 1964-02-27 1969-04-15 Schmidt Gmbh Karl Lubricant coating for friction surfaces and process for producing same
US4065365A (en) * 1975-03-18 1977-12-27 Aplicaciones Industriales De Cromo Duro, S.A. Method for improving frictional surface in cylinders or sleeves of internal combustion engines
GB1558683A (en) * 1977-10-26 1980-01-09 Tools For Bending Inc Surface or a chromium-containing composition
EP0042715A1 (de) * 1980-06-16 1981-12-30 The Fujikura Cable Works, Ltd. Verfahren zur Oberflächenbehandlung porösen Materials
WO2004111312A2 (de) * 2003-06-13 2004-12-23 Robert Bosch Gmbh Kontaktoberflächen für elektrische kontakte und verfahren zur herstellung

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2447980A (en) * 1945-01-29 1948-08-24 Mallory & Co Inc P R Method of making porous bearing surfaces
US3787294A (en) * 1971-12-07 1974-01-22 S Kurosaki Process for producing a solid lubricant self-supplying-type co-deposited metal film
JPS558588B2 (de) * 1972-02-10 1980-03-05
JPS57109242A (en) * 1980-12-26 1982-07-07 Seiko Epson Corp Porous thin film
JPS5913073A (ja) * 1982-07-14 1984-01-23 Usui Internatl Ind Co Ltd セラミツク被覆金属構造体
CN1007737B (zh) * 1988-04-16 1990-04-25 华东师范大学 多孔镍活性阴极及其制备方法
JPH102429A (ja) * 1996-06-14 1998-01-06 Hitachi Metals Ltd ガスコック
US20040168927A1 (en) * 2001-07-24 2004-09-02 Atsushi Matsushita Electroconductive structure and electroplating method using the structure
US6805972B2 (en) * 2002-08-27 2004-10-19 Johns Hopkins University Method of forming nanoporous membranes
ATE402675T1 (de) * 2002-11-13 2008-08-15 Setagon Inc Medizinprodukte mit porösen schichten und herstellungsverfahren dafür
EP2092092A1 (de) * 2006-11-15 2009-08-26 Massachusetts Institute Of Technology Verfahren zur zuschneidung der oberflächentopographie eines nanokristallinen oder amorphen metalls oder einer nanokristallinen oder amorphen legierung und mithilfe dieser verfahren hergestellte artikel

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2450339A (en) * 1943-09-17 1948-09-28 Mallory & Co Inc P R Method of making porous metal filters
US3438789A (en) * 1964-02-27 1969-04-15 Schmidt Gmbh Karl Lubricant coating for friction surfaces and process for producing same
US4065365A (en) * 1975-03-18 1977-12-27 Aplicaciones Industriales De Cromo Duro, S.A. Method for improving frictional surface in cylinders or sleeves of internal combustion engines
GB1558683A (en) * 1977-10-26 1980-01-09 Tools For Bending Inc Surface or a chromium-containing composition
EP0042715A1 (de) * 1980-06-16 1981-12-30 The Fujikura Cable Works, Ltd. Verfahren zur Oberflächenbehandlung porösen Materials
WO2004111312A2 (de) * 2003-06-13 2004-12-23 Robert Bosch Gmbh Kontaktoberflächen für elektrische kontakte und verfahren zur herstellung

Also Published As

Publication number Publication date
US20100137171A1 (en) 2010-06-03
DK2176447T3 (en) 2014-03-24
JP2010530475A (ja) 2010-09-09
EP2176447A1 (de) 2010-04-21
WO2008154925A1 (en) 2008-12-24
EP2176447B1 (de) 2013-12-25
JP5602013B2 (ja) 2014-10-08

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