CN100374613C - Ornament and method for preparation thereof - Google Patents

Ornament and method for preparation thereof Download PDF

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Publication number
CN100374613C
CN100374613C CNB008019088A CN00801908A CN100374613C CN 100374613 C CN100374613 C CN 100374613C CN B008019088 A CNB008019088 A CN B008019088A CN 00801908 A CN00801908 A CN 00801908A CN 100374613 C CN100374613 C CN 100374613C
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China
Prior art keywords
watchband
mentioned
watch
stainless steel
brinelling
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CNB008019088A
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Chinese (zh)
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CN1321203A (en
Inventor
串田八郎
花井贤司
安藤益嗣
井上健
滨野一己
田野仓幸夫
目黑昭
池田信二
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Citizen Watch Co Ltd
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Priority claimed from JP25290099A external-priority patent/JP4350225B2/en
Priority claimed from JP31943799A external-priority patent/JP4463353B2/en
Priority claimed from JP2000104454A external-priority patent/JP4451536B2/en
Application filed by Citizen Watch Co Ltd filed Critical Citizen Watch Co Ltd
Publication of CN1321203A publication Critical patent/CN1321203A/en
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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

Abstract

An ornament, such as external ornamental parts of a watch, which comprises a substrate comprising stainless steel, titanium or titanium alloy and having a hardened layer comprising a solid solution of at least one type of atom selected from the group consisting of a carbon atom, a nitrogen atom and oxygen atom in the substrate and, formed on the surface of the hardened layer, a hard coating film such as TiC or TiN. The ornament has excellent resistance to scratching without detriment to the corrosion-resistant property of the substrate and can have a variety of colors such as gold, and thus is significantly valuable from an ornamental point of view.

Description

Ornament and manufacture method thereof
Technical field
The present invention relates to ornament (also comprising component) and manufacture method thereof, in more detail, relate generally to ornament and the manufacture method thereof such as clock and watch exterior part that its base material has the hardened layer that the solid solution of solid solution atom is arranged (as cementation zone) that is formed at the extremely any degree of depth in surface.The invention still further relates to clock and watch exterior part and manufacture method thereof such as the austenitic stainless steel watch bracelet that relates to stainless steel clock and watch exterior part, particularly gas cementation through carburizing treatment and handled, glass holder, watchcase, bonnet, dial plate and have the slick surface that it doesn't matter " shaddock skin " that is the clock and watch exterior part and the manufacture method thereof of minute surface.
Background technology
Ornament clock and watch exterior parts (member) such as (as watch bracelet, glass holder, watchcase, bonnet, group needle handle, dial plates) adopts stainless steel, titanium or titanium alloy.Particularly stainless steel adopts erosion resistance and ornamental good austenitic stainless steel more.
For example, the sheet material that SUS 316 based materials or SUS 304 based materials by austenitic stainless steel are constituted carries out cold forging.Carry out machining or perforate processing more arbitrarily, be finish-machined to the shape of watch bracelet joint.Then, joint and the joint that obtains thus coupled together, just formed watchband.
But because the minute surface of austenitic stainless steel scratches easily, therefore directly clock and watch exterior parts such as the watch bracelet of use austenitic stainless steel, glass holder, watchcase, bonnet, dial plate exist the easy abrasive shortcoming of appearance.
In order to overcome such shortcoming, studied and made stainless steel surface hardened technology such as austenitic stainless steel by carburizing treatment.But the stainless steel surface that carburizing treatment is crossed can cause lattice deformability owing to the infiltration of carbon atom, and it is coarse that the surface becomes, and therefore, the stainless steel surface that carburizing treatment is crossed grinds again, and the technology that forms minute surface at last also in test.
For example, though the open communique of Japan special permission 1979 No. 86441 is undeclared to be austenitic stainless steel, report, accurate small component such as the gear that will make with soft steel or low-alloy converted steel etc., screw, axle class carry out solid carburizing under 900 ℃ of temperature handles, and this component surface carried out barreling, just can easily obtain minute surface.
But if the metal that contains a large amount of chromium that austenitic stainless steel is such carries out carburizing treatment at high temperature more than 700 ℃, then its stainless steel surface has chromium carbide and separates out.Its result, the chrome content of stainless steel itself reduces, and stainless erosion resistance significantly reduces.And, big because this chromium carbide is thick, therefore can not obtain high hardness in the stainless steel cementation zone.
Separate out in order to prevent above-mentioned chromium carbide, can consider austenitic stainless steel to be carried out the method for carburizing treatment at the low temperature below 700 ℃, but if carry out carburizing treatment at such low temperature, then owing to can form hinder the passive state film of carbon atom infiltration, thereby can't make the stainless steel surface sclerosis at stainless steel surface.
In recent years, people have studied in the erosion resistance that keeps the austenitic stainless steel excellence and have made its stainless steel surface hardened technology.For example, in the open communique of Japan special permission 1997 No. 71854, No. 268364 and No. 302456 disclosed technology, low temperature with 300～500 ℃ in the fluoro-gas atmosphere carries out fluoridation to austenitic stainless steel, makes above-mentioned passive state film become the carbon atom fluorinated film of infiltration easily.Then, the low temperature with 400～500 ℃ in the carburizing atmosphere carries out carburizing treatment to austenitic stainless steel, carries out cleanup acid treatment or mechanical mill (for example flexible abrasive blasting, barreling, polishing etc.) again.
The ornament that obtains like this (as watch bracelet), when keeping erosion resistance, the degree of depth from austenitic stainless steel surface to the 5～50 μ m of base material forms hard hardened layer, i.e. cementation zone.Thus, substrate surface becomes good minute surface, and the surface hardness of its minute surface is 500～700 Vickers' hardnesses (HV) simultaneously, and this is not carry out the inaccessible high rigidity of stainless steel that surface hardening is handled.
As mentioned above, owing to the ornament (comprise decorations body article) of austenitic stainless steel surface through hardening treatment is not easy to scratch, therefore have to keep advantage attractive in appearance for a long time.
But,,, also can scratch if be subjected to the effect of sharp very big external force even be the ornament of base material with the stainless steel of above-mentioned surface hardening.
Thereby wish to have with have than in the past ornament the promptly more excellent scuff resistance of high surface hardness more can stainless steel be the ornament and the manufacture method thereof of base material.
On the other hand, for ornaments such as the exterior part of wrist-watch or bracelets,, require it to have the value identical with other ornament as decorations body article.Therefore, usually having the decorative film on the surface of such decorations body article forms.Such decorative film is extensive use of the au-alloy film of wet type plating method formation etc.
But these au-alloy films are softer, scratch easily.Thereby, promptly use so soft au-alloy film to cover the decorations body article substrate surface that harden, owing to the au-alloy film is scratched, thereby damage its attractive in appearance as ornament.Such decorations body article exist can not give full play to the advantage that above-mentioned substrate surface has hardened.
Thereby, though wish to have hard ornament and the manufacture method thereof that promptly has excellent in resistance scratch performance of itself softer surface hardness that records from the au-alloy film surface of au-alloy film.
In addition, in the open communique of Japan special permission 1997 No. 71854, No. 268364 and No. 302456 described technology, owing at low temperatures austenitic stainless steel is carried out carburizing treatment, therefore stainless steel does not have chromium carbide and separates out, it is thick also can not become, but can form at the outermost surface of cementation zone mainly is the Fe in the stainless steel and the layer of C coexistence, and the chances are contains Fe 2O 3" casting skin " Deng the oxide compound of iron.In the described technology of these communiques, remove casting skin by cleanup acid treatment or mechanical mill.
But,,, can't remove its surface fully and go up the casting skin that forms, thereby can't make clock and watch exterior part surface become minute surface only by mechanical mills such as barreling and polishings for the stainless steel clock and watch exterior part that above-mentioned gas cementation was at low temperatures handled.This be because, nearly all clock and watch exterior part, ornamental attractive in appearance in order to obtain, all constitutes the shape of complexity, thereby the place that exists the inwall of inwall, depression in hole or bottom surface etc. not to grind.In addition, in the clock and watch exterior part that several component are formed by connecting, the face that these component are relative with other component also is difficult to grind.For example many watchbands are saved the watch bracelet that web member is formed by connecting, the gap between adjacent segments and the joint is more little, difficult more grinding.
In addition, only, can not make the surface of clock and watch exterior part become minute surface by cleanup acid treatment.Cleanup acid treatment described in the above-mentioned communique is to utilize strong acid solution to make the contained dissolved ferric iron of casting skin, makes casting skin from clock and watch exterior part sur-face peeling.But because stainless steel itself also contains iron, so the carburizing treatment laminar surface can be subjected to this strong acid solution erosion.As a result, the surface coarsening of carburizing treatment layer after cleanup acid treatment can not form minute surface.
Have, the needed precision work in surface of stainless steel clock and watch exterior part is not only and is become minute surface again.Ornamental attractive in appearance in order to obtain, require to carry out various machine finshings.For example require to be finish-machined to the honing etc. that carving has the hairline of massive parallel lines or is carved with a large amount of fine recesses.
But the stainless steel surface that carburizing treatment is crossed is owing to be hard surface, and therefore the problem that produces is to be difficult to carry out above-mentioned machine finshing.
Thereby, wish to have the erosion resistance of the excellence that stainless steels such as not damaging austenitic stainless steel had originally, have a stainless steel clock and watch exterior part that excellent scuff resistance energy and surface are minute surface again, the erosion resistance of the excellence that stainless steels such as not damaging austenitic stainless steel had is originally arranged, have stainless steel clock and watch exterior part that excellent scuff resistance energy and surface energy carry out machine finshings such as hairline processing and honing processing and their manufacture method again with hope.
In addition, the clock and watch exterior part that the gas carburizing treatment is crossed under 400～500 ℃ of such low temperature (as the surface of watchband joint) as mentioned above, though through grinding, but still can not become the outside needed good minute surface of clock and watch, can be observed " shaddock skin " that micro concavo-convex exists.
Its reason is that because gas cementation is handled, it is many that this crystal boundary of the carbon ratio of solid solution in the metal grain of stainless steel surface is wanted.That is, form in the granulous metal grain along with carbon is penetrated into, it is loose that metal grain becomes, and outwards expands, thereby produce jump between crystal grain and crystal boundary.If from stainless steel surface, crystal grain is than crystal boundary height.
The jump of above-mentioned crystal grain and crystal boundary is not even through a series of processing (being cleanup acid treatment, mechanical mill) after the gas cementation processing, can disappear yet.As a result, crystal grain can see with the naked eye easily from the stainless steel surface emersion great number of grains of emersion seems to be exactly the micro concavo-convex of stainless steel surface, i.e. " shaddock skin ".
Above-mentioned " shaddock skin " is not limited to stainless steel, is to handle the phenomenon that (for example carburizing treatment) Shi Junhui takes place at the metal that titanium or titanium alloy etc. is used for the clock and watch outside to carry out surface hardening less than near the temperature this metal recrystallization temperature.Specifically, be less than the phenomenon of carrying out under just over the temperature of recrystallization temperature taking place when surface hardening is handled.
In addition, above-mentioned " shaddock skin " is not limited to the carburizing treatment of carbon as the solid solution atom, is as the solid solution atom, with the phenomenon of carrying out less than near the temperature the recrystallization temperature of used metal all can taking place when surface hardening is handled with nitrogen or oxygen.
Thereby, wish to have a kind of so rakish clock and watch exterior part and manufacture method thereof: even the metal of the outside usefulness of clock and watch is handled to carry out surface hardening less than near the temperature this metal recrystallization temperature, its surface does not have what is called " shaddock skin " yet, and is very smooth, that is is minute surface.
The objective of the invention is to solve above-mentioned problems of the prior art, provide from the surface substrate surface that is formed with hardened layer (as cementation zone) to the degree of depth arbitrarily to have ornament more in the past than the surface hardness that ornament was high, be that scuff resistance can excellent ornament, particularly clock and watch exterior part.
In addition, other purpose of the present invention is, the surface that is provided at the ornament that constitutes by the above-mentioned base material that is formed with hardened layer form various tones such as gold and can not reduce surface hardness, promptly do not damage scuff resistance can ornament, particularly clock and watch exterior part.
Have, the purpose of the present invention except that above-mentioned is, the manufacture method of above-mentioned ornament is provided again.
In addition, the purpose of the present invention except that above-mentioned is, excellent anticorrosive that stainless steels such as not damaging austenitic stainless steel had originally is provided, has the stainless steel clock and watch exterior part that excellent scuff resistance energy and surface are minute surface again, excellent anticorrosive that stainless steels such as not damaging austenitic stainless steel had originally also is provided, has stainless steel clock and watch exterior part and a manufacture method thereof that machine finshings such as hairline processing and honing processing have been carried out on excellent scuff resistance energy and surface again.
Have again, the purpose of the present invention except that above-mentioned is, provide a kind of so rakish clock and watch exterior part and manufacture method thereof: even the metal of the outside usefulness of clock and watch is handled to carry out surface hardening less than near the temperature this metal recrystallization temperature, its surface does not have what is called " shaddock skin " yet, very smooth, that is be minute surface.
Disclosure of an invention
Ornament of the present invention is the ornament that a kind of its substrate surface to any degree of depth has hardened layer, and the solid solution atom is solid-solubilized in this hardened layer,
It is characterized in that, on the hardened layer surface of base material, form dura mater.
Above-mentioned solid solution atom normally is selected from least a in carbon atom, nitrogen-atoms and the Sauerstoffatom.
Above-mentioned base material preferably is made of stainless steel, titanium or titanium alloy.
Above-mentioned dura mater can be the film with tone different with above-mentioned substrate surface.
The surface hardness of above-mentioned dura mater is greater than the surface hardness of above-mentioned base material.
Above-mentioned dura mater preferably is made of IVa, the Va of periodictable and nitride, carbide, oxide compound, nitrogen carbide or the nitrogen oxycarbide of VIa family element.
Above-mentioned dura mater is the carbon dura mater preferably.
Between the hardened layer surface of above-mentioned carbon dura mater and above-mentioned base material, can form the middle layer.
Above-mentioned middle layer preferably constitutes by the Ti that forms on the hardened layer of above-mentioned base material surface or Cr lower floor with on Si or Ge upper strata that this time laminar surface forms.
In ornament of the present invention, can form at least two kinds of dura maters on the hardened layer surface of above-mentioned base material, in addition, also can be stacked to few two kinds of dura maters at the hardened layer upper layer of above-mentioned base material.
In addition, in ornament of the present invention, can form above-mentioned dura mater in the part on the hardened layer surface of above-mentioned base material.
In ornament of the present invention, can on above-mentioned dura mater, form the au-alloy film again.
Above-mentioned au-alloy film is preferably by being selected from least a metal among 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 the Pt and the film that constitutes of alloy of gold.
Above-mentioned ornament for example is the clock and watch exterior part.
The manufacture method of ornament of the present invention is characterised in that,
Surface at the stainless steel substrate with the hardened layer that the solid solution of solid solution atom is arranged that is formed at its extremely any degree of depth in surface forms dura mater.
The ornament that ornament manufacture method according to the present invention obtains, that is the invention described above ornament for example have clock and watch exterior parts such as watch bracelet.
Clock and watch exterior part of the present invention is made of stainless steel, and its surface is formed with cementation zone, and carbon is solid-solubilized in this cementation zone, that is, it be its surface be formed with cementation zone with the clock and watch exterior part of stainless steel as base material,
It is characterized in that the surface of this cementation zone is that Vickers' hardness (HV) is at the abrasive surface more than 500.
Above-mentioned abrasive surface preferably is minute surface.
In addition, clock and watch exterior part of the present invention is made of stainless steel, and its surface is formed with cementation zone, the carbon solid solution in cementation zone,
It is characterized in that this cementation zone surface is a machine finshing face.
The Vickers' hardness of above-mentioned machine finshing face (HV) is preferably in more than 500.Above-mentioned clock and watch exterior part is by forming machine finshing face on the surface, carries out carburizing treatment then and makes.
Watch bracelet of the present invention comprises interconnected a plurality of Stainless Steel Watch Band joint,
It is characterized in that, be formed with cementation zone on this watchband joint surface, the carbon solid solution in cementation zone,
This cementation zone surface is that Vickers' hardness (HV) is at the abrasive surface more than 500.
Above-mentioned abrasive surface preferably is minute surface.
In addition, watch bracelet of the present invention comprises interconnected a plurality of Stainless Steel Watch Band joint,
It is characterized in that, be formed with cementation zone on this watchband joint surface, the carbon solid solution in cementation zone,
This cementation zone surface is a machine finshing face.
These watch bracelets comprise watchband joint and watchband are saved interconnected stainless steel adapting piece, and at least a portion on this web member surface can be a cementation zone, and the carbon solid solution is in cementation zone.
Watch bracelet of the present invention preferably with web member with watchband joint and watchband joint interconnection after, this watchband joint is carried out carburizing treatment with web member, then this watchband joint surface is ground and the watch bracelet that obtains.
Watch bracelet of the present invention also can comprise the web member that does not form cementation zone.
Watch bracelet manufacture method of the present invention is characterised in that,
With a plurality of stainless steel adapting pieces a plurality of Stainless Steel Watch Band joints are connected, under the fluoro-gas atmosphere, this watchband joint are carried out fluoridation with web member in 400～500 ℃,
Carry out gas cementation in 400～500 ℃ and handle containing under the carburizing gas atmosphere of carbon monoxide then,
Then carry out cleanup acid treatment and washing processing,
At last this watchband is saved surperficial barreling.
Before above-mentioned fluoridation, machine finshing is carried out on the watchband joint surface that connects with above-mentioned web member, can obtain having the watch bracelet on machine finshing surface thus.
In addition, other manufacture method of watch bracelet of the present invention is characterised in that,
Under the fluoro-gas atmosphere, a plurality of Stainless Steel Watch Band joints are carried out fluoridation with a plurality of stainless steel adapting pieces in 250～600 ℃.
Carry out gas cementation in 400～500 ℃ and handle containing under the carburizing gas atmosphere of carbon monoxide then,
Then carry out cleanup acid treatment and washing processing,
This watchband is saved surperficial barreling,
With web member this watchband joint is connected.
Before above-mentioned fluoridation, machine finshing is carried out on above-mentioned a plurality of watchband joints surface, can obtain having the watch bracelet on machine finshing surface thus.
The manufacture method of the clock and watch exterior part except that watch bracelet of the present invention is characterised in that,
Under the fluoro-gas atmosphere, the stainless steel clock and watch exterior part mother metal beyond the watch bracelet that a plurality of Stainless Steel Watch Band joints is connected with a plurality of stainless steel adapting pieces is carried out fluoridation in 250～600 ℃,
Carry out gas cementation in 400～500 ℃ and handle containing under the carburizing gas atmosphere of carbon monoxide then,
Then carry out cleanup acid treatment and washing processing,
Again with this mother metal surface barreling.
Before the above-mentioned fluoridation, above-mentioned mother metal is carried out machine finshing, can obtain having the clock and watch exterior part on machine finshing surface thus.
The most handy above-mentioned watch bracelet manufacture method of the present invention of watch bracelet of the present invention makes.
In addition, the manufacture method of the most handy above-mentioned clock and watch exterior part except that watch bracelet of the present invention of clock and watch exterior part except that watch bracelet of the present invention makes.
Used stainless steel austenitic stainless steel preferably among the present invention.
Other clock and watch exterior part of the present invention is made of metal,
It is characterized in that there is deformation layer this metallic surface, this deformation layer comprises metal grain and is deformed into fibrous fibrous tissue, is formed with the hardened layer that makes the solid solution of solid solution atom at this deformation layer at least.
Above-mentioned deformation layer is that its surface load physical external force at least owing to metal forms.In the present invention, above-mentioned deformation layer preferably forms to the physical external force of extending at the metallic surface folk prescription basically owing to load.
Above-mentioned deformation layer is preferably formed as in metallic surface to 2～degree of depth of 100 μ m.
Above-mentioned hardened layer is preferably formed as in deformation layer surface to 5～degree of depth of 50 μ m.
Above-mentioned solid solution atom is selected from least a in carbon atom, nitrogen-atoms and the Sauerstoffatom.
The surface hardness of above-mentioned hardened layer minute surface is preferably in Vickers' hardness (HV) more than 500.
In addition, the manufacture method of other clock and watch exterior part of the present invention is,
The clock and watch exterior part is made of stainless steel,
It is characterized in that, apply physical external force, comprise the deformation layer that metal grain is deformed into fibrous fibrous tissue in stainless steel surface formation at least at this stainless steel surface,
Then this deformation layer surface is made the hardening treatment of solid solution atom solid solution, form hardened layer.
Above-mentioned deformation layer preferably forms to the physical external force of extending at the stainless steel surface folk prescription by stainless steel surface being applied basically.
Above-mentioned deformation layer is by applying stainless steel surface basically at the stainless steel surface folk prescription to the attrition process of the physical external force of extending or grind at least a formation of cutting in the processing.
More particularly,
Stainless steel surface is carried out machining or grinds and cut at least a of processing, form the surface of desired shape,
Then this shape face is carried out attrition process, forms above-mentioned deformation layer,
Perhaps, stainless steel surface ground cut processing, form the surface of desired shape, form above-mentioned deformation layer simultaneously.
The surface of above-mentioned desired shape can be the surface of being processed near flat, also can be curved surface.
Above-mentioned deformation layer is preferably formed as in the degree of depth of stainless steel surface to 2～100 μ m.
Above-mentioned hardened layer is preferably formed as in the degree of depth of above-mentioned deformation layer surface to 5～50 μ m.
Above-mentioned solid solution atom is selected from carbon atom, at least a in nitrogen-atoms and the Sauerstoffatom.
The surface hardness of above-mentioned hardened layer minute surface is preferably in Vickers' hardness (HV) more than 500.
Above-mentioned deformation layer is formed at the stainless steel surface that the clock and watch exterior part that forms by the big forging processing of deflection is used mother metal usually.
Above-mentioned hardening treatment is being carried out less than near the temperature the stainless steel recrystallization temperature usually.Hardening treatment also can the temperature more than recrystallization temperature be carried out, but owing to can not produce " shaddock skin " under this temperature condition, does not therefore need to form above-mentioned deformation layer.
Used stainless steel austenitic stainless steel preferably among the present invention.
In addition, in this manual, the example of " clock and watch exterior part " has watch bracelet, glass holder, watchcase, bonnet, dials needle handle, dial plate etc.
The simple declaration of drawing
Fig. 1 is the structural representation of the watchband joint among the embodiment of the invention A1.
Fig. 2 is the structural representation of the watchband joint among the embodiment of the invention A2.
Fig. 3 is the structural representation of the watchband joint among the embodiment of the invention A3.
Fig. 4 is the structural representation of the watchband joint among the embodiment of the invention A3.
Fig. 5 is the surface treatment procedure synoptic diagram of the watchband joint among the embodiment of the invention A4.
Fig. 6 is the surface treatment procedure synoptic diagram of the watchband joint among the embodiment of the invention A4.
Fig. 7 is the structural representation of the watchband joint among the embodiment of the invention A4.
Fig. 8 is the structural representation of the watchband joint among the embodiment of the invention A5.
Fig. 9 is the surface treatment procedure synoptic diagram of the watchband joint among the embodiment of the invention A6.
Figure 10 is the structural representation of the watchband joint among the embodiment of the invention A6.
Figure 11 is the surface treatment procedure synoptic diagram of the watchband joint among the embodiment of the invention A7.
Figure 12 is the surface treatment procedure synoptic diagram of the watchband joint among the embodiment of the invention A7.
Figure 13 is the structural representation of the watchband joint among the embodiment of the invention A7.
Figure 14 is the surface treatment procedure synoptic diagram of the watchband joint among the embodiment of the invention A8.
Figure 15 is the surface treatment procedure synoptic diagram of the watchband joint among the embodiment of the invention A8.
Figure 16 is the structural representation of the watchband joint among the embodiment of the invention A8.
The preferred forms of invention
Ornament of the present invention and manufacture method thereof at first are described.
Ornament of the present invention is made of base material with hardened layer that the solid solution of solid solution atom is arranged and the dura mater that forms on this hardened layer surface, as required, also can form the au-alloy film on dura mater.
Figure C0080190800141
The ornament that uses among the present invention has stainless steel, titanium metal and titanium alloy etc. with the object lesson of base material.
Stainless steel preferably adopts austenitic stainless steel.
In addition, described titanium metal is meant the metallic substance based on pure titanium, that is, and and with titanium the 1st class, titanium the 2nd class and titanium the 3rd class etc. of JIS standard definition.
Described titanium alloy is meant the metallic substance that adds aluminium, vanadium, iron etc. in the metal based on pure titanium, that is, and and titanium 60 classes of usefulness JIS standard definition, titanium 60E class etc.In addition, the intermetallic compound of various titanium alloys and various titanium bases is also included within the titanium alloy material.
In the present invention, the substrate surface that the solid solution of solid solution atom is constituted in above-mentioned metal or alloy forms hardened layer.
Used solid solution atom is selected from least a in carbon atom, nitrogen-atoms and the Sauerstoffatom.
Make the carbon atom solid solution in stainless steel (as austenitic stainless steel).Perhaps make nitrogen-atoms and Sauerstoffatom solid solution in stainless steel.
Also can make nitrogen-atoms and Sauerstoffatom solid solution in titanium or titanium alloy.In addition, also can make the carbon atom solid solution in titanium or titanium alloy.
Hardened layer is preferably formed as in the degree of depth of substrate surface to 5～50 μ m.
The surface hardness of hardened layer minute surface is preferably in Vickers' hardness (HV, 50g load) more than 500.
In the present invention, when for example in the base material that constitutes by the austenitic stainless steel that does not contain titanium metal, forming cementation zone, preferably pass through following operation as hardened layer.
(1) fluoridation
Before forming cementation zone, be preferably under the fluoro-gas atmosphere in 100～500 ℃, more preferably base material is carried out fluoridation in 150～300 ℃.
It is that stainless steel and Fe-Cr-Mn are stainless steel etc. that the example of this austenitic stainless steel has Fe-Cr-Ni-Mo.From carburated case depth and consideration in price, the austenitic stainless steel that uses among the present invention is the least possible stable form stainless steel of Ni content preferably.Consider from the erosion resistance aspect, preferably the stainless steel of content about 1.5～4 weight % of the many and valuable element Mo of Ni content.Even the example of only austenitic stainless steel is the stainless steel that obtains at the Mo of chromium content to be 15～25 weight % add in the also stable mutually stable form stainless steel of normal temperature processing austenite 1.5～4 weight %.
The object lesson of the fluoro-gas that can use when above-mentioned fluoridation has NF 3, CF 4, SF 4, C 2F 6, BF 3, CHF 3, HF, SF 6, WF 6, SiF 4, ClF 3Deng fluoride gas.These fluoride gas can use separately, also can two or morely share.In addition, except these gases, can also use other fluorine-containing fluoride gas of intramolecularly as above-mentioned fluoro-gas.Have again, can also use the F that above-mentioned fluoride gas pyrolysis is generated by pyrolysis installation 2Gas or the F for preparing in advance 2Gas is as above-mentioned fluoro-gas.Such fluoride gas and F 2Gas can mix use arbitrarily.
Above-mentioned fluoride gas and F 2Fluoro-gas such as gas can be distinguished use separately, but usually with using behind the inert gas dilutions such as nitrogen, argon gas.This concentration in such diluent gas of fluoro-gas is generally 10000～100000 capacity ppm, is 20000～70000 capacity ppm preferably, better is 30000～50000 capacity ppm.
The most suitable fluoro-gas that uses in the present invention is NF 3NF 3Be gas at normal temperatures, the chemical stability height, easy to use.Usually, with this NF 3Gas and nitrogen combination can be used in above-mentioned concentration range.
In the present invention, for example under the fluoro-gas atmosphere of above-mentioned concentration in 100～500 ℃ temperature, the base material that is processed into the regulation shape is carried out fluoridation.The time of fluoridation is different because of the kind of object being treated, size etc., is generally tens minutes to several hours.
Usually such fluoridation can form the film of fluoridizing of carbon atom permeate well at substrate surface.Thus, handle by the gas cementation as hardening treatment of carrying out below, carbon atom is able to spread to internal penetration from stainless steel surface, thereby is easy to form the brinelling layer.
(2) gas cementation is handled
Containing under the carburizing atmosphere of carbon monoxide,, be better than 400～480 ℃ of base materials most and carry out carburizing treatment the above-mentioned fluoridation of process in 400～500 ℃.
During this carburizing treatment used carburizing gas with carbon monoxide as carbon-source gas, the mixed gas of carbon monoxide and hydrogen, carbonic acid gas, nitrogen normally.
In the present invention, the gas cementation treatment temp is set at 400～500 ℃ low temperature, like this, Cr 23C 6Can not separate out in the brinelling layer Deng the crystal chromium carbide, the chromium atom in the austenitic stainless steel is not consumed, and can keep the erosion resistance of the excellence of brinelling layer thus.In addition, because the carburizing treatment temperature is a low temperature, therefore through this carburizing treatment, Cr 23C 6, Cr 7C 3, Cr 3C 2Can not become thick Deng the crystal chromium carbide, and, be not prone to the strength degradation that causes by the stainless steel internal softening yet.
According to above-mentioned gas carburizing treatment method, can be formed uniformly brinelling layer (the scattering and permeating layer of carbon) at the austenitic stainless steel substrate surface.And, through the above-mentioned gas carburizing treatment, can not generate the crystal chromium carbide, do not consume the chromium atom in the base material (yet claiming mother metal), thus, the brinelling layer can keep the erosion resistance with the excellence of the original equal extent of austenitic stainless steel.
It mainly is Fe and the layer that C coexists in the stainless steel that substrate surface after gas cementation is handled can form, and, may contain Fe that is 2O 3" casting skin " Deng the oxide compound of iron.
(3) cleanup acid treatment
Then, the ornament through the above-mentioned gas carburizing treatment is carried out cleanup acid treatment with base material (as clock and watch exterior part mother metal).Specifically, the clock and watch exterior part is immersed in the acidic solution with mother metal.
The acidic solution that uses in this cleanup acid treatment is not particularly limited, for example can uses hydrofluoric acid, nitric acid, hydrochloric acid, sulfuric acid, Neutral ammonium fluoride etc.These acid can be used separately, also can adopt the mixed solution of mixed solution, nitric acid and hydrochloric acid of mixed solution, nitric acid and hydrofluoric acid of Neutral ammonium fluoride and nitric acid or the mixed solution of sulfuric acid and nitric acid.
The concentration of these acidic solutions can determine suitably that for example, in the mixed solution of nitric acid and hydrochloric acid, preferably concentration of nitric acid is about 15～40 weight %, and concentration of hydrochloric acid is about 5～20 weight %.In addition, the concentration of salpeter solution is preferably about 10～30 weight %.
These acidic solutions can use at normal temperatures, also can at high temperature use.
As cleanup acid treatment, also can use electrolytic solutions such as nitric acid, sulfuric acid, carry out electrolysis treatment.
Dipping time in acidic solution depends on the kind of acidic solution, is about usually about 15～90 minutes.
Through this cleanup acid treatment, because of carburizing treatment is formed at the contained oxidized dissolving of iron in the casting skin on mother metal surface of clock and watch exterior part, casting skin is removed, but only by this cleanup acid treatment, can't remove casting skin fully.And, because iron is dissolved in the process in being immersed in acidic solution, make that handling the brinelling laminar surface that forms by gas cementation becomes coarse.
(4) washing is handled
Then, after above-mentioned cleanup acid treatment, ornament is washed processing with base material (as clock and watch exterior part mother metal).
Handle by this washing, the casting skin that flush away will be peeled off with mother metal from the clock and watch exterior part, flush away clock and watch exterior part makes the brinelling layer can not become more coarse because of acidic solution with the acidic solution that adheres on the mother metal fully simultaneously.Be formed at the clock and watch exterior part and remove fully but can't handle to make with the casting skin on mother metal surface by above-mentioned cleanup acid treatment and washing.
(5) milled processed
Then, the ornament of handling through washing is carried out barreling with base material (as clock and watch exterior part mother metal) surface.
Specifically, the clock and watch exterior part is put into the slot rolling of tumbling apparatus with mother metal, preferably use walnut bits and alumina series abrasive substance to put into slot rolling as grinding medium.Then with carrying out barreling in about 10 hours, the uneven surface of the outermost surface that is formed at the brinelling layer and residual casting skin are ground.
By with above-mentioned cleanup acid treatment, washing processing and barreling and usefulness, can remove fully and be formed at the casting skin of clock and watch exterior part with the mother metal surface.Even this clock and watch exterior part is complex-shaped with mother metal, this casting skin also can be removed fully.In addition, by this barreling, can make the clock and watch exterior part become minute surface with the mother metal surface.
If replace barreling with polishing, then very difficult removing fully is formed at the casting skin of clock and watch exterior part with the mother metal surface.
If the surface hardness (HV) of the cementation zone after the above-mentioned barreling when load 50g is then enough as the hardness of ornaments such as clock and watch exterior part more than 500.But preferably the surface hardness (HV) of cementation zone when load 50g is more than 600.
In the present invention, also can the clock and watch exterior part of barreling be polished with substrate surface with ornaments such as base materials again.
If the surface hardness (HV) of the cementation zone after the above-mentioned polishing when load 50g is then enough as the hardness of ornaments such as clock and watch exterior part more than 500.But preferably the surface hardness (HV) of cementation zone when load 50g is more than 600.
Figure C0080190800171
The film that the dura mater that constitutes ornament of the present invention preferably is made of nitride, carbide, oxide compound, nitrogen carbide or the nitrogen oxycarbide of periodictable IVa, Va, VIa family element.Wherein, be good with the carbon dura mater especially.
Between the hardened layer surface of this carbon dura mater and above-mentioned base material, can form the middle layer.
Such middle layer is preferably by the Ti or the Cr lower floor that form on the hardened layer of above-mentioned base material surface and constitute on Si or Ge upper strata that this time laminar surface forms.
In ornament of the present invention, can form or stacked at least two kinds of dura maters on the hardened layer surface of base material.
In ornament of the present invention, also can form dura mater in the part on the hardened layer surface of base material.
The dura mater that constitutes ornament of the present invention can be the film with tone different with above-mentioned substrate surface.
The surface hardness of dura mater is usually greater than the surface hardness of above-mentioned base material.
The concrete formation method of above-mentioned dura mater reaches the middle layer that is provided with between carbon dura mater and base material hardened layer surface concrete formation method is illustrated in the aftermentioned embodiment A.
Figure C0080190800181
In ornament of the present invention, also can on above-mentioned dura mater, form the au-alloy film again.
Such au-alloy film is preferably by the film that constitutes of alloy that is selected from least a metal and gold among Al, Si, V, Cr, Ti, Fe, Co, Ni, Cu, Zn, Ge, Y, Zr, Nb, Mo, Ru, Rh, Rd, Ag, Cd, In, Sn, Hf, Ta, W, Ir and the Pt.
The concrete formation method of above-mentioned au-alloy film is illustrated in the aftermentioned embodiment A.
Specify clock and watch exterior part of the present invention and manufacture method thereof below.
Clock and watch exterior part of the present invention can roughly be divided into watch bracelet and the two big classes of the clock and watch exterior part except that watch bracelet that a plurality of Stainless Steel Watch Band joints are formed by connecting with a plurality of stainless steel adapting pieces.
In the watchband joint and web member of the watch bracelet that constitutes the former, at least the watchband joint is carried out carburizing treatment, particularly preferably carry out gas cementation and handle, form the brinelling layer on the surface.
The clock and watch exterior part except that watch bracelet to the latter also carries out carburizing treatment, particularly preferably carries out gas cementation and handles, and forms the brinelling layer on the surface.
When a plurality of web members of the above-mentioned usefulness of manufacturing save the watch bracelet that is formed by connecting with a plurality of watchbands, owing to not only watchband is saved, and web member (joint pin, adjust pin that length uses etc.) also carried out carburizing treatment, formation hard cementation zone in the zone dark to tens of μ m from the web member surface thus.Its result, the hardness of web member improves, even along watchband length direction tractive watchband, joint pin or length adjustment are not flexible or fracture with pin yet.Thus, even apply very big external force on watch bracelet, the danger that the watchband joint comes off unintentionally is very little, has improved the intensity of the watchband that connects a plurality of watchband joints.
In addition, by forming the brinelling layer, length adjustment changes sometimes with the elastic force of pin, but this moment, length adjustment may become with pin and be difficult to extract, and is perhaps opposite, and becoming is easy to extract.Under such situation, through the barreling treatment process, pass through the polished finish operation again after, preferably will change length adjustment pin into pin through the length adjustment of carburizing treatment without the over carburizing processing.
" at least to the watchband joint " in above-mentioned " constituting in the former watchband joint and the web member of watch bracelet; at least the watchband joint is carried out carburizing treatment; particularly preferably carry out gas cementation and handle; form the brinelling layer on the surface " is meant and has such situation sometimes: through the barreling treatment process, after passing through the polished finish operation again, the length adjustment that carburizing treatment is crossed changes the length adjustment pin of handling without over carburizing into pin.
The watch bracelet that a plurality of stainless steel adapting pieces of usefulness of the present invention are formed by connecting a plurality of Stainless Steel Watch Bands joint with a plurality of web members with the connection of a plurality of watchbands joint after or before, watchband joint and web member are carried out carburizing treatment, particularly preferably carry out gas cementation and handle.
As the stainless steel of the material of above-mentioned watch bracelet and watch bracelet member (watchband joint and web member) austenitic stainless steel preferably particularly.The stainless steel that uses among the present invention does not contain titanium metal.
Above-mentioned austenitic stainless steel is the stainless steel that has the austenite phase more than the 60 weight % at normal temperatures, and it is that stainless steel and Fe-Cr-Mn are stainless steel etc. that its example has Fe-Cr-Ni-Mo.From carburated case depth and consideration in price, the austenitic stainless steel that uses among the present invention is the least possible stable form stainless steel of Ni content preferably.Consider from the erosion resistance aspect, preferably the stainless steel of content about 1.5～4 weight % of the many and valuable element Mo of Ni content.Even the example of only austenitic stainless steel is the stainless steel that obtains at the Mo of chromium content to be 15～25 weight % add in the also stable mutually stable form stainless steel of normal temperature processing austenite 1.5～4 weight %.
In the present invention, the massive parallel lines is arranged, be carved with the clock and watch exterior part on the machine finshing surface of a large amount of recesses in order to obtain having carving, can before fluoridation, carry out machine finshing to the watchband joint surface that connects with web member, watchband joint or the decorations body object mother metal surface before the connection.
Owing to handle, be formed at the watchband joint surface that connects with web member, the brinelling layer on the surface of the watchband joint before connecting or decorations body object mother metal is stone, therefore, is difficult to carry out machine finshing by gas cementation.In addition, before fluoridation, carry out machine finshing, more suitable in operation.Therefore, machine finshing is carried out before fluoridation.
Carve at watchband joint or the clock and watch exterior part except that watch bracelet by this machine finshing and should have certain degree of depth, like this, after the aftermentioned barreling and polishing, still can show the pattern of hairline and honing with the hairline on mother metal surface or recess etc.The degree of depth of hairline during to this machine finshing or recess etc. is not particularly limited, but usually about about 5～7 μ m.In addition, the degree of depth of hairline after barreling and the polishing or recess etc. is generally about 1～2 μ m.
In the present invention, the abrasive surface that also can form minute surface to passing through aftermentioned barreling and polishing carries out above-mentioned machine finshing.Be solid-solubilized in carbon concentration in the cementation zone from the surface to inside, descend gradually, hardened layer hardness also descends.Thereby through barreling and polishing, stone brinelling laminar surface is removed the thickness about 1～2 μ m, and like this, the surface hardness of cementation zone slightly reduces.Also can carry out machine finshing by above-mentioned abrasive surface.
When minute surface is made on watchband joint before the watchband joint surface that will be connected by web member, connection and the clock and watch exterior part mother metal surface except that watch bracelet, do not carry out above-mentioned machine finshing.
When making the face coexistence of minute surface and process machine finshing, adopt method in the past to get final product.For example, if the part of desiring to make minute surface is applied mask in advance, remove mask after the machine finshing, then machine finshing is only partly carried out at non-mask, has mask partly to be minute surface.
In addition, if the surface hardness (HV) of the cementation zone after the above-mentioned machine finshing when load 50g is then enough as the hardness of clock and watch exterior part more than 500.When preferably loading 50g more than 600.
Figure C0080190800201
Connect the watch bracelet that a plurality of Stainless Steel Watch Band joints form for a plurality of stainless steel adapting pieces of usefulness of the present invention, connect a plurality of Stainless Steel Watch Band joints with a plurality of stainless steel adapting pieces before or after connecting, under the fluoro-gas atmosphere,, be better than 300～500 ℃ most watchband joint and web member carried out fluoridation in 250～600 ℃.
For connecting clock and watch exterior part the watch bracelet that the watchband joint constitutes with web member, under the fluoro-gas atmosphere,, be better than 300～500 ℃ of mother metals (clock and watch exterior part mother metal) most and carry out fluoridation this clock and watch exterior part in 250～600 ℃ except that above-mentioned.
This fluoridation is used fluoro-gas.
The working concentration of the object lesson of fluoro-gas used herein, the object lesson of preferable fluoro-gas and fluoro-gas and using method and front are identical in the working concentration and the using method of the object lesson of the object lesson of the fluoro-gas described in ornament of the present invention and the manufacture method thereof, preferable fluoro-gas and fluoro-gas.
In the present invention, for example, the watch bracelet that is processed into the regulation shape is put into the stove that fluoridation is used with Stainless Steel Watch Band joint and web member or wrist-watch with glass holder, watchcase, bonnet, dial plate etc., under the fluoro-gas atmosphere of above-mentioned concentration, carry out fluoridation in 250～600 ℃ of temperature.The fluoridation time is different because of the kind of object being treated and size etc., usually from tens minutes to dozens of minutes.
Through such fluoridation, at the Cr that contains of object being treated surface formation 2O 3The passive state film become fluorinated film.Therefore the carbon atom good penetrability of this fluorinated film, is handled by the gas cementation of carrying out thereafter, and carbon atom can spread to internal penetration from stainless steel surface, thereby is easy to form the brinelling layer.
Figure C0080190800202
Containing under the carburizing atmosphere of carbon monoxide in 400～500 ℃, be better than 400～480 ℃ most and watchband joint, web member or wrist-watch exterior parts through above-mentioned fluoridation are carried out gas cementation with mother metal handle.
During this carburizing treatment used carburizing gas with carbon monoxide as carbon-source gas, the mixed gas of carbon monoxide and hydrogen, carbonic acid gas, nitrogen normally.
The carburizing ability of this carburizing gas (carbon potential: the Pc value) common CO and the CO in the using gas atmosphere 2Partial pressure value Pco and Pco 2, represent with following formula:
Pc＝(Pco) 2/Pco 2
If this Pc increases, then carburizing ability increases, and the surperficial carbon concentration of stainless steel (as austenitic stainless steel) raises, and surface hardness increases, but the coal ash that gas cementation is handled with generation in the stove also increases.But even this Pc value is set in more than a certain stone wall limit, the surface hardness of the brinelling layer of formation still has the limit.On the other hand, if this Pc value reduces, then carburizing ability reduces, and the carbon concentration on austenitic stainless steel surface descends, and surface hardness reduces.
In the present invention, because the gas cementation treatment temp is set at 400～500 ℃ low temperature, therefore, Cr 23C 6Can not separate out in the brinelling layer Deng the crystal chromium carbide, the chromium atom in the austenitic stainless steel does not consume, thereby can keep the erosion resistance of the excellence of brinelling layer.In addition, because the carburizing treatment temperature is a low temperature, therefore by this carburizing treatment, it is thick that chromium carbide can not become, and, be not prone to the strength degradation that causes by the stainless steel internal softening yet.
By above-mentioned gas carburizing treatment method, can be formed uniformly brinelling layer (the scattering and permeating layer of carbon) with the surface of mother metal at austenite stainless steel bracelet joint and web member thereof or austenitic stainless steel clock and watch exterior part.
In these brinelling layers, can not generate Cr 23C 6, Cr 7C 3, Cr 3C 2Deng the crystal chromium carbide,, then can only observe the ultra tiny metallic carbide of particle diameter below 0.1 μ m if observe with transmission electron microscope.Through the spectroscopic analysis of transmission electron microscope, these ultra tiny metallic carbide have the chemical constitution identical with mother metal, are not the crystal chromium carbides.These brinelling layers are formed mutually by the austenite identical with mother metal, and carbon atom intrusion, solid solution can not form chromium carbide in the metal lattice of mother metal.Because intrusion, the solid solution of these a large amount of carbon atoms, the brinelling layer produces very big lattice deformability.Owing to the complex effect of above-mentioned ultra tiny metallic carbide and lattice deformability, can improve the hardness of brinelling layer, obtain the such high rigidity of 700～1050 Vickers' hardnesses (HV).And, through the above-mentioned gas carburizing treatment, can not generate the crystal chromium carbide, the chromium atom in the mother metal does not consume, therefore, the erosion resistance of the excellence of maintenance of brinelling layer and the original equal extent of austenitic stainless steel.
Watchband joint, its web member or clock and watch exterior part after gas cementation is handled has casting skin as thin as a wafer to form with the surface of mother metal.
Figure C0080190800211
To above-mentioned watchband joint, its web member or the clock and watch exterior part of handling through gas cementation with mother metal carry out with the front in the identical cleanup acid treatment described in ornament of the present invention and the manufacture method thereof.Specifically, watchband joint, its web member or clock and watch exterior part are immersed in the acidic solution with parent material.
By this cleanup acid treatment, because of carburizing treatment is formed at the oxidized dissolving of iron that is comprised in watchband joint, its web member or the casting skin of clock and watch exterior part with the surface of mother metal, casting skin is removed, but only by this cleanup acid treatment, can't remove casting skin fully.And, because iron is dissolved in the process in being immersed in acidic solution, make that handling the brinelling laminar surface that forms by gas cementation becomes coarse.
Figure C0080190800212
After above-mentioned cleanup acid treatment, watchband joint, its web member or clock and watch exterior part are washed processing with mother metal.
Handle by this washing, the casting skin that flush away will save from watchband, its web member or clock and watch exterior part are peeled off with mother metal, flush away watchband joint, its web member or clock and watch exterior part make the brinelling layer can not become more coarse because of acidic solution with the acidic solution that adheres on the mother metal fully simultaneously.Be formed at watchband joint, its web member or clock and watch exterior part and remove fully but can't handle to make with the casting skin on mother metal surface by above-mentioned cleanup acid treatment and washing.
Figure C0080190800221
The ornament of handling through washing is carried out barreling with watchband joint, its web member or clock and watch exterior part with the mother metal surface.
Specifically, to connect watchband joint and the watch bracelet that obtains, the watchband joint, web member or the clock and watch exterior part that do not connect are put into the slot rolling of tumbling apparatus with mother metal with web member, and preferably use walnut bits and alumina series abrasive substance to put into slot rolling as grinding medium.Then with carrying out barreling in about 10 hours, the uneven surface that is formed at brinelling layer outermost surface and residual casting skin are ground.
By with above-mentioned cleanup acid treatment, washing processing and barreling and usefulness, can remove the watchband joint, the watchband joint that does not connect that are formed at connection fully, be intended for connecting the web member of watchband joint or clock and watch exterior part casting skin with the surface of mother metal.Even this clock and watch exterior part is complex-shaped with mother metal, this casting skin also can be removed fully.In addition, by this barreling, can make not watchband joint, the watchband joint that does not connect, be intended for connecting the web member of watchband joint or clock and watch exterior part and become minute surface with the surface of mother metal through the connection of machine finshings such as hairline processing.
If replace barreling, then be difficult to remove fully the watchband joint, the watchband joint that does not connect that are formed at connection, be intended for connecting the web member of watchband joint or clock and watch exterior part casting skin with the surface of mother metal with polishing.
If the surface hardness (HV) of the cementation zone after the above-mentioned barreling when load 50g is then enough as the hardness of ornaments such as clock and watch exterior part more than 500.But preferably the surface hardness (HV) of cementation zone when load 50g is more than 600.
Figure C0080190800222
In the present invention, also can polish again with the surface of mother metal the watchband joint of barreling, watchband joint or the clock and watch exterior part that connects.
If the surface hardness (HV) of the cementation zone after the above-mentioned polishing when load 50g is then enough as the hardness of ornaments such as clock and watch exterior part more than 500.But preferably the surface hardness (HV) of cementation zone when load 50g is more than 600.
Figure C0080190800223
The watchband joint that will not connect with web member connects, and makes watch bracelet.
Specify other clock and watch exterior part and manufacture method thereof of the present invention below.
Other clock and watch exterior part of the present invention at first is described.
Other clock and watch exterior part of the present invention is made of metal, and there is deformation layer this metallic surface, and this deformation layer comprises metal grain and is deformed into fibrous fibrous tissue, is formed with the hardened layer that makes the solid solution of solid solution atom at this deformation layer at least.
The object lesson that forms the metal of clock and watch exterior part has stainless steel, titanium metal and titanium alloy etc.Wherein, stainless steel austenitic stainless steel preferably.
Above-mentioned deformation layer is to contain the thin layer that metal grain is deformed into fibrous fibrous tissue in the metallic surface, is deformed into fibrous fibrous tissue in order to form metal grain, must apply physical external force on the surface at least of metal.Deformation layer preferably by be applied to the metallic surface basically folk prescription form to the physical external force of extending.
The means that the metallic surface is applied above-mentioned physical external force for example have attrition process and grind and cut processing.
As attrition process, specifically, well-known in the past polishing and polishing processing are for example arranged.
In the present invention, can after processing is polished in the metallic surface, polish, also can carry out barreling to the metallic surface the metallic surface being polished or polished first being processed.Also can polish or polish first being processed to the metallic surface, the metallic surface ground cut processing or machining.
Deformation layer is preferably formed as in metallic surface to 2～degree of depth of 100 μ m.
In the present invention, owing to making the solid solution of solid solution atom form hardened layer on above-mentioned deformation layer surface, therefore, after hardened layer formed, it is fibrous that metal grain still is.As a result, can not produce jump between crystal grain and the crystal boundary, detect by an unaided eye less than " shaddock skin ".Thereby, can obtain having the clock and watch exterior part of shiny surface that is minute surface.This shiny surface that is minute surface can be the planes, also can be curved surfaces.
Above-mentioned hardened layer is preferably formed as in deformation layer surface to 5～degree of depth of 50 μ m.
Above-mentioned solid solution atom is selected from least a in carbon atom, nitrogen-atoms and the Sauerstoffatom.
The surface hardness of above-mentioned hardened layer minute surface is preferably in Vickers' hardness (HV) more than 500.
Figure C0080190800232
Figure C0080190800233
Other clock and watch exterior part for the invention described above applies physical external force at its stainless steel surface, forms at stainless steel surface at least to comprise the deformation layer that metal grain is deformed into fibrous fibrous tissue.
This deformation layer preferably by stainless steel surface is applied to stainless steel surface basically folk prescription form to the physical external force of extending.
The means that the metallic surface is applied above-mentioned physical external force for example have attrition process and grind and cut processing.
As attrition process, specifically, polishing and the polishing processing known are altogether so far for example arranged.
In this polishing processing, the upper surface that makes clock and watch exterior part mother metal outwardly, be fixed on the outer surface of runner, make this runner rotation then, diamond or sintered carbide tools (for example tungsten, carbide) roof pressure are used on the upper surface of mother metal at the clock and watch exterior part, ground the upper surface of clock and watch exterior part with mother metal.
In the present invention, can after processing is polished in the metallic surface, polish, also can carry out barreling to the metallic surface the metallic surface being polished or polished first being processed.Also can the metallic surface be ground cut processing or machining the metallic surface being carried out or polishing first being processed.
Grind at this and to cut in the processing, with the clock and watch exterior part with the upper surface roof pressure of mother metal on the emery wheel of rotation, grind the upper surface of cutting clock and watch exterior part usefulness mother metal with the sand grains of emery wheel.In the present invention, reduce and to grind the power of cutting and carry out machining.Reduce the means grind the power of cutting and for example have the sand grains that makes emery wheel to become smooth, reduce the sand grains number or reduce the method for cutting agent etc. of grinding.
In the present invention, can carry out machining or grind and cut at least a in the processing, form the surface of desired shape, by this shape face is carried out attrition process, form above-mentioned deformation layer then stainless steel surface.Also can grind and cut processing, form the surface of desired shape, form above-mentioned deformation layer simultaneously stainless steel surface.
The surface of above-mentioned desired shape can be the surface of being processed near flat, also can be curved surface.
Enumerate with preferred sequence if will apply the various means of physical external force, then for polishing, polish, grind the order of cutting processing, machining.
In the present invention, it is desirable to especially and with grind cut processing with the polishing these two kinds of methods.
Deformation layer is preferably formed as in the degree of depth of stainless steel surface to 2～100 μ m.
In the present invention, above-mentioned deformation layer is formed at usually by the big forging processing of deflection (Cold Forging and forge hot processing) the clock and watch exterior part that the forms stainless steel surface of mother metal.
Figure C0080190800241
Then, make the hardening treatment of solid solution atom solid solution on above-mentioned deformation layer surface, form hardened layer.
Above-mentioned solid solution atom adopts and is selected from least a in carbon atom, nitrogen-atoms and the Sauerstoffatom.For example, make the carbon atom solid solution in austenitic stainless steel, or make nitrogen-atoms and Sauerstoffatom solid solution in titanium or titanium alloy.Perhaps, make the carbon atom solid solution in titanium or titanium alloy.
Hardened layer is preferably formed as in deformation layer surface to 5～degree of depth of 50 μ m.
The surface hardness of hardened layer minute surface is preferably in Vickers' hardness (HV) more than 500.
In the present invention, for example when the clock and watch exterior part that is made of the austenitic stainless steel that does not contain titanium metal forms cementation zone as hardened layer with the above-mentioned deformation layer of mother metal is surperficial, preferably make the clock and watch exterior part through following operation.
That is, at this moment, before forming cementation zone, be preferably under the fluoro-gas atmosphere in 100～500 ℃, better is carries out fluoridation in 150～300 ℃ of clock and watch exterior parts that the surface is formed with deformation layer with mother metal.
It is that stainless steel and Fe-Cr-Mn are stainless steel etc. that the example of this austenitic stainless steel has Fe-Cr-Ni-Mo-.From carburated case depth and consideration in price, the austenitic stainless steel that uses among the present invention, the least possible stable form stainless steel of Ni content preferably, but consider, the preferably stainless steel of content about 1.5～4 weight % of the many and valuable element Mo of Ni content from the erosion resistance aspect.In addition, even only austenitic stainless steel for example is to be to add the stainless steel that the Mo of 1.5～4 weight % obtains in the also stable mutually stable form stainless steel of 15～25 weight % normal temperature processing austenite at chromium content.
The working concentration of the object lesson of the object lesson of used fluoro-gas, preferable fluoro-gas and fluoro-gas and using method and front are identical in the working concentration and the using method of the object lesson of the object lesson of the fluoro-gas described in ornament of the present invention and the manufacture method thereof, preferable fluoro-gas and fluoro-gas during above-mentioned fluoridation.
In the present invention, for example, the watch bracelet that is processed into the regulation shape is put into the stove that fluoridation is used with Stainless Steel Watch Band joint and web member or wrist-watch with glass holder, watchcase, bonnet, dial plate etc., under the fluoro-gas atmosphere of above-mentioned concentration, carry out fluoridation in 100～500 ℃ of temperature.The fluoridation time is different because of the kind of object being treated and size etc., usually from tens minutes to dozens of minutes.
By above-mentioned fluoridation, can can form the film of fluoridizing of carbon atom good penetrability on the deformation layer surface, thus, handle by the gas cementation as hardening treatment of carrying out thereafter, carbon atom can spread to internal penetration from stainless steel surface, thereby is easy to form the brinelling layer.
The clock and watch exterior part that above-mentioned fluoridation is crossed carries out the front with mother metal to be handled in the gas cementation described in clock and watch exterior part of the present invention (comprising watch bracelet) and the manufacture method thereof, promptly containing under the carburizing atmosphere of carbon monoxide, be better than 400～480 ℃ most and carry out gas cementation and handle in 400～500 ℃.
In the present invention, the gas cementation treatment temp is set at 400～500 ℃ low temperature, like this, Cr 23C 6Can not separate out in the brinelling layer Deng the crystal chromium carbide, the chromium atom in the austenitic stainless steel is not consumed, and can keep the erosion resistance of the excellence of brinelling layer thus.In addition, because the carburizing treatment temperature is a low temperature, therefore through this carburizing treatment, it is thick that chromium carbide can not become, and, be not prone to the strength degradation that causes by the stainless steel internal softening yet.
By above-mentioned gas carburizing treatment method, can be formed uniformly brinelling layer (the scattering and permeating layer of carbon) with the mother metal surface at austenitic stainless steel clock and watch exterior part.
In these brinelling layers, can not generate Cr 23C 6, Cr 7C 3, Cr 3C 2Deng the crystal chromium carbide,, then can only observe the ultra tiny metallic carbide of particle diameter below 0.1 μ m if observe with transmission electron microscope.Through the spectroscopic analysis of transmission electron microscope, these ultra tiny metallic carbide have the chemical constitution identical with mother metal, are not the crystal chromium carbides.These brinelling layers are formed mutually by the austenite identical with mother metal, and carbon atom intrusion, solid solution can not form chromium carbide in the metal lattice of mother metal.Because intrusion, the solid solution of these a large amount of carbon atoms, the brinelling layer produces very big lattice deformability.Owing to the complex effect of above-mentioned ultra tiny metallic carbide and lattice deformability, can improve the hardness of brinelling layer, obtain the such high rigidity of 700～1050 Vickers' hardnesses (HV).And, through the above-mentioned gas carburizing treatment, can not generate the crystal chromium carbide, the chromium atom in the mother metal does not consume, therefore, the erosion resistance of the excellence of maintenance of brinelling layer and the original equal extent of austenitic stainless steel.
Clock and watch exterior part after gas cementation is handled has casting skin as thin as a wafer to form with the surface of mother metal.
Then, to the above-mentioned clock and watch exterior part of handling through gas cementation with mother metal carry out with the front in the identical cleanup acid treatment described in ornament of the present invention and the manufacture method thereof.
By this cleanup acid treatment, because of carburizing treatment is formed at the oxidized dissolving of iron that is comprised in the casting skin of clock and watch exterior part with the surface of mother metal, casting skin is removed, but only by this cleanup acid treatment, can't remove casting skin fully.And, because iron is dissolved in the process in being immersed in acidic solution, make that handling the brinelling laminar surface that forms by gas cementation becomes coarse.
After above-mentioned cleanup acid treatment, the clock and watch exterior part is washed processing with mother metal.
Handle by this washing, the casting skin that flush away will be peeled off with mother metal from the clock and watch exterior part, flush away clock and watch exterior part makes the brinelling layer can not become more coarse because of acidic solution with the acidic solution that adheres on the mother metal fully simultaneously.Be formed at the clock and watch exterior part and remove fully but can't handle to make with the casting skin on mother metal surface by above-mentioned cleanup acid treatment and washing.
Then, the clock and watch exterior part of handling through washing is carried out barreling with the mother metal surface.
Specifically, the clock and watch exterior part is put into the slot rolling of tumbling apparatus with mother metal, preferably use walnut bits and alumina series abrasive substance to put into slot rolling as grinding medium.Then with carrying out barreling in about 10 hours, the uneven surface that is formed at brinelling layer outermost surface and residual casting skin are ground.
By with above-mentioned cleanup acid treatment, washing processing and barreling and usefulness, can remove fully and be formed at the casting skin of clock and watch exterior part with the surface of mother metal.Even this clock and watch exterior part is complex-shaped with mother metal, this casting skin also can be removed fully.In addition, by this barreling, can make the clock and watch exterior part become minute surface with the surface of mother metal.
If replace barreling with polishing, then very difficult removing fully is formed at the casting skin of clock and watch exterior part with the mother metal surface.
If the surface hardness (HV) of the cementation zone after the above-mentioned barreling when load 50g is then enough as the hardness of ornaments such as clock and watch exterior part more than 500.But preferably the surface hardness (HV) of cementation zone when load 50g is more than 600.
In the present invention, also can the clock and watch exterior part of barreling be polished with the surface of mother metal again.
If the surface hardness (HV) of the cementation zone after the above-mentioned polishing when load 5.0g is then enough as the hardness of clock and watch exterior part more than 500.But preferably the surface hardness (HV) of cementation zone when load 50g is more than 600.
The invention effect
Ornament of the present invention is because its substrate surface has the solid solution of solid solution atom in hardened layer wherein to any degree of depth, and the hardened layer surface also has dura mater, therefore has the scuff resistance energy of very high surface hardness and excellence.
In addition, owing to can surface hardness be reduced, but also can make it have various tones such as gold, thereby can improve its decorative value at all or part of formation au-alloy film on the above-mentioned dura mater surface of ornament of the present invention.
Use ornament manufacture method of the present invention, but the ornament of the invention described above is made on high productivity ground, as the clock and watch exterior part.
In addition, according to the present invention, can provide do not damage the original excellent anticorrosive of stainless steel (particularly austenitic stainless steel), scuff resistance can be excellent and be the austenitic stainless steel clock and watch exterior part (comprising watch bracelet) of minute surface and do not damage the erosion resistance, scuff resistance of the original excellence of stainless steel (particularly austenitic stainless steel) can be excellent and can carry out that hairline is processed on the surface and the austenitic stainless steel clock and watch exterior part (comprising watch bracelet) of machine finshings such as honing processing and the manufacture method of these clock and watch exterior parts on the surface.
Other clock and watch exterior part of the present invention is because its clock and watch exterior part comprises the deformation layer that metal grain is deformed into fibrous fibrous tissue with the formation of the metallic surface of mother metal after, at least on deformation layer, form the hardened layer that makes the solid solution of solid solution atom, therefore have the surface that is the minute surface of slick nothing " shaddock skin ", outward appearance as smart as a new pin.
According to the manufacture method of other clock and watch exterior part of the present invention, can provide above-mentioned rakish other clock and watch exterior part of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is described, but the present invention is not limited to these embodiment.
[embodiment of ornament of the present invention and manufacture method thereof]
Embodiment A 1
The mother metal made from austenitic stainless steel SUS 316 based materials is carried out forge hot, cold forging, machining and perforate processing etc., make the watch bracelet joint.
Then, web member is inserted the pin-and-hole that is located in each watchband joint, a plurality of watchband joints are connected, it can be rotated mutually, the surface of above-mentioned watchband joint is waited by polishing grind, be finish-machined to minute surface, make watch bracelet.
Several watchbands joints that these a plurality of watchbands are saved in the watch bracelet that is formed by connecting are to save from the watchband that adjacent watchband joint takes off, and promptly so-called length adjustment saves with watchband, so that can come the reconciliation statement strip length according to the thickness of wearer's wrist.Except that length adjustment is to be difficult for saving the isolating watchband joint that is connected with adjacent watchband with the watchband joint the watchband joint.
Web member is used for length adjustment with the web member (length adjustment pin) of watchband joint and be used for the web member (joint pin and split pipe, annular knurl pin) that other watchband saves.
Then, pack into this watch bracelet in the metal system retort furnace after, be warming up to 480 ℃.In retort furnace, be blown into the fluoro-gas (NF of 5 capacity % then 2N with 95 capacity % 2Mixed gas), continue 15 minutes, carry out fluoridation.
Then, after the fluoro-gas discharge, be blown into the carburizing gas (H of the CO of 10 capacity %, 20 capacity % 2, 1 capacity % CO 2N with 69 capacity % 2Mixed gas), kept 12 hours with 480 ℃, carry out after the carburizing treatment watchband being taken out from retort furnace.
Watchband surface after the carburizing treatment of taking out has casting skin and forms.
Then, this watchband was flooded 20 minutes in the acidic aqueous solution that contains Neutral ammonium fluoride 3～5 capacity % and nitric acid 2～3 capacity %.
Through this cleanup acid treatment, be formed at the contained oxidized dissolving of iron in the surperficial casting skin of watchband joint, the major part of casting skin is removed.In addition, the inwall of facing surfaces, pin-and-hole and the web member (being joint pin, split pipe, length adjustment pin) that connects the watchband joint also be can't see casting skin in the adjacent watchband joint.
But what the surface of watchband joint promptly formed through carburizing treatment soaks the carbon-coating surface owing to iron in the process that impregnated in acidic aqueous solution is dissolved, thereby becomes uneven surface.
Then, the watchband through cleanup acid treatment is washed.
Then, will be placed in the slot rolling of tumbling apparatus, again walnut bits and alumina series abrasive are put into slot rolling as grinding medium through the watchband of washing.Carried out barreling with about 10 hours then, the uneven surface that is formed at watchband joint cementation zone outermost surface is ground.Like this, the cementation zone surface is removed the dark zone of 1～2 μ m, and watchband joint surface is that the outermost surface of cementation zone becomes minute surface.
By the watch bracelet that is minute surface that above-mentioned operation obtains, its scuff resistance can be excellent, and have the erosion resistance with the original excellent anticorrosive equal extent of SUS316 based material.The surface hardness (HV) of cementation zone when load 50g reaches 700.
Like this, owing in advance a plurality of watchband joints are connected into after the watchband form, carry out fluoridation, gas cementation processing, cleanup acid treatment, washing processing and barreling and handle, therefore operation easily in these treatment process, productivity height.Can reduce required staff of operation and time, reduce processing cost.
In addition, because web member is also carried out carburizing treatment, therefore formed the hard cementation zone in web member surface to number+μ m depth areas.As a result, the hardness of web member increases, even along watchband length direction tractive watchband, joint pin or length adjustment are not flexible or fracture with pin yet.
But,,, also be difficult to remove the casting skin that is formed on the web member even therefore carry out cleanup acid treatment or milled processed because joint pin or length adjustment are stayed in the pin-and-hole that is arranged in each watchband joint with web members such as pins.On cleanup acid treatment or milled processed rear connectors still during residual casting skin, as long as change the web member of residual casting skin into new web member.After changing like this, just can obtain the watchband that web member does not only form cementation zone.
Particularly in web member, if there is casting skin residual, then this pin is difficult to extract from the watchband joint length adjustment, is difficult to come the reconciliation statement strip length according to wearer's wrist thickness with pin.At this moment, only needing to change the length adjustment in the web member into new component with web member gets final product.After changing like this, just can obtain length adjustment does not only form cementation zone with web member watchband.
Then, on each watchband joint cementation zone, form the dura mater of golden tone.
As shown in Figure 1, save on the cementation zone 2 on 1 surface being formed at watchband,, form by titanium nitride membrane 3 as golden dura mater by the ion plating method of one of dry type plating method.
The following describes the formation method of titanium nitride membrane.
At first, the watchband that will be formed with cementation zone 2 cleans with organic solvents such as Virahols, is placed in the apparatus for ionically plating.Apparatus for ionically plating can be the general device that uses, and therefore omits its explanation and corresponding accompanying drawing.
Then, be vented to 1.0 * 10 in will installing -5Behind the Torr, import helium, until 3.0 * 10 as rare gas element -5Torr.
Then, thermoelectron filament and plasma electrode in the drive unit, the plasma body of formation argon.Apply on watchband-the 50V current potential simultaneously, bombardment was cleaned 10 minutes.
Then, after stopping to import argon gas, in device, import nitrogen to 2.0 * 10 -5Torr.
Then, produce plasma body with the electron beam gun in the device after, make titanium evaporation 10 minutes, be to form the thick TiN film of 0.5 μ m on the cementation zone 2 of watchband joint 1 on the whole surface of watchband.
The watchband that obtains like this owing to the TiN film has and metallographic optical characteristics together, thereby presents uniform golden tone.Can further improve the decorative value of watchband like this.
In addition, when loading 50g, reached 800 by the surface hardness (HV) of the watchband joint 1 of these TiN film 3 coatings.The watchband joint 1 that is coated by TiN film 3 has excellent abrasive, erosion resistance and scuff resistance.
Like this, by forming the TiN film 3 harder than cementation zone 2, watchband joint 1 more difficult scratch that (carburizing treatment) crossed is handled in surface hardening.
In addition,, be not limited to above-mentioned ion plating method, also can adopt well-known means such as sputtering method and vacuum vapour deposition as the dry type plating method.
In addition, the golden dura mater that forms with the dry type plating method can be the film that nitride, carbide, oxide compound, nitrogen carbide or nitrogen oxycarbide by IVa, the Va of periodictable, VIa family element (Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W) constitute.
At IVa, Va, VIa family element with M indication cycle table, when representing the nitride of M with MNx, along with the X value of expression degree of nitriding is littler than 1, the tone of the film of the nitride MMx of above-mentioned M from gold to faint yellow close.In addition, along with the X value of expression degree of nitriding is bigger than 1, the gold of film can appear redness.In addition, if the X value of expression degree of nitriding then can form the golden NMx film near gold or au-alloy tone in 0.9～1.1 scope.Particularly the X value at the expression degree of nitriding is X=1 hour, and the MNx film has enough hardness, presents the gold of the most approaching gold or au-alloy tone simultaneously.
IVa, Vav, the carbide of VIa family element M, oxide compound, nitrogen carbide, nitrogen oxycarbide for periodictable, by their degree of carbonisation, oxidisability, degree of nitriding are controlled within the limits prescribed, can make their film have the gold of the most approaching gold or au-alloy tone.
Particularly TiN film and ZrN film not only have enough hardness, and present the gold of the most approaching gold or au-alloy tone, are preferable therefore.
In addition, if the NMx film is thinner, then film can not obtain effective wear resistance, erosion resistance and scuff resistance.But if film is thicker, then the film formation time is long, and the film cost improves.Thereby the thickness of NMx film is 0.1～10 μ m preferably, is 0.2～5 μ m better.
Embodiment A 2
Formed on the watchband joint of cementation zone using, formed dura mater with embodiment A 1 different tones with embodiment A 1 same procedure.
As shown in Figure 2, save on the cementation zone 2 on 1 surface being formed at watchband, form the dura mater of titanium carbide film 4 as white color by the dry type plating method.
Adopt the ion plating method of one of dry type plating method, in the ethylene gas atmosphere, make the titanium evaporation, form TiC film 4 on the surface of watchband joint 1.Other film formation condition is with reference to embodiment A 1.
The watchband that obtains like this, because the formation of TiC film 4, thereby present uniform white color.Can further improve the decorative value of watchband thus.
The surface hardness (HV) of the watchband joint 1 that coats with TiC film 4 reaches 800 when load 50g.The watchband joint 1 that has coated TiC film 4 has excellent abrasive, erosion resistance and scuff resistance.
Like this, by forming the TiC film 4 harder than cementation zone 2, surface hardening is handled the watchband joint 1 that (carburizing treatment) cross and more is difficult to scratch.
Embodiment A 3
Formed on the watchband joint of cementation zone using, formed the dura mater of carbon dura mater as black tone with embodiment A 1 same procedure.Because the carbon dura mater has similar adamantine excellent specific property, be well-known therefore as diamond-like carbon (DLC).
As shown in Figure 3, save on the cementation zone 2 on 1 surface being formed at watchband, form black carbon dura mater 5 by the dry type plating method.
Carbon dura mater 5 is for example in order to method formation down.
At first, the watchband that has formed cementation zone 2 is cleaned with organic solvents such as Virahols, be placed in the vacuum unit.On cementation zone 2, form the thick carbon dura mater 5 of 2 μ m with the high frequency plasma cvd method by following condition.
(formation condition)
Gaseous species: methane gas
Become film pressure: 0.1Torr
High frequency power: 300W
Film forming speed: per minute 0.1 μ m
Like this, on cementation zone 2, form the good carbon dura mater 5 of tack.
The watchband that obtains thus is because the formation of carbon dura mater 5, thereby presents uniform black tone.Thereby can further improve the decorative value of watchband.
In addition, brought up to 5000 by the surface hardness (HV) of the watchband joint 1 of these carbon dura mater 5 coatings from 3000.Like this, by forming the carbon dura mater 5 harder than cementation zone 2, surface hardening is handled the watchband joint 1 that (carburizing treatment) cross and more is difficult to scratch.
The thickness of carbon dura mater 5 is 0.1～5 μ m preferably, is 0.5～3 μ m better.
In addition, except available RFP-CVD method forms carbon dura mater 4, can also adopt various gas phases such as DC plasma CVD method or ECR method to become embrane method.In addition, also can adopt physical vapor depositions such as ionic fluid method, sputtering method or ion plating method.
In addition, as shown in Figure 4, if form intermediate layer film 6 between cementation zone 2 and carbon dura mater 5, then carbon dura mater 5 can more closely save 1 surface attached to watchband, and is therefore more satisfactory.
The for example available following method formation method of intermediate layer film 6.
By dry type plating method (as sputtering method), on cementation zone 2, form the thick Ti film 6a of 0.1 μ m.By sputtering method, on Ti film 6a, form the thick Si film 6b of 0.3 μ m again.
Then, for example forming the thick carbon dura mater 5 of 2 μ m with the high frequency plasma cvd method by above-mentioned condition on Si film 6b gets final product.
Above-mentioned Ti film 6a can change chromium (Cr) film into.In addition, above-mentioned Si film 6b can change germanium (Ge) film into.
As middle layer (film), except above-mentioned laminate film, also can be the IVa family of individual layer or the carbide of Va family metal.The titanium carbide film that particularly contains too much carbon since with the adhesion strength height of carbon dura mater, therefore more satisfactory.
Embodiment 4
Using a part that has formed the watchband joint surface of cementation zone with embodiment A 1 same procedure to form the dura mater of golden tone.
As shown in Figure 7, save the part on 1 surface,, form the dura mater of titanium nitride membrane 7 as golden tone by the ion plating method of one of dry type plating method at watchband.
The following describes the part formation method of golden TiN film 7.
At first, as shown in Figure 5, in each surperficial desired portion of the watchband joint 1 that has formed cementation zone 2, printing forms mask layer 8 by organic mask agent or the agent of mask seal that Resins, epoxy constitutes.
Then, the organic solvents such as watchband joint 1 usefulness Virahol that formed mask layer 8 are cleaned, be placed in the apparatus for ionically plating.
Apparatus for ionically plating can be the general device that uses, and therefore omits its explanation and corresponding accompanying drawing.
Then, be vented to 1.0 * 10 in will installing -5Behind the Torr, send into inert argon gas to 3.0 * 10 -3Torr.Then, thermoelectron filament and plasma electrode in the drive unit, the plasma body of formation argon.Respectively apply a 50V current potential simultaneously on watchband joint 1, bombardment was cleaned 10 minutes.
Then, after stopping to send into argon gas, in device, send into nitrogen to 2.0 * 10 -3Torr.Then, produce plasma body with the electron beam gun in the device after, make titanium evaporation 10 minutes, as shown in Figure 6, form 0.5 μ m thick TiN film 7 and 7a respectively on the surface of the hardened layer 2 of watchband joint 1 and on the surface of mask layer 8.
Then, be used in the stripping solution that has added formic acid and hydrogen peroxide in ethyl methyl ketone (EMK) or the ethyl methyl ketone (EMK) and make mask layer 8 swellings, mask layer 8 and stacked in the above TiN film 7a are peeled off by peeling off method.
Like this, as shown in Figure 7, obtain having part that is golden tone that is coated by TiN film 7 and the watchband joint that is stainless argenteous part that is not coated by the TiN film.Thereby can further improve the decorative value of watchband.
As the mask means, except the method that chemical mask is set of present embodiment explanation, also can adopt mechanical mask means.Promptly before forming titanium nitride membrane, cover the arbitrary portion of watchband joint in advance with metal cap, behind the formation titanium nitride membrane, remove this cover and get final product.Adopt such mask means, the watchband joint part that is covered by cover is not coated by titanium nitride membrane, and the part that is covered by cover is not then coated by titanium nitride membrane.
In the present embodiment, with the dura mater of titanium nitride membrane as the part formation that saves 1 surface at watchband, but as illustrating among the embodiment A1, the film that nitride, carbide, oxide compound, nitrogen carbide or the nitrogen oxycarbide of also available IVa by periodictable, Va, VIa family element constitutes is as the golden dura mater that forms with the dry type plating method.
Particularly if a part that saves 1 surface at watchband forms used titanium carbide film in the embodiment A 2, then can obtain having the titanium carbide film white color part and do not have the watchband joint that presents the argenteous part of stainless steel of titanium carbide film.
Perhaps, if a part that saves 1 surface at watchband forms used carbon dura mater in the embodiment A 3, then can obtain having the carbon dura mater black tone part and do not have the watchband joint that presents the argenteous part of stainless steel of carbon dura mater.
Embodiment A 5
Using the surface that has formed the watchband joint of cementation zone with embodiment A 1 same procedure to form the dura mater of golden tone.On golden dura mater, form the au-alloy film again.
As shown in Figure 8, the surface at the watchband joint 1 that has formed cementation zone 2 by the ion plating method of one of dry type plating method, forms the titanium nitride membrane 9 of golden dura mater.On TiN film 9, form gold-titanium alloy thin films 10 as the au-alloy film.
The following describes the formation method of TiN film in the present embodiment 9 and gold-titanium alloy thin films 10.
At first, the watchband that has formed cementation zone 2 is cleaned with organic solvents such as Virahols, be placed in the apparatus for ionically plating.Apparatus for ionically plating can be the general device that uses, and therefore omits its explanation and corresponding accompanying drawing.
Then, be vented to 1.0 * 10 in will installing -5Behind the Torr, send into inert argon gas to 3.0 * 10 -3Torr.
Then, thermoelectron filament and plasma electrode in the drive unit, the plasma body of formation argon.Simultaneously watchband joint 1 is respectively applied-the 50V current potential, bombardment was cleaned 10 minutes.
Then, behind the generation of the electron beam gun in device plasma body, make titanium evaporation 10 minutes, form the thick TiN film 9 of 0.5 μ m on the whole surface of watchband joint 1.
Then, make the evaporation of titanium stop and stopping to send into nitrogen, be vented to 1.0 * 10 in will installing -5Torr.Then, in device, send into argon gas to 1.0 * 10 -3Torr after the generation gas ions, makes the gold-titanium mixture evaporation that is made of golden 50 atom % and titanium 50 atom %, forms gold-titanium alloy thin films 10.Then, when the thickness of gold-titanium alloy thin films 10 reaches 0.3 μ m, stop gold-titanium mixture evaporation.
The watchband joint that obtains like this presents uniform golden tone.Thereby can improve the decorative value of watchband.In addition, by forming gold-titanium alloy thin films 10, can obtain having than TiN film 9 watchband of the golden tone of warm colour more as the outermost layer film.Thereby can make watchband more attractive in appearance.
Usually, if the thickness of au-alloy film itself then can not obtain effective wear resistance, erosion resistance or scuff resistance below 10 μ m.Gold is very expensive metal.Thereby, if form thick au-alloy film, then will increase substantially the film cost.But in the present embodiment, hard TiN film is set below the outermost layer film that constitutes by the au-alloy film.Because this TiN film has excellent abrasive, erosion resistance and scuff resistance, therefore the outermost layer film that is made of the au-alloy film can be thinner.In the present embodiment, owing to form the TiN film, form thin au-alloy film more thereon, thereby can reduce the usage quantity of high price gold, can reduce the film cost thus.
In addition, the outermost layer film that is made of thin au-alloy film might the part wearing and tearing, make that the TiN film below it exposes, and still, the wearing and tearing of the outermost layer film of any locality will never be noticeable.This be because, the TiN film have and metallographic with optical characteristics, be golden tone, what manifest below the wearing part of the outermost layer film that constitutes from the au-alloy film by golden tone is the TiN film of identical golden tone.Thereby even the outermost layer film that is made of the au-alloy film is thinner, its wearing and tearing can not discovered yet, thereby can keep the value as the attractive in appearance of the watchband of adoring the body article and decoration.
In an embodiment, be as dura mater with titanium nitride membrane, in addition, as the golden dura mater that forms with the dry type plating method, the film that also can adopt nitride, carbide, oxide compound, nitrogen carbide or nitrogen oxycarbide by IVa, the Va of periodictable, VIa family element to constitute.
As the au-alloy film, except that above-mentioned gold-titanium alloy thin films, also can be by the film that constitutes of alloy that is selected from least a metal and gold among Al, 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 the Pt.
But, if be selected from decorations body article and the skin contact that some au-alloy films of aforesaid combination coat, then may be because of electrolytic solutions such as sweat make the metal ion stripping, the skin that decorations body article are contacted produces metal allergy.Particularly the nickel ion of known stripping is the maximum metal ion of metal allergy case.And iron is the few metal of metal allergy case.About the metal allergy case of titanium, do not appear in the newspapers as yet.Thereby, if consider the metal allergy, then as the au-alloy film of outermost layer film preferably gold-iron alloy or gold-titanium alloy.
Embodiment A 6
Also can be only on the dura mater of the golden tone that forms on the part surface of the described watchband joint that cementation zone arranged of embodiment A 4, form embodiment A 5 described au-alloy films again.
Partly form as the titanium nitride membrane 11 of the dura mater of golden tone with as the method for the gold-titanium alloy thin films 12 of au-alloy film with Fig. 9 and Figure 10 simple declaration below.
At first, as shown in Figure 9, in each surperficial desired portion of the watchband joint 1 that has formed cementation zone 2, printing forms mask layer 8 by organic mask agent or the agent of mask seal that Resins, epoxy constitutes.
Then, the organic solvents such as watchband joint 1 usefulness Virahol that formed mask layer 8 are cleaned, be placed in the apparatus for ionically plating.
Then, adopt the ion plating method of one of dry type plating method, form 0.5 μ m thick TiN film 11 and 11a on cementation zone 2 surfaces of watchband joint 1 and the surface of mask layer 8.Then, on TiN film 11 and 11a, form thick gold-titanium alloy thin films 12 and the 12a of 0.3 μ m.
Then, be used in the stripping solution that has added formic acid and hydrogen peroxide in ethyl methyl ketone (EMK) or the ethyl methyl ketone (EMK) and make mask layer 8 swellings, by peeling off method, mask layer 8 and stacked in the above TiN film 11a and gold-titanium alloy thin films 12a are peeled off.
Like this, as shown in figure 10, obtain having part that presents golden tone that has formed TiN film 11 and gold-titanium alloy thin films 12 and the watchband that presents the argenteous part of stainless steel that does not form these films.
In the present embodiment, also as described in the embodiment 5, can adopt the various dura maters beyond the titanium nitride.In addition, also can adopt gold-titanium alloy thin films various au-alloy films in addition.
Embodiment A 7
Using watchband joint surface formation the 1st dura mater that has formed cementation zone with embodiment A 1 same procedure.Again at the part formation on the 1st dura mater surface and the 2nd dura mater of the different tones of the 1st dura mater.
As shown in figure 11, use the method identical, form the titanium nitride membrane 3 that the 1st dura mater is golden tone on the surface of the watchband joint 1 that has formed cementation zone 2 with embodiment A 1.In the surperficial desired portion of TiN film 3, printing is that organic mask agent or the mask that resin constitutes prints agent etc. by epoxy, forms mask layer 13.
Then, as shown in figure 12, use the method identical with embodiment A 2, forming the 2nd dura mater on the surface of TiN film 3 is the titanium carbide film 14 of white color, forms TiC film 14a on the surface of mask layer 13.
Then, make mask layer 13 swellings, by peeling off method, mask layer 13 and stacked in the above TiC film 14a are peeled off with stripping solution.
Use aforesaid method, as shown in figure 12, obtain having the watchband joint of the golden tone part that white portion that the TiC film 14 that is layered in metal Ti N film 3 part surfaces presented and TiN film 3 presented.Like this, can further improve the decorative value of watchband.In addition, by forming TiN film 3 and the TiC film 14 harder than cementation zone 2, surface hardening is handled the watchband joint 1 that (carburizing treatment) cross and more is difficult to scratch.
Dura mater in the present embodiment as described in embodiment A5, can be the various dura maters beyond titanium nitride or the titanium carbide film.Perhaps, can be with any film in the 1st dura mater and the 2nd dura mater as embodiment 3 described carbon dura maters.In addition, according to the kind of these films, the kind of mask layer 13 and stripping solution can suitably be selected.
With IVa, Va, the VIa family element of M indication cycle table, when MNx represented the nitride of M, the 1st dura mater and the 2nd dura mater also can all be the MNx films.At this moment, if make the X value of expression degree of nitriding in the 1st dura mater different with X value in the 2nd dura mater when forming each dura mater, then the tone of the 1st dura mater and the 2nd dura mater can dissimilate.Like this too for carbide, oxide compound, nitrogen carbide, nitrogen oxycarbide.
Embodiment A 8
Using a part that has formed the watchband joint surface of cementation zone with embodiment A 1 same procedure to form the 1st dura mater.Again at another part formation on watchband joint surface and the 2nd dura mater of the different tones of the 1st dura mater.
As shown in figure 14, use the method identical with embodiment A 4, the part on the surface of the watchband joint 1 that has formed cementation zone 2 forms the titanium nitride membrane 7 that the 1st dura mater is golden tone.Save a surperficial desirable part of 1 on the surface of TiN film 7 and coupled watchband, form mask layer 15.
Then, as shown in figure 15, use the method identical, form the titanium carbide film 16 that the 2nd dura mater is a white color in the remaining surface of TiN film 7, mask layer 15 and watchband joint 1 with embodiment A 2.
Then, make mask layer 15 swellings, by peeling off method, mask layer 15 and stacked in the above TiC film 16 are peeled off with stripping solution.
Use aforesaid method, as shown in figure 16, the part that obtains having the part of the golden tone that TiN film 7 presented, white that TiC film 16 is presented and watchband save the three color table bands joint of 1 surperficial exposed portions serve.Like this, can further improve the decorative value of watchband.
The selection of the selection of the 1st dura mater and the 2nd dura mater and stripping solution and mask layer is with reference to embodiment 7.In addition, form embodiment A 5 described au-alloy films on any that also can be in the 1st dura mater and the 2nd dura mater or both.
In the foregoing description A2 and embodiment A 4～A8, what adopt as the dry type plating method is ion plating method, but also can adopt well-known film such as sputtering method or vacuum vapour deposition to form means.
In addition, in above-mentioned all embodiment, be that example is illustrated with the watch bracelet joint.But the present invention also can be applicable to the parts that mechanical type or polarity formula drive unit are housed resemble the wristwatch case.The present invention is also applicable to other all ornaments (comprising parts).
[about the embodiment of clock and watch exterior part of the present invention and manufacture method thereof]
Embodiment B 1
The mother metal that SUS 316 based materials of austenitic stainless steel are constituted carries out forge hot, cold forging, machining and perforate processing etc., makes the watch bracelet joint.
Then, web member is inserted the pin-and-hole that each watchband joint break-through is provided with, a plurality of watchband joints are connected with joint, and can rotate mutually, the surface of aforementioned watchband joint is waited by polishing grind, be finish-machined to minute surface, finish watch bracelet.
In addition, with the watch bracelet that these a plurality of watchband joints are formed by connecting, its several watchband joints are to save from the watchband that adjacent watchband joint takes off, and promptly so-called length adjustment saves with watchband, so that can come the reconciliation statement strip length according to the thickness of wearer's wrist.Except that length adjustment is to be not easy to throw off such watchband joint that is connected with adjacent watchband joint with the watchband joint the watchband joint.In addition, web member uses the web member (joint pin and split pipe, annular knurl pin) that web member (length adjustment pin) that length adjustment saves with watchband and other watchband are saved.
Then, pack into this watch bracelet in the metal system retort furnace after, be warming up to 480 ℃.Then with the fluoro-gas (NF of 5 capacity % 2N with 95 capacity % 2Mixed gas) be blown in the retort furnace 15 minutes, carry out fluoridation.
Then, after the fluoro-gas discharge, be blown into the carburizing gas (H of the CO of 10 capacity %, 20 capacity % 2, 1 capacity % CO 2N with 69 capacity % 2Mixed gas), keep carrying out in 12 hours watchband being taken out from retort furnace after the carburizing treatment with 480 ℃.
Watchband surface after the carburizing treatment of taking out forms casting skin.
Then, this watchband is immersed in the acidic aqueous solution that contains Neutral ammonium fluoride 3～5 capacity % and nitric acid 2～3 capacity % 20 minutes.
Through this cleanup acid treatment, the contained oxidized dissolving of iron in the casting skin that watchband joint surface forms, the major part of having removed casting skin.In addition, the inwall of the face that adjacent watchband joint is relative with joint, pin-and-hole and to connect watchband joint and the web member that saves be that joint pin, split pipe, length adjustment also be can't see casting skin with pin.
But, the surface of watchband joint promptly since carburizing treatment form soak the carbon-coating surface owing to impregnated in acidic aqueous solution, and make dissolved ferric iron, form uneven surface.
Then, the watchband of cleanup acid treatment is washed.
Then, the watchband of having washed is placed in the slot rolling of tumbling apparatus, again with the walnut bits and change the aluminium based abrasive and put into slot rolling as grinding medium.Then with carrying out barreling in about 10 hours, the uneven surface of the most surperficial formation of watchband joint cementation zone is ground.Like this, remove the zone of 1～2 μ m degree of depth from the cementation zone surface, watchband joint surface is that the outermost surface of cementation zone becomes minute surface.
By the watch bracelet that is minute surface that above operation obtains, scuff resistance can be excellent, and have the erosion resistance with the original excellent anticorrosive equal extent of SUS316 based material.Owing in advance a plurality of watchband joints are connected to form after the watchband form, carry out above-mentioned each treatment process, therefore can reduce the required artificial and time of processing operation, can reduce processing cost.
In addition, because web member also carries out carburizing treatment, therefore surface to the tens of μ m depth areas from web member form the hard cementation zone.As a result, the hardness of web member increases, even along watchband length direction stretching watchband, joint pin or length adjustment are not flexible or fracture with pin yet.
In this Embodiment B 1, because a plurality of watchbands joint is connected to form after the watchband form, carry out fluoridation, gas cementation processing, cleanup acid treatment, washing processing and barreling are handled, and therefore the operation ratio of watchband joint is easier to the productivity height in these treatment process.
Embodiment B 2
Be in Embodiment B 1, to carry out before the fluoridation, save a positive side surface (when being worn on the wrist, being surface) at watchband and form a large amount of hairlines along the watchband length direction towards the outside, in addition identical with Embodiment B 1, obtain watch bracelet.
Hairline precision work has been passed through on the surface of the watch bracelet that obtains, and scuff resistance can be excellent, has kept the erosion resistance with the erosion resistance same degree of the original excellence of SUS316 based material.
Embodiment B 3
Be in Embodiment B 1, to replace watch bracelet with the Watch glass frame, in addition identical with Embodiment B 1, obtain the accurately machined glass holder of minute surface.
The glass holder that obtains, scuff resistance can be excellent, kept the erosion resistance with the erosion resistance same degree of the original excellence of SUS 316 based materials.
Embodiment B 4
Be in embodiment 1, to replace watch bracelet with wristwatch case, in addition identical with Embodiment B 1, obtain the accurately machined watchcase of minute surface.
The watchcase scuff resistance that obtains can be excellent, kept the erosion resistance with the erosion resistance same degree of the original excellence of SUS 316 based materials.
Embodiment B 5
Be in embodiment 1, to replace watch bracelet with the wrist-watch bonnet, in addition identical with Embodiment B 1, obtain the accurately machined bonnet of minute surface.
The bonnet that obtains, scuff resistance can be excellent, kept the erosion resistance with the erosion resistance same degree of the original excellence of SUS 316 based materials.
Embodiment B 6
Be in embodiment 1, to replace watch bracelet with Watch dail plate, in addition identical with Embodiment B 1, obtain the accurately machined dial plate of minute surface.
The dial plate that obtains, scuff resistance can be excellent, kept the erosion resistance of the erosion resistance same degree of the excellence that had originally with SUS 316 based materials.
(embodiment of relevant other clock and watch exterior part of the present invention and manufacture method thereof)
Embodiment C 1
Having prepared by austenitic stainless steel is the bar that SUS 316 based materials constitute.This bar cross section forms the rectangle of band fillet, so that consistent with the shape of watch bracelet joint.Width according to the watchband joint cuts off bar.
Then, break-through is provided with the pin-and-hole that joint pin inserts on the member of this cut-out, finishes the watch bracelet joint.
Then, joint pin is inserted the pin-and-hole that each watchband joint break-through is provided with, a plurality of watchband joints are connected with joint, and can rotate mutually, watch bracelet is finished in assembling.
Then, the upper surface of each watchband joint band fillet of watch bracelet (on the wrist of wearing time, be towards the front of outside one side surface) is polished.
With the section of electron microscope observation through the watchband joint upper surface of polishing, the result can confirm that because the added external force effect of polishing, the metal grain of stainless steel surface is stretched along the polishing wheel sense of rotation, forms and is deformed into fibrous fibrous tissue.Forming the deformation layer that contains the aforementioned fibers tissue from watchband joint upper surface to 3～7 μ m depth areas.
Then, pack into this watch bracelet in the metal system retort furnace after, be warming up to 480 ℃.Then with the fluoro-gas (NF of 5 capacity % 2N with 95 capacity % 2Mixed gas) be blown in the retort furnace 15 minutes, carry out fluoridation.
Then, after the fluoro-gas discharge, be blown into the carburizing gas (H of the CO of 10 capacity %, 20 capacity % 2, 1 capacity % CO 2N with 69 capacity % 2Mixed gas), keep carrying out in 12 hours watchband being taken out from retort furnace after the carburizing treatment with 480 ℃.
Watchband surface after the carburizing treatment of taking out forms casting skin.
Then, this watchband is immersed in the acidic aqueous solution that contains Neutral ammonium fluoride 3～5 capacity % and nitric acid 2～3 capacity % 20 minutes.
Through this cleanup acid treatment, the contained oxidized dissolving of iron in the casting skin that watchband joint surface forms, the major part of having removed casting skin.In addition, adjacent watchband joint face, the inwall of pin-and-hole and the web member of connection watchband joint and joint relative with joint is that joint pin also be can't see casting skin.
But, the surface of watchband joint promptly since carburizing treatment form soak the carbon-coating surface owing to impregnated in acidic aqueous solution, and make dissolved ferric iron, form uneven surface.
Then, the watchband of cleanup acid treatment is washed.
Then, the watchband of having washed is placed in the slot rolling of tumbling apparatus, again with the walnut bits and change the aluminium based abrasive and put into slot rolling as grinding medium.Then with carrying out barreling in about 10 hours, the uneven surface of the most surperficial formation of watchband joint cementation zone is ground.
By this barreling, the cementation zone surface is removed 0.3～1 μ m, and the upper surface of watchband joint becomes " the shaddock skin " that the clock and watch outside will form micro concavo-convex.
Then, with the joint of the watchband after electron microscope observation barreling section, the result is formed up to the cementation zone of 18～20 μ m degree of depth from watchband joint upper surface.
Embodiment C 2
Having prepared the blood austenitic stainless steel is the cylinder that SUS 316 based materials constitute.The edge applies external force by the central shaft at the circular section segment center of aforementioned cylinder, and cylinder is carried out cold forging, this cylinder is forged into the shape of watch bracelet joint.
Then, break-through is arranged on and connects the pin-and-hole that pin inserts on forging member, finishes the watch bracelet joint.
Then, joint pin is inserted the pin-and-hole that each watchband joint break-through is provided with, a plurality of watchband joints are connected with joint, and can rotate mutually, watch bracelet is finished in assembling.
Then, by each watchband joint upper surface (when being worn on wrist on, be towards the front of outside one side surface) the formation flat minute surface of polishing processing with watch bracelet.The upper surface that is about to watchband is fixed on the outer surface of runner towards the outside, makes this runner rotation then, and diamond tool is pressed on the watchband upper surface.
With the section of electron microscope observation through the watchband joint upper surface of polishing processing, the result can confirm that because the added external force effect of polishing processing, the metal grain of stainless steel surface is stretched along the runner sense of rotation, forms to be deformed into fibrous fibrous tissue.Forming the deformation layer that contains the aforementioned fibers tissue from watchband joint upper surface to 5～10 μ m depth areas.
Then, pack into this watch bracelet in the metal system retort furnace after, be warming up to 480 ℃.Then with the fluoro-gas (NF of 5 capacity % 2N with 95 capacity % 2Mixed gas) be blown in the retort furnace 15 minutes, carry out fluoridation.
Then, after the fluoro-gas discharge, be blown into the carburizing gas (H of the CO of 10 capacity %, 20 capacity % 2, 1 capacity % CO 2N with 69 capacity % 2Mixed gas), keep carrying out in 12 hours watchband being taken out from retort furnace after the carburizing treatment with 480 ℃.
Watchband surface after the carburizing treatment of taking out forms casting skin.
Then, this watchband is immersed in the acidic aqueous solution that contains Neutral ammonium fluoride 3～5 capacity % and nitric acid 2～3 capacity % 20 minutes.
Through this cleanup acid treatment, the contained oxidized dissolving of iron in the casting skin that watchband joint surface forms, the major part of having removed casting skin.In addition, adjacent watchband joint face, the inwall of pin-and-hole and the joint pin of connection watchband joint and joint relative with joint also be can't see casting skin.
But, the surface of watchband joint promptly since carburizing treatment form soak the carbon-coating surface owing to impregnated in acidic aqueous solution, and make dissolved ferric iron, form uneven surface.
Then, the watchband of cleanup acid treatment is washed.
Then, the watchband of having washed is placed in the slot rolling of tumbling apparatus, again with the walnut bits and change the aluminium based abrasive and put into slot rolling as grinding medium.Then with carrying out barreling in about 10 hours, the uneven surface of the most surperficial formation of watchband joint cementation zone is ground.
By this barreling, the cementation zone surface is removed 0.5～1.5 μ m, and the upper surface of watchband joint becomes the minute surface of the smooth beauty of clock and watch external demand." the shaddock layer " of the formation micro concavo-convex of on this surface, can't see fully.
Then, with the joint of the watchband after electron microscope observation barreling section, the result is formed up to the cementation zone of 18～20 μ m degree of depth from watchband joint upper surface.
Embodiment C 3
Identical with Embodiment C 2, watch bracelet is finished in assembling.
Then,, again the upper surface of each watchband joint is ground by polishing then, form minute surface by machining each watchband joint upper surface formation plane with watch bracelet.
Section with the above-mentioned watchband joint upper surface that obtains of electron microscope observation, the result can confirm, and is identical with Embodiment C 1, because the added external force effect of polishing, the metal grain of stainless steel surface is stretched along the polishing wheel sense of rotation, forms to be deformed into fibrous fibrous tissue.Forming the deformation layer that contains the aforementioned fibers tissue from watchband joint upper surface to 3～6 μ m depth areas.
Then, pack into this watch bracelet in the metal system retort furnace after, be warming up to 480 ℃.Then with the fluoro-gas (NF of 5 capacity % 2N with 95 capacity % 2Mixed gas) be blown in the retort furnace 15 minutes, carry out fluoridation.
Then, after the fluoro-gas discharge, be blown into the carburizing gas (H of the CO of 10 capacity %, 20 capacity % 2, 1 capacity % CO 2N with 69 capacity % 2Mixed gas), keep carrying out in 12 hours watchband being taken out from retort furnace after the carburizing treatment with 480 ℃.
Watchband surface after the carburizing treatment of taking out forms casting skin.
Then, this watchband is immersed in the acidic aqueous solution that contains Neutral ammonium fluoride 3～5 capacity % and nitric acid 2～3 capacity % 20 minutes.
Through this cleanup acid treatment, the contained oxidized dissolving of iron in the casting skin that watchband joint surface forms, the major part of having removed casting skin.In addition, adjacent watchband joint face, the inwall of pin-and-hole and the joint pin of connection watchband joint and joint relative with joint also be can't see casting skin.
But, the surface of watchband joint promptly since carburizing treatment form soak the carbon-coating surface owing to impregnated in acidic aqueous solution, and make dissolved ferric iron, form uneven surface.
Then, the watchband of cleanup acid treatment is washed.
Then, the watchband of having washed is placed in the slot rolling of tumbling apparatus, again with the walnut bits and change the aluminium based abrasive and put into slot rolling as grinding medium.Then with carrying out barreling in about 10 hours, the uneven surface of the most surperficial formation of watchband joint cementation zone is ground.
By this barreling, the cementation zone surface is removed 1～2 μ m, and the upper surface of watchband joint becomes the minute surface of the smooth beauty of clock and watch external demand.On this surface, can't see " the shaddock layer " that form micro concavo-convex fully.
Then, with the joint of the watchband after electron microscope observation barreling section, the result is formed up to the cementation zone of 20～25 μ m degree of depth from watchband joint upper surface.
Embodiment C 4
Identical with Embodiment C 2, watch bracelet is finished in assembling.
Then, grind grinding of the power of cutting by reduction and cut processing, make each watchband joint upper surface of watch bracelet form flat mirror.The upper surface that is about to watch bracelet compresses the emery wheel of rotation, and the upper surface that each watchband is saved with the sand grains of emery wheel grinds to be cut.
Then, again the upper surface of each watchband joint is ground, form minute surface by polishing.
Section with the above-mentioned watchband joint upper surface that obtains of electron microscope observation, the result can confirm, identical with Embodiment C 1, add and polish added external force effect owing to grind to cut, the metal grain of stainless steel surface is stretched along emery wheel and polishing wheel sense of rotation, formation is deformed into fibrous fibrous tissue, is forming the deformation layer that contains the aforementioned fibers tissue from watchband joint upper surface to 7～12 μ m degree zone.
Then, pack into this watch bracelet in the metal system retort furnace after, be warming up to 480 ℃.Then with the fluoro-gas (NF of 5 capacity % 2N with 95 capacity % 2Mixed gas) be blown in the retort furnace 15 minutes, carry out fluoridation.
Then, after the fluoro-gas discharge, be blown into the carburizing gas (H of the CO of 10 capacity %, 20 capacity % 2, 1 capacity % CO 2N with 69 capacity % 2Mixed gas), keep carrying out in 12 hours watchband being taken out from retort furnace after the carburizing treatment with 480 ℃.
Watchband surface after the carburizing treatment of taking out forms casting skin.
Then, this watchband is immersed in the acidic aqueous solution that contains Neutral ammonium fluoride 3～5 capacity % and nitric acid 2～3 capacity % 20 minutes.
Through this cleanup acid treatment, the contained oxidized dissolving of iron in the casting skin that watchband joint surface forms, the major part of having removed casting skin.In addition, adjacent watchband joint face, the inwall of pin-and-hole and the joint pin of connection watchband joint and joint relative with joint also be can't see casting skin.
But, the surface of watchband joint promptly since carburizing treatment form soak the carbon-coating surface owing to impregnated in acidic aqueous solution, and make dissolved ferric iron, form uneven surface.
Then, the watchband of cleanup acid treatment is washed.
Then, the watchband of having washed is placed in the slot rolling of tumbling apparatus, again with the walnut bits and change the aluminium based abrasive and put into slot rolling as grinding medium.Then with carrying out barreling in about 10 hours, the uneven surface of the most surperficial formation of watchband joint cementation zone is ground.
By this barreling, the cementation zone surface is removed 1.5～2.5 μ m, and the upper surface of watchband joint becomes the minute surface of the smooth beauty of clock and watch external demand.On this surface, can't see " the shaddock skin " that form micro concavo-convex fully.
Then, with the joint of the watchband after electron microscope observation barreling section, the result is formed up to the cementation zone of 15～20 μ m degree of depth from watchband joint upper surface.
In this Embodiment C 4, cut owing to grind grinding of the power of cutting by reduction, can make each table joint upper surface form flat mirror, can make the metal grain of near surface become fibrous tissue simultaneously, therefore can reduce manufacturing process.Thereby, cut processing by adopting such grinding, can reduce manufacturing cost.
Embodiment C 5
Identical with Embodiment C 2, watch bracelet is finished in assembling.
Then, grind grinding of the power of cutting by reduction and cut processing each watchband joint upper surface formation flat mirror watch bracelet.The upper surface that is about to watch bracelet compresses the emery wheel of rotation, and the upper surface that each watchband is saved with the sand grains of emery wheel grinds to be cut.
With the section of the above-mentioned watchband joint upper surface that obtains of electron microscope observation, the result can confirm, the metal grain of stainless steel surface grinds grinding of the power of cutting along reduction and cuts the emery wheel sense of rotation and be stretched, and forms and is deformed into fibrous fibrous tissue.Forming the deformation layer that contains the aforementioned fibers tissue from watchband joint upper surface to 2～5 μ m depth areas.
Then, pack into this watch bracelet in the metal system retort furnace after, be warming up to 480 ℃.Then with the fluoro-gas (NF of 5 capacity % 2N with 95 capacity % 2Mixed gas) be blown in the retort furnace 15 minutes, carry out fluoridation.
Then, after the fluoro-gas discharge, be blown into the carburizing gas (H of the CO of 10 capacity %, 20 capacity % 2, 1 capacity % CO 2N with 69 capacity % 2Mixed gas), keep carrying out in 12 hours watchband being taken out from retort furnace after the carburizing treatment with 480 ℃.
Watchband surface after the carburizing treatment of taking out forms casting skin.
Then, this watchband is immersed in the acidic aqueous solution that contains Neutral ammonium fluoride 3～5 capacity % and nitric acid 2～3 capacity % 20 minutes.
Through this cleanup acid treatment, the contained oxidized dissolving of iron in the casting skin that watchband joint surface forms, the major part of having removed casting skin.In addition, adjacent watchband joint face, the inwall of pin-and-hole and the web member of connection watchband joint and joint relative with joint is that joint pin also be can't see casting skin.
But, the surface of watchband joint promptly since carburizing treatment form soak the carbon-coating surface owing to impregnated in acidic aqueous solution, and make dissolved ferric iron, form uneven surface.
Then, the watchband of cleanup acid treatment is washed.
Then, the watchband of having washed is placed in the slot rolling of tumbling apparatus, again with the walnut bits and change the aluminium based abrasive and put into slot rolling as grinding medium.Then with carrying out barreling in about 10 hours, the uneven surface of the most surperficial formation of watchband joint cementation zone is ground.
By this barreling, the cementation zone surface is removed 1～2 μ m, and the upper surface of watchband joint becomes the minute surface of the smooth beauty of clock and watch external demand.Can't see " the shaddock skin " that form micro concavo-convex from the teeth outwards fully.
Then, with the joint of the watchband after electron microscope observation barreling section, the result is formed up to the cementation zone of 20～30 μ m degree of depth from watchband joint upper surface.
In this Embodiment C 5, cut owing to grind grinding of the power of cutting by reduction, can make each table joint upper surface form flat mirror, can make the metal grain of near surface become fibrous tissue simultaneously, therefore can reduce manufacturing process.Thereby, cut processing by adopting such grinding, can reduce manufacturing cost.
Embodiment C 6
Having prepared by austenitic stainless steel is the cylinder that SUS 316 based materials constitute.The edge applies external force by the central shaft at the cylindrical section center of aforementioned cylinder, and cylinder is carried out cold forging, and this cylinder is forged member circlewise.
Then, week and periphery in the forged member are cut into the size of requirement.
Then, the upper surface of this member is ground, finish the glass holder of upper surface and minute surface.
With the section of electron microscope observation through the glass holder of grinding, the result can confirm that owing to grind added external force effect, the metal grain of stainless steel surface is stretched along the grinding miller sense of rotation, forms and is deformed into fibrous fibrous tissue.Forming the deformation layer that contains the aforementioned fibers tissue from glass holder upper surface to 3～5 μ m depth areas.
Then, pack into this glass holder in the metal system retort furnace after, be warming up to 480 ℃.Then with the fluoro-gas (NF of 5 capacity % 2N with 95 capacity % 2Mixed gas) be blown in the retort furnace 15 minutes, carry out fluoridation.
Then, after the fluoro-gas discharge, be blown into the carburizing gas (H of the CO of 10 capacity %, 20 capacity % 2, 1 capacity % CO 2N with 69 capacity % 2Mixed gas), keep carrying out in 12 hours glass holder being taken out from retort furnace after the carburizing treatment with 480 ℃.
Glass holder surface after the carburizing treatment of taking out forms casting skin.
Then, this glass holder is immersed in the acidic aqueous solution that contains Neutral ammonium fluoride 3～5 capacity % and nitric acid 2～3 capacity % 20 minutes.
By this cleanup acid treatment, the contained oxidized dissolving of iron in the casting skin that the glass holder surface forms, the major part of having removed casting skin.
But, the surface of glass holder promptly since carburizing treatment form soak the carbon-coating surface owing to impregnated in acidic aqueous solution, and make dissolved ferric iron, form uneven surface.
Then, the glass holder of cleanup acid treatment is washed.
Then, the glass holder of having washed is placed in the slot rolling of tumbling apparatus, again walnut bits and alumina series abrasive is put into slot rolling as grinding medium.Then with carrying out barreling in about 10 hours, the uneven surface of surperficial formation of glass holder cementation zone is ground.
By this barreling, the cementation zone surface is removed 1～2 μ m, and the glass holder upper surface forms the outside desired smooth beautiful minute surface of clock and watch, and " the shaddock skin " that forms micro concavo-convex can't see on this surface fully.
With the glass holder section after the electron microscope observation barreling, the result forms the cementation zone of 20～23 μ m degree of depth from the glass holder upper surface.

Claims (31)

1. ornament, it comprises:
Stainless steel substrate,
Brinelling layer from its substrate surface to any degree of depth, carbon atom is solid-solubilized in this brinelling layer, does not have the crystal chromium carbide in formed sosoloid,
Dura mater on the described brinelling laminar surface of base material,
It is characterized in that,
Described brinelling layer has by removing the uneven surface that is formed at its outside surface and grind the minute surface that obtains, and its Vickers' hardness is more than 500,
The surface hardness of described dura mater is greater than the surface hardness of described brinelling layer.
2. ornament as claimed in claim 1 is characterized in that, above-mentioned dura mater has the tone different with above-mentioned substrate surface.
3. ornament as claimed in claim 1 is characterized in that, above-mentioned dura mater is made of IVa, the Va of periodictable and nitride, carbide, oxide compound, nitrogen carbide or the nitrogen oxycarbide of VIa family element.
4. ornament as claimed in claim 1 is characterized in that, above-mentioned dura mater is the carbon dura mater.
5. ornament as claimed in claim 4 is characterized in that, between the brinelling laminar surface of above-mentioned carbon dura mater and above-mentioned base material the middle layer is arranged.
6. ornament as claimed in claim 5 is characterized in that, Ti that above-mentioned middle layer is formed by the brinelling laminar surface at above-mentioned base material or Cr lower floor with constitute on Si or Ge upper strata that this time laminar surface forms.
7. ornament as claimed in claim 1 is characterized in that, is formed with at least two kinds of dura maters at the brinelling laminar surface of above-mentioned base material.
8. ornament as claimed in claim 1 is characterized in that, the brinelling laminar surface of above-mentioned base material stacked at least two kinds of dura maters.
9. ornament as claimed in claim 1 is characterized in that, is formed with above-mentioned dura mater in the part of the brinelling laminar surface of above-mentioned base material.
10. ornament as claimed in claim 1 is characterized in that, is formed with the au-alloy film on above-mentioned dura mater.
11. ornament as claimed in claim 10, it is characterized in that above-mentioned au-alloy film is at least a metal and golden alloy that is selected among 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 the Pt.
12. ornament as claimed in claim 1 is characterized in that, above-mentioned ornament is the clock and watch exterior parts.
13. the manufacture method of an ornament, it may further comprise the steps:
Stainless steel substrate is provided,
In 400-500 ℃ substrate surface is carried out carburizing in containing the carburizing atmosphere of carbon monoxide, form the brinelling layer from substrate surface to any degree of depth, carbon atom is solid-solubilized in this brinelling layer, does not have the crystal chromium carbide in formed sosoloid,
On the brinelling laminar surface of base material, form dura mater,
Described brinelling layer has by removing the uneven surface that is formed at its outside surface and grind the minute surface that obtains, and its Vickers' hardness is more than 500,
The surface hardness of described dura mater is greater than the surface hardness of described brinelling layer.
14. the manufacture method of ornament as claimed in claim 13 is characterized in that, above-mentioned ornament is the clock and watch exterior parts.
15. a clock and watch exterior part, it comprises:
Stainless steel substrate,
Brinelling layer from substrate surface to any degree of depth, the carbon solid solution does not have the crystal chromium carbide in the formed sosoloid in this brinelling layer,
It is characterized in that this brinelling layer has by removing the uneven surface that is formed at its outside surface and grinding the minute surface that obtains, its Vickers' hardness is more than 500.
16. a watch bracelet, it comprises interconnected a plurality of Stainless Steel Watch Band joint,
Be formed with the brinelling layer on this watchband joint surface to any degree of depth, the carbon solid solution does not have the crystal chromium carbide in the formed sosoloid in this brinelling layer,
It is characterized in that this brinelling layer has by removing the uneven surface that is formed at its outside surface and grinding the minute surface that obtains, its Vickers' hardness is more than 500.
17. watch bracelet as claimed in claim 16 is characterized in that,
The watchband joint is interconnection by stainless steel adapting piece with the watchband joint,
At least a portion on this web member surface is formed with from the surface brinelling layer of the degree of depth extremely arbitrarily, and the carbon solid solution does not have the crystal chromium carbide in formed sosoloid in this brinelling layer.
18. watch bracelet as claimed in claim 16 is characterized in that, by with web member watchband joint and watchband joint being carried out carburizing treatment to this watchband joint with this web member after interconnection, then this watchband joint surface is ground and obtains.
19. watch bracelet as claimed in claim 18 is characterized in that, also comprises the web member that is not formed with the brinelling layer.
20. method of making watch bracelet, described watch bracelet comprises interconnected a plurality of Stainless Steel Watch Band joint, be formed with the brinelling layer in this watchband joint surface to any degree of depth, the carbon solid solution is in this brinelling layer, there is not the crystal chromium carbide in the formed sosoloid, this brinelling layer has by removing the uneven surface that is formed at its outside surface and grinding the minute surface that obtains, and its Vickers' hardness is more than 500
The method includes the steps of:
After with a plurality of stainless steel adapting pieces a plurality of Stainless Steel Watch Bands joint being connected, under the fluoro-gas atmosphere, this watchband joint is carried out fluoridation with this web member in 400-500 ℃,
Carry out gas cementation in 400-500 ℃ and handle containing under the carburizing gas atmosphere of carbon monoxide then, form from the surface to the brinelling layer of the degree of depth arbitrarily, carbon is solid-solubilized in this brinelling layer, does not have the crystal chromium carbide in formed sosoloid,
Then carry out cleanup acid treatment and washing processing,
Again barreling is carried out on this watchband joint surface, removed the uneven surface that is formed at its outside surface, make it have Vickers' hardness at the minute surface more than 500.
21. the manufacture method of watch bracelet as claimed in claim 20 is characterized in that, barreling is carried out on above-mentioned watchband joint surface after, grind again.
22. the manufacture method of watch bracelet as claimed in claim 20 is characterized in that, before the above-mentioned fluoridation, machine finshing is carried out on the watchband joint surface that connects with above-mentioned web member, obtains having the watch bracelet on machine finshing surface thus.
23. the manufacture method of watch bracelet as claimed in claim 21 is characterized in that, before the above-mentioned fluoridation, machine finshing is carried out on the watchband joint surface that connects with above-mentioned web member, obtains having the watch bracelet on machine finshing surface thus.
24. method of making watch bracelet, described watch bracelet comprises interconnected a plurality of Stainless Steel Watch Band joint, be formed with the brinelling layer in this watchband joint surface to any degree of depth, the carbon solid solution is in this brinelling layer, there is not the crystal chromium carbide in the formed sosoloid, this brinelling layer has by removing the uneven surface that is formed at its outside surface and grinding the minute surface that obtains, and its Vickers' hardness is more than 500
The method includes the steps of: under the fluoro-gas atmosphere, a plurality of Stainless Steel Watch Band joints are carried out fluoridation with a plurality of stainless steel adapting pieces in 250-600 ℃,
In 400-500 ℃ fluorizated watchband joint and web member are carried out gas cementation and handle containing under the carburizing gas atmosphere of carbon monoxide then, the brinelling layer of formation extremely any degree of depth from the surface, carbon atom is solid-solubilized in this brinelling layer, does not have the crystal chromium carbide in formed sosoloid
Then carry out cleanup acid treatment and washing processing,
Again barreling is carried out on this watchband joint surface, is removed the uneven surface that is formed at its outside surface, make it have Vickers' hardness at the minute surface more than 500,
With this web member this watchband is connected at last.
25. the manufacture method of watch bracelet as claimed in claim 24 is characterized in that, barreling is carried out on above-mentioned watchband joint surface after, grind again.
26. the manufacture method of watch bracelet as claimed in claim 24 is characterized in that, before the above-mentioned fluoridation, machine finshing is carried out on above-mentioned a plurality of watchband joints surface, obtains having the watch bracelet on machine finshing surface thus.
27. the manufacture method of watch bracelet as claimed in claim 25 is characterized in that, before the above-mentioned fluoridation, machine finshing is carried out on above-mentioned a plurality of watchband joints surface, obtains having the watch bracelet on machine finshing surface thus.
28. a method of making the clock and watch exterior part, described clock and watch exterior part comprises:
Stainless steel substrate,
Brinelling layer from substrate surface to any degree of depth, the carbon solid solution does not have the crystal chromium carbide in the formed sosoloid in this brinelling layer,
This brinelling layer has by removing the uneven surface that is formed at its outside surface and grind the minute surface that obtains, and its Vickers' hardness is more than 500,
Described method comprises following steps:
Under the fluoro-gas atmosphere in 250-600 ℃ to the stainless steel clock and watch exterior part mother metal that a plurality of parts of stainless steel connect being carried out fluoridation with a plurality of stainless steel adapting pieces,
Carry out gas cementation in 400-500 ℃ and handle containing under the carburizing gas atmosphere of carbon monoxide then, form from the surface to the brinelling layer of the degree of depth arbitrarily, carbon atom is solid-solubilized in this brinelling layer, does not have the crystal chromium carbide in formed sosoloid,
Then carry out cleanup acid treatment and washing processing,
With this mother metal surface barreling, remove the uneven surface that is formed at its outside surface again, make it have Vickers' hardness at the minute surface more than 500.
29. the manufacture method of clock and watch exterior part as claimed in claim 28 is characterized in that, barreling is carried out on above-mentioned mother metal surface after, grind again.
30. the manufacture method of clock and watch exterior part as claimed in claim 28 is characterized in that, before the above-mentioned fluoridation, above-mentioned mother metal is carried out machine finshing, obtains having the clock and watch exterior part on machine finshing surface thus.
31. the manufacture method of clock and watch exterior part as claimed in claim 29 is characterized in that, before the above-mentioned fluoridation, above-mentioned mother metal is carried out machine finshing, obtains having the clock and watch exterior part on machine finshing surface thus.
CNB008019088A 1999-09-07 2000-09-07 Ornament and method for preparation thereof Expired - Fee Related CN100374613C (en)

Applications Claiming Priority (9)

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JP252900/1999 1999-09-07
JP25290099A JP4350225B2 (en) 1999-09-07 1999-09-07 Watch exterior parts and manufacturing method thereof
JP252900/99 1999-09-07
JP319437/1999 1999-11-10
JP319437/99 1999-11-10
JP31943799A JP4463353B2 (en) 1999-11-10 1999-11-10 Watch exterior parts and manufacturing method thereof
JP2000104454A JP4451536B2 (en) 2000-04-06 2000-04-06 Decorative member and manufacturing method thereof
JP104454/00 2000-04-06
JP104454/2000 2000-04-06

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