JPH0420976B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is an amorphous amorphous alloy with the formula
It can be expressed as TiaBbYc, where a, b, and c are atomic percent, and Y is one arbitrarily selected from the element group of carbon, aluminum, tin, indium, and antimony.
Amorphous alloys comprising additional alloying elements of species. Conventional conventional alloys have a certain crystalline structure in which the constituent elements form a solid solution or a semimetallic compound. In this interior, the semimetal and metal are well dissolved in solid solution, and the bonding between internal atoms is good. In addition, the material is shaped by casting, etc., and the alloyed melt is solidified and then molded in the necessary steps, and subjected to appropriate heat treatment, etc., and then put into practical use. Alternatively, the component elements constituting the composition may be mixed in the form of powder, sintered, and molded for practical use. In this way, conventional crystalline alloys have been manufactured and utilized based on empirical and learned academic principles, improving their quality and increasing their stability and reliability. On the other hand, it has been confirmed that amorphous alloys can be used in specific fields because of their unique qualities, and some of them are in practical use, albeit in small quantities. Now, research and practical development are proceeding with great expectations, and many new academic proposals are being made. Most of the amorphous alloys thus provided are manufactured by the melt quenching method. Amorphous alloys are produced by spraying a molten alloy of a certain composition onto the outer circumferential wall of a cooled rotating disk and allowing it to reach room temperature without rapidly solidifying and forming crystals. In addition to water cooling, the rotating disk is cooled using liquid helium or nitrogen, and the atmosphere is also cooled. It is known that the amorphous alloy thus obtained has high hardness. However, it has shortcomings in strength and corrosion resistance, and even if some parts show good test results in terms of mechanical strength and corrosion resistance, they are used as parts with the expectation of long-term use, and then suddenly break. There are drawbacks such as: It also has the drawbacks of stress corrosion cracking, pitting corrosion, and acid embrittlement. It also has the disadvantage of poor fatigue strength. These drawbacks also appear in crystalline alloys, but in the case of amorphous alloys, the concepts that can be applied to crystalline alloys cannot be applied as they are, so it can be said that there are extremely large unknowns and inexperienced problems. Amorphous amorphous alloys have been recognized for their electrical and magnetic properties.
Although it has come to be put into practical use in this field, it is still treated as something special. The reason why it is not possible to mass produce large products is due to the above-mentioned drawbacks. Although it has such drawbacks, the cause is
It is said that this is due to the fact that the inside of the alloy is not uniform, for example, the solid solution between the metal and the metalloid is not sufficient, and the bonding force between atoms is uneven and weak. Efforts are required to investigate and develop these issues, but from the perspective of industrial applicability, it is possible to actually provide an amorphous alloy that eliminates these drawbacks and has high hardness and high corrosion resistance as a product. If so, it would be extremely meaningful and the practical field would be expanded. In view of the above-mentioned current situation, the present invention is an amorphous alloy having high hardness and high corrosion resistance, and a method for producing the alloy. The purpose is to solidify it and provide it. That is, the composition of the amorphous alloy is based on titanium and boron expressed by the formula TiaBbYc (referred to as B alloy). a, b, c are atomic percent, 50a<70, 15b35, 0.5c35, 30
<b+c50, Y is carbon, aluminum,
It is one additional element arbitrarily selected from the group of elements tin, indium, and antimony. These alloys are placed in one plasma region, with the alloy base material serving as one electrode and the copper cooling substrate provided opposite this electrode serving as the other electrode, and the atmosphere between the two electrodes being neutral or alloy-free. It is sputtered in an inert gas that does not react with the metal and released as a gaseous alloy.
energizing the alloy base material with plasma on the substrate,
It was manufactured by a method of depositing and forming an alloy layer. The alloy produced in this way is amorphous, has high hardness, high corrosion resistance, has a uniform structure throughout, has sufficient interatomic bonding strength, and has no inclusions or dislocations that can become a starting point for fracture or corrosion. You'll get quality products that you won't find anywhere else. Moreover, compared to those produced by the melt quenching method, products with larger shapes and widths can be obtained. And there are very few restrictions on the shape. Next, the present invention will be described with reference to some examples. FIG. 1 is a partially sectional plan view of an example of an apparatus used for producing the amorphous alloy of the present invention. Figure 2 is an X-ray diffraction intensity diagram of the alloy of the present invention with a Ti ₅₀ B ₁₅ C ₃₅ composition, and Figure 3 is an X-ray diffraction intensity diagram of an alloy with a Ti ₆₀ B ₂₀ C ₂₀ composition of 1N HCl, 1N H ₂ SO ₄ , 1N _FIG. 4 is a polarization curve diagram of pure titanium in the liquid for comparison.

【table】

[Table] (Note) 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, Table 2 shows the hardness of typical compositions. All of the materials exhibiting such high hardness also had extremely good wear resistance. Also, the third
As shown in the table, the hydrochloric acid corrosion resistance was also very good. Part 3 is about the most representative ones.
The polarization curve is shown in the figure, but other compositions are also available.
Although not shown, a similar curve was shown.

[Table] (Note 1) From these series of test results, it was confirmed that the following alloy composition is suitable. That is, for alloy B, a, b, and c are atomic percent, and 50a<70, 15b35, 0.5
c35, 30<b+c50. (Note 2) Compared to the corrosion rate of crystalline alloys, the third
As shown in the table, the orders are significantly different. The alloys of the invention are very significantly better. (The above is the explanation of the table.) Table 1 shows some examples of practical compositions of the amorphous alloy of the present invention. The Bitkers hardness of the obtained amorphous alloy is shown in Table 2. Table 3 shows the corrosion rates of typical compositions of the alloys of the present invention in 1N hydrochloric acid at 30°C. A method for producing the composition alloy of the present invention shown in these tables will be explained using the apparatus illustrated in FIG. A sealed chamber 4 having a space 4A surrounded by a left wall 2A, a right wall 2B, and a cylindrical or polyhedral peripheral wall 1 discharges internal air through parts 11C and 11D for exhaust to reduce pressure. Can be sealed. Space 4A of chamber 4 is first reduced in pressure to about 10 ^-8 Torr, and then filled with high purity argon to maintain a pressure of about 10 ^-2 Torr. If the pressure is increased to more than 10 ^-2 Torr, the substrate temperature will rise and amorphous amorphous cannot be obtained, and if the pressure is lowered too much, the precipitation rate will be slow, making it unsuitable for practical use. A range of 10 ^-3 to ^{10 -1} Torr is suitable. Instead of argon, the gas may be filled with another neutral or inert gas that does not react with the alloy composition elements. Outer ends 11 of electrodes 5, 6, 7
A, 11B, and 11E are cooling fluid (mainly water) lead-in/out ports. Now, in FIG. 1, the anode electrode 7 attached to the left wall 2A of the chamber 4 is passed through the circuit 1 through the right wall 2B.
Coil 8 made of tungsten wire connected with 7.
Seal and package. The anode 7 has a stainless steel electrode plate, and its cooling part 11E and the electrode plate 7
It is cooled by passing water through a circulation hole (not shown) provided inside connected to the inside. The coil 8 is supplied with a voltage of about 10V and a current of 40A from the power supply 3 via the circuit 17.
energize. A maximum voltage of 100V is applied to the anode electrode 7 through the circuit 13A. Plasma is generated within a region 78 surrounded by a dotted line in the figure. In this plasma region, one target electrode 6 to which a surface layer 16 made of a master alloy material is fixed, and the other electrode 5 having a steel cooling substrate 15 provided opposite to this electrode 6 as a surface layer are provided. The master alloy material is melted into a predetermined shape by arc melting so that it contains a predetermined composition.
For example, it is formed into a button-shaped disc and is held on a target holder and sputtered. Electrode 6
is cooled by passing water from the cooling part 11B provided at the outer end to an internal circulation hole (not shown). The electrode 5 cools the substrate 15 and the electrode 5 by passing fluid from a cooling section 11A provided at the outer end to an internal circulation hole (not shown). The electrodes 5 and 6 are fixedly supported on the peripheral wall 1 of the chamber 4. A circuit 12 is passed through the electrode 5, connected to the cathode of a DC power source, and a voltage with a maximum voltage of 500 V is applied.A circuit 14 is passed through the electrode 6, connected to the anode of the DC power source, and a maximum voltage of about 300 mA and a voltage of 1 to 500 V is applied. A 2KV DC current is applied and a strong voltage electric field is applied to sputter and release the alloy components from the mother alloy material 16 of the target electrode 6, and the ions generated in the plasma are energized and accelerated by the strong electric field. The emitted atoms of the target electrode surface base material 16 are deposited on the polar surface of the cooling substrate 15 of the counter electrode 5, and an deposited alloy layer is gradually deposited.
On the cooling substrate 15, the amorphous alloy layer is directly solidified from the gas without going through a melt. The size of the mother alloy material 16, the size of the substrate 15,
By varying the cooling of electrode 5, the intensity of the plasma, the intensity of the voltage and current applied to electrodes 5 and 6, etc., the formation rate and size of the deposited alloy can be adjusted. A Ti ₅₀ B ₁₅ C ₃₅ composition was used as the master alloy material, and the amorphous alloy layer obtained by continuous sputtering for about 10 hours had a diameter of about 40 mm and a thickness of about 50 μm. Ti ₅₀ B ₁₅ C ₃₅ shown in Table 2 has a significantly higher Vickers hardness of 1677 than pure metal, which is 6.5 times higher than pure titanium. Figure 2 shows the results of X-ray diffraction of the master alloy material of Ti ₅₀ B ₁₅ C ₃₅ composition before sputtering and the sputter deposited alloy. Sputter alloy exhibits a diffuse X-ray diffraction intensity curve characteristic of an amorphous structure.
Alloys of the present invention with other compositions (not shown) exhibit similar X-ray diffraction intensity curves. The Vickers hardness of this alloy is shown in Table 2, and the reason for this high hardness is that the solid solution dispersion of metallic and semimetallic substances in the alloy extends throughout the interior. uniform,
This is thought to be due to the extremely good bonding force between atoms, no inclusions, and no dislocations. moreover
Regarding the corrosion resistance of alloys with Ti ₆₀ B ₂₀ C ₂₀ composition, 1N
The polarization curves in HCl, 1N H ₂ SO ₄ and 1N HNO ₃ are shown in FIG. Table 3 shows the corrosion rates of the alloys of the present invention having other compositions in 1N hydrochloric acid at 30°C.
These also showed polarization curves similar to those in FIG. 3, although not shown. For comparison, the polarization curve of pure titanium was
As shown in the figure. It was clearly confirmed that the amorphous alloy with this composition has high corrosion resistance comparable to pure titanium in any acid. Furthermore, the amorphous alloy deposited on the steel substrate of the electrode 5 having a composition of Ti ₅₀ B ₁₅ C ₃₅ was analyzed using an X-ray microanalyzer (XMA device) and found to be well adhered, with no internal defects. It was confirmed that the concentration of alloying elements was uniform throughout. As already explained, the amorphous amorphous alloy of the present invention is sputtered from one electrode with the master alloy material as the surface layer in a plasma generation region in a reduced pressure neutral or inert atmosphere that does not react with alloying elements.
It can be produced by coagulating and adhering it onto a cooled steel substrate on the surface of the other counter electrode, and directly solidifying and depositing it from a gas without going through a melt. In addition, alloys with compositions that are difficult to produce using the melt quenching method can be produced, and their sizes are also relatively large. The alloy of the composition of the present invention produced in this way has strong interatomic bonds throughout, a uniform solid solution of metals and semimetals, no internal defects, high acid resistance, and high hardness. An alloy with the formula TiaBbYc (B alloy) (where a, b, and c are atomic percentages and Y is an additional alloying element) can be manufactured, and alloys with these compositions are those manufactured by the melt quenching method. In comparison, it has a very uniform and good internal structure, so unlike amorphous alloys produced by melt quenching, it does not suddenly break during use or cause stress corrosion cracking. It can also be recognized that it has high hardness and high corrosion resistance, as well as high wear resistance. The amorphous amorphous alloy of the present invention having these properties is useful and practical in many fields, such as being used for various containers, container linings, nozzles, dies, etc., and future development is expected.

[Brief explanation of drawings]

FIG. 1 is a partially sectional plan view of an embodiment of the apparatus used for manufacturing the amorphous alloy of the present invention. Second
The figure is an X-ray diffraction intensity curve diagram of the alloy of Ti ₅₀ B ₁₅ C ₃₅ composition of the present invention. Figure 3 is a polarization curve diagram showing the corrosion resistance of an alloy with a Ti ₆₀ B ₂₀ C ₂₀ composition. Figure 4 is a polarization curve diagram of pure titanium in the same liquid. 1... Peripheral wall, 2A, 2B... Wall, 3... Power supply,
4... Sealed chamber, 4A... Indoor space, 5, 6... Both electrodes facing each other, 15... Substrate to be cooled, 16...
Master alloy material, 7... Anode electrode, 8... Tungsten wire coil, 10A, 10B... Electrode support, 11A, 11B, 11E... Cooling fluid inlet/outlet part, 11C, 11D... Exhaust part, 12, 13
A, 13B, 14, 17...Circuit, 78...Plasma generation region.

Claims (1)

[Claims] 1 Represented by the formula TiaBbYc, where a, b, and c are atomic percentages, 50a<70, 15b35, 0.5
Highly corrosion-resistant amorphous amorphous, characterized by a composition based on titanium and boron, where c35, 30 < b + c50, and Y is one additional alloying element arbitrarily selected from the group of elements carbon, aluminum, tin, indium, antimony. alloy.