EP0312024B1 - Verfahren zur Herstellung von Metallfasergegenständen - Google Patents

Verfahren zur Herstellung von Metallfasergegenständen Download PDF

Info

Publication number
EP0312024B1
EP0312024B1 EP88116953A EP88116953A EP0312024B1 EP 0312024 B1 EP0312024 B1 EP 0312024B1 EP 88116953 A EP88116953 A EP 88116953A EP 88116953 A EP88116953 A EP 88116953A EP 0312024 B1 EP0312024 B1 EP 0312024B1
Authority
EP
European Patent Office
Prior art keywords
fabric
fibers
plating
metal
plated
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
EP88116953A
Other languages
English (en)
French (fr)
Other versions
EP0312024A1 (de
Inventor
Motohiko Yoshizumi
Daisuke Shibuta
Akira Nakabayashi
Hiroaki Yamasaki
Masaki Hirooka
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.)
Japan Vilene Co Ltd
Mitsubishi Materials Corp
Original Assignee
Japan Vilene Co Ltd
Mitsubishi Materials Corp
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 JP62258321A external-priority patent/JP2628659B2/ja
Priority claimed from JP62258322A external-priority patent/JPH0711956B2/ja
Application filed by Japan Vilene Co Ltd, Mitsubishi Materials Corp filed Critical Japan Vilene Co Ltd
Publication of EP0312024A1 publication Critical patent/EP0312024A1/de
Application granted granted Critical
Publication of EP0312024B1 publication Critical patent/EP0312024B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06Q—DECORATING TEXTILES
    • D06Q1/00—Decorating textiles
    • D06Q1/04—Decorating textiles by metallising
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles

Definitions

  • This invention relates to a method for preparing flexible metal fiber articles used as electrodes, various filters, parabola antennas, and the like.
  • foamed metal materials such as foamed nickel by plating a foamed resin body with nickel for instance, firing the plated foamed resin in the atmosphere and reducing the formed nickel oxide.
  • This method is also complicated in the process steps and the products obtained is too hard to be used easily although the products are uniform.
  • metal fiber articles are utilized because of their electric conductivity and high porosity (void fraction).
  • the porosity is 95% at the highest in the product of JP-A56-35702, which is made by forming a nonwoven fabric of nickel fibers and sintering it with nickel powder. That of the nonwoven fabric of the nickel fibers made by vibration cutting is 91% and that of the foamed nickel is 93%.
  • the metal fiber articles other than the foamed nickel exhibit obvious non-uniformity in the thickness of fibers and in the porosity.
  • This invention is intended to solve the above-described problems, that is, the complexity of manufacturing process steps, non-uniformity in the product, difficulty of making articles having porosity of higher than 95%, lack of flexibility in the final products (hardness and brittleness) and to provide an improved process for a cadmium electrode with a nickel substrate.
  • This invention provides a method for preparing flexible metal fiber articles comprising forming a metal coating on a piece of an organic fiber fabric by plating and heating the thus coated fabric in a reducing gas atmosphere. Also, this invention provides a process for preparing a cadmium electrode with a nickel substrate.
  • the object of the invention is a method for preparing flexible metal fiber articles comprising forming metal on the fibers of an organic fiber fabric and heating the fabric in a reducing gas atmosphere so as to remove the organic fibers, wherein the fibers are plated with the desired metal by
  • This process of the present invention is applicable to all metals that can be precipitated from an aqueous solution.
  • Preferred are Cu, Ni, Ag and Co.
  • fabric encompasses woven, nonwoven and knit fabrics.
  • any of electroless plating, electrolytic plating and vapor deposition plating and any combination thereof can be employed.
  • the plating step is started with the refining using a surfactant.
  • the refined fabric is activated with a Sn/Pd catalyst system, whereafter it is immersed in an electroless plating solution containing a metal salt, a complexing agent, a reducing agent, etc.
  • a metal salt e.g., sodium borohydride, dimethylamine, borane, sodium hypophosphite, hydrazine and derivatives thereof, formalin, etc.
  • formalin is preferred in the case of Cu, and hydrazine and derivatives thereof are preferred in the case of Ni and Co.
  • electrolytic plating is applied after the scouring and vapor deposition or electroless plating.
  • electroless plating is employed after vapor deposition plating.
  • Organic fibers consisting of elements C and H; C, H and O; or C, H, O and N are preferred. Especially preferred are organic fibers consisting of the elements C, C and H, or the elements C, H and O. Organic fibers containing other elements are apt to char or leave ash.
  • Typical fibers constituted of C and H are fibers of polyolefins such as polyethylene and polypropylene.
  • Those of C, H and O are rayon fibers, acetate fibers, polyvinyl alcohol fibers, polyester fibers, etc., and those of C, H, O and N are polyamide fibers and acrylonitrile fibers.
  • Preferred are polyethylene, polypropylene and acrylic fibers.
  • As a reducing gas hydrogen gas, ammonia gas, carbon monoxide gas, thermally cracked ammonia gas or any mixture thereof can be used.
  • the flow rate of the reducing gas must be varied in accordance with the size of the furnace used, heating temperature, etc. and cannot be simply specified. There is a tendency for the heating rate to increase as the gas flow rate increases.
  • the reducing as can be diluted with an inert gas such as nitrogen, argon, etc.
  • Heating is conducted at 250°C - 1200°C, preferably 300°C - 1200°C, and more preferably 500°C - 1000°C. At temperatures below 250°C, too long time is required, and yet heating is often incomplete. At temperatures over 1200°C, the material is excessively sintered and loses flexibility.
  • the heating time depends upon the temperature and, therefore, it cannot be specifically defined, but is generally between 15 minutes and 4 hours, preferably 30 minutes and 2 hours.
  • the electroless plating can be carried out by any known conventional process.
  • a substrate fiber fabric is scoured, activated with a SnCl2/PdCl2 catalyst, and thereafter is immersed in an electroless plating solution containing a Ni salt, a complexing agent, a reducing agent, a pH-adjuster, a stabilizer, additives, etc.
  • the thus produced metal fiber articles can be further plated with another metal or metals by processes known per se. Needless to say, the formed flexible metal fiber articles cannot be exposed to a temperature at which the plated metal or metals deteriorate.
  • Ni coating of the fiber substrate is effected by connecting it to the cathode and immersing it in a plating solution containing cadmium oxide, sodium cyanide, any additives, etc. and applying electric current to the plating bath.
  • the reducing gas is practically ammonia gas, hydrogen gas, or a mixture thereof or one of these diluted with an inert gas such as argon.
  • the heating is carried out at a temperature between 250°C - 300°C. At temperatures lower than 250°C, excessively long time is required and often heating is incomplete. At temperatures over 300°C, Cd is apt to volatilize.
  • the heating time is 1 - 10 hours, preferably 2 - 5 hours.
  • the thus treated fabric was activated by immersion in 500ml of an aqueous solution containing 1g/l PdCl2 and 1ml/l HCl for 10 minutes, thereafter it was immersed in 500ml of an electroless nickel plating solution of the following composition at 80°C for deposition of Ni.
  • the treated fabric was rinsed with water and dried, it weighed 3.38g, which proved that 1.96g of Ni was deposited.
  • the plated fabric was placed in a furnace and heated at 800°C for 1 hour as hydrogen gas was passed through the furnace at the rate of 2l/min After cooling, it weighed 1.93g and consisted of Ni only in the state of flexible nonwoven fabric. The size was 41x43x2.8mm and the porosity was 97.7%.
  • This fabric was immersed in 500ml of an electroless copper-plating solution of the following composition at 30°C for deposition of copper.
  • the treated fabric After rinsing and drying, the treated fabric weighed 2.76g, which means that 1.49g of copper deposited.
  • the plated fabric was placed in a furnace and heated at 500°C for 2 hours as NH3 gas was passed at the rate of 2l/min. After cooling, it weighed 1.48g and consisted of copper only in the state of a flexible nonwoven fabric. The size was 37x39x2.7mm and the porosity was 95.7%.
  • the thus treated fabric was immersed in 200ml of an electroless cobalt-plating solution of the following composition which was warmed to 80°C for deposition of cobalt.
  • Cobalt chloride 23.5g/l Rochelle salt 100g/l Hydrated hydrazine 50ml/l Sodium hydroxide 50g/l
  • the thus treated fabric was immersed in 250ml of an elctcroless silver-plating solution of the following composition at 25°C for deposition of silver.
  • the treated fabric After rinsing and drying, the treated fabric weighed 3.10g, which means that 1.23g of silver deposited.
  • the thus plated fabric was placed in a furnace and heated at 600°C for 2 hours as hydrogen gas passed through the furnace at the rate of 2l/min. After cooling, it weighed 1.23g and consisted of silver only in the state of a flexible nonwoven fabric. The size was 43x44x1.8mm and the porosity was 96.6%.
  • a 25cm2 (5x5cm) piece of nonwoven fabric made of 3d rayon fibers and weighing 1.51g was scoured and immersed in 500ml of an aqueous solution containing 10g/l SnCl2 and 10ml /l HCl for 10 minutes.
  • the thus treated fabric was activated by immersing in 500ml of an aqueous solution containing 1g/l PdCl2 and 1ml/l HCl for 10 minutes, whereafter it was immersed in 500ml of an electroless plating solution of the following composition at 80°C for deposition of Ni.
  • the stainless steel plate bearing the treated fabric was immersed in a solution of the following composition Cadmium oxide 25g/l Sodium cyanide 120g/l Dextrin 1g/l and subjected to electrolysis with 5A/dm2 electric current density at room temperature for 20 minutes.
  • the resulting product was rinsed with water and dried. It weighed 5.29g.
  • the product was heated in a furnace through which ammonia gas was passed at the rate of 3l/min at 290°C for 2 hours. After cooling, a metal fabric in the exact same shape as the original nonwoven fabric weighing 3.76g remained. Chemical analysis revealed that it consisted of 1.97g Ni and 1.79g Cd.
  • a 25cm2 (5x5cm) piece of nonwoven fabric made of 1.5d acryl fibers and weighing 1.33g was scoured and activated with a SnCl2/PdCl2 catalyst system in the same manner as in Example 5, and was further plated with nickel and cadmium under the same conditions.
  • the resulting product weighed 5.17g after washing with water and drying. This was heated in a furnace through which hydrogen gas was flown at the rate of 3l/min at 290°C for 5 hours. After cooling, a metal fabric in the exact same shape as the original nonwoven fabric weighing 3.81g remained. Chemical analysis revealed that it consists of 1.92g Ni and 1.89g Cd.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Organic Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemically Coating (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Electroplating Methods And Accessories (AREA)

Claims (6)

  1. Verfahren zur Herstellung flexibler Metallfasererzeugnisse unter Bildung von Metall auf den Fasern eines organischen Fasergewebes und Erwärmen des Gewebes in einer reduzierenden Gasatmosphäre zur Entfernung der organischen Fasern, wobei die Fasern mit dem gewünschten Metall plattiert werden durch
    (i) chemisches Plattieren,
    (ii) chemisches Plattieren und nachfolgendes elektrolytisches Plattieren,
    (iii) Plattieren durch Aufdampfung unter nachfolgendem chemischem Plattieren oder
    (iv) Plattieren durch Aufdampfung unter nachfolgendem elektrolytischem Plattieren
    und Erwärmen des so plattierten Gewebes in einer reduzierenden Gasatmosphäre bei 250 bis 1200°C.
  2. Verfahren nach Anspruch 1, worin wenigstens eines der Metalle Cu, Ni, Ag und Co zum Plattieren verwendet wird.
  3. Verfahren nach einem der Ansprüche 1 oder 2, worin die organische Faser aus den Elementen C und H besteht, den Elementen C, H und O oder den Elementen C, H, O und N.
  4. Verfahren nach Anspruch 3, worin die organische Faser aus den Elementen C und H oder den Elementen C, H und O besteht.
  5. Verfahren nach Anspruch 4, worin die organische Faser ausgewählt ist unter Polyethylen-, Polypropylen- und Acrylfasern.
  6. Verfahren zur Herstellung einer Cd-Elektrode mit einem Ni-Substrat unter Bildung einer Ni-Beschichtung auf einem Stück eines organischen Fasergewebes, worin die Beschichtung durch chemisches Plattieren, Ausbildung einer Cd-Beschichtung auf der auf diese Weise gebildeten Ni-Beschichtung durch elektrolytisches Plattieren und unter Erwärmen des auf diese Weise behandelten Gewebes in einer reduzierenden Gasatmosphäre bei 250 bis 300°C erfolgt.
EP88116953A 1987-10-15 1988-10-12 Verfahren zur Herstellung von Metallfasergegenständen Expired - Lifetime EP0312024B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP258321/87 1987-10-15
JP62258321A JP2628659B2 (ja) 1987-10-15 1987-10-15 金属繊維体の製造方法
JP62258322A JPH0711956B2 (ja) 1987-10-15 1987-10-15 Ｎｉ基板Ｃｄ電極の製造方法
JP258322/87 1987-10-15

Publications (2)

Publication Number Publication Date
EP0312024A1 EP0312024A1 (de) 1989-04-19
EP0312024B1 true EP0312024B1 (de) 1992-06-24

Family

ID=26543644

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88116953A Expired - Lifetime EP0312024B1 (de) 1987-10-15 1988-10-12 Verfahren zur Herstellung von Metallfasergegenständen

Country Status (3)

Country Link
EP (1) EP0312024B1 (de)
KR (1) KR940002752B1 (de)
DE (1) DE3872344T2 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4933129A (en) * 1988-07-25 1990-06-12 Ultrafibre, Inc. Process for producing nonwoven insulating webs
FR2782885B1 (fr) * 1998-08-25 2000-11-10 Gemplus Card Int Procede de fabrication d'une antenne pour un support d'informations comportant un circuit electronique
KR100307710B1 (ko) * 1999-09-06 2001-09-24 김상렬 도전성 섬유의 제조시 색상을 부여하는 방법
CN104928657A (zh) * 2015-06-30 2015-09-23 复旦大学 一种大豆纤维吸波材料的制备方法
KR101976685B1 (ko) * 2016-07-14 2019-05-10 한국에너지기술연구원 전극용 탄소소재 제조방법 및 전극용 탄소소재

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3399979A (en) * 1963-11-01 1968-09-03 Union Carbide Corp Process for producing metal nitride fibers, textiles and shapes
GB1370893A (en) * 1971-02-09 1974-10-16 Ici Ltd Metallised thermoplastic films

Also Published As

Publication number Publication date
DE3872344D1 (de) 1992-07-30
EP0312024A1 (de) 1989-04-19
DE3872344T2 (de) 1992-12-24
KR890006849A (ko) 1989-06-16
KR940002752B1 (ko) 1994-04-02

Similar Documents

Publication Publication Date Title
US4900618A (en) Oxidation-resistant metal coatings
US3095309A (en) Electroless copper plating
KR102194260B1 (ko) 금속 다공체 및 금속 다공체의 제조 방법
JP2004502871A (ja) 無電解銀めっき
Feldstein et al. Electron microscope investigation of mixed stannous chloride/palladium chloride catalysts for plating dielectric substrates
US3486928A (en) Bath and process for platinum and platinum alloys
CN1314533C (zh) 一种复合泡沫金属及其制备方法
US3754939A (en) Electroless deposition of palladium alloys
EP0312024B1 (de) Verfahren zur Herstellung von Metallfasergegenständen
CA2539656A1 (en) Improved silver plating method and articles made therefrom
US2872312A (en) Electroless plating of non-conductors
US5160373A (en) Electroless plating bath
US4171393A (en) Electroless plating method requiring no reducing agent in the plating bath
RU2398049C2 (ru) Усовершенствованные стабилизация и рабочие характеристики автокаталитических способов нанесения покрытия методом химического восстановления
US3697296A (en) Electroless gold plating bath and process
CA1205604A (en) Electroless direct deposition of gold on metallized ceramics
US3940512A (en) Method and apparatus for concomitant particulate deposition in electroless plating, and the product thereof
JP2628659B2 (ja) 金属繊維体の製造方法
JPS63165582A (ja) 金属被覆繊維の製造方法
US20020094433A1 (en) Electrically conductive foam and method of preparation thereof
JP2000355789A (ja) 耐火合金製の高気孔率網状気泡三次元金属構造体及びその製造方法
JPH08225865A (ja) 三次元網状構造金属多孔体の製造方法
US5419829A (en) Electroplating process
DE1941494C3 (de) Dreidimensionale zellulare Metallstruktur aus einer Legierung und Verfahren zu ihrer Herstellung
JP3586902B2 (ja) 金属被覆ガラス繊維製品の製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19881012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB NL

17Q First examination report despatched

Effective date: 19910121

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: JAPAN VILENE COMPANY,LTD

Owner name: MITSUBISHI MATERIALS CORPORATION

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB NL

REF Corresponds to:

Ref document number: 3872344

Country of ref document: DE

Date of ref document: 19920730

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20010914

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20010925

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20011005

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20011011

Year of fee payment: 14

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021012

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030501

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030501

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20021012

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030630

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20030501

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST