JPS5928623B2 - Amorphous alloy with excellent strength, corrosion resistance and magnetic properties - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an alloy from which an amorphous state can be easily obtained.

Here, an amorphous alloy is an alloy whose atomic arrangement does not have long-range regular periodicity, does not show diffraction lines characteristic of crystals in ordinary X-ray diffraction or electron beam diffraction, and does not exhibit the characteristic diffraction lines of crystals. Refers to those that exhibit similar halo patterns. Note that the amorphous alloy defined in the present invention refers to one in which the amorphous content is 50% or more.
Amorphous alloys have unique properties such as high strength and high corrosion resistance, and have been actively researched recently.

Amorphous alloys are manufactured by methods such as rapid solidification of molten alloys, vapor deposition methods, or electrodeposition methods. Among these, when using the rapid solidification method, it is necessary to increase the cooling rate in order to obtain an amorphous state, and the size is often 10
It reaches as much as 6°C/sec. However, rapid solidification at such a cooling rate is accompanied by many difficulties both mechanically and operationally, which limits the path to industrialization. Conventionally, amorphous alloys are composed of transition elements such as Fe, Ni, and Pd and P.
It is obtained by combining metalloid elements such as , C, B, and Si, but the ease with which it becomes amorphous and its stability vary depending on its composition. According to Japanese Unexamined Patent Publication No. 49-91014, an alloy mainly composed of Fe, Ni, Cr, Co and V and containing 10 to 30 at % of elements selected from P, C and B has excellent glass forming properties. , 0.1 to 15, preferably 0.5 to 6 atomic % of Ae, Si, Sn, Sb, Ge,
It is described that it can be obtained by adding specific elements such as In and Be. According to the research of the present inventor, S
i, Aι is effective in improving the thermal stability of amorphous alloys, but when added in large amounts, the fluidity of the molten alloy deteriorates;
There are problems with workability.

In addition, alloys mainly composed of Fe, which are economically advantageous, are
It has the characteristic that it is less likely to become amorphous than systems containing i, Pd, etc. Among these, those with a composition of Fe80p13c7 (subscripts are atomic %) are easy to manufacture, but
It has been found that when the composition of P and C is changed, or when P is reduced and B is substituted, it becomes difficult to make it amorphous, and the stability is also unfavorable. However, P is one of the environmentally unfavorable elements for human storage, and in consideration of the working conditions when producing an amorphous alloy, it is desirable to reduce the P content as much as possible. In order to easily obtain an amorphous alloy industrially, the present inventor conducted extensive research on the component system and manufacturing method, and in particular, in order to reduce P and improve the shape of the obtained material, It has been found that the addition of S is effective.

The gist of the present invention is that S is 0.03 to 5 atomic%.
one or more of B, C, Sl, and P in total of 7 to
30 atom%, or further contains one or more of Cr, Ni, MO as a subsidiary component of 0.1 to 6
It is an amorphous alloy containing 0 atomic % or further 0.01 to 2 atomic % of N, with the balance consisting of Fe and unavoidable impurities, and has excellent strength, corrosion resistance, and magnetic properties.

Here, B, C, Si, and P are metalloid elements.

The reasons for limiting the component ranges of various elements in the present invention will be described below. First, the addition of S is a feature of the present invention, and it reduces the cooling rate necessary for becoming amorphous.
Further, it is added to improve the shape of the obtained amorphous alloy.

In order to obtain this effect, S needs to be at least 0.03 atomic %, but if the amount is too large, it will cause embrittlement and become impractical, so the upper limit was set at 5 atomic %. The metalloid element is added as an essential component in order to stabilize the amorphous state and obtain an amorphous alloy at an industrially practical cooling rate.

Therefore, if the total amount of metalloid elements is less than 7 atomic %, the effect cannot be obtained, and if the amount is too large, it will become brittle and workability will be reduced, so the upper limit was set at 30 atomic %. One of the features of the present invention is to reduce P, which is harmful to human reserves, and therefore it is preferable to keep P at 5 atomic % or less and S at 0.3 to 1.0 atomic %. It is better. Cr, Ni, MO, etc. as subsidiary components are added to further improve certain strength, thermal stability, corrosion resistance, magnetism, etc. of the amorphous alloy.

The composition of these elements must be matched with the applied cooling rate to obtain an amorphous alloy, but
No effect of added elements was observed below 60 atom%.
In the above cases, the characteristics of Fe as a main component are lost, so the range of addition was determined for each. When Tamashi N is added, there is a significant improvement in corrosion resistance, especially in the coexistence with Cr and MO, and this is effective when the amount of N added is 0.01 atomic % or more, and when the amount of N added is 2 atomic % or more. Since it is industrially difficult to add
The addition range was determined separately. Amorphous alloys containing Fe as a main component are more difficult to turn into amorphous than alloys containing N1 or Pd as main components, so adding S is significant. The above amorphous alloys are mainly produced by rapid solidification from a molten state, but the cooling rate is 5x from the melting point to 300°C.
The temperature should be kept at 103°C/second or higher.

Examples of the present invention are described below.

Example 1 An alloy with a composition of Fe7, B5c15s, 0.2 to 0
．． 6? The molten alloy was melted in a quartz crucible with a range of nozzle diameters, and then quenched by injection using a rotary centrifugal casting machine using a copper plate as a cooling medium to obtain a ribbon-shaped alloy having a width of 1 to 3 W11 and a thickness of 10 to 100 Pm.

When this alloy was confirmed by X-ray diffraction and electron beam diffraction, it exhibited a halo pattern characteristic of an amorphous alloy. A component system excluding S from the above alloy composition, that is, Fe8OB
In the 5C,5 alloy, it is difficult to produce an amorphous alloy unless the cooling rate is maintained at 106°C/sec or higher, and S is 0.0
By adding 3 to 5 at%, the cooling rate can be increased to 104℃/
It has now become possible to produce amorphous alloys even at slow speeds of about seconds.
The properties of the alloy of the present invention are shown in Table 1, and its strength exceeds that of alloys with known compositions.

Example 2 A ribbon-shaped alloy having a composition of Fe75p13c7s and having a width of 1 to 3W11 and a thickness of 100 μm was obtained in the same manner as in Example 1.

When this alloy was confirmed by X-ray diffraction and electron beam diffraction, it exhibited a halo pattern characteristic of an amorphous alloy. As shown in Table 1, the properties of the alloy of the present invention are not much different from known alloys in terms of strength and corrosion resistance, but as shown in Figure 1, it shows interesting results in magnetic properties. That is, the magnetization curve exhibits a snake-shaped curve, unlike that of ordinary amorphous alloys. This characteristic becomes clearer when heat treated at 250° C. for 30 minutes, and this characteristic is lost when heated at a higher temperature. Alloys with this snake-like characteristic are also useful as two-stage memory elements. This characteristic can only be obtained by adding 0.5 to 5 at % of S. Example 3 An alloy having a composition of Fe6, B5c15s, and si5cr5 was manufactured in the same manner as in Example 1.

When the alloy of the present invention was confirmed by electron beam diffraction and X-ray diffraction, it exhibited a halo pattern characteristic of amorphous alloys. The properties of the alloy of the present invention are shown in Table 1, and the strength level is significantly higher than that of known component systems. Example 4 An amorphous alloy having a composition of Fe67.5p5c15s2.5si5cr5 was obtained in the same manner as in Example 1.

The properties of the alloy of the present invention are shown in Table 1, and it shows that it has high strength, has a significantly slow corrosion rate even when immersed in a 501) sulfuric acid solution heated to 80°C, and has excellent corrosion resistance compared to known alloy systems. ing. Example 5 An alloy having a composition of Fe66.4p8c8cr, 1N0.6Ni5s1 was produced in the same manner as in Example 1 to obtain an amorphous alloy.

The properties of the alloy of the present invention are shown in Table 1, and it has extremely high strength and excellent corrosion resistance. In addition, although the examples in the specification of the present invention show ribbon-shaped products manufactured using a rotary centrifugal casting machine using a copper plate as a cooling medium, the alloy of the present invention can also be produced by a rolling method or by injection quenching. It is also possible to coat the surface of other materials by a rapid dipping method or the like.

Therefore, the shape is not limited to a ribbon shape, but it can also be manufactured in the form of a foil, a line, a powder, or a coating material for a different material. In addition, practical test materials are not necessarily limited to completely amorphous alloys depending on the intended use; even if some crystalline parts are mixed into the material, the same properties as fully amorphous alloys can be obtained. It will be done. The alloy of the present invention can be used in conventional amorphous alloys, such as wire ropes, composite reinforcing materials for rubber, concrete, plastics, etc., and corrosion-resistant high-strength foils. Easy to use as surface coating material for parts and structural materials.

Moreover, as mentioned above, its unique magnetic properties can be used for electronic device parts, and its uses are extremely wide. Example 6 An alloy having a composition of Fe66.4p8c8M011N0.6Ni5s1 was produced in the same manner as in Example 1 to obtain an amorphous alloy.

The properties of the alloy of the present invention are shown in Table 1, and it has high strength and excellent corrosion resistance.

[Brief explanation of drawings]

FIG. 1 shows the magnetization characteristics of the Fe75pl3c7s5 alloy according to the present invention.

Claims (1)

[Claims] 1 S is 0.03 to 5 atomic %, B, C, Si, P 1
An amorphous alloy with excellent strength, corrosion resistance, and magnetic properties, containing a total of 7 to 30 at % of one or more species, with the balance being Fe and unavoidable impurities. 2 S to 0.03 to 5 atomic%, B, C, Si, P to 1
The total amount of the species or two or more species is 7 to 30 atom%, and the total amount of one or more of Cr, Ni, and Mo is 0.1 to 60 atom%, and N is 0.01 to 2 atom%. An amorphous alloy with excellent strength, corrosion resistance, and magnetic properties, with the remainder consisting of Fe and unavoidable impurities.