US3496004A - Methods of surface-treating hook members of metal slide fasteners and slide fasteners thus obtained - Google Patents

Methods of surface-treating hook members of metal slide fasteners and slide fasteners thus obtained Download PDF

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US3496004A
US3496004A US560207A US3496004DA US3496004A US 3496004 A US3496004 A US 3496004A US 560207 A US560207 A US 560207A US 3496004D A US3496004D A US 3496004DA US 3496004 A US3496004 A US 3496004A
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Prior art keywords
metal
tin
slide fasteners
fasteners
antimony
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US560207A
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English (en)
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Libero Molinari
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Dollfus Mieg and Cie DMC
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Dollfus Mieg and Cie DMC
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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
    • 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
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44B—BUTTONS, PINS, BUCKLES, SLIDE FASTENERS, OR THE LIKE
    • A44B19/00—Slide fasteners
    • A44B19/42—Making by processes not fully provided for in one other class, e.g. B21D53/50, B21F45/18, B22D17/16, B29D5/00
    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • 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
    • C25D7/02—Slide fasteners
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T24/00—Buckles, buttons, clasps, etc.
    • Y10T24/25—Zipper or required component thereof
    • Y10T24/2539—Interlocking surface constructed from plural elements in series
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24008—Structurally defined web or sheet [e.g., overall dimension, etc.] including fastener for attaching to external surface

Definitions

  • the fasteners are immersed with their textile support in a complex solution possessing a high electrical potential of tin, cadmium or antimony.
  • the solution has a pH lower than 12 and the temperature is lower than 60 C. and preferably between 30 and 60 C. t
  • This invention is concerned with improvements in the surface treatment of interlocking or hook members of metal slide fasteners.
  • slide fasteners or zippers consist of interlocking members obtained by cutting, stamping or injection from wires, flat sections or like stock of copper alloys (such as tombacs and brasses), aluminum alloys such as scleral or duralinox, or zinc alloys.
  • copper alloys such as tombacs and brasses
  • aluminum alloys such as scleral or duralinox, or zinc alloys.
  • these members are barrel-polished and possibly nickel-plated, if stainless slide fasteners are desired, and subsequently get along the edges of textile tapes or ribbons by using so-called sorting machines.
  • nickel-plating by reduction of nickel ions
  • bronzing by surface oxidation
  • surface treatments utilized for copper-alloy or zinc-alloy slide fasteners.
  • cadmium plating was never applied owing most probably to its high cost and to the special cares required therefor, and on the other hand the direct chromium plating of these hook members is impracticable in the case of loose small parts.
  • this technique was also disregarded due to the readily available advantages and great simplicity characterising the galvanic nickel plating treatment.
  • slide fasteners whether they are obtained according to the old method or by applying the new method, consist of hook or interlocking members having a high coefficient of friction, in spite of the polishing operations to which they may be subjected, this coeflicient of friction being detrimental to the movements of the sliding element and accelerating the wear thereof, and, therefore, the useful life of the slide fastener.
  • nickel plating as applied by the conventional methods of galvanizing to the interlocking members obtained according to the old manufacturing methods will properly protect slide fasteners from oxidation, it cannot overcome the inconvenience set forth hereinabove. The same applies to the above-mentioned combined copper-tin coating method.
  • tinned designates coatings of metals namely tin coatings of antimony, cadmium, as well as antimony and tin coatings, cadmium and tin coatings, and vice-versa, these last named coatings being applied in the form of successive layers.
  • sliding fasteners can be tinned at any desired stage of their manufacture, notably when the interlocking members are completely finished, even when the left-hand and right-hand members of the slide fastener are in their interlocked position.
  • the conditions in which the surface treatment can be applied will be described hereinafter.
  • This invention as far as the aforesaid three metals: tin, cadmium and antimony, is concerned, is applicable to all types of sliding fasteners comprising copper or copper-alloy interlocking members, and in the specific case of tin and cadmium, to all types of sliding fasteners having zinc and zinc-alloy interlocking members.
  • sliding fasteners are copper alloys, aluminium alloys, zinc alloys, or in the case of spira fasteners, brass wires or stainless-steel wires. It is not ap parent, so far, that it has been possible to manufacture commercial-quality sliding fasteners from iron or mild steel stock, in spite of the considerable advantages likely to be derived from the use of these materials, due to the lower cost of ferrous metals in comparison with that of non-ferrous metals.
  • the present invention permits of utilizing iron and iron or ferrous alloys in the industry of sliding fasteners by resorting to a suitable coating of tin and/ or cadmium and/or antimony, the iron or iron-alloy inter-locking members of the sliding fastener which are thus coated and protected having a remarkable resistance to corrosion and oxidation. 4
  • the present invention therefore includes the timing.
  • Tin by combining its Well known corrosion resistance with a self-lubricating property particularly advantageous as far as the operation of the sliding member along the interlocking members is concerned, will thus constitute an ideal substitute for nickel; if desired, it may be either superposed to the nickel or, finally, combined therewith according to known processes for simultaneously depositing tin and nickel.
  • the electrolytic baths utilized may be those well known in galvanizing for depositing the metals contemplated in the present invention, but these baths having high concentration of metal salts and being extremely alkaline (tin-cadmium) or very acid (antimony) are obviously noxious to the dyes applied to the textile support and also the strength of the textile fibres incorporated therein, which may even preclude the use of raw or unbleached ribbons. Moreover, the teachings will be deposited .with a certain slowness and the elimination of bases and cyanides will require particular care. 7 i 7,
  • sliding fasteners in the form of separate or assembled strips, especially iron and ferrous-alloy sliding fastenings, according toihe non-electrolytic methods to be disclosed presently.
  • a typical bath of this character may have the following composition:
  • Trisodic phosphate do 45 Sodium cyanide do 10 Temperature C 30 to 35 pH 10 to 12
  • the trisodic phosphate may be replaced wholly or partly by'another alkaline affected by the setting operation.
  • An advantageous method of combining this requirement with a bright appearance and a low cost of the sliding fastener will consist in coating the interlocking members with a suitable layer of zinc or cadmium and to coat this layer in turn with a finishing tin layer to impart a bright appearance to the article.
  • a typical complex may be for instance the combination of metal salts either with other metal salts or 'with neutral molecules (hydrates ammonia, sodium or potassium chloride, organic amines, cyanides, tartrates, citratcs, thiourea, glycocoll, etc.).
  • the following complexed solution may be used for depositing pure tin on brass and tombac sliding fasteners:
  • Sodium tartrate and potassium tartrate develop with stannous chloride a complex sodium cyanide salt and leads to a solution.
  • stannous chloride a complex sodium cyanide salt and leads to a solution.
  • 1 to 2 microns of tins will be deposited within 20 minutes.
  • the best conditions of use of these complex tin solutions are a pH value ranging from 8 to 9 and a temperature ranging from 30 to 40 C.
  • antimony various salts of this metal, such as antimony trichloride, antimony trioxide, metaantimonious acid, etc. will be used by complexing them with citric acid, potassium citrate, thiourea, etc.
  • the optimum conditions of use of complex antimony solutions are a pH value ranging from 1 to 3 and a temperature ranging from 50 to C.
  • the thickness of the coatings likely to be thus obtained although greater than that of the coatings obtained by simple immersion, is none the less limited and under the best conditions it cannot exceed a few microns.
  • aluminium and its alloys are used preferably as contact metals and the passivation of the contact metal is avoided by attacking the aluminium or alloyutilized in the process by incorporating soda or potash into the complexed solution, either directly or indirectly by hydrolysis of a suitable alkaline salt.
  • the aluminium Under the influence of the base, the aluminium will form an aluminate solution with consequent release of hydrogen in the nascent state which activates the reduction of the metal complexes thus dissolved.
  • an essential fact to be noted is that the release of hydrogen, through a somewhat mechanical or physical action, prevents the dissolved metallic ions from depositing on the contact surface which thus remains active.
  • aluminate ions are released, they will not adhere to the surface to be treated and therefore they will not interfere with the desired deposit or coating.
  • This wire may consist of a single aluminium or aluminium-alloy filament, or a textile cord of cotton or like material, coated with a thin film of aluminium or aluminium-alloy.
  • the contact wire can be broken very frequently, provided that one fragment of the contact wire contacts each member of the sliding fastener, and
  • Solutions without cyanide of the type set forth hereinabove may also be used by adding a base thereto It is only necessary to complex, say, tin chloride, with Rochelle salt and/or thiorea, and to add a base as set forth hereinabove.
  • salts such as cadmium oxide or cadmium sulfate may be used, which will be complexed according to the conventional methods of making complexes, as exemplified hereinabove.
  • FIGURE 1 illustrates diagrammatically by way of example a sliding fastener of a well-known type comprising metal interlocking members 10 and 11 set on supporting ribbons or tapes 12 and 13, and a sliding member 14.
  • the contact metal consists of aluminium wires 16 and 17 threaded between the interlocking members and the ribbons or tapes.
  • FIGURE 2 illustrates on a larger scale and in crosssectional view a single hook member 10 coated with a tin layer 18according to the method of the present invention.
  • FIGURE 3 illustrates similarly on a larger scale that the contact metal consists of a thin aluminium film 19 coiled around a cotton wick or like cord 20.
  • a method of coating slide fasteners having hooking elements of copper, zinc, iron or the alloys thereof, mounted upon a textile support without recourse to an electric current or to an exterior source of electricity with a coating of tin, cadmium or antimony comprising immersing said fasteners with their textile support in a complex solution having a high electrical potential containing a. metal selected from the group consisting of tin, cadmium and antimony, said solution having a pH lower than 12 and the temperature being between 30 and 60 C. and comprising a strong base in a quantity between 1 to 2% of the total volume of said solution, the elements of said slide fasteners being placed in contact with an electronegative metal taken from a group consisting of aluminum, magnesium or their alloys.
  • said electronegative metal is aluminum in the form of an aluminum or aluminum alloy wire, wound about a textile wick, said wire being inserted between said hooking elements and said textile support during the fastening thereof.
  • a method of coating slide fasteners having hooking elements of copper, zinc, iron or the alloys thereof, mounted upon a textile support without recourse to an electric current or to an exterior source of electricity with a coating of tin, cadmium 0r antimony comprising immersing said fasteners with their textile support in a complex solution having a high electrical potential con- 4 .1 taining a metal selected from the group conisting of tin,
  • said solution having a pH lower than 12 and the temperature being between 30 and 60" C.
  • said complex solution being carried out in the presence of an electronegative contact metal in a solution such as aluminum, magnesium or their alloys to increase the necessary electric potential by displacing the coating metal, and said contact metal being aluminum in the form of an aluminum or aluminum alloy wire wound about a textile wick inserted betwen the hooking elements and the textile Supportduring the fastening thereof.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Slide Fasteners (AREA)
  • Chemically Coating (AREA)
US560207A 1965-07-02 1966-06-24 Methods of surface-treating hook members of metal slide fasteners and slide fasteners thus obtained Expired - Lifetime US3496004A (en)

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US (1) US3496004A (forum.php)
BE (1) BE683209A (forum.php)
CH (1) CH457948A (forum.php)
DE (1) DE1610351A1 (forum.php)
GB (1) GB1155862A (forum.php)
NL (1) NL6609128A (forum.php)
OA (1) OA02083A (forum.php)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2163953A1 (es) * 1998-08-05 2002-02-01 Cremallera Catalana S A Metodo para la fabricacion de cremalleras.

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2159510A (en) * 1937-04-05 1939-05-23 Battelle Memorial Institute Method of coating copper or its alloys with tin
US2264580A (en) * 1938-08-11 1941-12-02 Whitehall Patents Corp Method of making separable fasteners
US2264324A (en) * 1938-08-11 1941-12-02 Whitehall Patents Corp Method of making separable fasteners
US2282511A (en) * 1940-03-20 1942-05-12 American Brass Co Coating cupreous surfaces with tin
US2326707A (en) * 1940-05-29 1943-08-10 Crown Fastener Corp Apparatus for electroplating
US2369620A (en) * 1941-03-07 1945-02-13 Battelle Development Corp Method of coating cupreous metal with tin
US2735788A (en) * 1956-02-21 Immersion tinning from stannate
US3072498A (en) * 1961-02-28 1963-01-08 Texaco Inc Method of tin plating copper
GB955775A (en) * 1961-08-07 1964-04-22 Dow Chemical Co Process for the electroles coating of metals or metal articles

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2735788A (en) * 1956-02-21 Immersion tinning from stannate
US2159510A (en) * 1937-04-05 1939-05-23 Battelle Memorial Institute Method of coating copper or its alloys with tin
US2264580A (en) * 1938-08-11 1941-12-02 Whitehall Patents Corp Method of making separable fasteners
US2264324A (en) * 1938-08-11 1941-12-02 Whitehall Patents Corp Method of making separable fasteners
US2282511A (en) * 1940-03-20 1942-05-12 American Brass Co Coating cupreous surfaces with tin
US2326707A (en) * 1940-05-29 1943-08-10 Crown Fastener Corp Apparatus for electroplating
US2369620A (en) * 1941-03-07 1945-02-13 Battelle Development Corp Method of coating cupreous metal with tin
US3072498A (en) * 1961-02-28 1963-01-08 Texaco Inc Method of tin plating copper
GB955775A (en) * 1961-08-07 1964-04-22 Dow Chemical Co Process for the electroles coating of metals or metal articles

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2163953A1 (es) * 1998-08-05 2002-02-01 Cremallera Catalana S A Metodo para la fabricacion de cremalleras.

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BE683209A (forum.php) 1966-12-01
OA02083A (fr) 1970-05-05
DE1610351A1 (de) 1971-04-01
GB1155862A (en) 1969-06-25
CH457948A (fr) 1968-06-15
NL6609128A (forum.php) 1967-01-03

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