JPS6231064B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an amorphous alloy that can be expressed as a chromium-carbon alloy Cra″Cb″Yc″ (where a″, b″, and c″ are atomic percentages) and a method for producing the alloy. In conventional common alloys, the constituent elements form a solid solution or a compound and have a certain crystalline structure. Then, it is solidified from that alloying temperature, that is, from the alloyed state, and further processed at an appropriate cooling rate. As a processing method, the alloy is solidified and formed in a casting mold, then deformed, subjected to the required heat treatment, and then used. In addition, the component elements are powdered, mixed uniformly, and then sintered under pressure at an appropriate temperature to be shaped and used. Thus, over a long period of time, a large number of alloys have been invented and are now effectively used in many applications. For these crystalline alloys, there has been a method for manufacturing alloys that have an amorphous structure from the beginning, but it is not easy to manufacture and cannot be mass-produced. It was not possible to put it into practical use for reasons such as insufficient guarantees regarding product quality maintenance. In addition, simply changing an existing crystalline alloy to amorphous (hereinafter also referred to as amorphous) without changing its composition, or using it for the same purpose for which the alloy is conventionally suited, will not be enough. It's meaningless. If the amorphous alloy itself is new and its new properties can be reliably obtained and its properties are suitable for completely new fields of application, it will be put to practical use and new demands will gradually increase and develop. In addition, while the academic foundation for conventional crystalline alloys has been established, there are still many unknown fields regarding amorphous alloys, and the academic foundation will likely advance as the practical application of this field progresses. In general, amorphous alloys can include many combinations of components. Many manufacturing methods are also possible. It is important at present to establish an alloy of the new composition and a method for manufacturing the alloy. Some amorphous alloys are already being put into practical use. For example, they are used as magnetic materials, superconducting materials, catalysts, and hydrogen storage materials by manufacturing them in ribbons, thin wires, powder particles, and other shapes and forming them into appropriate shapes. Most of these are manufactured by melt quenching or vapor deposition. In the melt quenching method, a molten alloy is dropped onto a metal plate, rapidly cooled and solidified, and an amorphized solid is produced by controlling the temperature change of the metal plate and the temperature of the atmosphere to provide a high overall cooling rate. Cooling systems using helium fluid or liquid nitrogen have been developed for this purpose. The vapor deposition method has the disadvantage of slow vapor deposition rate. Compared to crystalline alloys, the amorphous alloys manufactured in this way have higher hardness, but are brittle and difficult to deform during processing, and have drawbacks such as sudden breakage during use and poor corrosion resistance. be. In terms of corrosion resistance, stress corrosion cracking, pitting corrosion,
Alkali or acid embrittlement is likely to occur. It is also prone to fatigue damage. The reason for this is said to be that amorphous alloys have a weak bonding force inside the metal, and it is difficult to make the entire structure uniform, and the natural structure cannot be improved by processing. Thus, although amorphous alloys have properties different from crystalline alloys and are expected to be new and effective in many application fields, their inherent drawbacks and the difficulty of maintaining reliability of their properties However, it has not yet been fully used and put into practical use. In view of the above-mentioned current situation, the present invention is an amorphous amorphous alloy having high hardness and high corrosion resistance.
It is represented by Cra″Cb″Yc″, where Y is silicon, aluminum, phosphorus, germanium, tin, indium,
one additional alloying element arbitrarily selected from the group consisting of antimony, with a″ from 79.5 to 45 and b″ from 20 to
The object of the present invention is to provide an amorphous alloy (hereinafter referred to as Y alloy) in which 50, c'' is 0.5 to 35 atomic percent, and a method for producing the same. Manufactured by agglomerating metals, that is, forming solid alloys directly from gaseous metals on a substrate without going through a molten state.Thus, by forming alloy solids directly from gases, one type of This results in the formation of an amorphous alloy with a disordered atomic arrangement that has uniform bonding strength inside the alloy and does not have the regular atomic arrangement of conventionally known crystalline materials.Next, regarding the present invention Examples will be shown and explained.Table 1 is a typical composition table of the present invention.Second
The table shows the hardness of the composition of the present invention and pure metals, titanium, chromium, iron, and copper for comparison. FIG. 1 is a partially sectional side view showing an embodiment of an apparatus for producing the alloy of the present invention. Second
The figure is a model graph of X-ray diffraction of the alloy shown in Table 1 No. 5 of the present invention. FIG. 3 shows the polarization lines of IN, a representative example of the alloy of the present invention, in hydrochloric acid. Table 3 shows the corrosion rate of IN, a representative example of the alloy of the present invention, in hydrochloric acid at 30°C.

【table】

【table】

[Table] Vickers hardness (Hv) was measured at a minimum of 5 locations and a maximum of 10 locations for each sample whose representative examples are shown in Table 2 of the present invention. All showed uniform hardness. The same was true for samples with other compositions of the present invention. Among them, the hardness of the typical compositions shown in Table 2 is shown. Pure metals Ti, Cr in Table 2,
All of the alloys of the present invention, which exhibited such high hardness compared to Fe and Cu, also had extremely good wear resistance. Furthermore, as shown in Table 3, the hydrochloric acid corrosion resistance was also very good. Typical alloys
The polarization curve (D) shown in Figure 3 for Cr ₄₅ C ₂₀ Si ₃₅ (No. 5 in Table 1) shows almost the same anodic current density as pure Cr(C), and a high current density comparable to that of pure Cr. Shows corrosion resistance. Although not shown, samples with other compositions also showed completely similar curves.

[Table] A method for producing an amorphous amorphous alloy of the present invention will be described using an apparatus, an example of which is shown in a partially cross-sectional side view in FIG. In the apparatus of FIG. 1, a chamber 4 having a space 4A surrounded by a left side wall 2, a right side wall 3 and a peripheral wall 1 of the container can be sealed. Chamber 4 is initially evacuated to 10 ^-8 Torr and filled with a neutral or alloy inert gas such as high purity argon to maintain the pressure at 10 ^-2 Torr. If the pressure is too high, above 10 ^-2 Torr, the substrate temperature will rise, making it impossible to obtain amorphous amorphous, and if the pressure is too low, the precipitation rate will slow, making it unsuitable for practical use. A range of 10 ^-3 to ^{10 -1} Torr is suitable. A coil 8 made of a tungsten filament is mounted on the right side wall 3 of the chamber 4, and a water-cooled stainless steel anode electrode 7 is sealed and supported on the left side wall.
Electricity of approximately 10 V and 40 A is applied to the coil 8 from the power source 9 through the circuits 18, 12 and 14, and plasma is generated within a region 78 shown in the figure by a dotted line. In the chamber 4, one water-cooled target electrode 6 is fixed to the surface layer of the master alloy material supported on the lower peripheral wall 1.
This electrode 6 is provided with the other electrode 5 for cooling the other copper substrate, which is fixed to the surface layer and is supported by the upper peripheral wall 1, which is arranged to face the other copper substrate in the plasma region 78. The surface of the electrode 6 is sputtered to emit alloy composition atoms, and the ions generated in the plasma are
A strong electric field of 2 KV and a maximum of about 300 mA is applied to accelerate the electrode 5 and deposit it on the surface of the copper substrate, thereby producing a deposited amorphous alloy on the surface of the substrate 5. The master alloy material is previously formed into a predetermined shape, for example, a button-shaped disc, by arc melting so as to contain a predetermined composition, and is held on a target holder and sputtered. The target 6 and the copper substrate 5 are water-cooled, and cooling the substrate increases the cooling rate of the alloy and increases the freezing effect. After continuous sputtering for 10 hours, the deposited layer of amorphous amorphous alloy has a diameter of about 40 mm and a thickness of about 50 mm.
It was μm. The crystalline master alloy Cr ₄₅ C ₂₀ Si ₃₅ of the Cr ₄₅ C ₂₀ Si ₃₅ alloy in No. 5 of Table 1 before sputtering exhibits an X-ray diffraction intensity curve B shown by the dotted line in Fig. 2. Amorphous amorphous alloy formed in
Cr ₄₅ C ₂₀ Si ₃₅ exhibits a diffuse X-ray diffraction intensity curve A characteristic of amorphous amorphous. Alloys of the present invention with other compositions, not shown, also exhibit similar X-ray diffraction intensity curves. To confirm that it is an amorphous alloy, create an X-ray diffraction intensity line. Ordinary crystalline alloys usually exhibit diffraction lines with specific angles, whereas amorphous alloys exhibit gradual diffraction patterns. In addition, as shown in Table 2, this alloy has the following properties:
The Vickers hardness is extremely high. Even when compared with pure metals, it is recognized that there is a significant difference. In this way, an amorphous alloy manufactured by sputtering a crystalline alloy in a plasma, emitting it as a gaseous alloy, and forming a deposited layer on a cooling substrate is not limited to the above embodiments. It was confirmed that conclusions can be drawn for all compositions of Y alloys of the present invention. The alloy of the present invention has a large amount of semimetallic elements (boron, aluminum, silicon, carbon, tin, germanium, phosphorus, etc.) that are difficult to form in solid solution in ordinary crystalline alloys, As a result, it has high hardness. In addition, the deposited layer is formed by sputtering in plasma and has good purity and uniformity, and is free of inclusions and inherent dislocations. As a result, the atomic bonding becomes uniform and good,
It does not contain anything that could be a starting point for destruction or a source of corrosion. Therefore, it exhibits high hardness, high strength, high corrosion resistance, and reliability in use. In addition, the shape of the amorphous amorphous alloy formed as a deposited layer on the substrate in the above example is relatively large, and is made by a melt quenching method in which it is quenched by spraying it onto the outer periphery of a widely used copper disk. There are no restrictions on its shape, such as width or thickness, compared to what can be manufactured. The reason why the amorphous amorphous alloy having the exemplary composition of the present invention exhibits high hardness is due to the good bonding and solid solution between the metal and the metalloid. In addition, its corrosion resistance is shown in Figure 3, the polarization curve D of IN in hydrochloric acid.
As shown in comparison with the polarization curve C of pure chromium in the same solution, it exhibits almost the same high corrosion resistance. Table 3 lists 30 of the alloys of the invention with other compositions.
The corrosion rate in HCl in °C is shown. These also showed polarization curves similar to those in FIG. 3, although not shown. As already explained, the present invention utilizes the formula
Cra″Cb″Yc″ (a″ is 79.5~45, b″ is 20~50, c″ is
0.5 to 35 atom%), Y represents a certain group of atoms,
It is an amorphous alloy consisting of a composition having a good internal structure, containing no inclusions or dislocations, and being uniform throughout. As a result of the uniform solid solution of each alloy atom and the good bond between metal and metalloid, it has high hardness, high corrosion resistance, and high strength. In addition, the method of manufacturing an amorphous amorphous alloy of the present invention, in which the alloy is directly solidified from a gas state to form a deposited layer, can form a shape with a relatively large width and thickness, compared to the widely used melt quenching method. Forms an amorphous alloy. The manufacturing method of the present invention involves forming a plasma region in a sealed chamber in a neutral gas such as argon or an inert gas that does not react with the alloy of the present invention, and sputtering an electrode target within the region with a constant composition. This method uses a crystalline alloy and manufactures the amorphous alloy as a deposited layer on opposing cooling copper substrates. Furthermore, according to the present invention, it is possible to form a solid solution with large amounts of elements such as boron, carbon, silicon, phosphorus, aluminum, tin, germanium, indium, and antimony, which cannot be obtained by the melt quenching method. It is also advantageous in that it can be done. The alloy of the present invention produced in this manner has high hardness, high strength, and high corrosion resistance. In addition, the inside is uniform and the interatomic bonding is extremely good, and reliability during use is significantly improved.

[Brief explanation of the drawing]

FIG. 1 is a partially sectional side view illustrating an example of an apparatus for applying the method for producing an amorphous alloy of the present invention.
FIG. 2 shows an example of the composition of the alloy of the present invention.
A comparison diagram of the line diffraction intensity curve and that of a crystalline alloy with the same composition. FIG. 3 shows an exemplary composition alloy of the present invention.
A comparison diagram of the polarization curve D of Cr ₄₅ C ₂₀ Si ₃₅ in hydrochloric acid and that of pure chromium C. 1, 2, 3, 10, 11...peripheral wall, 4...sealed chamber, 4A...space, 5...cooling substrate, 6...target electrode, 7...anode, 78...plasma region, 9... Power supply, 12, 13, 14...circuit.

Claims (1)

[Claims] 1 Represented by the formula Cra″Cb″Yc″, where a″ is 79.5 to 45 atomic percent and b″ is 20 to 50 atomic percent.
c″ is 0.5 to 35 atomic percent, and Y is 1 arbitrarily selected from the element group of silicon, germanium, phosphorus, aluminum, tin, indium, and antimony.
An amorphous amorphous alloy with high hardness and high corrosion resistance characterized by a composition in which additional alloying elements of species are present. 2 In a method for producing an amorphous alloy by forming a plasma region in a sealed chamber filled with a gas that does not react with the alloy to be produced and providing opposing electrodes within the region, A plasma region is provided, a base metal alloy is fixed on the surface of one target electrode within the plasma region, and the surface of the other electrode, which is provided with a cooling substrate, is placed opposite to the electrode, and an electric current is applied to the base metal alloy on the surface of the target electrode. A formula characterized in that a gaseous alloy produced by sputtering is collected and solidified on the cooled substrate surface in the plasma to form an amorphous alloy deposited layer.
Represented by Cra″Cb″Yc″, a″ is 79.5 to 45 atomic percent, b″ is 20 to 50 atomic percent, and c″ is 0.5 to 45 atomic percent.
Amorphous amorphous having high hardness and high corrosion resistance with a composition of 35 atomic percent and Y being one additional alloying element arbitrarily selected from the group of elements silicon, germanium, phosphorus, aluminum, tin, indium, antimony. Alloy manufacturing method.