JPS601372B2 - Method for producing amorphous alloy with excellent strength and corrosion resistance - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an amorphous alloy with excellent corrosion resistance.

Recently, fiber-reinforced or laminated composite materials have been progressing,
There is a strong demand for the fibers and foils used as such materials to be of high quality and inexpensive. Metals are generally excellent materials in terms of strength and malleability, but forming them into fibers or foils requires many steps and requires a large amount of manufacturing cost.

For example, metal whisker crystals are ideal fiber materials with high strength, but they are expensive because they are produced through chemical reactions and phase changes such as precipitation from solutions, reduction, and vapor condensation.
It is also difficult to mass produce. In addition, metal pongee wire, such as piano wire, is extremely expensive because it requires repeated processes of wire drawing and interpolation. The same applies to metal foil. Therefore, methods of directly producing metal fibers and metal foils from molten metal have been studied as an inexpensive means of producing these materials.

However, metal fibers and foils produced by conventional methods have been extremely inadequate in terms of strength and ductility. However, recently, an alloy of iron or nickel containing more than 10% of phosphorus and a few percent of carbon or even a few percent of chromium has been rapidly solidified by spraying it from a molten state onto a metal conductor with good thermal conductivity. It has been discovered that by making the material amorphous, a material with excellent strength and axial elongation can be obtained. However, obtaining such an amorphous state depends to a large extent on the component system and cooling conditions, and the component systems that have been published have been empirically limited to the above range. Therefore, the present inventors conducted extensive research on the component system and manufacturing conditions to obtain an amorphous state, and first determined that iron, cobalt, and nickel, which are transition elements of group 8 of the periodic table, or any of these elements may be used as the basic component. One or two metalloid elements based on the mixed components of
It has been found that it is sufficient to add seeds or more. The amorphous metal thus obtained has much superior strength and malleability when compared to conventional crystalline rapidly solidified metals. However, if the corrosion resistance could be improved even further, it would be very effective in expanding the range of uses.

'Therefore, the present inventors investigated the effects of various alloy additions based on the above basic components and found that titanium, zirconium, and hafnium, elements of the umbrella group of the periodic table, are effective for this purpose. Ta. Furthermore, they discovered that when iron and titanium are combined, the hydrogen storage capacity increases significantly. This property is an important technology for the use of hydrogen, which has recently attracted attention as a non-polluting energy source. According to the findings of the present inventors, the amount of the Group 8 elements added should be determined from the viewpoint of deteriorating the quality of the entire alloy, and in order to do so, the melting point of the entire alloy must be determined by the Group 8 elements constituting the alloy. It is effective to keep the temperature within +150° C. of the highest temperature of the eutectic temperature of the binary alloy of either of these and any of the added metalloid elements. Furthermore, regarding cooling conditions, it is necessary to rapidly cool the alloy from a molten state to a temperature of 30,000° C. or more at a rate of 1 degree C. per second or more. Naoko), the amorphous structure is the normal
In line diffraction, it is a state in which diffraction lines characteristic of metal crystals are not observed.

In addition, metalloid elements refer to boron, carbon, poppy, element, and phosphorus. In the present invention, the three elements iron, cobalt, and nickel were targeted as the Group 8 transition elements that form the matrix of the alloy, but it is easy to see that other Group 8 elements may have similar effects. Conceivable. It goes without saying that unavoidable impurities are included as ingredients. At present, the theoretical basis on which the combination of the above components makes it easy to create an amorphous metal alloy and has excellent corrosion resistance and hydrogen storage properties is not clear.

The present invention was obtained as a result of systematic experiments on the relationship between the tendency to form an amorphous structure, the type of added element, and the cooling rate. That is, the research conducted by the present inventors has revealed regularity on the periodic table regarding the types of added elements. One of the key points of the present invention is to ensure an amorphous state by combining a Group 8 transition element and a metalloid element, and to add an umbrella group element to improve the properties. Conventionally, amorphous metals based on iron, nickel, or palladium have been announced, but as a result of a series of research on replacing the base iron with other elements, the inventor found that not only nickel but also cobalt can be substituted. Although an amorphous metal can be obtained, it has been found that substitution with manganese and copper, which are out of Group 8, results in an amorphous metal, which increases the metal by 1 kg.

On the other hand, the elements combined with these base ingredients are:
It was previously known to simultaneously add more than 10% phosphorus and several % carbon.

However, the present inventors conducted extensive research on these, and found that combining two or more metalloid elements is effective for making the metalloid amorphous. It has been found that even when added up to the limit (approximately 20%), an amorphous state is maintained, and furthermore, it has excellent not only strength but also corrosion resistance. Regarding the amount of these additives, previous research has limited the total amount of additive elements other than iron or nickel to about 20 atomic %, and no regular guideline for component design has been obtained. As a result of extensive experiments, the inventors of the present invention determined that the melting point of the alloy was one of the criteria. This clarifies that the melting point of the alloy is determined by the relationship with temperature.In other words, as mentioned earlier, it is necessary to lower the melting point of the alloy to a certain level, and it is necessary to lower the melting point of the alloy to a certain degree. It is effective to adjust the components, including the umbrella group elements, so that the eutectic temperature of the binary alloy with any of the metalloid elements to be added is 150 oo or less, or more likely 10,000 or less, than the highest one. Of course, even if the alloy components were adjusted in this way, it would be impossible to obtain an amorphous metal depending on the cooling rate. .

The first area that requires rapid cooling is during solidification, but after solidification,
When kept at a high temperature for a long time, crystallization occurs due to atomic diffusion, so it is necessary to maintain a sufficient cooling rate even after solidification. Strictly speaking, it is conceivable that the required cooling rates are different during solidification and after solidification, but it is difficult to actually control them separately. Based on experiments with various cooling rates and theoretical predictions, the present inventors determined that the cooling rate should be 1 pm until crystallization stops at approximately 300°C. It has been found that it is necessary to cool at a speed of ○/second or more. The amorphous alloy thus obtained has superior strength, malleability, and corrosion resistance compared to ordinary crystalline rapidly solidified alloys.

Therefore, its uses include wire rope, steel cord,
In addition to filters, fiber-reinforced composite materials, concrete reinforcement materials, meshes, fog-proofing materials, soundproofing materials, etc., there are also hydrogen-absorbing materials. The present invention is extremely significant in that it has discovered a law in designing an amorphous alloy that is free from conventional limited experience, and has also achieved excellent properties. Example 7 The melting point of the 0 at. % Fe-15 at. % P-5 at. % C-10 at. -C system eutectic temperature is lower than 114,500 (see Figure 2).

The metal fiber, which was rapidly solidified from the molten state by cooling at 1° C./second, showed an amorphous state. Its characteristics are listed in the table below. In addition, an alloy with the following composition is prepared from a molten state.

The material that was rapidly solidified by cooling at ○/second exhibited an amorphous state, and its properties were as follows. Note that the corrosion resistance of the above alloy was as good as in the previous case.

[Brief explanation of the drawing]

Figure 1 shows iron-15 atomic% P- produced by the method of the present invention.
This is an X-ray diffraction photograph of a 5 atomic % C-10 atomic % Ti amorphous alloy showing an amorphous state. Figure 2 is a phase diagram of an iron-carbon binary alloy, with 15 atomic% iron
Melting point of phosphorus-5 at% C-10 at% Ti metal 1110
℃ is 15 from the eutectic temperature of iron and carbon binary system 1145oo
It shows that the temperature is below 1295 pm (shaded area) which is 0°C higher. Ta-zu younger brother Eha phantom

Claims (1)

[Claims] 1 As basic components, one or more of iron, cobalt, and nickel; as metalloid elements, one or more of boron, carbon, phosphorus, and silicon; and one or more of titanium, zirconium, and hafnium. The melting point of the alloy is +1 from the highest temperature among the eutectic temperatures of the binary system of the basic component and the metalloid element that make up the alloy.
50℃ or less, and the alloy is rapidly solidified from a molten state to 300℃ at a cooling rate of 10^5℃/second or more, and has excellent strength and corrosion resistance. A method for producing an amorphous alloy.