EP1146136B1 - Ornament and method for preparation thereof - Google Patents

Ornament and method for preparation thereof Download PDF

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Publication number
EP1146136B1
EP1146136B1 EP00956994A EP00956994A EP1146136B1 EP 1146136 B1 EP1146136 B1 EP 1146136B1 EP 00956994 A EP00956994 A EP 00956994A EP 00956994 A EP00956994 A EP 00956994A EP 1146136 B1 EP1146136 B1 EP 1146136B1
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EP
European Patent Office
Prior art keywords
coating
band
stainless steel
band pieces
carburized
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
EP00956994A
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German (de)
English (en)
French (fr)
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EP1146136A1 (en
EP1146136A4 (en
Inventor
Hachirou Citizen Watch Co. Ltd. KUSHIDA
Kenji Citizen Watch Co. Ltd. HANAI
Yoshitugu Citizen Watch Co. Ltd. ANDOU
Takeshi Citizen Watch Co. Ltd. INOUE
Kazumi Citizen Watch Co. Ltd. HAMANO
Yukio Citizen Watch Co. Ltd. TANOKURA
Akira Citizen Watch Co. Ltd. MEGURO
Shinji Ageo Seimitsu Kabushikikaisha IKEDA
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.)
Citizen Holdings Co Ltd
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Citizen Holdings Co Ltd
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 JP25290099A external-priority patent/JP4350225B2/ja
Priority claimed from JP31943799A external-priority patent/JP4463353B2/ja
Priority claimed from JP2000104454A external-priority patent/JP4451536B2/ja
Application filed by Citizen Holdings Co Ltd filed Critical Citizen Holdings Co Ltd
Publication of EP1146136A1 publication Critical patent/EP1146136A1/en
Publication of EP1146136A4 publication Critical patent/EP1146136A4/en
Application granted granted Critical
Publication of EP1146136B1 publication Critical patent/EP1146136B1/en
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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
    • 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/20—Carburising
    • C23C8/22—Carburising of ferrous surfaces
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • A44C27/001—Materials for manufacturing jewellery
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • A44C27/001—Materials for manufacturing jewellery
    • A44C27/005—Coating layers for jewellery
    • A44C27/006—Metallic coatings
    • 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/341—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one carbide layer
    • 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/347—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with layers adapted for cutting tools or wear applications
    • 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/36—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including layers graded in composition or physical properties
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02—Pretreatment of the material to be coated
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/34—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases more than one element being applied in more than one step
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80—After-treatment
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
    • G04B37/223—Materials or processes of manufacturing pocket watch or wrist watch cases metallic cases coated with a nonmetallic layer
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B45/00—Time pieces of which the indicating means or cases provoke special effects, e.g. aesthetic effects

Definitions

  • the present invention relates to a decorative item (including parts) and a process for producing the same. More particularly, the present invention primarily relates to a decorative item, such as an exterior part of timepiece, in which use is made of a basis material having a hardened layer, for example, a carburized (cemented) layer extending from a surface thereof to an arbitrary depth wherein a solute atom is diffused so as to form a solid solution, and relates to a process for producing the decorative item.
  • a decorative item such as an exterior part of timepiece, in which use is made of a basis material having a hardened layer, for example, a carburized (cemented) layer extending from a surface thereof to an arbitrary depth wherein a solute atom is diffused so as to form a solid solution
  • the present invention is concerned with an exterior part of timepiece constituted by a carburized stainless steel, especially an exterior part of timepiece, such as a wristwatch band, bezel, casing, back lid or dial, constituted by a gas carburized austenitic stainless steel, and is concerned with a process for producing the same. Still further, the present invention is concerned with an exterior part of timepiece having a smooth or specular surface free of what is known as "orange peel" and with a process for producing the same.
  • an exterior part (member) of timepiece such as a wristwatch band, bezel, casing, back lid, buckle or dial
  • use is made of stainless steel, titanium or a titanium alloy.
  • austenitic stainless steel which is excellent in corrosion resistance and ornamental capacity is widely employed as the stainless steel.
  • a plate of austenitic stainless steel SUS 316 or SUS 304 is subjected to cold forging.
  • the forged plate is arbitrarily cut or drilled (punched) and finished into the shape of wristwatch band piece.
  • the thus obtained band pieces are connected to each other to obtain a completed wristwatch band.
  • the austenitic stainless steel has a drawback in that its specular surface is easily scratched to cause the appearance of the wristwatch band, bezel, casing, back lid, dial or other exterior part of timepiece constituted by the austenitic stainless steel per se to easily deteriorate.
  • a specular surface can be easily obtained by subjecting fine precision parts, such as a gear, a spring and a shaft, constituted by a low carbon steel, a low alloy case hardening steel or the like, although there is no description of austenitic stainless steel, to pack carburizing (solid carburizing) at 900°C and thereafter subjecting the surface of such parts to barrel polishing.
  • fine precision parts such as a gear, a spring and a shaft, constituted by a low carbon steel, a low alloy case hardening steel or the like, although there is no description of austenitic stainless steel, to pack carburizing (solid carburizing) at 900°C and thereafter subjecting the surface of such parts to barrel polishing.
  • chromium carbide is precipitated in a surface portion of stainless steel.
  • the chromium content of stainless steel per se is reduced to cause the corrosion resistance of the stainless steel to extremely deteriorate.
  • the chromium carbide becomes bulky, thereby posing such a problem that the carburized region of stainless steel cannot have high hardness.
  • the method of carburizing austenitic stainless steel at low temperatures such as less than 700°C for the purpose of avoiding the above precipitation of chromium carbide can be contemplated.
  • a passive film which hinders the penetration of carbon atoms is formed on the surface of stainless steel to thereby disenable hardening of the stainless steel surface.
  • austenitic stainless steel is fluorinated in a fluorogas atmosphere at low temperatures such as 300 to 500°C to convert the above passive film to a fluorinated film through which carbon atoms can be easily penetrated.
  • the fluorinated austenitic stainless steel is sequentially subjected to gas carburizing in a carburizing gas atmosphere at low temperatures such as 400 to 500°C and to pickling or mechanical polishing (for example, soft blasting, barrel polishing or buffing).
  • a hardened layer i.e., carburized layer extending from a surface of austenitic stainless steel as a basis material to a depth of 5 to 50 ⁇ m is formed while maintaining the corrosion resistance thereof. Therefore, not only does the basis material exhibit a beautiful specular surface but also the specular surface has a Vickers hardness (HV) as high as 500 to 700, which cannot be attained by stainless steel provided with no surface hardening treatment.
  • HV Vickers hardness
  • the decorative item (including personal ornament) constituted by the austenitic stainless steel having its surface hardened is resistant to scratching, so that there is an advantage such that the beauty thereof can be maintained for a prolonged period of time.
  • the decorative item such as an exterior part of wristwatch or a bracelet
  • it as a personal ornament, must have the same ornamental value as those of other decorative items.
  • the personal ornament at its surface is often furnished with an ornamental coating.
  • an ornamental coating For example, a gold alloy coating formed by wet plating is widely employed as such an ornamental coating.
  • the gold alloy coating is soft and easily scratched. Accordingly, even if the hardened basis material surface of personal ornament is covered with the soft gold alloy coating, the gold alloy coating would be scratched to spoil the beauty as decorative item.
  • This personal ornament has a drawback in that the above advantage of hardening of basis material surface cannot be utilized.
  • austenitic stainless steel is carburized at low temperature, so that precipitation and bulking of chromium carbide in stainless steel would not occur.
  • a layer wherein, mainly, Fe and C in stainless steel are simultaneously present, possibly "mill scale (roll scale, black scale)" containing an iron oxide such as Fe 2 O 3 is formed on an outermost surface of carburized layer.
  • the mill scale is removed by pickling or mechanical polishing.
  • timepiece exterior parts constituted by stainless steel which has been gas carburized at low temperature as mentioned above, completely removing the mill scale formed on the surface thereof so as to render the exterior part surface specular cannot be accomplished only by performing mechanical polishing such as barrel polishing or buffing.
  • mechanical polishing such as barrel polishing or buffing.
  • timepiece exterior parts have complex configuration because of the attainment of ornamental beauty with the result that there are places which cannot be polished, such as inside wall of holes and inside wall and bottom of recessed portions.
  • timepiece exterior parts comprising a plurality of parts connected to each other, it is difficult to polish part interfaces.
  • a wristwatch band comprising a multiplicity of band pieces connected to each other by means of connecting parts, the smaller the interstice of mutually neighboring band pieces, the more difficult the polishing thereof.
  • the surface of timepiece exterior parts cannot also be rendered specular only by pickling.
  • iron contained in the mill scale is leached with a strong acid solution to remove the mill scale from the surface of timepiece exterior parts.
  • iron is also contained in stainless steel per se, so that the surface of carburized layer is corroded by the strong acid solution. As a result, the surface of carburized layer after pickling is roughened and cannot be specular.
  • finishing to be effected on the surface of timepiece exterior parts constituted by stainless steel is not limited to specular finishing.
  • various mechanical finishings are required. For example, hairline finishing wherein a multiplicity of mutually parallel nicks are engraved or honing wherein a multiplicity of fine recesses are engraved is required.
  • the carburized stainless steel has a drawback in that its surface is so hard that it is difficult to effect the above mechanical finishing thereon.
  • timepiece exterior parts for example, band pieces gas carburized at low temperatures such as 400 to 500°C as mentioned above are not furnished with a beautiful specular surface required for exterior ornamentation of timepieces, and the surface thereof is observed as "orange peel" having fine unevennesses, despite the implementation of polishing.
  • the reason is that, by the gas carburization, a greater amount of carbon is diffused within the metal crystal grains of stainless steel surface than in the metal crystal grain boundaries. That is, when carbon is penetrated in the metal crystal grains, the metal crystal grains become bulky and swell outward with the result that a thickness difference occurs between the crystal grains and the crystal grain boundaries. When viewed from the surface of stainless steel, the crystal grains are higher than the crystal grain boundaries.
  • This "orange peel” is a phenomenon which commonly occurs when not only stainless steel but also titanium, a titanium alloy and other metals for use in exterior ornamentation of timepieces are subjected to surface hardening, for example, carburizing at temperature which is close to the recrystallization temperature of the metal or below.
  • the orange peel is a phenomenon which occurs when surface hardening is performed at below a temperature slightly over the recrystallization temperature of the metal.
  • this "orange peel” is not limited to carburization wherein carbon is used as a solute atom, and is a phenomenon which commonly occurs when surface hardening is performed with the use of nitrogen or oxygen as a solute atom at temperature which is close to the recrystallization temperature of the employed metal or below.
  • US-A-5308707 discloses a process for imparting to a n article a corroision and wear resistance and a color comprising solid-state diffusion of atoms, for example carbon or nitrogen, into the article and applying a layer of carbon on the surface thus treated.
  • a basis material having a hardened layer for example, a carburized layer extending from a surface thereof to an arbitrary depth
  • the basis material surface having a higher surface hardness, i.e., greater scratch resistance than that of the conventional decorative item, especially an exterior part of timepiece with such characteristic.
  • the present invention relates to an exterior part of a timepiece as defined in claim 1.
  • the hard coating and the basis material at its surface may exhibit respective tones which are different from each other.
  • the hard coating preferably has a surface hardness greater than that of the basis material.
  • the hard coating is preferably a hard coating of carbon.
  • An intermediate layer may be disposed between the hard coating of carbon and a surface of the hardened layer of the basis material.
  • the intermediate layer comprise a lower layer of Ti or Cr disposed on the hardened layer surface of the basis material and an upper layer of Si or Ge disposed on a surface of the lower layer.
  • At least two hard coatings may be formed on the hardened layer surface of the basis material, or at least two hard coatings may be laminated on the hardened layer surface of the basis material.
  • the hard coating may be disposed on portion of the hardened layer surface of the basis material.
  • the decorative item of the present invention may further comprise a gold alloy coating disposed on a surface of the hard coating.
  • the gold alloy coating be constituted of an alloy of gold and at least one metal selected from the group consisting of Al, Si, V, Cr, Ti, Fe, Co, Ni, Cu, Zn, Ge, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Hf, Ta, W, Ir and Pt.
  • the decorative item is an exterior part of timepiece.
  • One form of exterior part of timepiece according to the present invention comprises a stainless steel having at its surface a carburized layer wherein carbon is diffused therein so as to form a solid solution (namely, exterior part of timepiece comprising a basis material of stainless steel provided at its surface with a carburized layer), wherein the carburized layer has a polished surface whose Vickers hardness (HV) is 500 or more.
  • HV Vickers hardness
  • the polished surface is specular.
  • One form of wristwatch band of the present invention comprises a plurality of band pieces of stainless steel connected to each other, each of the band pieces having at its surface a carburized layer wherein carbon is diffused so as to form a solid solution, wherein the carburized layer has a polished surface whose Vickers hardness (HV) is 500 or more.
  • HV Vickers hardness
  • the polished surface is specular.
  • the band pieces may be connected to each other by means of connecting parts of stainless steel, each of the connecting parts having at at least portion of its surface a carburized layer wherein carbon is diffused so as to form a solid solution.
  • the wristwatch band be one produced by connecting the band pieces to each other by means of connecting parts, carburizing the band pieces and the connecting parts, and thereafter polishing surfaces of the band pieces.
  • the wristwatch bands of the present invention may further comprise connecting parts having no carburized layer.
  • One mode of process for producing a wristwatch band according to the present invention comprises the steps of:
  • a wristwatch band having machined surfaces can be obtained by machining surfaces of the band pieces connected by means of the connecting parts prior to the fluorination.
  • Another mode of process for producing a wristwatch band according to the present invention comprises the steps of:
  • a wristwatch band having machined surfaces can be obtained by machining surfaces of the plurality of band pieces prior to the fluorination.
  • the process for producing an exterior part of timepiece other than a wristwatch band according to the present invention comprises the steps of:
  • An exterior part of timepiece other than wristwatch band having machined surfaces can be obtained by machining surfaces of the base material prior to the fluorination.
  • the wristwatch band of the present invention be one obtained by the above process for producing a wristwatch band according to the present invention.
  • the exterior part of timepiece other than wristwatch band according to the present invention be one obtained by the above process for producing an exterior part of timepiece other than wristwatch band according to the present invention.
  • Austenitic stainless steel is preferably employed as the stainless steel for use in the present invention.
  • Austenitic stainless steel is preferably employed as the stainless steel for use in the present invention.
  • exterior part of timepiece means, for example, a wristwatch band, bezel, casing, back lid, buckle and dial.
  • Fig. 1 is a schematic view of the structure of band pieces produced in Example A1 of the present invention.
  • Fig. 2 is a schematic view of the structure of band pieces produced in Example A2 of the present invention.
  • Fig. 3 is a schematic view of the structure of band pieces produced in Example A3 of the present invention.
  • Fig. 4 is a schematic view of the structure of band pieces produced in Example A3 of the present invention.
  • Fig. 5 is a schematic view showing a surface treatment for band pieces carried out in Example A4 of the present invention.
  • Fig. 6 is a schematic view showing a further surface treatment for band pieces carried out in Example A4 of the present invention.
  • Fig. 7 is a schematic view of the structure of band pieces produced in Example A5 of the present invention.
  • FIG. 8 is a schematic view of the structure of band pieces produced in Example A5 of the present invention.
  • Fig. 9 is a schematic view showing a surface treatment for band pieces carried out in Example A6 of the present invention.
  • Fig. 10 is a schematic view of the structure of band pieces produced in Example A6 of the present invention.
  • Fig. 11 is a schematic view showing a surface treatment for band pieces carried out in Example A7 of the present invention.
  • Fig. 12 is a schematic view showing a further surface treatment for band pieces carried out in Example A7 of the present invention.
  • Fig. 13 is a schematic view of the structure of band pieces produced in Example A7 of the present invention.
  • Fig. 14 is a schematic view showing a surface treatment for band pieces carried out in Example A8 of the present invention.
  • Fig. 15 is a schematic view showing a further surface treatment for band pieces carried out in Example A8 of the present invention.
  • Fig. 16 is a schematic view of the structure of band pieces produced in Example A8 of the
  • the decorative item of the present invention comprises a basis material having a hardened layer wherein a solute atom is diffused so as to form a solid solution; and at least one hard coating disposed on a surface of the hardened layer.
  • the decorative item may further comprise a gold alloy coating disposed on a surface of the hard coating.
  • the basis material for use in the decorative item of the present invention is stainless steel.
  • austenitic stainless steel is preferably employed as the stainless steel.
  • a solute atom is diffused in a surface of the above basis material constituted of a metal or alloy so as to form a solid solution, thereby providing a hardened layer.
  • the above solute atom is carbon.
  • Carbon atoms may be diffused in stainless steel, for example, austenitic stainless steel.
  • the hardened layer is preferably so formed as to extend from a surface of the basis material to a depth of 5 to 50 ⁇ m.
  • the hardened layer has a specular surface whose Vickers hardness (HV; loaded with 50 g) is 500 or greater.
  • the formation of a carburized layer as the hardened layer in the basis material constituted of austenitic stainless steel containing no titanium metals is preferably carried out through the following process.
  • the basis material be fluorinated in a fluorogas atmosphere at 100 to 500°C, especially 150 to 300°C.
  • the above austenitic stainless steel can be, for example, Fe-Cr-Ni-Mo stainless steel or Fe-Cr-Mn stainless steel.
  • Stable stainless steel whose Ni content is minimized is preferably employed as the austenitic stainless steel in the present invention from the viewpoint of depth of carburized hardened layer and cost. From the viewpoint of corrosion resistance, however, stainless steel whose Ni content is high and containing a valence element Mo in an amount of about 1.5 to 4% by weight is preferably employed.
  • As the optimum austenitic stainless steel there can be mentioned stainless steel obtained by adding 1.5 to 4% by weight of Mo to stable stainless steel whose chromium content is in the range of 15 to 25% by weight and wherein the austenitic phase is stable despite working effected at ordinary temperatures.
  • the fluorogas for use in the above fluorination can be, for example, a gas of any of fluorocompounds such as NF 3 , CF 4 , SF 4 , C 2 F 6 , BF 3 , CHF 3 , HF, SF 6 , WF 6 , SiF 4 and CIF 3 .
  • fluorocompound gases can be used individually or in combination.
  • gases of other compounds containing fluorine in molecules thereof can be used as the above fluorogas.
  • F 2 gas formed by thermal cracking of these fluorocompound gases by means of a thermal cracking apparatus or F 2 gas otherwise prepared in advance can be used as the above fluorogas.
  • the above fluorocompound gases and F 2 gas can be used in an arbitrary combination.
  • the fluorogases such as the above fluorocompound gases and F 2 gas, although can be used alone, are generally diluted with an inert gas such as nitrogen gas or argon gas before use.
  • concentration of fluorogas per se in the diluted gas is generally in the range of 10,000 to 100,000 ppm by volume, preferably 20,000 to 70,000 ppm by volume, and still preferably 30,000 to 50,000 ppm by volume.
  • the fluorogas most favorably employed in the present invention is NF 3 .
  • the NF 3 is gaseous at ordinary temperatures and has high chemical stability, and its handling is easy.
  • the NF 3 gas is generally combined with nitrogen gas and used at concentrations which fall within the above range.
  • the fluorination of the present invention is carried out by disposing, for example, a basis material wrought into a given shape in a fluorogas atmosphere of the above concentration at 100 to 500°C.
  • the period of fluorination although varied depending on the type and size of fluorinated material, etc., is generally in the range of ten-odd minutes to some hours.
  • This fluorination leads to formation of a fluorinated coating highly permeable for carbon atoms on the surface of basis material. Accordingly, the subsequent gas carburization as hardening operation causes carbon atoms to penetrate and diffuse from the surface of stainless steel to the internal part thereof, so that a carburized hardened layer can be formed easily.
  • the thus fluorinated base material is gas carburized in a carburizing gas atmosphere containing carbon monoxide at 400 to 500°C, preferably 400 to 480°C.
  • the carburizing gas for use in this carburization contains carbon monoxide as a carbon source gas. It is generally used in the form of a mixed gas composed of carbon monoxide, hydrogen, carbon dioxide and nitrogen.
  • crystalline chromium carbide such as Cr 23 C 6 would not precipitate in the carburized hardened layer to avoid consumption of chromium atoms of the austenitic stainless steel.
  • the carburized hardened layer can maintain excellent corrosion resistance.
  • bulking of crystalline chromium carbide such as Cr 23 C 6 , Cr 7 C 3 or Cr 3 C 2 by the carburization would not occur, and strength lowering due to softening of the internal part of stainless steel would be slight.
  • the carburized hardened layer (carbon diffusion penetration layer) is uniformly formed at the surface of the basis material constituted of austenitic stainless steel. Furthermore, the above gas carburization would not lead to occurrence of crystalline chromium carbide and to consumption of chromium atoms of the basis material (also referred to as "base material"). As a result, the carburized hardened layer can maintain corrosion resistance that is substantially equal to the excellent corrosion resistance inherently possessed by the austenitic stainless steel.
  • the basis material for decorative item for example, the base material for exterior part of timepiece is pickled.
  • the base material for exterior part of timepiece is immersed in an acid solution.
  • the acid solution for use in this pickling is not particularly limited.
  • it can be a solution of any of hydrofluoric acid, nitric acid, hydrochloric acid, sulfuric acid and ammonium fluoride.
  • These acids can be used alone, and also can be used in the form of a solution of a mixture of ammonium fluoride and nitric acid, a mixture of nitric acid and hydrofluoric acid, a mixture of nitric acid and hydrochloric acid or a mixture of sulfuric acid and nitric acid.
  • the concentration of acid solution can be appropriately determined, with respect to, for example, a solution of a mixture of nitric acid and hydrochloric acid, it is preferred that the nitric acid concentration range from about 15 to 40% by weight and that the hydrochloric acid concentration range from about 5 to 20% by weight. With respect to a nitric acid solution, it is preferred that the concentration thereof range from about 10 to 30% by weight.
  • the acid solution can be used at both ordinary temperatures and high temperatures.
  • electrolysis may be performed with the use of an electrolytic solution such as nitric acid or sulfuric acid.
  • the immersion time in the acid solution is generally in the range of about 15 to 90 min.
  • the iron contained in the mill scale formed on the surface of the base material for exterior part of timepiece, attributed to the carburization, is oxidized and diffused away to attain removal of the mill scale.
  • this pickling cannot accomplish complete removal of the mill scale.
  • the surface of hardened layer formed by the gas carburization is roughened by the dissolution of iron caused by the immersion in the acid solution.
  • the basis material for decorative item for example, the base material for exterior part of timepiece is rinsed (washed).
  • the surface of the basis material for decorative item for example, the base material for exterior part of timepiece is subjected to barrel polishing.
  • the base material for exterior part of timepiece is set inside a barrel vessel of a barrel polishing machine.
  • a barrel vessel of a barrel polishing machine Preferably, walnut chips and alumina abrasive as polishing mediums are placed in the barrel vessel. Barrel polishing is carried out for a period of about 10 hr to polish the rough surface formed at the outermost surface of carburized hardened layer as well as remaining mill scale.
  • the mill scale formed on the surface of the base material for exterior part of timepiece can be completely removed by the combination of the above pickling, rinsing and barrel polishing. Even if the base material for exterior part of timepiece has complex configuration, the mill scale can be completely removed therefrom. Further, the base material for exterior part of timepiece can be polished by the barrel polishing so as to have a specular surface.
  • the surface hardness (HV) of the carburized layer after the barrel polishing is at least 500 as measured under a load of 50 g, it is satisfactory as that of the exterior part of timepiece and other decorative items. It is preferred that the surface hardness (HV) be at least 600 as measured under a load of 50 g.
  • the surface of the basis material for decorative item such as the base material for exterior part of timepiece may further be buffed.
  • the surface hardness (HV) of the carburized layer is at least 500 as measured under a load of 50 g, it is satisfactory as that of the exterior part of timepiece and other decorative items. It is preferred that the surface hardness (HV) be at least 600 as measured under a load of 50 g.
  • a hard coating of carbon is especially preferred.
  • An intermediate layer can be disposed between this hard coating of carbon and a surface of the hardened layer of the basis material.
  • the intermediate layer comprise a lower layer of Ti or Cr disposed on the hardened layer surface of the basis material and an upper layer of Si or Ge disposed on a surface of the lower layer.
  • At least two hard coatings may be formed on the hardened layer surface of the basis material, or at least two hard coatings may be laminated on the hardened layer surface of the basis material.
  • the hard coating may be disposed on portion of the hardened layer surface of the basis material.
  • the hard coating as a constituent of the decorative item of the present invention may be one exhibiting a tone which is different from that of the surface of the basis material.
  • the surface hardness of the hard coating is generally greater than that of the basis material.
  • the decorative item of the present invention may further comprise a gold alloy coating disposed on the hard coating.
  • the gold alloy coating be constituted of, for example, an alloy of gold and at least one metal selected from the group consisting of Al, Si, V, Cr, Ti, Fe, Co, Ni, Cu, Zn, Ge, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Hf, Ta, W, Ir and Pt.
  • the exterior part of timepiece according to the present invention can be classified into a wristwatch band as obtained by connecting a plurality of band pieces of stainless steel to each other by means of a plurality of connecting parts of stainless steel and an exterior part of timepiece other than the wristwatch band.
  • the band pieces and connecting parts constituting the former wristwatch band are carburized, preferably gas carburized, so that a carburized hardened layer is formed at the surface thereof.
  • the latter exterior part of timepiece other than the wristwatch band is also carburized, preferably gas carburized, so that a carburized hardened layer is formed at the surface thereof.
  • the connecting parts are carburized, so that a hard carburized layer is formed in the connecting parts in a region extending from the surface thereof to a depth of tens of microns ( ⁇ m).
  • the connecting parts such as connecting pins and length adjustment pins, are resistant to bend or breakage. Therefore, even if extremely large external force is applied to the wristwatch band, accidental disconnection of band pieces is rare. Thus, the strength of the band comprising a large number of band pieces connected to each other is high.
  • the band pieces and connecting parts constituting the former wristwatch band are carburized, preferably gas carburized, so that a carburized hardened layer is formed at the surface thereof
  • the terminology “at least the band pieces” means that, after the barrel polishing step and further buffing step, the carburized length adjustment pins may be replaced by noncarburized length adjustment pins.
  • the wristwatch band comprising a plurality of band pieces of stainless steel connected to each other by means of a plurality of connecting parts of stainless steel according to the present invention
  • the band pieces are carburized, preferably gas carburized, before or after the connection of a plurality of band pieces by means of a plurality of connecting parts.
  • the stainless steel for use as the material of the wristwatch band or constituent parts thereof (band pieces or connecting parts) be austenitic stainless steel.
  • the stainless steel for use in the present invention does not contain titanium metals.
  • the above austenitic stainless steel is a stainless steel whose at least 60% by weight has an austenite phase at ordinary temperatures.
  • an Fe-Cr-Ni-Mo stainless steel or an Fe-Cr-Mn stainless steel there can be mentioned an Fe-Cr-Ni-Mo stainless steel or an Fe-Cr-Mn stainless steel.
  • the austenitic stainless steel for use in the present invention while a stable stainless steel whose Ni content is minimized is preferred from the viewpoint of depth of carburized hardened layer and cost, a stainless steel having a high Ni content and containing Mo being a valence element in an amount of about 1.5 to 4% by weight is preferred from the viewpoint of corrosion resistance.
  • the most suitable austenitic stainless steel there can be mentioned one obtained by adding 1.5 to 4% by weight of Mo to a stable stainless steel having a chromium content of 15 to 25% by weight wherein the austenite phase is stable even if processed at ordinary temperatures.
  • the surface of the base materials for band pieces connected to each other by means of connecting parts, or band pieces prior to connection, or personal ornaments can be machined prior to the fluorination in order to obtain exterior parts of timepiece with surfaces having been subjected to machining, such as hairline finishing wherein a vast plurality of mutually parallel nicks are engraved or honing wherein a vast plurality of recessed portions are cut.
  • the carburized hardened layer formed in the surface by gas carburizing is so hard that machining thereof is extremely difficult.
  • the machining is performed prior to the fluorination because of working convenience.
  • the depth of hairline, honing recessed portions or the like, engraved by the above machining in the surface of the base materials for band pieces or exterior parts of timepiece other than the wristwatch band, is naturally to be such that hairline or honing patterns appear even after barrel polishing and further buffing described later.
  • the depth of hairline, honing recessed portions or the like although not particularly limited, is generally in the range of about 5 to 7 ⁇ m.
  • the depth of hairline, honing recessed portions or the like is generally in the range of about 1 to 2 ⁇ m.
  • the above machining can be performed on the surface having been polished by the barrel polishing and further buffing described later so as to be specular.
  • the concentration of carbon of solid solution is lowered in accordance with the increase of the depth from the surface thereof, so that the hardness of the layer is decreased. Therefore, removing the region to about 1 - 2 ⁇ m from the extremely hard surface of carburized hardened layer by the barrel polishing and further buffing leads to slight lowering of the surface hardness of the carburized hardened layer.
  • the resultant polished surface can be machined.
  • This machining is not performed when the surface of the base materials for band pieces connected to each other by means of connecting parts, or band pieces prior to connection or exterior parts of timepiece other than the wristwatch band, is rendered specular.
  • first masking portions to be rendered specular For causing both the specular surface and the machined surface to be simultaneously present, conventional methods can be employed. For example, first masking portions to be rendered specular, subsequently machining and thereafter removing the mask enables machining only the nonmasked portions while the masked portions are specular.
  • HV surface hardness
  • the band pieces are fluorinated by heating them in a fluorogas atmosphere at 250 to 600°C, preferably 300 to 500°C, before or after the connection of a plurality of band pieces of stainless steel by means of a plurality of connecting parts of stainless steel.
  • the base material thereof (base material for exterior parts of timepiece) is fluorinated by heating it in a fluorogas atmosphere at 250 to 600°C, preferably 300 to 500°C.
  • Fluorogases are employed in the fluorination.
  • fluorogases employed in this fluorination examples of preferred fluorogases, the fluorogas concentration in the use thereof and the method of application thereof are the same as described hereinbefore with respect to the decorative item of the present invention and the process for producing the same.
  • this fluorination is carried out, for example, by placing, after shaping into given morphology, stainless steel band pieces and connecting parts for the wristwatch band, or wristwatch bezels, casings, back lids, dials, etc., in a fluorination furnace and heating them in a fluorogas atmosphere of the aforementioned concentration at 250 to 600°C.
  • the fluorination time although depending on the type and size of materials to be fluorinated, is generally in the range of ten-odd minutes to tens of minutes.
  • the passive coating containing Cr 2 O 3 formed at the surface of materials to be fluorinated is converted to a fluorinated coating.
  • This fluorinated coating exhibits high penetrability for carbon atoms. Therefore, in the subsequent gas carburizing, carbon atoms are penetrated and diffused from the surface of stainless steel toward the internal part thereof, thereby enabling easily forming the carburized hardened layer.
  • the thus fluorinated base materials for band pieces, connecting parts or other exterior parts of wristwatch are gas carburized at 400 to 500°C, preferably 400 to 480°C, in a carburizing gas atmosphere containing carbon monoxide.
  • carbon monoxide is used as a carbon source gas.
  • the carburizing gas is generally applied in the form of a mixed gas consisting of carbon monoxide and any of hydrogen, carbon dioxide and nitrogen.
  • the carburization capability is enhanced, and the surface carbon concentration of stainless steel, for example, austenitic stainless steel is increased to increase the surface hardness, but the amount of soot formed in the gas carburization furnace is also increased.
  • the Pc value is set over a given limiting point, there is a limit in the surface hardness of resultant carburized hardened layer.
  • the carburization capability is diminished, and the surface carbon concentration of austenitic stainless steel is lowered to result in lowering of the surface hardness.
  • the gas carburization temperature by lowering the gas carburization temperature to 400 to 500°C, precipitation of crystalline chromium carbide such as Cr 23 C 6 in the carburized hardened layer and hence consumption of chromium atoms in the austenitic stainless steel can be avoided to enable maintaining the excellent corrosion resistance of the carburized hardened layer. Further, because of the low carburization temperature, not only can bulky enlargement of chromium carbides by the carburization be avoided but also the strength lowering by softening of the internal part of stainless steel is slight.
  • the carburized hardened layer (layer wherein carbon is diffused and penetrated) is homogeneously formed at the surface of the base materials for austenitic stainless steel band pieces and connecting parts thereof, or other austenitic stainless steel exterior parts of timepiece.
  • the carburized hardened layer suffers a conspicuous lattice strain.
  • a hardness enhancement of the carburized hardened layer is realized.
  • a Vickers hardness (HV) as high as 700 to 1050 can be attained.
  • the above gas carburizing does not lead to formation of crystalline chromium carbides and to consumption of chromium atoms in the base material, the carburized hardened layer has the same level of excellent corrosion resistance as that inherently possessed by the austenitic stainless steel.
  • An extremely thin mill scale is formed on the gas carburized surface of the base materials for band pieces and connecting parts thereof, or other exterior parts of timepiece.
  • the base materials for band pieces and connecting parts thereof, or other exterior parts of timepiece, after the above gas carburizing, are pickled in the same manner as described hereinbefore with respect to the decorative item of the present invention and the process for producing the same.
  • the base materials for band pieces and connecting parts thereof, or other exterior parts of timepiece are immersed in an acid solution.
  • the base materials for band pieces and connecting parts thereof, or other exterior parts of timepiece are rinsed.
  • This rinsing enables not only washing away any mill scale being peeled from the base materials for band pieces and connecting parts thereof, or other exterior parts of timepiece, but also completely washing away the acid solution sticking to the base materials for band pieces and connecting parts thereof, or other exterior parts of timepiece, so as to avoid further advance of roughening of the carburized hardened layer by the acid solution.
  • the mill scale formed on the surface of the base materials for band pieces and connecting parts thereof, or other exterior parts of timepiece cannot be completely removed by the above pickling and rinsing.
  • the rinsed surface of the base materials for band pieces and connecting parts thereof, or other exterior parts of timepiece is subjected to barrel polishing.
  • the base materials for the wristwatch band obtained by connecting band pieces to each other by means of connecting parts, or band pieces and connecting parts prior to connection, or other exterior parts of timepiece are disposed inside a barrel vessel of a barrel polishing apparatus.
  • Polishing mediums preferably walnut chips and alumina abrasive, are placed in the barrel vessel.
  • a barrel polishing is performed over a period of about 10 hr, thereby removing rough faces formed on the outermost surface of the carburized hardened layer of band pieces, etc. and also the mill scale remaining on the outermost surface.
  • the mill scale formed on the surface of the base materials for mutually connected band pieces, unconnected band pieces, connecting parts to be employed for connecting band pieces to each other, or other exterior parts of timepiece can be completely removed by sequentially carrying out the pickling, the rinsing and the barrel polishing. Even if the base materials for these exterior parts of timepiece have complex configuration, the mill scale can be completely removed.
  • the surface of the base materials for mutually connected band pieces, unconnected band pieces, connecting parts to be employed for connecting band pieces to each other, or other exterior parts of timepiece can be rendered specular by this barrel polishing.
  • HV surface hardness
  • the surface of the base materials for band pieces, mutually connected band pieces, or other exterior parts of timepiece may further be buffed.
  • HV surface hardness
  • Unconnected band pieces are connected to each other by means of connecting parts to thereby obtain a completed wristwatch band.
  • the decorative item of the present invention comprises a basis material having a hardened layer extending from a surface thereof to an arbitrary depth wherein a solute atom is diffused so as to form a solid solution; and at least one hard coating disposed on a surface of the hardened layer of the basis material.
  • the decorative item of the present invention can have a gold alloy coating superimposed on an entire surface or part of surface of the above hard coating. Therefore, the decorative item can exhibit golden color or other various tones without detriment to the surface hardness to have enhanced ornamental value.
  • the process for producing a decorative item according to the invention enables obtaining the above decorative item, such as an exterior part of timepiece, according to the present invention with high productivity.
  • an exterior part of timepiece (including a wristwatch band) of stainless steel especially austenitic stainless steel, which is excellent in scratch resistance and has a specular surface without detriment to the excellent corrosion resistance inherently possessed by austenitic stainless steel
  • an exterior part of timepiece (including a wristwatch band) of stainless steel especially austenitic stainless steel, which is excellent in scratch resistance and has a surface subjected to machining, such as hairline finishing or honing, without detriment to the excellent corrosion resistance inherently possessed by austenitic stainless steel
  • processes for producing these exterior parts of timepiece are provided.
  • the process for producing another form of exterior part of timepiece according to the present invention enables providing the above other form of exterior part of timepiece with excellent appearance according to the present invention.
  • a base material of austenitic stainless steel SUS 316 was shaped by hot forging, cold forging, cutting and drilling and the like into wristwatch band pieces.
  • a plurality of band pieces were rotatably connected to each other by inserting connecting parts in pinholes provided by drilling in each of the band pieces.
  • the surface of the thus connected band pieces was buffed or otherwise polished so as to become specular.
  • wristwatch bands were completed.
  • each wristwatch band comprising a large number of band pieces connected to each other
  • some of the band pieces are those wherein each is separable from neighboring band pieces so as to enable regulating the band length in conformity with the size of the wrist of the wearer, i.e., band pieces for length regulation.
  • the band pieces other than the length regulation band pieces are those which are connected to each other so that each is not easily separable from neighboring band pieces.
  • connecting parts use was made of connecting parts for connecting length regulation band pieces to each other (length regulation pins) and connecting parts for connecting other band pieces to each other (connecting pins, split pipes and knurled pins).
  • the wristwatch bands were placed in a metallic muffle furnace and heated. The temperature was raised to 480°C, and a fluorogas (mixed gas consisting of 5% by volume of NF 2 and 95% by volume of N 2 ) was blown into the muffle furnace for 15 min. Thus, the wristwatch bands were fluorinated.
  • a fluorogas mixed gas consisting of 5% by volume of NF 2 and 95% by volume of N 2
  • the fluorogas was discharged from the muffle furnace. While blowing a carburizing gas (mixed gas consisting of 10% by volume of CO, 20% by volume of H 2 , 1% by volume of CO 2 and 69% by volume of N 2 ), the wristwatch bands were held in the muffle furnace at 480°C for 12 hr, thereby carburizing the wristwatch bands. The wristwatch bands were taken out from the muffle furnace.
  • a carburizing gas mixtureed gas consisting of 10% by volume of CO, 20% by volume of H 2 , 1% by volume of CO 2 and 69% by volume of N 2
  • the wristwatch bands were immersed in an acid aqueous solution containing 3 to 5% by volume of ammonium fluoride and 2 to 3% by volume of nitric acid for 20 min.
  • band pieces namely the surface of the carburized layer formed by the carburization, was roughened by the dissolution of iron caused by the immersion in the acid aqueous solution.
  • the pickled wristwatch bands were rinsed.
  • the rinsed wristwatch bands were disposed inside a barrel vessel of a barrel polishing apparatus. Walnut chips and alumina abrasive as polishing mediums were placed in the barrel vessel. A barrel polishing was performed over a period of about 10 hr, thereby removing rough faces formed on the outermost surface of the carburized layer of band pieces. As a result of this barrel polishing, a region of the carburized layer extending from the surface thereof to a depth of 1 to 2 ⁇ m was removed, and the surface of band pieces, namely the outermost surface of the carburized layer, became specular.
  • the wristwatch bands with a specular surface obtained by the above processing, was excellent in scratch resistance and maintained the same excellent corrosion resistance as inherently possessed by SUS 316.
  • the surface hardness (HV) of the carburized layer reached 700 under a load of 50 g.
  • the connecting parts were also carburized so that a hard carburized layer was formed in a region of each of the connecting parts extending from the surface thereof to a depth of tens of microns ( ⁇ m).
  • ⁇ m microns
  • connecting parts such as connecting pins and length regulation pins remain held in the pinholes provided in band pieces by drilling, so that it is difficult to remove the mill scale formed on the connecting parts by pickling and polishing.
  • mill scale remains on the connecting parts after the pickling and polishing, it is desirable to replace the connecting parts with mill scale remaining thereon by new connecting parts. This replacement leads to formation of wristwatch bands whose connecting parts only are not furnished with carburized layers.
  • a golden hard coating was formed on the carburized layer of each of the band pieces.
  • TiN coating 3 constituted of titanium nitride, as a golden hard coating, was formed by the ion plating technique being a dry plating technique on carburized layer 2 formed at a surface of band piece 1.
  • Wristwatch band furnished with carburized layer 2 was rinsed with an organic solvent such as isopropyl alcohol and disposed in an ion plating apparatus.
  • organic solvent such as isopropyl alcohol
  • Common ion plating apparatus can be employed, so that a description and drawing with respect to the ion plating apparatus will be omitted herein.
  • the ion plating apparatus was exhausted to 1.0 x 10 -5 Torr (1.3 x 10 -3 Pa), and thereafter an argon gas as an inert gas was introduced therein up to 3.0 x 10 -3 Torr (0.4 Pa).
  • a thermionic filament and a plasma electrode disposed inside the ion plating apparatus were operated to produce argon plasma. Simultaneously, a voltage of -50 V was applied to the wristwatch band, and a bombardment cleaning of the wristwatch band was performed for 10 min.
  • the thus obtained wristwatch bands exhibited homogeneous golden tone. This enabled enhancing the ornamental value of the wristwatch bands.
  • the surface hardness (HV) of the band pieces 1 covered with the TiN coating 3 reached 800 under a load of 50 g.
  • the band pieces 1 covered with the TiN coating 3 had excellent resistances to wear, corrosion and scratch.
  • the scratch resistance of the band pieces 1 having undergone surface hardening (carburization) was increased by the above formation of the TiN coating 3 which was harder than the carburized layer 2.
  • the dry plating method is not limited to the above ion plating technique, and use can be made of common means such as the sputtering technique or vacuum evaporation coating (vacuum deposition) technique.
  • the golden hard coating formed by the dry plating method can be constituted of TiN or ZrN.
  • M represents an element of Group 4a, 5a or 6a of the periodic table and a nitride of M is represented by MNx
  • the smaller than 1 the value of x representing the degree of nitriding the closer to light yellow the golden tone of the coating of the nitride MNx.
  • the greater than 1 the value of x representing the degree of nitriding the more reddish the golden color of the coating.
  • the value of x representing the degree of nitriding is in the range of 0.9 to 1.1, a golden color close to the tone of gold or a gold alloy can be realized by the coating of the nitride MNx.
  • the coating of the nitride MNx is not only a hard coating with satisfactory hardness but also exhibits a golden color most close to the tone of gold or a gold alloy.
  • the TiN coating and a ZrN coating are especially preferred because these are not only hard coatings with satisfactory hardness but also exhibit a golden color most close to the tone of gold or a gold alloy.
  • the thickness of the coating of the nitride MNx is preferably controlled so as to fall within the range of 0.1 to 10 ⁇ m, still preferably 0.2 to 5 ⁇ m.
  • Example A1 A hard coating with a tone different from that of Example A1 was formed on the band pieces furnished with carburized layers in the same manner as in Example A1.
  • TiC coating 4 constituted of titanium carbide, as a hard coating with white tone, was formed by a dry plating technique on carburized layer 2 formed at a surface of band piece 1.
  • titanium was evaporated in an ethylene gas atmosphere, and TiC coating 4 was formed on a surface of band piece 1.
  • Other coating conditions were the same as in Example A1.
  • the surface hardness (HV) of the band pieces 1 covered with the TiC coating 4 reached 800 under a load of 50 g.
  • the band pieces 1 covered with the TiC coating 4 had excellent resistances to wear, corrosion and scratch.
  • the scratch resistance of the band pieces 1 having undergone surface hardening (carburization) was increased by the above formation of the TiC coating 4 which was harder than the carburized layer 2.
  • a carbon hard coating as a hard coating with black tone was formed on the band pieces furnished with carburized layers in the same manner as in Example A1.
  • the carbon hard coating because of having excellent characteristics similar to those of diamond, is widely known as diamondlike carbon (DLC).
  • black carbon hard coating 5 was formed by a dry plating technique on carburized layer 2 formed at a surface of band piece 1.
  • the method of forming the carbon hard coating 5 was, for example, as follows.
  • gas species methane gas
  • coating pressure 0.1 Torr (13.3 Pa)
  • high-frequency power 300 watt
  • coating rate 0.1 ⁇ m per minute.
  • the carbon hard coating 5 was formed on the carburized layer 2 with high adherence therebetween.
  • the surface hardness (HV) of the band pieces 1 covered with the carbon hard coating 5 reached 3000 to 5000.
  • the scratch resistance of the band pieces 1 having undergone surface hardening (carburization) was increased by the above formation of the carbon hard coating 5 which was harder than the carburized layer 2.
  • the thickness of the carbon hard coating 5 was preferably controlled so as to fall within the range of 0.1 to 5 ⁇ m, still preferably 0.5 to 3 ⁇ m.
  • carbon hard coating 5 can be accomplished by, besides the above RFP-CVD technique, various gas-phase coating methods such as the DC plasma CVD technique and the ECR technique. Alternatively, physical evaporation coating methods such as the ion beam technique, the sputtering technique and the ion plating technique may be employed.
  • the method of forming the intermediate layer coating 6 was, for example, as follows.
  • Ti coating 6a with a thickness of 0.1 ⁇ m was formed on the carburized layer 2 by a dry plating method, for example, the sputtering technique. Further, Si coating 6b with a thickness of 0.3 ⁇ m was formed on the Ti coating 6a by the sputtering technique.
  • the carbon hard coating 5 with a thickness of 2 ⁇ m was formed on the Si coating 6b by, for example, the radio-frequency plasma CVD technique .under the aforementioned conditions.
  • the above Ti coating 6a can be replaced by a chromium (Cr) coating.
  • the above Si coating 6b can be replaced by a germanium (Ge) coating.
  • the intermediate layer (coating) may be constituted of a single layer of a carbide of Group IVa or Va metal, in place of the above laminate coating.
  • a coating of a titanium carbide containing excess carbon is preferred from the viewpoint of a high adherence strength to the carbon hard coating.
  • a hard coating with golden tone was formed on part of a surface of each of the band pieces furnished with carburized layers in the same manner as in Example A1.
  • TiN coating 7 constituted of titanium nitride, as a hard coating with golden tone, was formed by the ion plating technique being a dry plating technique on part of a surface of band piece 1.
  • masking layer 8 desired part of each of respective surfaces of band pieces 1 furnished with carburized layers 2 was printed with an organic masking agent, or masking ink, of epoxy resin to form masking layer 8.
  • the band pieces 1 having the masking layer 8 formed thereon were rinsed with an organic solvent such as isopropyl alcohol and disposed in an ion plating apparatus.
  • the ion plating apparatus was exhausted to 1.0 x 10 -5 Torr 1.3 x 10 -3 Pa), and thereafter an argon gas as an inert gas was introduced therein up to 3.0 x 10 -3 Torr (0.4 Pa). Then, a thermionic filament and a plasma electrode disposed inside the ion plating apparatus were operated to produce argon plasma. Simultaneously, a voltage of -50 V was applied to each of the band pieces 1, and a bombardment cleaning thereof was performed for 10 min.
  • the masking layer 8 was swelled with the use of ethyl methyl ketone (EMK) or a stripping solution obtained by adding formic acid and hydrogen peroxide to ethyl methyl ketone (EMK), and the masking layer 8 and the TiN coating 7a superimposed thereon were stripped off by the liftoff method.
  • EK ethyl methyl ketone
  • EMK ethyl methyl ketone
  • masking means use can be made of mechanical masking means in place of the providing of chemical masking layer described in this Example. That is, masking can be accomplished by covering arbitrary parts of band pieces with metallic caps before the formation of titanium nitride (TiN) coating and removing the metallic caps after the formation of titanium nitride coating. When this masking means is employed, no titanium nitride coating is formed on parts of band pieces covered with the metallic caps, while a titanium nitride coating is formed on parts of band pieces not covered with the metallic caps.
  • TiN titanium nitride
  • the titanium nitride coating was employed as the hard coating formed on parts of surfaces of band pieces 1, the golden hard coating formed by the dry plating method can also be constituted of ZrN.
  • Example A3 when the carbon hard coating employed in Example A3 is formed on parts of surfaces of band pieces 1, there can be obtained band pieces having parts covered with the carbon hard coating to exhibit black tone and parts not covered with any carbon hard coating to exhibit silvery white of stainless steel.
  • a hard coating with golden tone was formed on the surface of band pieces furnished with carburized layers in the same manner as in Example A1. Further, a gold alloy coating was formed on the golden hard coating.
  • TiN coating 9 constituted of titanium nitride, as a hard coating with golden tone, was formed by the ion plating technique being a dry plating technique on the surface of band piece 1 furnished with carburized layer 2.
  • Gold-titanium alloy coating 10 as a gold alloy coating was formed on the TiN coating 9.
  • bands furnished with carburized layers 2 were rinsed with an organic solvent such as isopropyl alcohol and disposed in an ion plating apparatus.
  • an organic solvent such as isopropyl alcohol
  • Common ion plating apparatus can be employed, so that a description and drawing with respect to the ion plating apparatus will be omitted herein.
  • the ion plating apparatus was exhausted to 1.0 x 10 -5 Torr (1.3 x 10 -3 Pa), and thereafter an argon gas as an inert gas was introduced therein up to 3.0 x 10 -3 Torr (0.4 Pa).
  • a thermionic filament and a plasma electrode disposed inside the ion plating apparatus were operated to produce argon plasma. Simultaneously, a voltage of -50 V was applied to each of the band pieces 1, and a bombardment cleaning thereof was performed for 10 min.
  • An argon gas was introduced in the ion plating apparatus up to 1.0 x 10 -3 Torr (0.13 Pa), and plasma was produced.
  • a gold-titanium mixture consisting of 50 atomic % of gold and 50 atomic % of titanium was evaporated, thereby forming gold-titanium alloy coating 10.
  • the thickness of gold-titanium alloy coating 10 became 0.3 ⁇ m, the evaporation of the gold-titanium mixture was terminated.
  • band pieces exhibited homogeneous golden tone. This enabled enhancing the ornamental value of the wristwatch bands. Further, the formation of gold-titanium alloy coating 10 as an outermost layer coating enabled obtaining wristwatch bands which exhibited golden tone having greater warmth than that of the TiN coating 9. This enabled lending enhanced beauty to the wristwatch bands.
  • the gold alloy coating per se cannot have effective resistances to wear, corrosion and scratch unless the thickness thereof is greater than 10 ⁇ m.
  • Gold is a very expensive metal. Therefore, increasing the thickness of the gold alloy coating invites an extreme increase of coating cost.
  • the hard TiN coating was provided under the outermost layer coating constituted of a gold alloy. This TiN coating has excellent resistances to wear, corrosion and scratch, so that the outermost layer coating constituted of a gold alloy can be thinned. Accordingly, in this Example, there is such an advantage that the usage of expensive gold can be reduced by the sequential formation of TiN'coating and thin gold alloy coating, thereby enabling lowering coating cost.
  • the thin formed outermost layer coating constituted of a gold alloy might be partially worn to expose the underlying TiN coating, any partial wearing of the outermost layer coating would never be conspicuous. The reason is that the TiN coating has the same optical characteristics as gold and exhibits golden tone. Even if the outermost layer coating constituted of a gold alloy with golden tone is partially worn, the underlying TiN coating with the same golden tone is exposed there. Therefore, even if the outermost layer coating constituted of a gold alloy is thinned, the wearing is not visible to enable maintaining the beauty of wristwatch bands as a personal ornament and the ornamental value thereof.
  • the golden hard coating formed by the dry plating method can also be constituted of ZrN.
  • the gold alloy coating can be, besides the above gold-titanium alloy coating, a coating constituted of an alloy of gold and at least one metal selected from the group consisting of A1, Si, V, Cr, Fe, Co, Ni, Cu, Zn, Ge, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Hf, Ta, W, Ir and Pt.
  • metal ions may be leached by an electrolytic solution such as sweat and have a possibility for causing metal allergy when contacted with human skin equipped with the personal ornaments.
  • leached nickel ions are known as the metal ion for which the greatest number of metal allergy cases are reported.
  • iron is the metal for which the number of metal allergy cases is extremely small. No metal allergy case has been reported with respect to titanium. Therefore, from the viewpoint of metal allergy, it is preferred that the gold alloy coating as the outermost layer coating be constituted of a gold-iron alloy or a gold-titanium alloy.
  • the gold alloy coating described in Example A5 may further be formed only on the hard coating with golden tone partially formed on the surface of band pieces furnished with carburized layers as described in Example A4.
  • TiN coating 11 constituted of titanium nitride as a hard coating with golden tone and gold-titanium alloy coating 12 as a gold alloy coating
  • Figs. 9 and 10 The method of partially forming TiN coating 11 constituted of titanium nitride as a hard coating with golden tone and gold-titanium alloy coating 12 as a gold alloy coating will be briefly described with reference to Figs. 9 and 10 .
  • masking layer 8 desired part of each of respective surfaces of band pieces 1 furnished with carburized layers 2 was printed with an organic masking agent, or masking ink, of epoxy resin to form masking layer 8.
  • the band pieces 1 having the masking layer 8 formed thereon were rinsed with an organic solvent such as isopropyl alcohol and disposed in an ion plating apparatus.
  • TiN coating 11, 11a was formed on the surface of carburized layers 2 of band pieces 1 and the surface of the masking layer 8 so that the total coating thickness became 0.5 ⁇ m. Thereafter, 0.3 ⁇ m thick gold-titanium alloy coating 12, 12a was formed on the TiN coating 11, 11a.
  • the masking layer 8 was swelled with the use of ethyl methyl ketone (EMK) or a stripping solution obtained by adding formic acid and hydrogen peroxide to ethyl methyl ketone (EMK), and the masking layer 8 and the TiN coating 11a and gold-titanium alloy coating 12a superimposed thereon were stripped off by the liftoff method.
  • EK ethyl methyl ketone
  • EMK ethyl methyl ketone
  • EMK ethyl methyl ketone
  • Example A5 use can be made of various hard coatings other than the titanium nitride coating. Also, use can be made of various gold alloy coatings other than the gold-titanium alloy coating.
  • the first hard coating was formed on the surface of band pieces furnished with carburized layers in the same manner as in Example A1. Further, the second hard coating with tone different from that of the first hard coating was formed on part of the surface of the first hard coating.
  • golden tone TiN coating 3 constituted of titanium nitride as the first hard coating was formed on the surface of band pieces 1 furnished with carburized layers 2 in the same manner as in Example A1.
  • Masking layer 13 was formed on desired part of the surface of the TiN coating 3 by, for example, printing with an organic masking agent, or masking ink, of epoxy resin.
  • white tone TiC coating 14 constituted of titanium carbide as the second hard coating was formed on the surface of the TiN coating 3, and the TiC coating 14a on the surface of the masking layer 13, in the same manner as in Example A2.
  • the masking layer 13 was swelled with the use of a stripping solution, and the masking layer 13 and the TiC coating 14a superimposed thereon were stripped off by the liftoff method.
  • Example A5 use can be made of various hard coatings other than the titanium nitride and titanium carbide coatings. Also, either of the first hard coating and the second hard coating can be replaced by the carbon hard coating of Example A3. The types of masking layer 13 and stripping solution can appropriately be selected in conformity with the type of such coatings.
  • both the first hard coating and the second hard coating can be constituted of MNx. If the first hard coating and the second hard coating are constituted so that the value of x representing the degree of nitriding of the former is different from that of the latter, the tone of the first hard coating can be differentiated from that of the second hard coating. This is true with respect to the carbide, oxide, nitrido-carbide and nitrido-carbido-oxide as well.
  • the first hard coating was formed on part of the surface of band pieces furnished with carburized layers in the same manner as in Example A1. Further, the second hard coating with tone different from that of the first hard coating was formed on other part of the surface of band pieces.
  • golden tone TiN coating 7 constituted of titanium nitride as the first hard coating was formed on part of the surface of band pieces 1 furnished with carburized layers 2 in the same manner as in Example A4.
  • Masking layer 15 was formed on the surface of the TiN coating 7 and desired part of the surface of band pieces 1 continuing therefrom.
  • white tone TiC coating 16 constituted of titanium carbide as the second hard coating was formed on the TiN coating 7, the masking layer 15 and remaining part of the surface of band pieces 1, in the same manner as in Example A2.
  • the masking layer 15 was swelled with the use of a stripping solution, and the masking layer 15 and the TiC coating 16 superimposed thereon were stripped off by the liftoff method.
  • Example A7 Selection of the first hard coating and second hard coating and selection of the stripping solution and masking layer are the same as described in Example A7.
  • the same gold alloy coating as described in Example A5 may be formed on either or both of the first hard coating and the second hard coating.
  • the ion plating technique was employed as the dry plating method in the above Examples A2 and A4 to A8, use can be made of other common coating forming methods such as the sputtering technique and vacuum evaporation coating technique.
  • the invention was described with reference to band pieces for wristwatch bands.
  • the present invention is also applicable to items for accommodating mechanical or electronic driving mechanism, such as a wristwatch casing.
  • the present invention is applicable to all other decorative items (including components thereof).
  • a base material of austenitic stainless steel SUS 316 was shaped by hot forging, cold forging, cutting and drilling into wristwatch band pieces.
  • a plurality of band pieces were rotatably connected to each other by inserting connecting parts in pinholes provided by drilling in each of the band pieces.
  • the surface of the thus connected band pieces was buffed or otherwise polished so as to become specular.
  • wristwatch bands were completed.
  • each wristwatch band comprising a large number of band pieces connected to each other
  • some of the band pieces are those wherein each is separable from neighboring band pieces so as to enable regulating the band length in conformity with the size of the wrist of the wearer, i.e., band pieces for length regulation.
  • the band pieces other than the length regulation band pieces are those which are connected to each other so that each is not easily separable from neighboring band pieces.
  • connecting parts use was made of connecting parts for connecting length regulation band pieces to each other (length regulation pins) and connecting parts for connecting other band pieces to each other (connecting pins, split pipes and knurled pins).
  • the wristwatch bands were placed in a metallic muffle furnace and heated. The temperature was raised to 480°C, and a fluorogas (mixed gas consisting of 5% by volume of NF 2 and 95% by volume of N 2 ) was blown into the muffle furnace for 15 min. Thus, the wristwatch bands were fluorinated.
  • a fluorogas mixed gas consisting of 5% by volume of NF 2 and 95% by volume of N 2
  • the fluorogas was discharged from the muffle furnace. While blowing a carburizing gas (mixed gas consisting of 10% by volume of CO, 20% by volume of H 2 , 1% by volume of CO 2 and 69% by volume of N 2 ), the wristwatch bands were held in the muffle furnace at 480°C for 12 hr, thereby carburizing the wristwatch bands. The wristwatch bands were taken out from the muffle furnace.
  • a carburizing gas mixtureed gas consisting of 10% by volume of CO, 20% by volume of H 2 , 1% by volume of CO 2 and 69% by volume of N 2
  • the wristwatch bands were immersed in an acid aqueous solution containing 3 to 5% by volume of ammonium fluoride and 2 to 3% by volume of nitric acid for 20 min.
  • band pieces namely the surface of the carburized layer formed by the carburization, was roughened by the dissolution of iron caused by the immersion in the acid aqueous solution.
  • the pickled wristwatch bands were rinsed.
  • the rinsed wristwatch bands were disposed inside a barrel vessel of a barrel polishing apparatus. Walnut chips and alumina abrasive as polishing mediums were placed in the barrel vessel. A barrel polishing was performed over a period of about 10 hr, thereby removing rough faces formed on the outermost surface of the carburized layer of band pieces. As a result of this barrel polishing, a region of the carburized layer extending from the surface thereof to a depth of 1 to 2 ⁇ m was removed, and the surface of band pieces, namely the outermost surface of the carburized layer, became specular.
  • the wristwatch bands with a specular surface obtained by the above processing, was excellent in scratch resistance and maintained the same excellent corrosion resistance as inherently possessed by SUS 316.
  • SUS 316 excellent corrosion resistance
  • the connecting parts were also carburized so that a hard carburized layer was formed in a region of each of the connecting parts extending from the surface thereof to a depth of tens of microns ( ⁇ m).
  • ⁇ m microns
  • Wristwatch bands were produced in the same manner as in Example B1, except that, before the fluorination, a multiplicity of hairlines were formed along the band length on outer surfaces (when worn round the wrist, surfaces arranged outside) of band pieces.
  • the resultant wristwatch bands had hairline-finished surfaces, which were excellent in scratch resistance and maintained the same excellent corrosion resistance as inherently possessed by SUS 316.
  • Bezels finished so as to have a specular surface were produced in the same manner as in Example B1, except that the wristwatch bands were replaced by bezels for wristwatch.
  • the resultant bezels were excellent in scratch resistance and maintained the same excellent corrosion resistance as inherently possessed by SUS 316.
  • the resultant casings were excellent in scratch resistance and maintained the same excellent corrosion resistance as inherently possessed by SUS 316.
  • the resultant back lids were excellent in scratch resistance and maintained the same excellent corrosion resistance as inherently possessed by SUS 316.
  • Dials finished so as to have a specular surface were produced in the same manner as in Example B1, except that the wristwatch bands were replaced by dials for wristwatch.
  • the resultant dials were excellent in scratch resistance and maintained the same excellent corrosion resistance as inherently possessed by SUS 316.
  • a rodlike material of austenitic stainless steel SUS 316 was provided.
  • the rodlike material had a rounded rectangular section conforming to the morphology of wristwatch band pieces.
  • the rodlike material was sliced at intervals conforming to band piece widths.
  • Pinholes for insertion of connecting pins were drilled in the obtained slices, thereby completing band pieces for wristwatch bands.
  • a plurality of band pieces were rotatably connected to each other by inserting connecting pins in pinholes provided by drilling in each of the band pieces, thereby assembling wristwatch bands.
  • a section of the buffed upper surface portion of band pieces was observed through an electron microscope. As a result, it was recognized that metal crystal grains of the stainless steel surface portion were drawn in the direction of buff rotation by the external force applied by buffing, thereby creating a fibrous structure of metal crystal grains deformed in fibrous form. A deformed layer including this fibrous structure was formed so as to extend from the upper surface of band pieces to a depth of 3 to 7 ⁇ m.
  • the wristwatch bands were placed in a metallic muffle furnace and heated. The temperature was raised to 480°C, and a fluorogas (mixed gas consisting of 5% by volume of NF 2 and 95% by volume of N 2 ) was blown into the muffle furnace for 15 min. Thus, the wristwatch bands were fluorinated.
  • a fluorogas mixed gas consisting of 5% by volume of NF 2 and 95% by volume of N 2
  • the fluorogas was discharged from the muffle furnace. While blowing a carburizing gas (mixed gas consisting of 10% by volume of CO, 20% by volume of H 2 , 1% by volume of CO 2 and 69% by volume of N 2 ), the wristwatch bands were held in the muffle furnace at 480°C for 12 hr, thereby carburizing the wristwatch bands. The wristwatch bands were taken out from the muffle furnace.
  • a carburizing gas mixtureed gas consisting of 10% by volume of CO, 20% by volume of H 2 , 1% by volume of CO 2 and 69% by volume of N 2
  • the wristwatch bands were immersed in an acid aqueous solution containing 3 to 5% by volume of ammonium fluoride and 2 to 3% by volume of nitric acid for 20 min.
  • band pieces namely the surface of the carburized layer formed by the carburization, was roughened by the dissolution of iron caused by the immersion in the acid aqueous solution.
  • the pickled wristwatch bands were rinsed.
  • the rinsed wristwatch bands were disposed inside a barrel vessel of a barrel polishing apparatus. Walnut chips and alumina abrasive as polishing mediums were placed in the barrel vessel. A barrel polishing was performed over a period of about 10 hr, thereby removing rough faces formed on the outermost surface of the carburized layer of band pieces.
  • Cylinders of austenitic stainless steel SUS 316 were provided.
  • the cylinders were cold forged into the configuration of wristwatch band pieces in such a manner that an external force is applied along the central axis passing through the center of a circular section of the cylinders.
  • Pinholes for insertion of connecting pins were drilled in the thus forged members, thereby completing band pieces for wristwatch bands.
  • a plurality of band pieces were rotatably connected to each other by inserting connecting pins in pinholes provided by drilling in each of the band pieces, thereby assembling wristwatch bands.
  • a section of the burnished upper surface portion of band pieces was observed through an electron microscope. As a result, it was recognized that metal crystal grains of the stainless steel surface portion were drawn in the direction of rotary wheel rotation by the external force applied by burnishing, thereby creating a fibrous structure of metal crystal grains deformed in fibrous form. A deformed layer including this fibrous structure was formed so as to extend from the upper surface of band pieces to a depth of 5 to 10 ⁇ m.
  • the wristwatch bands were placed in a metallic muffle furnace and heated. The temperature was raised to 480°C, and a fluorogas (mixed gas consisting of 5% by volume of NF 2 and 95% by volume of N 2 ) was blown into the muffle furnace for 15 min. Thus, the wristwatch bands were fluorinated.
  • a fluorogas mixed gas consisting of 5% by volume of NF 2 and 95% by volume of N 2
  • the fluorogas was discharged from the muffle furnace. While blowing a carburizing gas (mixed gas consisting of 10% by volume of CO, 20% by volume of H 2 , 1% by volume of CO 2 and 69% by volume of N 2 ), the wristwatch bands were held in the muffle furnace at 480°C for 12 hr, thereby carburizing the wristwatch bands. The wristwatch bands were taken out from the muffle furnace.
  • a carburizing gas mixtureed gas consisting of 10% by volume of CO, 20% by volume of H 2 , 1% by volume of CO 2 and 69% by volume of N 2
  • the wristwatch bands were immersed in an acid aqueous solution containing 3 to 5% by volume of ammonium fluoride and 2 to 3% by volume of nitric acid for 20 min.
  • band pieces namely the surface of the carburized layer formed by the carburization, was roughened by the dissolution of iron caused by the immersion in the acid aqueous solution.
  • the pickled wristwatch bands were rinsed.
  • the rinsed wristwatch bands were disposed inside a barrel vessel of a barrel polishing apparatus. Walnut chips and alumina abrasive as polishing mediums were placed in the barrel vessel. A barrel polishing was performed over a period of about 10 hr, thereby removing rough faces formed on the outermost surface of the carburized layer of band pieces.
  • Example C1 A section of the resultant upper surface portion of band pieces was observed through an electron microscope. As a result, it was recognized that, in the same manner as in Example C1, metal crystal grains of the stainless steel surface portion were drawn in the direction of buff rotation by the external force applied by buffing, thereby creating a fibrous structure of metal crystal grains deformed in fibrous form. A deformed layer including this fibrous structure was formed so as to extend from the upper surface of band pieces to a depth of 3 to 6 ⁇ m.
  • the wristwatch bands were placed in a metallic muffle furnace and heated. The temperature was raised to 480°C, and a fluorogas (mixed gas consisting of 5% by volume of NF 2 and 95% by volume of N 2 ) was blown into the muffle furnace for 15 min. Thus, the wristwatch bands were fluorinated.
  • a fluorogas mixed gas consisting of 5% by volume of NF 2 and 95% by volume of N 2
  • the fluorogas was discharged from the muffle furnace. While blowing a carburizing gas (mixed gas consisting of 10% by volume of CO, 20% by volume of H 2 , 1% by volume of CO 2 and 69% by volume of N 2 ), the wristwatch bands were held in the muffle furnace at 480°C for 12 hr, thereby carburizing the wristwatch bands. The wristwatch bands were taken out from the muffle furnace.
  • a carburizing gas mixtureed gas consisting of 10% by volume of CO, 20% by volume of H 2 , 1% by volume of CO 2 and 69% by volume of N 2
  • the wristwatch bands were immersed in an acid aqueous solution containing 3 to 5% by volume of ammonium fluoride and 2 to 3% by volume of nitric acid for 20 min.
  • band pieces namely the surface of the carburized layer formed by the carburization, was roughened by the dissolution of iron caused by the immersion in the acid aqueous solution.
  • the pickled wristwatch bands were rinsed.
  • the rinsed wristwatch bands were disposed inside a barrel vessel of a barrel polishing apparatus. Walnut chips and alumina abrasive as polishing mediums were placed in the barrel vessel. A barrel polishing was performed over a period of about 10 hr, thereby removing rough faces formed on the outermost surface of the carburized layer of band pieces.
  • band pieces The upper surface of band pieces was further buffed so as to obtain a desirable specular surface.
  • the wristwatch bands were placed in a metallic muffle furnace and heated. The temperature was raised to 480°C, and a fluorogas (mixed gas consisting of 5% by volume of NF 2 and 95% by volume of N 2 ) was blown into the muffle furnace for 15 min. Thus, the wristwatch bands were fluorinated.
  • a fluorogas mixed gas consisting of 5% by volume of NF 2 and 95% by volume of N 2
  • the fluorogas was discharged from the muffle furnace. While blowing a carburizing gas (mixed gas consisting of 10% by volume of CO, 20% by volume of H 2 , 1% by volume of CO 2 and 69% by volume of N 2 ), the wristwatch bands were held in the muffle furnace at 480°C for 12 hr, thereby carburizing the wristwatch bands. The wristwatch bands were taken out from the muffle furnace.
  • a carburizing gas mixtureed gas consisting of 10% by volume of CO, 20% by volume of H 2 , 1% by volume of CO 2 and 69% by volume of N 2
  • the wristwatch bands were immersed in an acid aqueous solution containing 3 to 5% by volume of ammonium fluoride and 2 to 3% by volume of nitric acid for 20 min.
  • band pieces namely the surface of the carburized layer formed by the carburization, was roughened by the dissolution of iron caused by the immersion in the acid aqueous solution.
  • the pickled wristwatch bands were rinsed.
  • the rinsed wristwatch bands were disposed inside a barrel vessel of a barrel polishing apparatus. Walnut chips and alumina abrasive as polishing mediums were placed in the barrel vessel. A barrel polishing was performed over a period of about 10 hr, thereby removing rough faces formed on the outermost surface of the carburized layer of band pieces.
  • the wristwatch bands were placed in a metallic muffle furnace and heated. The temperature was raised to 480°C, and a fluorogas (mixed gas consisting of 5% by volume of NF 2 and 95% by volume of N 2 ) was blown into the muffle furnace for 15 min. Thus, the wristwatch bands were fluorinated.
  • a fluorogas mixed gas consisting of 5% by volume of NF 2 and 95% by volume of N 2
  • the fluorogas was discharged from the muffle furnace. While blowing a carburizing gas (mixed gas consisting of 10% by volume of CO, 20% by volume of H 2 , 1% by volume of CO 2 and 69% by volume of N 2 ), the wristwatch bands were held in the muffle furnace at 480°C for 12 hr, thereby carburizing the wristwatch bands. The wristwatch bands were taken out from the muffle furnace.
  • a carburizing gas mixtureed gas consisting of 10% by volume of CO, 20% by volume of H 2 , 1% by volume of CO 2 and 69% by volume of N 2
  • the wristwatch bands were immersed in an acid aqueous solution containing 3 to 5% by volume of ammonium fluoride and 2 to 3% by volume of nitric acid for 20 min.
  • band pieces namely the surface of the carburized layer formed by the carburization, was roughened by the dissolution of iron caused by the immersion in the acid aqueous solution.
  • the pickled wristwatch bands were rinsed.
  • the rinsed wristwatch bands were disposed inside a barrel vessel of a barrel polishing apparatus. Walnut chips and alumina abrasive as polishing mediums were placed in the barrel vessel. A barrel polishing was performed over a period of about 10 hr, thereby removing rough faces formed on the outermost surface of the carburized layer of band pieces.
  • Cylinders of austenitic stainless steel SUS 316 were provided.
  • the cylinders were cold forged into ring members in such a manner that an external force is applied along the central axis passing through the center of a circular section of the cylinders.
  • a section of the buffed bezels was observed through an electron microscope. As a result, it was recognized that metal crystal grains of the stainless steel surface portion were drawn in the direction of buff rotation by the external force applied by buffing, thereby creating a fibrous structure of metal crystal grains deformed in fibrous form. A deformed layer including this fibrous structure was formed so as to extend from the upper surface of bezels to a depth of 3 to 5 ⁇ m.
  • the bezels were placed in a metallic muffle furnace and heated. The temperature was raised to 480°C, and a fluorogas (mixed gas consisting of 5% by volume of NF 2 and 95% by volume of N 2 ) was blown into the muffle furnace for 15 min. Thus, the bezels were fluorinated.
  • a fluorogas mixed gas consisting of 5% by volume of NF 2 and 95% by volume of N 2
  • the fluorogas was discharged from the muffle furnace. While blowing a carburizing gas (mixed gas consisting of 10% by volume of CO, 20% by volume of H 2 , 1% by volume of CO 2 and 69% by volume of N 2 ), the bezels were held in the muffle furnace at 480°C for 12 hr, thereby carburizing the bezels. The bezels were taken out from the muffle furnace.
  • a carburizing gas mixtureed gas consisting of 10% by volume of CO, 20% by volume of H 2 , 1% by volume of CO 2 and 69% by volume of N 2
  • the bezels were immersed in an acid aqueous solution containing 3 to 5% by volume of ammonium fluoride and 2 to 3% by volume of nitric acid for 20 min.
  • the pickled bezels were rinsed.
  • the rinsed bezels were disposed inside a barrel vessel of a barrel polishing apparatus. Walnut chips and alumina abrasive as polishing mediums were placed in the barrel vessel. A barrel polishing was performed over a period of about 10 hr, thereby removing rough faces formed on the outermost surface of the carburized layer of bezels.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
EP00956994A 1999-09-07 2000-09-07 Ornament and method for preparation thereof Expired - Lifetime EP1146136B1 (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP25290099A JP4350225B2 (ja) 1999-09-07 1999-09-07 時計外装部品およびその製造方法
JP25290099 1999-09-07
JP31943799 1999-11-10
JP31943799A JP4463353B2 (ja) 1999-11-10 1999-11-10 時計外装部品およびその製造方法
JP2000104454A JP4451536B2 (ja) 2000-04-06 2000-04-06 装飾部材およびその製造方法
JP2000104454 2000-04-06
PCT/JP2000/006086 WO2001018275A1 (fr) 1999-09-07 2000-09-07 Ornement et son procede de preparation

Publications (3)

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EP1146136A1 EP1146136A1 (en) 2001-10-17
EP1146136A4 EP1146136A4 (en) 2006-09-06
EP1146136B1 true EP1146136B1 (en) 2011-06-22

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KR (1) KR100754811B1 (zh)
CN (1) CN100374613C (zh)
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WO (1) WO2001018275A1 (zh)

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CN103361593A (zh) * 2013-06-21 2013-10-23 燕山大学 表面强化锆材料及其无氢渗碳镀方法
CN105385983B (zh) * 2015-11-09 2017-10-24 中国矿业大学 一种以纳米碳材料的热扩散为预处理的硬质涂层制备方法
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DE112019000101T5 (de) * 2019-03-05 2020-11-19 National University Corporation Nagoya University Schneidverfahren mit diamantschneidwerkzeug
CN113885303B (zh) * 2021-10-27 2022-08-23 东莞得利钟表有限公司 一种利用航天发射器回收料制作手表壳件的工艺
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US20220151348A1 (en) * 2011-06-03 2022-05-19 Frederick Goldman, Inc. Multi-coated metallic products and methods of making the same

Also Published As

Publication number Publication date
KR100754811B1 (ko) 2007-09-04
HK1040421B (zh) 2011-11-18
KR20010085998A (ko) 2001-09-07
EP1146136A1 (en) 2001-10-17
EP1146136A4 (en) 2006-09-06
WO2001018275A1 (fr) 2001-03-15
CN100374613C (zh) 2008-03-12
HK1040421A1 (en) 2002-06-07
CN1321203A (zh) 2001-11-07

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