WO2012121023A1 - 装飾部品用材料 - Google Patents
装飾部品用材料 Download PDFInfo
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- WO2012121023A1 WO2012121023A1 PCT/JP2012/054453 JP2012054453W WO2012121023A1 WO 2012121023 A1 WO2012121023 A1 WO 2012121023A1 JP 2012054453 W JP2012054453 W JP 2012054453W WO 2012121023 A1 WO2012121023 A1 WO 2012121023A1
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- WIPO (PCT)
- Prior art keywords
- carbide
- sintered body
- decorative part
- mass
- additive
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F3/15—Hot isostatic pressing
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
Definitions
- the present invention relates to a decorative part material suitable for a case of a watch or a case for an exterior of various electronic devices.
- the present invention relates to a decorative part material including a sintered body having a silver metallic color tone.
- stainless steel is likely to be scratched by scratches due to contact with hard materials.
- the cemented carbide has a larger specific gravity than a metal material such as stainless steel, and the product becomes heavy.
- plating also has sufficient characteristics against scratches and wear, the constituent elements of the plating react and elute due to sweat, which may cause metal allergy.
- Patent Documents 1 to 6 have been proposed as countermeasures for these problems.
- Patent Documents 1 to 3 all exhibit a golden color tone. However, the design of gold is constrained by the product design, and a silver metallic tone is desired.
- Patent Document 4 discloses a silver sintered alloy having titanium carbide as a main hard phase.
- titanium carbide is easily discolored by corrosion and has poor sinterability, and defects such as voids are likely to occur in the obtained sintered structure.
- Watches and jewelry parts are often required to have a beautiful glossy finish with a mirror-finished surface, so that materials that are prone to tissue defects still have problems as materials for mirror finishing.
- Patent Document 5 discloses a sintered alloy whose main hard phase is a hard phase of titanium nitride and titanium carbide. This sintered alloy has a color tone that combines silver and purple to pink. This color tone changes in color depending on the mixed state of the two components of the hard phase, and is not high-quality.
- Patent Document 6 discloses a fishing line guiding and watch decorative part using titanium carbonitride as a main hard phase. However, this part has a silvery reddish color and restricts the product design.
- the present invention has been made in view of the above circumstances, and one of its purposes is to provide a lightweight decorative part material having a silver metallic color tone.
- Another object of the present invention is to provide a decorative part material suitable for mirror surface processing with few defects in the tissue.
- Another object of the present invention is to provide a decorative part material that is non-magnetic and excellent in corrosion resistance.
- the material for decorative parts of the present invention includes a main hard phase formed with a solid solution composed of titanium carbonitride and titanium carbide, a main binder phase composed of nickel, and a group consisting of molybdenum carbide, niobium carbide, tungsten carbide, and tantalum carbide.
- a sintered body comprising at least one selected first additive and a second additive made of at least one of chromium and chromium carbide, the balance being made of inevitable impurities is provided.
- the amount of N in the sintered body is 2.0 to 6.0% by mass.
- the color tone of this sintered body is a value of L * a * b * color system obtained by a spectrocolorimeter and satisfies the following values.
- the material for decorative parts having a silver metallic color tone can be obtained.
- it can be used as a high-grade decorative part material having a fine metallic structure with little nest and segregation of binder phase and a beautiful blackish-brown silver metallic luster.
- the specific gravity of the sintered body is 5.5 to 7.5.
- This configuration is lighter than stainless steel with a specific gravity of about 7.7 to 8.0, and can contribute to weight reduction of products obtained from this material.
- One form of the decorative part material of the present invention is that the sintered body is non-magnetic.
- the decorative part material of the present invention it is possible to include 10% by mass to 15% by mass of nickel as the main binder phase and 8.0% by mass to 15.0% by mass of the first additive.
- the porosity of the sintered body is A-2 class or higher as defined in ANSI / ASTM B276-54.
- a sintered body having few structural defects such as voids can be obtained, and a decorative part material suitable for mirror finishing can be obtained.
- a lightweight decorative part material having a silver metallic color tone can be obtained.
- tissue photograph of sample No. 6 in a test example. It is a structure
- This material includes a sintered body including a main hard phase, a main binder phase, a first additive, and a second additive. Each component will be described in detail below.
- the main hard phase is a component that occupies 60% by mass or more of the sintered body, and is a component that contributes mainly to ensuring the hardness of the decorative part material.
- the main hard phase is composed of a solid solution formed from titanium carbonitride and titanium carbide. Titanium carbonitride has a metallic glossy brown or grey-gold color tone, a black color of titanium carbide, a silver color of nickel as the first additive, etc. be able to.
- Titanium carbonitride in the main hard phase also contributes to controlling the amount of N in the sintered body.
- the content of titanium carbide in the main hard phase is preferably 20 to 50% by mass.
- the reason why the lower limit is set to 20% by mass is that it is easy to obtain a color tone of silver metallic rather than gold.
- the upper limit is set to 50% by mass because titanium carbide is easily ignited in a high-temperature atmosphere and has low sinterability. If it is excessively contained, it tends to cause structural defects such as nests.
- the content of titanium carbide in the main hard phase is preferably 30 to 50% by mass.
- the average particle size of this main hard phase is preferably 3 ⁇ m or less, more preferably 1 ⁇ m or less.
- Such a sintered structure of a fine hard phase is suitable as a material to be mirror-finished with high hardness, excellent scratch resistance, few structure defects.
- the main binder phase functions as a binder that bonds the main hard phase, particularly titanium carbonitride and other additive crystals.
- Nickel is used for the main binder phase.
- Nickel, together with the second additive material such as chromium, has a function as a binder, and also acts to increase the corrosion resistance of the decorative part material and make it non-magnetic.
- the preferable content of nickel in the decorative part material is 7 to 15% by mass.
- the lower limit By setting the lower limit to 7% by mass, the main hard phase can be appropriately bonded, and a dense decorative part material with appropriate toughness can be obtained.
- the upper limit By setting the upper limit to 15% by mass, a decrease in the hardness of the decorative part material can be suppressed.
- a more preferable nickel content is 10 to 15% by mass.
- the total content of the main binder phase, the first additive described later, and the second additive is less than 40% by mass. Within that range, the content of the main binder phase and the first additive may be the same.
- the first additive has a function as a color tone adjusting material in addition to a function as a reinforcing phase of the decorative part material.
- the first additive at least one carbide selected from the group consisting of molybdenum carbide, niobium carbide, tungsten carbide, and tantalum carbide is used.
- These carbides usually do not dissolve in titanium nitride, and exist together with titanium carbide as a peripheral structure of titanium nitride, etc., and a part of them decomposes into a metal component and carbon to dissolve in nickel. .
- carbon atoms are taken into the nickel metal crystal, the melting point of nickel as the main binder phase is lowered, the sintering temperature can be lowered, and the wettability between titanium carbide and nickel is improved. Accordingly, a sintered body with improved sinterability and few tissue defects such as nests can be obtained.
- the first additive acts to suppress the grain growth of the main hard phase, the crystal grain boundary increases, and the light incident on the surface of the sintered body is reflected by the specular reflection by the crystals constituting the surface and the crystal grains. Strongly affected by diffuse reflection by the field. As a result, among the values of the L * a * b * color system, it mainly contributes to increasing the brightness index L * .
- the function of the first additive as a grain growth inhibitor contributes to the refinement of the structure of the sintered body, and thus contributes to a sintered body with high hardness and denseness and with few structure defects. To do.
- the preferable content of the first additive is 8 to 15% by mass.
- the functions as the reinforcing phase and the color tone adjusting material can be appropriately exhibited.
- the upper limit By setting the upper limit to 15% by mass, the sintered body can be reduced in weight.
- At least one of chromium and chromium carbide is used.
- at least a part of chromium has a function as a binder phase together with nickel as metallic chromium, and suppresses elution of nickel and contributes to improving corrosion resistance.
- Chromium has a lower specific gravity than nickel and contributes to reducing the weight of the sintered body.
- at least a part of chromium carbide also decomposes into chromium and carbon during sintering, and the chromium dissolves in the binder phase nickel, thereby suppressing nickel elution and contributing to improving corrosion resistance.
- chromium carbide has a lower specific gravity than chromium and contributes to weight reduction of the sintered body.
- the content of at least one of chromium and chromium carbide is preferably 2 to 5% by mass.
- the content of at least one of chromium and chromium carbide is preferably 2 to 5% by mass.
- the corrosion resistance can be improved.
- the upper limit to 5% by mass, it is possible to obtain a silver metallic color tone having a fine structure, in particular, a blackish glossy metallic color tone.
- N amount The amount of N in the sintered body is 2.0 to 6.0 mass%. By this N amount regulation, it is easy to obtain a beautiful glossy surface of black metallic silver, and to maintain corrosion resistance. This N amount can be measured by an oxygen / nitrogen analyzer.
- Inevitable impurities include silicon, phosphorus, sulfur, manganese, iron and the like, which may affect the color tone of the sintered body surface. Therefore, it is preferable that each is 1 mass% or less.
- L * a * b * color system values As for the color tone of the surface of the sintered body constituting the decorative part material, the value of L * a * b * color system obtained by the spectrocolorimeter satisfies the following numerical values.
- a * indicates an index from red to green. When a positive value is increased, a red tone is indicated. Conversely, when a negative value is increased, a green tone is indicated.
- b * indicates a yellow to blue color tone. When a positive value is increased, a yellow color tone is indicated. Conversely, when a negative value is increased, a blue color tone is indicated.
- a material for decorative parts having a silver metallic color tone can be obtained.
- it can be used as a decorative part material having a black metallic color.
- each value of a * and b * is preferably a negative value.
- the specific gravity of the sintered body is preferably 5.5 to 7.5.
- Such specific gravity is significantly lighter than cemented carbide. In particular, it is preferably 6.0 or less. If the specific gravity is 6.0 or less, it is lighter than stainless steel.
- the magnetic properties of the decorative part material are preferably non-magnetic.
- a watch case or the like is made of this material, a precision instrument such as a movement is accommodated in the case, so that the operation accuracy is not affected as much as possible.
- the non-magnetic sintered body can be realized, for example, by containing a predetermined amount of the above-described nickel, chromium, and chromium carbide.
- the decorative part material preferably has a Vickers hardness (Hv) of 8 GPa or more. This is for obtaining sufficient scratch resistance against scratches and the like. In particular, it is more preferable to have a hardness of 12 GPa or more, and further 15 GPa or more.
- the bending strength of the decorative part material is preferably 1.2 GPa or more in order to realize sufficient toughness of the part obtained from this material. In particular, it is more preferable to have a bending strength of 1.5 GPa or more, and further 2.0 GPa or more.
- the surface roughness of the decorative part material preferably satisfies 0.05 to 0.25 ⁇ m in terms of arithmetic average height (Ra). If such a mirror surface is provided, high-quality gloss can be obtained as various decorative parts. Such a mirror surface can be realized by lapping using a lapping machine.
- the material for decorative parts of the present invention can be suitably used for decorative parts for jewelry, decorative parts for watches, decorative parts for mobile devices, decorative parts for building materials, decorative parts for living parts, and the like.
- decorative parts for jewelry include rings, brooches, necklaces, earrings, tie pins, tie tacks, buttons, bracelets, and pendants.
- decorative parts for a watch include a watch case and a band piece.
- decorative parts for mobile devices mobile communication devices / terminals (cell phones, PHS, broadcast receivers, etc.) or portable information devices / terminals (cameras, portable AV devices, computers, portable computers, PDAs, electronic dictionaries, etc.) Examples include operation buttons such as number keys and various input keys of a portable device, a case, and a frame-like component that fixes a display.
- Examples of the decorative parts for building materials include tiles that decorate floors, walls, and ceilings, and door handles.
- decorative parts for daily use include decorative parts for kitchen parts such as spoons and forks.
- the decorative part material can be manufactured, for example, through the steps of raw material preparation ⁇ mixing of raw materials ⁇ molding ⁇ binder removal ⁇ sintering. Each step will be described in more detail.
- raw material powders of a main hard phase, a main binder phase, a first additive, and a second additive are prepared.
- the average particle diameter of the raw material powder for the main hard phase is preferably about 1 to 5 ⁇ m.
- the average particle diameter of the raw powder for the main binder phase (nickel) is preferably about 1 to 5 ⁇ m.
- the average particle diameter of the raw material powder of the first additive (carbide) is preferably about 3 to 8 ⁇ m.
- the average particle diameter of the raw material powder of the second additive (at least one of chromium and chromium carbide) is preferably about 3 to 8 ⁇ m.
- Each raw material powder mentioned above is mixed as uniformly as possible by an appropriate mixing means such as a ball mill.
- the raw material powder is mixed and pulverized with an organic solvent such as ethanol or methanol.
- a binder is added to the mixed raw material powder, and it is granulated by spray drying using a drying means such as a spray dryer.
- the binder include paraffin wax and polyethylene glycol.
- the content of the binder is preferably about 2 to 4% by mass with respect to the total of the raw material powder and the binder.
- the molding is performed by filling the mold with the raw material powder that has undergone the above mixing step and molding it into a predetermined shape with a predetermined pressure.
- the molding method include a dry pressure molding method, a cold isostatic pressing method, an injection molding method, and an extrusion molding method.
- the pressure during molding is preferably about 10 to 15 MPa.
- the shape of a molded object selects the appropriate shape which does not become an excessively complicated shape according to the shape of the components calculated
- the final part shape may be appropriately machined after sintering, if necessary.
- the molded body is heated to remove the binder.
- This heat treatment is preferably performed at a temperature at which the binder can be vaporized, for example, about 500 ° C. to 600 ° C.
- the atmosphere at that time is preferably an inert gas atmosphere such as nitrogen.
- the molded body after the binder removal is heated and held at a predetermined temperature to produce a sintered body.
- the sintering temperature is preferably about 1200 to 1800 ° C, particularly about 1300 to 1600 ° C. If it is such temperature, heat sintering will become enough and a sintered compact with a high relative density will be obtained.
- the holding time at the heating temperature is practically about 1 to 2 hours.
- the atmosphere during heating is preferably an inert gas such as nitrogen or argon or a vacuum (about 0.1 to 0.5 Pa). After this sintering, a further dense sintered body can be obtained by applying HIP (hot isostatic pressing).
- Example 1 Several samples including examples of the present invention were prepared and evaluated. First, after blending the raw material powders in the proportions shown in Table 1, ethanol is added as an organic solvent and mixed and ground for 15 hours using a ball mill. Next, paraffin wax is added as a binder and spray-dried using a spray dryer to obtain a mixed powder. The obtained powder is compressed into a predetermined shape by compressing at 12 MPa by a dry pressure molding method. Subsequently, the binder is removed at 600 ° C. in a nitrogen atmosphere. Thereafter, it was machined as necessary, and further fired in a vacuum of 0.5 Pa at 1420 ° C. for 1 hour. Furthermore, a sintered body having a relative density of 95% or more was obtained by subjecting the obtained fired body to a high-temperature and high-pressure HIP treatment at 1380 ° C.
- the magnetism was evaluated by measuring the saturation magnetic quantity.
- the color tone is based on JIS Z 8722-2000 using a spectrocolorimeter (CM-3700d manufactured by Konica Minolta Holdings), the light source is CIE standard light source D65, the viewing angle is set to 10 °, The color tone was measured.
- the mirror surface state was evaluated based on whether the void level in the 200 ⁇ field of view of the metal microscope and the porosity defined by ANSI / ASTM B276-54 were above A-2 class. In the mirror surface state, if there is a segregation of a nest or a binder phase such as nickel or cobalt in the structure of the sintered body, it appears as a dent on the surface.
- the void level “0” per 1 cm 2 of the unit area is indicated as “ ⁇ ”, and “1” or “3” as “ ⁇ ”.
- the amount of N was measured with an oxygen / nitrogen analyzer manufactured by LECO.
- Sample Nos. 4-6 and Nos. 10-12 are non-magnetic materials having a specific gravity of 6.0 or less, a bending strength of 1.6 GPa or more and a Vickers hardness of 15.0 GPa or more, and 0.35 ⁇ g
- the amount of Ni dissolution was less than / cm 2 , and the color was black metallic silver.
- the mirror surface state had few voids, and the porosity defined by ANSI / ASTM was A-2 class or higher.
- samples No.5, No.6, No.11, No.12 with a TiC ratio of 30% to 50% by mass in the main hard phase have a high bending strength and a significant amount of Ni elution. It was low.
- the structure of sample No. 6 is seen, it can be seen that the structure is very fine as shown in FIG.
- Samples Nos. 4 to 6 and Samples Nos. 10 to 12 are different samples in that the material of the second additive is metal chromium or chromium carbide, but substantially the same composition (for example, sample No. 4 and sample No. 4). Comparing the samples No. 10 etc.), it can be seen that the same alloy properties, alloy nest level and color tone are obtained.
- Sample No. 1 in which the main hard phase is composed only of TiC has an insufficient mirror surface state. This is thought to be due to the low sinterability.
- Sample No. 2 whose main hard phase is composed only of TiCN has a golden color tone and cannot obtain a silver metallic color tone.
- sample No. 3 with a small TiCN content did not provide a sufficient mirror surface state.
- this invention is not limited to the above-mentioned embodiment at all, and can be suitably changed within the range which does not deviate from the summary of this invention.
- the decorative part material of the present invention can be suitably used for decorative parts for jewelry, decorative parts for watches, decorative parts for portable devices, decorative parts for building materials, religious crafts, decorative parts for living parts, and the like.
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Abstract
Description
L*=9~14
a*=-2~3
b*=-6~0
この材料は、主硬質相、主結合相、第一添加材、及び第二添加材を含む焼結体を備える。各構成要素を以下に詳しく説明する。
主硬質相は、焼結体の60質量%以上を占める成分であり、主に装飾部品用材料の硬度の確保に寄与する成分である。この主硬質相は、炭窒化チタン及び炭化チタンから形成された固溶体で構成される。炭窒化チタンの金属光沢のある茶褐色又は灰金色系の色調、炭化チタンの黒色、第一添加材であるニッケルの銀色などとのバランスにより、シルバーメタリック、特に、黒味を帯びたシルバーメタリックの色調を呈することができる。
主結合相は、主硬質相、特に炭窒化チタンや他の添加材の結晶を結合する結合材としての機能を持つ。この主結合相には、ニッケルを用いる。ニッケルは、第二添加材のクロムなどと共に、結合材としての機能を持つ他、装飾部品用材料の耐食性を高め、非磁性とすることに作用する。
第一添加材は、装飾部品用材料の強化相としての機能に加え、色調調整材としての機能を備える。この第一添加材には、炭化モリブデン、炭化ニオブ、炭化タングステン、及び炭化タンタルよりなる群から選択される少なくとも1種の炭化物が利用される。
第二添加材には、クロム及び炭化クロムの少なくとも一方が用いられる。そのうち、クロムの少なくとも一部は、金属クロムとしてニッケルと共に結合相としての機能を有すると共に、ニッケルの溶出を抑制し、耐食性を向上させることに寄与する。また、クロムはニッケルに比べると比重が小さく、焼結体を軽量化することにも寄与する。一方、炭化クロムの少なくとも一部も、焼結中にクロムと炭素に分解して、そのクロムが結合相であるニッケル中に溶け込むことでニッケルの溶出を抑制し、耐食性を向上させることに寄与する。さらに炭化クロムはクロムに比べても比重が小さく、焼結体の軽量化にも寄与する。
焼結体中のN量は、2.0~6.0質量%とする。このN量の規定により、黒みを帯びたシルバーメタリックの美しい光沢面を得やすく、かつ耐食性を維持し易い。このN量は、酸素・窒素分析装置により測定することができる。
不可避不純物としては珪素,リン,イオウ,マンガン,鉄等が挙げられるが、これらは焼結体表面の色調に影響を及ぼす虞がある。よって、各々1質量%以下であることが好適である。
装飾部品用材料を構成する焼結体の表面の色調は、分光測色計にて得られるL*a*b*表色系の値が、次の数値を満たす。
L*=9~14
a*=-2~3
b*=-6~0
L*は色の明度(L*=0は黒、L*=100は白の拡散色)を示し、この値が高いほど輝きを感じる。a*は赤~緑の指標を示し、正の値が大きくなると赤い色調を示し、逆に負の値が大きくなると緑色の色調を示す。b*は黄~青の色調を示し、正の値が大きくなると黄色い色調を示し、逆に負の値が大きくなると青色の色調を示す。
一般に、装飾部品用材料は軽い方が好まれる。よって、焼結体の比重が5.5~7.5であることが好ましい。このような比重であれば、超硬合金より大幅に軽量である。特に、6.0以下であることが好適である。比重が6.0以下であれば、ステンレスよりも軽量である。
装飾部品用材料の磁気特性は、非磁性であることが好ましい。この材料で時計のケースなどを構成する場合、ケース内部にムーブメントなどの精密機器が収納されるため、その動作精度に極力影響を及ぼさないようにするためである。非磁性の焼結体は、例えば、上述したニッケルとクロム及び炭化クロムの少なくとも一方を所定量含有することで実現できる。
装飾部品用材料の硬度は、ビッカース硬度(Hv)で8GPa以上であることが好ましい。スクラッチなどに対して十分な耐傷性を得るためである。特に、12GPa以上、さらには15GPa以上の硬度を備えることが一層好ましい。
装飾部品用材料の抗折力は、この材料から得られた部品の十分な靭性を実現するため、1.2GPa以上であることが好ましい。特に、1.5GPa以上、さらには2.0GPa以上の抗折力を備えることが一層好ましい。
装飾部品用材料の表面粗さは、算術平均高さ(Ra)で0.05μm~0.25μmを満たすことが好ましい。このような鏡面を備えていれば、各種装飾部品として高級感のある光沢を得ることができる。このような鏡面は、ラップ盤を用いたラップ加工などにより実現できる。
本発明の装飾部品用材料は、装身具用装飾部品,時計用装飾部品,携帯機器用装飾部品,建材用装飾部品,生活部品用装飾部品等に好適に利用できる。装身具用装飾部品としては、リング,ブローチ,ネックレス,イヤリング,ネクタイピン,タイタック,ボタン,ブレスレット,ペンダントなどが挙げられる。時計用装飾部品としては、腕時計用ケース,バンド駒などが挙げられる。携帯機器用装飾部品としては、携帯通信機器・端末(携帯電話,PHS,および放送受信機等)または携帯情報機器・端末(カメラ,ポータブルAV機器,計算機,ポータブルコンピュータ,PDAおよび電子辞書等)である携帯機器のナンバーキー,各種入力キー等の操作ボタン,ケース,ディスプレイを固定する枠状部品等が挙げられる。建材用装飾部品としては、床,壁,天井を飾るタイルあるいはドアの取手等が挙げられる。生活部品用装飾部品としては、スプーン,フォーク等のキッチン部品用装飾部品などが挙げられる。
上記の装飾部品用材料は、例えば、原料の準備→原料の混合→成形→脱バインダ→焼結の各工程を経て製造することができる。各工程をより詳しく説明する。
原料の準備工程では、主硬質相、主結合相、第一添加材、第二添加材の各原料粉末を用意する。主硬質相の原料粉末の平均粒径は1~5μm程度が好ましい。主結合相(ニッケル)の原料粉末の平均粒径は1~5μm程度が好ましい。第一添加材(炭化物)の原料粉末の平均粒径は3~8μm程度が好ましい。第二添加材(クロム及び炭化クロムの少なくとも一方)の原料粉末の平均粒径は3~8μm程度が好ましい。このような平均粒径であれば、粉末として適度に扱いやすく、次述する混合が比較的容易にできる上、焼結後に微細な組織を形成し易い。
上述した各原料粉末は、ボールミルなどの適宜な混合手段でできるだけ均一に混合する。通常は、原料粉末にエタノール、メタノールなどの有機溶媒を合わせて混合・粉砕する。続いて、この混合の原料粉末にバインダを加え、スプレードライヤーなどの乾燥手段を用いて噴霧乾燥して造粒する。バインダとしては、パラフィンワックスやポリエチレングリコールなどが挙げられる。このバインダの含有量は、上記原料粉末とバインダの合計に対して、2~4質量%程度が好ましい。
成形は、上記混合工程を経た原料粉末を金型に充填し、所定の圧力で所定の形状に成形する。成形方法としては、乾式加圧成形法、冷間静水圧成形法、射出成形法、押出成形法などが挙げられる。この成形時の圧力は、10~15MPa程度が好ましい。また、成形体の形状は、求められる部品の形状に応じて、過度に複雑形状とならないような適宜な形状を選択する。最終的な部品形状へは、必要に応じて、焼結後に適宜な機械加工を行えばよい。
脱バインダ工程では、成形体を加熱して、バインダを除去する。この熱処理は、バインダを気化できる程度の温度、例えば500℃~600℃程度で行うことが好ましい。その際の雰囲気は、窒素などの不活性ガス雰囲気とすることが好適である。
焼結工程では、脱バインダ後の成形体を所定の温度に加熱・保持して、焼結体を作製する。焼結温度は、1200~1800℃、特に1300~1600℃程度が好ましい。このような温度であれば、加熱焼結が十分になり、相対密度の高い焼結体が得られる。加熱温度での保持時間は、1時間~2時間程度が実用的である。加熱時の雰囲気は、窒素,アルゴンなどの不活性ガス又は真空(0.1~0.5Pa程度)とすることが好ましい。この焼結後、さらにHIP(熱間静水圧プレス)を施すことで、さらに緻密な焼結体が得られる。
本発明の実施例を含む幾つかの試料を作製して、それら試料の評価を行った。まず、表1に示す割合で原料粉末を配合した後、有機溶媒としてエタノールを加え、ボールミルを用いて15時間混合粉砕する。次に、バインダとしてパラフィンワックスを添加し、スプレードライヤーを用いて噴霧乾燥して、混合粉末とする。得られた粉末を乾式加圧成形法により12MPaで圧縮して所定の形状に成形する。続いて、窒素雰囲気で600℃にて脱バインダを行う。その後、必要に応じて機械加工を施し、さらに0.5Paの真空中で1420℃にて1時間保持して焼成した。さらに、得られた焼成体を1380℃にて高温高圧のHIP処理を施すことで相対密度95%以上の焼結体を得た。
Claims (5)
- 炭窒化チタン及び炭化チタンから形成された固溶体からなる主硬質相と、
ニッケルからなる主結合相と、
炭化モリブデン、炭化ニオブ、炭化タングステン、及び炭化タンタルよりなる群から選択される少なくとも1種の第一添加材と、
クロム及び炭化クロムの少なくとも一方からなる第二添加材とを含み、
残部が不可避的不純物からなる焼結体を備え、
この焼結体中のN量が2.0~6.0質量%であり、
この焼結体の色調は、分光測色計にて得られるL*a*b*表色系の値で、
L*=9~14、
a*=-2~3、
b*=-6~0
であることを特徴とする装飾部品用材料。 - 前記焼結体の比重が5.5~7.5であることを特徴とする請求項1に記載の装飾部品用材料。
- 前記焼結体が非磁性であることを特徴とする請求項1又は2に記載の装飾部品用材料。
- 前記主結合相であるニッケルを10質量%以上15質量%以下、
前記第一添加材を8.0質量%以上15.0質量%以下含有することを特徴とする請求項1~3のいずれか1項に記載の装飾部品用材料。 - 前記焼結体の有孔度が、ANSI/ASTM B276-54にて規定されるA-2クラス以上であることを特徴とする請求項1~4のいずれか1項に記載の装飾部品用材料。
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CA2801479A CA2801479C (en) | 2011-03-07 | 2012-02-23 | Material for decorative parts |
EP12755004.4A EP2568055B1 (en) | 2011-03-07 | 2012-02-23 | Material for decorative part |
US13/702,776 US8992657B2 (en) | 2011-03-07 | 2012-02-23 | Material for decorative parts |
JP2012528981A JP5864421B2 (ja) | 2011-03-07 | 2012-02-23 | 装飾部品用材料 |
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EP (1) | EP2568055B1 (ja) |
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WO2014112314A1 (ja) * | 2013-01-16 | 2014-07-24 | 並木精密宝石株式会社 | 装飾部材 |
JP5900638B2 (ja) * | 2012-10-02 | 2016-04-06 | 株式会社タンガロイ | サーメット工具 |
WO2016114394A1 (ja) * | 2015-01-16 | 2016-07-21 | 京セラ株式会社 | サーメット製装飾部品 |
WO2016136894A1 (ja) * | 2015-02-26 | 2016-09-01 | 京セラ株式会社 | サーメット製装飾部材ならびにこれを用いてなる時計、携帯端末機および装身具 |
WO2019151317A1 (ja) * | 2018-01-30 | 2019-08-08 | 京セラ株式会社 | 装飾部品 |
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WO2015183990A2 (en) * | 2014-05-27 | 2015-12-03 | Frederick Goldman, Inc. | Titanium-based alloys and articles formed from such alloys |
AT14387U1 (de) * | 2014-12-05 | 2015-10-15 | Ceratizit Luxembourg S R L | Kugelförmiges Verschleissteil |
CN109778044A (zh) * | 2019-01-29 | 2019-05-21 | 广汉鸿达硬质合金有限责任公司 | 一种装饰品彩色合金材料 |
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JPWO2019151317A1 (ja) * | 2018-01-30 | 2021-01-14 | 京セラ株式会社 | 装飾部品 |
JP7036840B2 (ja) | 2018-01-30 | 2022-03-15 | 京セラ株式会社 | 装飾部品 |
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EP2568055A4 (en) | 2014-09-03 |
CA2801479A1 (en) | 2012-09-13 |
CA2801479C (en) | 2015-07-07 |
EP2568055A1 (en) | 2013-03-13 |
JP5864421B2 (ja) | 2016-02-17 |
JPWO2012121023A1 (ja) | 2014-07-17 |
US8992657B2 (en) | 2015-03-31 |
US20130087019A1 (en) | 2013-04-11 |
EP2568055B1 (en) | 2016-11-02 |
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