JP3808354B2 - Toning method for zirconium-based amorphous alloys - Google Patents

Description

表１に示される結果から、Ｚｒ基非晶質合金はＳＵＳ３０４に比べ高耐食性を示すが、酸化処理を行なっても耐食性は劣化しないのが分かる。
【００２９】
次に、Ｚｒ基非晶質合金（Ｚｒ₅₅Ｎｉ₅Ａｌ₁₀Ｃｕ₃₀）について、各種熱処理温度で処理時間を種々変化させて酸化処理したときに形成される膜厚変化を図４に示す。
図４から明らかなように、同一処理温度でも処理時間を変えることによって膜厚、従って表面の色調を制御できることがわかる。
【００３０】
【発明の効果】
以上のように、本発明によれば、Ｚｒ基非晶質合金に熱処理を施し、その表面に形成される皮膜の膜厚を制御することにより、比較的簡単にかつ均一に茶系、グレー系又は黒色系の任意の色調に調色でき、それによって高級感を持ち、意匠性にも優れる非晶質合金製品を提供できる。
また、本発明の方法は熱処理法であるため、簡易な装置を用い、低コストで非晶質合金製成形品の表面に一体的な強固な不動態膜を形成できると同時に調色を行なうことができる。また、熱処理による不動態化法であるため、被処理物を固定していても均一に不動態膜を容易に生成でき、従来の硬質膜のコーティングのように被コーティング物を回転させたりしなくてもよく、処理装置も複雑でなく、簡単な構成とすることができる。さらに、形成される膜は母材と一体的な強固な硬質層であり、コーティング膜のような剥離が問題となることはない。特に酸化処理の場合、大気中で行なえるため、高価な真空装置を必要とせず、より経済的に調色と不動態化を同時に行なうことができる。
【００３１】
本発明の方法を適用して得られるＺｒ基非晶質合金製成形品は、任意の色調に調色できると共に、優れた機械的強度や化学的性質に加えて耐摩耗性に優れるため、様々な分野の部品や製品として適用可能であり、例えばセンサー部品、ダイヤフラム等の機械部品、ゴルフクラブヘッド構成部品（フェース、クラウン、ソール等）などのスポーツ用品分野、化学プラント、髄内釘や歯科部品（義歯等）などの医療生体部品、薬品容器、医療器具部品、時計、腕輪、バックル等の装飾部品、触媒反応層等の化学分野、建築部品、光コネクタ構成部品（キャピラリー、フェルール、スリーブ、Ｖ溝基板等）などの光学部品などの部品や製品として適している。
【図面の簡単な説明】
【図１】Ｚｒ基非晶質合金（Ｚｒ₅₅Ｎｉ₅Ａｌ₁₀Ｃｕ₃₀）のＴＴＴ曲線と熱処理条件を示すグラフである。
【図２】Ｚｒ基非晶質合金（Ｚｒ₅₅Ｎｉ₅Ａｌ₁₀Ｃｕ₃₀）のＴＴＴ曲線と好ましい熱処理条件を示すグラフである。
【図３】Ｚｒ基非晶質合金（Ｚｒ₅₅Ｎｉ₅Ａｌ₁₀Ｃｕ₃₀）を図２の符号Ａで示す条件で熱処理したときに得られた皮膜のＸ線回折図である。
【図４】Ｚｒ基非晶質合金（Ｚｒ₅₅Ｎｉ₅Ａｌ₁₀Ｃｕ₃₀）を種々の条件で熱処理したときの熱処理条件と膜厚の関係を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for toning a zirconium-based amorphous alloy to brown, gray or black. The method of the present invention is applied to various amorphous alloy molded articles, for example, sports parts such as sensor parts, mechanical parts such as diaphragms, golf club head components (faces, crowns, soles, etc.), chemical plants, intramedullary nails. And medical parts such as dental parts (dentures, etc.), chemical containers, medical equipment parts, watches, bracelets, buckles and other decorative parts, catalytic reaction layers and other chemical fields, building parts, optical connector components (capillaries, ferrules, The present invention can be applied to a surface treatment that performs toning at the same time as a passivation treatment is performed on the surface of a component such as an optical component such as a sleeve or a V-groove substrate) or a product.
[0002]
[Prior art]
In many cases, a molded product made of a metal material is unnecessary or easy to process, compared to a ceramic molded product. Among metal materials, amorphous alloys (metal glasses) reproduce the shape and dimensions of the mold very faithfully, both by mold casting from molten metal and by molding by viscous flow using the glass transition region. Further, there is an advantage that a highly accurate molded product can be manufactured at a low cost without performing subsequent processing. In addition, since amorphous alloys are excellent in mechanical strength and chemical properties, they are applied to various parts and products. For example, Japanese Patent Application Laid-Open No. 10-186176 and Japanese Patent Application Laid-Open No. 10-311923 are made of amorphous alloys. Japanese Patent Application Laid-Open No. 11-104281 discloses a golf club head in which at least a face portion is made of an amorphous alloy, such as ferrules, capillaries, and sleeves.
[0003]
An amorphous alloy having an amorphous structure is known to have high corrosion resistance because it has no crystal grain boundaries. Utilizing the high corrosion resistance of this amorphous alloy, it can be applied to various products. For example, Japanese Patent Laid-Open No. 52-84461 has proposed that a watch metal band is made of an amorphous metal, and Japanese Patent Laid-Open No. 54-122614, etc. It has been proposed to use amorphous metal for watch exterior parts such as lids, battery covers, crowns, switch buttons, and rotating bezels. In addition, stainless steel and Ti alloy having high corrosion resistance are widely used for watches, medical bio parts, and the like, and it can be expected that an amorphous alloy is applied to such applications.
[0004]
[Problems to be solved by the invention]
As described above, there are a wide variety of fields in which amorphous alloys can be applied. However, the color tone of the amorphous alloy is determined by its composition, so it cannot meet the current diverse demands such as not only corrosion resistance and mechanical properties, but also a high-class feeling and excellent design. Is the current situation.
For this reason, it is conceivable to coat a decorative film of various colors, but the simple characteristic of the amorphous alloy, which is high corrosion resistance, is diminished. In addition, there are applications where it is inappropriate to coat a normal film such as a medical biopart, a chemical container, a medical instrument part, and an optical connector component.
[0005]
Therefore, the basic object of the present invention is to provide a method for toning the tea, gray or black color relatively easily and uniformly while maintaining the excellent characteristics inherent in the zirconium-based amorphous alloy. Therefore, it is to provide an amorphous alloy product that has a high-class feeling and is excellent in design, to meet the current various demands.
Furthermore, the object of the present invention is to passivate only the surface portion of a molded article without changing the amorphous structure of the base material and without changing the dimensions at a lower processing cost than the conventional surface hardening method. An object of the present invention is to provide a method capable of adjusting the color to brown, gray or black.
[0006]
[Means for Solving the Problems]
In order to achieve the above object, according to the present invention, the film thickness of a film formed on the surface of a zirconium-based amorphous alloy containing an amorphous phase having a volume ratio of at least 50% by performing heat treatment is reduced. In the L ^* a ^* b ^* color system (CIE 1976) (JIS Z8729), L ^* <35, −20 <a ^* <20, −20 <b ^* <20, and the film thickness is 0.00 . 1-8 μm black system, 35 ≦ L ^* ≦ 70, −20 <a ^* <20, −20 <b ^* <20 and the film thickness exceeds 8 μm (gray system), or 35 ≦ L ^* , -20 <a ^* <20, 20 ≦ b ^* , and a toning method for a zirconium-based amorphous alloy, characterized in that the toning is performed for a tea system having a film thickness of less than 0.1 μm. The
[0007]
Preferably, the heat treatment is performed in an air atmosphere to form a film containing an alloy element oxide, particularly a tetragonal zirconia film, preferably a partially stabilized zirconia film in which other constituent elements of the alloy are dissolved. In another aspect, the heat treatment is performed in an atmosphere containing oxygen or / and nitrogen or in an air atmosphere, and the film formed on the surface of the zirconium-based amorphous alloy is a film containing an oxide or nitride of an alloy element. There is formed a film whose content continuously decreases in the depth direction from the surface portion.
[0008]
In a more specific and preferred embodiment, the heat treatment is performed at a temperature equal to or higher than the minimum temperature of the oxidation reaction or nitridation reaction of at least one constituent element of the base material itself, particularly Zr, and more preferably, the heat treatment is performed as (1) treatment. 350 ° C.-treatment time 10 minutes, (2) treatment temperature 350 ° C.-treatment time 120 minutes, (3) treatment temperature 420 ° C.-treatment time 120 minutes, (4) treatment temperature 450 ° C.-treatment time 10 minutes (1 ) To (4).
Particularly preferably, a black film having a film thickness of 0.1 to 8 μm is formed by the heat treatment.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The present inventor can adjust the color tone of the brown, gray or black color to any color tone by controlling the film thickness of the film formed on the surface of the Zr-based amorphous alloy by heat treatment. The headline and the present invention have been completed.
Here, the relationship between the film thickness and the color tone will be described. When the film to be formed is a tetragonal zirconia film, the film is brown when the film thickness is less than 0.1 μm, and black when it is 0.1 to 8 μm. If it exceeds 8 μm, it will be gray.
[0010]
This film thickness can be controlled by heat treatment conditions such as heat treatment temperature and treatment time. When the heat treatment temperature is increased, the film formation rate is increased, so that a high-temperature treatment can form a thick film in a short time. However, since it is necessary to perform heat treatment at the temperature and time in the amorphous region of the isothermal transformation curve (TTT curve) of the material to be used, the maximum processing time at each processing temperature is determined from the TTT curve of the material.
In general, the relationship between the film thickness and the heat treatment conditions is as follows.
Tea system (<0.1 μm): heat treatment temperature of 400 ° C. or less and heat treatment time of 10 minutes or less,
Black type (0.1 to 8 μm): heat treatment time of 10 ° C. or more at a heat treatment temperature of 400 ° C. or less, heat treatment time of 2 hours or less at a heat treatment temperature of 400 ° C. or more,
Gray system (> 8 μm): heat treatment temperature of 400 ° C. or more, heat treatment time of 2 hours or more, less than maximum time of TTT curve range.
[0011]
The preferred embodiment of the heat treatment method of the present invention will be described. An amorphous alloy molded article is heat-treated in an atmosphere containing oxygen (or nitrogen) at a temperature and time within an amorphous region of the TTT curve of the material. A passive film (ceramic hard layer) having a desired film thickness (color tone) is formed on the surface of the molded product. As described above, an arbitrary color tone of brown, gray or black can be obtained according to the film thickness at this time, but basically an atmosphere containing oxygen since it is a heat treatment method of a Zr-based amorphous alloy. When heat treatment is performed below, a tetragonal zirconia film or a partially stabilized zirconia film in which other constituent elements are dissolved is formed.
[0012]
Further, since the method of the present invention is a heat treatment method of a Zr-based amorphous alloy, a simple passive device can be used to produce a strong passive film integrated with the surface of the base material at a low cost. Simultaneously with the toning, surface hardening is performed, and the corrosion resistance and wear resistance are further improved. In addition, because it is a heat treatment, a uniform passive film can be easily generated even if the workpiece is fixed, and it is not necessary to rotate the coating as in the case of conventional hard film coating. The apparatus is not complicated and can be configured simply. Usually, peeling of a film is a major problem in the coating of a hard film, but in the method of the present invention, oxides or nitrides are generated by ceramization of at least one constituent element of the base material itself, for example, oxidation reaction or nitridation reaction In addition, in order to form a ceramic-based hard film having an inclined structure in which the generation ratio of these ceramic fine particles, and hence the content ratio in the base material, is higher on the surface in contact with the processing atmosphere and gradually decreases in the depth direction. It is an integral and strong hard layer, and peeling such as a coating film does not cause a problem, and surface roughness and size change hardly occur. In particular, in the case of oxidation treatment, since it can be performed in the atmosphere, an expensive vacuum apparatus is not required and it can be said to be a more economical method. Also, the processing operation can be performed more easily than the conventional steel oxidation and nitriding techniques.
[0013]
As the reactive gas used in the toning method of the Zr-based amorphous alloy according to the present invention, oxygen, air, nitrogen, ammonia or the like is used. Oxygen and nitrogen are concentrations that cause oxidation and nitriding, and can be used as an atmosphere containing 1 ppm or more of each, for example, an inert gas atmosphere such as Ar or a vacuum atmosphere. It is also possible to mix and H ₂ in order to accelerate the reaction. When air is used, the surface of the amorphous alloy molded article can be easily oxidized by heat treatment in the atmosphere. The heat treatment is performed at a temperature and time at which at least one constituent element of the base metal itself, in particular, Zr oxidation reaction or nitridation reaction occurs, and the base metal itself does not crystallize, that is, an isothermal transformation curve (TTT) of the material. Curve) in the amorphous region. The thickness (depth) and structural gradient of the passive film formed on the alloy surface change by changing the temperature and time of the heat treatment, but also by changing the concentration (partial pressure) of the reactive gas, A ceramic hard layer having a structure gradient can be formed by increasing the content of the ceramic component continuously or stepwise toward the surface. Even when such a passive film is formed, the surface roughness and size change hardly occur.
[0014]
The Zr-based amorphous alloy to which the present invention is applied may be a part or product made of a substantially amorphous alloy containing an amorphous phase with a volume ratio of 50% or more, and a specific material It is not limited to those. For example, various conventionally known Zr-based amorphous materials such as amorphous alloys described in JP-A-10-186176, JP-A-10-311923, JP-A-11-104281, JP-A-11-189855, etc. Alloys can be used. More preferably, it can be suitably applied to an amorphous alloy molded product having a composition represented by the following general formula (1).
[0015]
Formula ^{_{(1): Zr a M 1}} b Ln c M 2 d M 3 e M 4 f
Where M ¹ is at least one element selected from the group consisting of Ni, Cu, Fe, Co, Mn, Nb, Ti, V, Cr, Zn, Al, and Ga, and Ln is Y, La, Ce, Nd, At least one element selected from the group consisting of Sm, Gd, Tb, Dy, Ho, Yb, and Mm (Misch metal, which is an aggregate of rare earth elements), M ² is composed of Be, B, C, N, and O At least one element selected from the group, M ³ is at least one element selected from the group consisting of Ta, W and Mo, and M ⁴ is at least one element selected from the group consisting of Au, Pt, Pd and Ag The elements a, b, c, d, e and f are atomic%, 25 ≦ a ≦ 85, 15 ≦ b ≦ 75, 0 ≦ c ≦ 30, 0 ≦ d ≦ 30, 0 ≦ e ≦ 15, 0 ≦ f ≦ 15.
[0016]
The amorphous alloy includes amorphous alloys represented by the following general formulas (1-a) to (1-p).
Formula (1-a): Zr _a M ¹ _b
In this amorphous alloy, the M ¹ element coexists with Zr, so the mixing enthalpy is negative and large, and the amorphous forming ability is good.
Formula (1-b): Zr _a M ¹ _b Ln _c
Like this amorphous alloy, the thermal stability of amorphous is improved by adding a rare earth element to the alloy of the general formula (1-a).
[0017]
General formula (1-c): Zr _a M ¹ _b M ² _d
Formula (1-d): Zr _a M ¹ _b Ln _c M ² _d
Like these amorphous alloys, filling the gaps in the amorphous structure with the element M ² (Be, B, C, N, O) having a small atomic radius stabilizes the structure and improves the amorphous forming ability. To do.
[0018]
Formula (1-e): Zr _a M ¹ _b M ³ _e
Formula (1-f): Zr _a M ¹ _b Ln _c M ³ _e
General formula (1-g): Zr _a M ¹ _b M ² _d M ³ _e
Formula (1-h): Zr _a M ¹ _b Ln _c M ² _d M ³ _e
When these refractory metals M ³ (Ta, W, Mo) are added like these amorphous alloys, heat resistance and corrosion resistance are improved without affecting the amorphous forming ability.
[0019]
Formula (1-i): Zr _a M ¹ _b M ⁴ _f
Formula (1-j): Zr _a M ¹ _b Ln _c M ⁴ _f
Formula (1-k): Zr _a M ¹ _b M ² _d M ⁴ _f
General formula (1-l): Zr _a M ¹ _b Ln _c M ² _d M ⁴ _f
Formula (1-m): Zr _a M ¹ _b M ³ _e M ⁴ _f
Formula (1-n): Zr _a M ¹ _b Ln _c M ³ _e M ⁴ _f
Formula (1-o): Zr _a M ¹ _b M ² _d M ³ _e M ⁴ _f
Formula (1-p): Zr _a M ¹ _b Ln _c M ² _d M ³ _e M ⁴ _f
In the case of an amorphous alloy containing these noble metals M ⁴ (Au, Pt, Pd, Ag), it does not become brittle even if crystallization occurs.
[0020]
Among the amorphous alloys described above, a Zr-TM-Al-based (TM: transition metal) amorphous alloy having a very wide temperature difference between the glass transition temperature (Tg) and the crystallization temperature (Tx) has high strength and high strength. In addition to being corrosion resistant, the supercooled liquid region (glass transition region) ΔTx = Tx−Tg is extremely wide as 60 K or more, and in this temperature region, very good workability is exhibited even at low stress of several tens of MPa or less due to viscous flow. In addition, the amorphous bulk material can be obtained even by a casting method with a cooling rate of about several tens of K / s. These alloys can form amorphous materials both at the same time by casting from a molten metal and by forming by viscous flow using a glass transition region, and at the same time reproduce the mold shape and dimensions very faithfully.
[0021]
These Zr-TM-Al-based amorphous alloys used in the present invention have a very large ΔTx range, although they vary depending on the alloy composition and measurement method. For example, ΔTx of Zr ₆₀ Al ₁₅ Co _2.5 Ni _7.5 Cu ₁₅ alloy (Tg: 652K, Tx: 768K) is as extremely wide as 116K. The hardness is 460 (DPN) in Vickers hardness (Hv) from room temperature to around Tg, the tensile strength reaches 1,600 MPa, and the bending strength reaches 3,000 MPa. The thermal expansion coefficient α is as small as 1 × 10 ⁻⁵ / K from room temperature to around Tg, the Young's modulus is 91 GPa, and the elastic limit during compression exceeds 4 to 5%. Further, the toughness is high, and the Charpy impact value is 60 to 70 kJ / m ² . As described above, when the glass transition region is heated while exhibiting very high strength characteristics, the flow stress is reduced to about 10 MPa. For this reason, it is extremely easy to process, and it is a feature of this alloy that it can be formed into a minute part having a complicated shape and a high precision part with low stress. In addition, because of the properties of so-called glass (amorphous), the processed (deformed) surface is extremely smooth, and there is virtually no occurrence of a step where a slip band appears on the surface like when a crystalline alloy is deformed. have.
[0022]
In general, when an amorphous alloy is heated to the glass transition region, crystallization starts by holding for a long time. However, an alloy having a wide ΔTx like this alloy has a stable amorphous phase, and the temperature in ΔTx is appropriately set. If selected, crystals are not generated for up to about 2 hours, and there is no need to worry about crystallization in a normal molding process.
In addition, this alloy exhibits this characteristic even when solidified from the molten metal. In general, rapid cooling is required for the production of an amorphous alloy, but this alloy can easily obtain a bulk material composed of an amorphous single phase from a molten metal by cooling at a cooling rate of about 10 K / s. The solidified surface is still very smooth, and has a transfer property that faithfully reproduces even micron-order polishing scratches on the mold surface.
Therefore, if this alloy is applied as a casting material, if the mold surface has surface quality that satisfies the required characteristics of the molded product, molding that satisfies the predetermined shape, dimensional accuracy, and surface quality by the mold casting method. The product can be manufactured with high productivity by a single process, and the steps of dimension adjustment and surface roughness adjustment can be omitted or shortened.
[0023]
【Example】
In the following, some examples for specifically confirming the effects of the present invention will be shown, but the present invention is not limited to the following examples.
FIG. 1 shows an example of a heat treatment condition according to the present invention for a Zr-based amorphous alloy (Zr ₅₅ Ni ₅ Al ₁₀ Cu ₃₀ ). Since the TTT curve of this alloy is as shown in FIG. 1, the conditions of the amorphous regions (1) and (2) in the figure (however, 180 ° C. or higher (generally referred to as Zr oxidation minimum temperature), 1 minute or longer) ), The amorphous alloy surface can be easily oxidized. In the case of nitriding, since the reaction temperature of Zr and N is 400 ° C. or higher, processing is performed in the region (2) in FIG.
[0024]
By performing the heat treatment under such conditions, a strong passive film (ceramic hard layer) having high wear resistance is formed on the amorphous alloy surface. At this time, since the oxides and nitrides with low formation free energy of the elements constituting the amorphous alloy change preferentially, the composition of the passive film corresponds to that. In the case of the Zr-based amorphous alloy, a ceramic hard layer containing an oxide mainly composed of ZrO ₂ is formed on the surface of the Zr-based amorphous alloy (base material) by heat treatment in the atmosphere, and The content ratio of the oxide is inclined so as to gradually decrease in the depth direction from the surface.
[0025]
Further, the Knoop hardness of the surface is increased by the heat treatment, and the Knoop hardness is increased as the processing temperature is increased, and the wear resistance is improved. Further, the Knoop hardness increases as the treatment time increases even at the same heat treatment temperature. However, if the heat treatment is performed for an excessively long time, the layer thickness will be thick and the wear resistance will be excellent, but the surface roughness will deteriorate rapidly, so that the molded product will require a surface roughness on the order of submicrons. Is difficult to apply.
Therefore, the preferable processing temperature and processing time for effectively performing the toning and surface hardening of the Zr-based amorphous alloy are the regions surrounded by hatching in FIG. 2, that is, (1) processing temperature 350 ° C.-processing. 10 minutes, (2) treatment temperature 350 ° C.—treatment time 120 minutes, (3) treatment temperature 420 ° C.—treatment time 120 minutes, (4) treatment temperature 450 ° C.—treatment time 10 minutes (1) to (4) It is within the range surrounded by.
[0026]
FIG. 3 shows X-ray diffraction data of a Zr-based amorphous alloy (Zr ₅₅ Ni ₅ Al ₁₀ Cu ₃₀ ) oxidized under the conditions indicated by symbol A in FIG.
From the X-ray diffraction diagram shown in FIG. 3, it can be seen that there is a peak based on tetragonal zirconia. This is because the composition of the treatment film is preferentially changed (oxidized) when the formation energy of the element constituting the Zr-based amorphous alloy is low, so that zirconia forms a rich gradient film. is there.
[0027]
Zirconia has a low-temperature type (monoclinic system) and a high-temperature type (tetragonal system), and phase transitions around 1000 ° C. Monoclinic zirconia is weak and unstable even at low temperatures (about 100 ° C.). Therefore, in optical connector parts such as ferrules, partially stabilized zirconia (tetragonal system) having high strength is used by adding several percent of an additive such as yttria to zirconia. In the case of the oxidation treatment of the Zr-based amorphous alloy, from FIG. 3, other constituent elements are dissolved in zirconia, and a stable partially stabilized zirconia (tetragonal ZrO ₂ ) film is formed on the surface. I understand that. Moreover, it became black different from the conventional metal color by producing | generating a thick film | membrane on the surface.
[0028]
In FIG. 2, a Zr-based amorphous alloy (Zr ₅₅ Ni ₅ Al ₁₀ Cu ₃₀ ) oxidized under the conditions indicated by symbol A, an untreated Zr-based amorphous alloy, and SUS304 are each contained in 1 N hydrochloric acid. Table 1 shows the corrosion rate when immersed in the substrate.
[Table 1]

From the results shown in Table 1, it can be seen that the Zr-based amorphous alloy exhibits higher corrosion resistance than SUS304, but the corrosion resistance is not deteriorated even when oxidation treatment is performed.
[0029]
Next, FIG. 4 shows changes in film thickness formed when the Zr-based amorphous alloy (Zr ₅₅ Ni ₅ Al ₁₀ Cu ₃₀ ) is oxidized by variously changing the treatment time at various heat treatment temperatures.
As is apparent from FIG. 4, it can be seen that the film thickness and hence the color tone of the surface can be controlled by changing the processing time even at the same processing temperature.
[0030]
【The invention's effect】
As described above, according to the present invention, the heat treatment is performed on the Zr-based amorphous alloy, and the film thickness of the film formed on the surface is controlled, so that the tea system and the gray system can be relatively easily and uniformly performed. Alternatively, it is possible to provide an amorphous alloy product that can be adjusted to an arbitrary color tone of black color, thereby having a high-class feeling and excellent in design.
In addition, since the method of the present invention is a heat treatment method, a simple apparatus can be used to form a strong solid passive film on the surface of an amorphous alloy molded product at a low cost, and at the same time to perform color matching. Can do. In addition, since it is a passivation method by heat treatment, even if the workpiece is fixed, it is possible to easily generate a uniform passive film without rotating the coating like conventional hard film coating. In addition, the processing apparatus is not complicated and can have a simple configuration. Furthermore, the film to be formed is a strong hard layer integrated with the base material, and peeling like a coating film does not cause a problem. In particular, in the case of oxidation treatment, since it can be performed in the atmosphere, an expensive vacuum apparatus is not required, and toning and passivation can be simultaneously performed more economically.
[0031]
The Zr-based amorphous alloy molded product obtained by applying the method of the present invention can be adjusted to an arbitrary color tone and has excellent mechanical strength and chemical properties, as well as excellent wear resistance. It can be applied as parts and products in various fields, for example, sports parts such as sensor parts, mechanical parts such as diaphragms, golf club head components (faces, crowns, soles, etc.), chemical plants, intramedullary nails and dental parts. Biomedical parts such as dentures, chemical containers, medical instrument parts, watches, bracelets, buckles and other decorative parts, catalytic reaction layer and other chemical fields, building parts, optical connector components (capillaries, ferrules, sleeves, V Suitable as parts and products such as optical parts such as groove substrates).
[Brief description of the drawings]
FIG. 1 is a graph showing a TTT curve and heat treatment conditions of a Zr-based amorphous alloy (Zr ₅₅ Ni ₅ Al ₁₀ Cu ₃₀ ).
FIG. 2 is a graph showing a TTT curve of Zr-based amorphous alloy (Zr ₅₅ Ni ₅ Al ₁₀ Cu ₃₀ ) and preferable heat treatment conditions.
3 is an X-ray diffraction pattern of a film obtained when a Zr-based amorphous alloy (Zr ₅₅ Ni ₅ Al ₁₀ Cu ₃₀ ) is heat-treated under the conditions indicated by symbol A in FIG.
FIG. 4 is a graph showing the relationship between heat treatment conditions and film thickness when a Zr-based amorphous alloy (Zr ₅₅ Ni ₅ Al ₁₀ Cu ₃₀ ) is heat-treated under various conditions.

Claims (9)

A heat treatment is applied to a zirconium-based amorphous alloy containing an amorphous phase with a volume ratio of at least 50% to control the film thickness of the film formed on the surface, and the L ^* a ^* b ^* color system (CIE) 1976) (JIS Z8729), L ^* <35, −20 <a ^* <20, −20 <b ^* <20, and a film thickness of 0.1 to 8 μm, a black system, 35 ≦ L ^* ≦ 70, -20 <a ^* <20, −20 <b ^* <20, and a gray system having a film thickness exceeding 8 μm, or 35 ≦ L ^* , −20 <a ^* <20, 20 ≦ b ^* , and A method for toning a zirconium-based amorphous alloy, characterized in that the color is adjusted to a brown system having a film thickness of less than 0.1 μm .   The toning method according to claim 1, wherein the heat treatment is performed in an air atmosphere.   The toning method according to claim 1 or 2, wherein the film formed on the surface of the zirconium-based amorphous alloy is a film containing an oxide of an alloy element.   The toning method according to any one of claims 1 to 3, wherein the coating film formed on the surface of the zirconium-based amorphous alloy is a tetragonal zirconia film.   The toning method according to claim 4, wherein the tetragonal zirconia film is a partially stabilized zirconia film in which other constituent elements of the alloy are dissolved.   The film formed on the surface of the zirconium-based amorphous alloy is a film containing an oxide or nitride of an alloy element, and the content ratio is continuously reduced from the surface portion in the depth direction. The toning method according to claim 1. The heat treatment includes (1) treatment temperature 350 ° C.—treatment time 10 minutes, (2) treatment temperature 350 ° C.—treatment time 120 minutes, (3) treatment temperature 420 ° C.—treatment time 120 minutes, and (4) treatment temperature 450 ° C. The toning method according to any one of claims 1 to 6 , wherein the toning method is performed within a range surrounded by (1) to (4) of a processing time of 10 minutes. By the heat treatment method toning according to any one of claims 1 to 7, characterized in that to form a black coating of a thickness 0.1～8Myuemu. The zirconium-based amorphous alloy is a sensor component, a mechanical component, a golf club head component, a medical biocomponent, a chemical container, a medical instrument component, a decorative component, a catalytic reaction layer, a building component, or an optical component. The toning method according to any one of claims 1 to 8 .

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