JPS6119702B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an amorphous alloy containing an iron group element and zirconium as basic components and having a small temperature coefficient of elastic modulus. The elastic modulus of ordinary metals and alloys decreases as the temperature rises. For example, in ordinary spring materials, the temperature coefficient of elastic modulus is about -30 × 10 ^-5 to -40 × 10 ^-5 , but Alloys whose modulus changes little with temperature are known as Elinvar type alloys or constant modulus alloys, and these properties are generally referred to as Elinvar characteristics. Elinvar-type alloys include Elinvar (Ni approx. 36% by weight, Cr approx. 9% by weight, Fe approx. 55% by weight)
and Super Elinvar (Co5~10% by weight, Ni36~
39% by weight, Cr5-10% by weight, balance Fe) or coelin bar (about 60% by weight Co, about 30% by weight Fe, Cr
(approximately 10% by weight), and all of these alloys are crystalline. These alloys have a large ΔE effect at temperatures below the Curie temperature (hereinafter referred to as Tc), which reduces the temperature coefficient of elastic modulus to less than a fraction of that of ordinary metals and alloys. I'm taking advantage of what I do. However, these crystalline Elinvar type alloys have low mechanical strength, particularly tensile strength and hardness, and have the disadvantage that in order to improve them, they must be used by increasing the processing rate by cold working. Furthermore, the conventional Elinvar alloy has the disadvantage that it does not exhibit Elinvar characteristics in a low temperature range because it undergoes phase transformation up to the temperature of liquid nitrogen. In addition to the alloys mentioned above, there are other alloys with a small temperature coefficient of elasticity, such as Fe-Pd alloys and Fe-Pt alloys, but they have the disadvantage of being very expensive because they contain expensive precious metals as their main components. There is. In general, Elinvar type alloys are mainly used in the form of thin wires, thin plates, or thin films as parts of precision instruments, electromagnetic devices, and measuring instruments, such as sound bars, acoustic bars, mechanical filters, delay lines, magnetostrictive vibrators, torque meters, etc. However, although the existing crystalline Elinvar-type alloys are relatively malleable, they require a complex manufacturing process that involves multiple stages of processing and heat treatment from an ingot to a thin plate of the required thickness. The fuel and electricity costs required are also significant. On the other hand, Fe-B amorphous alloys are known to exhibit excellent elinvar properties over a wide temperature range, but Fe-B binary amorphous alloys have poor corrosion resistance and heat resistance, and these properties In order to improve Fe, B
Addition of other elements had the disadvantage that Elinvar properties sharply deteriorated. The present invention has a smaller temperature coefficient of elastic modulus over a wide temperature range than the crystalline Elinbar type alloys that have been used in the past, and also has an already known Fe alloy.
- The purpose is to provide an amorphous alloy that also solves the problems of the B-based amorphous Elinbar type alloy, and it contains Zr8 to 14% in atomic % and the balance is Fe.
In an amorphous alloy consisting of
This invention relates to an amorphous alloy with a small temperature coefficient of elasticity, the basic composition of which is an amorphous alloy in which a portion of Fe is replaced with one or both of Co and Ni. Next, the present invention will be explained in detail. Normally, solid metals and alloys have a crystalline structure, but they can be turned into liquids by rapidly cooling an alloy with an appropriate composition from a liquid state, or by using various techniques such as vapor deposition, sputtering, and plating. A solid with an amorphous structure that does not have a similar periodic atomic arrangement is obtained, and such metals are called amorphous metals or amorphous alloys (hereinafter, amorphous metals or amorphous alloys are collectively referred to as amorphous). (referred to as quality alloy). As mentioned above, it is well known that this amorphous alloy can be obtained by appropriately using various techniques (for example, Japanese Patent Application Laid-Open No. 49-91014). It is known that amorphous alloys can be obtained in a wider composition range than those obtained by liquid quenching. As an example of the liquid quenching method, liquid metal is continuously jetted onto the outer peripheral surface of one disk rotating at high speed, or onto the surface of a rotating disk or twin rolls by continuously spouting liquid metal between two rolls rotating counter-rotating to each other at high speed. There is a method of rapid solidification at a cooling rate of about 10 ⁴ to ^{10 6} °C/sec. In addition, when looking at the composition of amorphous alloys, they can be broadly classified into those consisting of a metal-metalloid combination and those consisting of a metal-metal combination. The Fe-B-based amorphous Elinbar type alloy contains B, which is one of the metalloids, as an amorphous forming element.
It contains 30 atomic % (hereinafter atomic % is simply referred to as %), and is a type of amorphous alloy consisting of a combination of a transition metal element and a metalloid element. On the other hand, the alloy of the present invention is essentially the latter, that is, an amorphous alloy consisting of an iron group element, which is a transition metal, and zirconium.
In No. 43838, we newly discovered that some of the various amorphous alloys containing iron group elements and zirconium have ferromagnetism, and filed a patent application. Furthermore, the present inventors have conducted various pioneering research and inventions on amorphous alloys containing iron group elements and Zr.
Patent applications were filed under Nos.-160758 and 55-19844. Among them, in No. 55-19844, it was newly discovered that some of the alloys have a small coefficient of thermal expansion of ±0.5 × 10 ^-6 or less, and that the temperature coefficient of elastic modulus is almost zero. A patent application was filed. As a result of further research into the amorphous alloy containing the above-mentioned iron group elements and Zr, the present inventors have discovered an amorphous alloy containing the above-mentioned iron group elements and zirconium as main components, and containing specific subcomponents as necessary. The present invention was completed based on the new finding that the temperature coefficient of elastic modulus of an alloy has a very small value over an extremely wide temperature range by subjecting this alloy to a predetermined heat treatment. Amorphous alloys of the invention as well as already known
Table 1 shows the elastic modulus (near room temperature), temperature coefficient of elastic modulus, thermal expansion coefficient, and hardness of several examples of Fe-B-based amorphous alloys and crystalline Elinbar type alloys. In the same table, for example, No. 1 Fe ₉₀ Zr ₁₀ has Fe.
Indicates that the alloy consists of 90 atomic % and 10 atomic % Zr.

[Table] In Table 1, alloys No. 1 to No. 24 are amorphous alloys with a small temperature coefficient of elastic modulus of the present invention,
Nos. 25 to 30 are comparative examples. No.25 of comparative examples
Nos. 27 to 27 are already known Fe-B based amorphous alloys, and Nos. 28 to 30 are conventional crystalline Elinbar type alloys. Among the alloys of the present invention, alloys containing no Ni or Co (first
Table No. 1, No. 6 to 9) have a Curie temperature Tc of -30
The temperature coefficient of the elastic modulus at room temperature shows a relatively large negative value because it is relatively low at ℃ to +120℃, but at −100℃
It has a small negative value in the temperature range of ~+0°C. In addition, the alloy containing Co and Ni of the present invention (Table 1 No. 2
~5, No.10~24), the temperature change in the elastic modulus is small over a wide temperature range of -100℃ to +100℃, for example
Comparing the No. 4 invention alloy with the crystalline Elinvar type alloys No. 28 to 30, the temperature coefficient of elastic modulus is almost the same as that of the conventional crystalline Elinvar type alloy, and they have excellent Elinvar properties. I understand that. Moreover, the coefficient of thermal expansion α of each alloy
(10 ^-6 /℃), the absolute value of the coefficient of thermal expansion of alloy No. 4 is less than 1/10 of that of alloys No. 28 to 30 at around room temperature, indicating excellent invar properties. It can be seen that it has both Elinvar properties and Invar properties that are equal to or better than No. 25 Fe-B based amorphous alloy. This is a major feature that cannot be obtained with conventional crystalline alloys, and having both Elinvar and Invar properties in one alloy is suitable for application to precision measurement equipment that requires extremely high accuracy. Extremely advantageous. In addition, Fe-B binary amorphous alloys have low corrosion resistance or heat resistance, and these properties can be improved by adding a third element other than Fe and B.
Unlike the Fe-Co-B alloy No. 27, the coefficient of thermal expansion increases rapidly, and it has the disadvantage that it does not have both Invar and Elinvar properties. On the other hand, the alloy of the present invention is No. 10
~24, even when 5 to 10% of elements other than iron group elements and Zr are added, the temperature coefficient of elastic modulus and coefficient of thermal expansion of the alloy hardly change. Therefore, it can be seen that the elastic modulus can also be adjusted. This is also another great feature of the alloy of the present invention. Further, as seen in alloy No. 5 in Table 1, the amorphous alloy of the present invention obtained by ultra-quenching from the molten state is further annealed at a temperature below the crystallization temperature, and then quenched or slowly cooled. By doing so, it is possible to obtain the amorphous alloy of the present invention having a small temperature coefficient of elastic modulus. In this case, it is advantageous for the annealing atmosphere to be non-oxidizing or vacuum. The crystallization temperature of the alloy of the present invention varies depending on its component composition, but is approximately within the range of 400 to 600°C, and when annealed at a temperature higher than the crystallization temperature, it crystallizes and the temperature coefficient of elastic modulus suddenly changes. increases to The above annealing and the subsequent rapid cooling or slow cooling have the effect of removing distortion during rapid solidification and stabilizing Elinvar properties. Such heat treatment is particularly effective at 100℃
By maintaining the temperature in the temperature range from 1 minute to below the crystallization temperature for 1 minute to 500 hours, the alloy of the present invention having even better Elinvar properties can be obtained. Next, the alloy of the present invention will be explained based on research data. All the alloys explained below are made into amorphous material by ultra-rapidly cooling and solidifying from a molten state, and are in the form of a tape with a width of about 2 mm and a thickness of about 20 μm obtained by the single roll method shown in Figure 1a. It is a sample. First, the relationship between the heat treatment of the alloy of the present invention and the Elinvar properties will be explained. For example, using ribbon-shaped samples of the Fe ₇₂ Co ₁₈ Zr ₁₀ amorphous alloy shown in Table 1 No. 2, the results of measuring the temperature coefficient of elastic modulus after performing various heat treatments are shown in the second table.
Shown in the table.

【table】

[Table] As shown in the same table, in the rapidly cooled state, the temperature coefficient of elastic modulus of Fe ₇₂ Co ₁₈ Zr ₁₀ amorphous alloy is - from 0℃ to 50℃.
It shows a negative value of 2.3×10 ^-5 , and +25.1 at 100℃ or higher.
×10 ^-5 , which is a positive value. The temperature coefficient e of the elastic modulus is small near room temperature, but is relatively large at high temperatures of 100°C or higher. However, by applying appropriate heat treatment, the insulation value of the temperature coefficient of elastic modulus near room temperature can be reduced, and moreover, the temperature coefficient of elastic modulus can show a stable value without changing much even in a wide temperature range. I understand. It is also seen that the above heat treatment reduces the absolute value of the coefficient of thermal expansion and at the same time provides excellent invar characteristics. In particular, the alloys shown in Table 2 No. 4 are
It is heated for 30 minutes and then slowly cooled to -50°C to 100°C.
The temperature coefficient of elastic modulus is
It can be seen that it has both excellent Elinvar characteristics of 0.0×10 ⁻⁵ to +0.2×10 ⁻⁵ and excellent Invar characteristics of a thermal expansion coefficient α of 0.19×10 ⁻⁶ . FIG. 2a is a diagram showing the results of measuring temperature changes in the thermoelastic modulus of a rapidly cooled ribbon of Fe ₇₂ Co ₁₃ . ₅ Ni ₄ . ₅ Zr ₁₀ amorphous alloy from low temperature to above the crystallization temperature. In the figure, the curve 5 shows the super-quenched alloy heated to above the crystallization temperature, and the curve 6 shows the curve cooled from below the crystallization temperature. The temperature coefficient of the elastic modulus of the rapidly cooled ribbon near room temperature is approximately 0, and at 200℃
The temperature coefficient of elastic modulus between ~Tc is +24.0
×10 ^-5 , the elastic modulus decreases from around Tc, and its temperature coefficient becomes -27×10 ^-5 . Moreover, the value increases again to +35×10 ^-5 due to crystallization. In addition, the curve for cooling from before the crystallization temperature is similar to the curve for rapidly solidified alloys, and the temperature coefficient of elastic modulus is slightly lower than −0.2.
It is about ×10 ^-5 . Therefore, it can be considered that heating and cooling within this temperature range practically does not change the temperature coefficient of the elastic modulus. Figure 2b shows the results of examining changes in the elastic modulus of various alloys with temperature up to about 200°C, with Zr constant at 10 atomic %. Figures 3a and b show the ratios of Fe and Co or Fe and Ni for (Fe _1-x Co _x ) ₉₀ Zr ₁₀ and (Fe _1-x Ni _x ) ₉₀ Zr ₁₀ ternary amorphous alloys, respectively. The graph shows the change in the temperature coefficient of elastic modulus near room temperature when the temperature is changed. Since the temperature coefficient of elastic modulus varies over a wide range from negative to positive with respect to the amount of Co or Ni, it is possible to obtain an alloy having an arbitrary temperature coefficient of elastic modulus depending on the application. As shown in FIG. 4, the temperature coefficient of elastic modulus of the Fe-Co-Zr amorphous alloy and the Fe-Ni-Zr amorphous alloy does not change much even if the Zr content changes. Considering this together with Figure 3 a and b, we get
To obtain an alloy of arbitrary elasticity and temperature coefficient,
It can be seen that the objective can be achieved simply by changing the ratio of Fe, Co, and Ni, whose composition is easily controlled, and is hardly affected by the amount of Zr, which is easily oxidized and whose composition is relatively difficult to control. This is extremely advantageous in producing the alloy of the present invention on an industrial scale. Furthermore, based on the (Fe ₀ . ₈ Co ₀ . ₂ ) ₉₀ Zr ₁₀ amorphous alloy, a portion of Fe and Co are various types of groups (a) to (d) described in claim 6. The relationship between the temperature coefficient of elastic modulus at room temperature and the concentration of each added element for various alloys represented by the formula (Fe _{0. 8} Co ₀ . ₂ ) _90-x M _x Zr ₁₀ is determined by substituting each element with a fourth element. It was measured. FIG. 5 shows, as a representative example, the results obtained when six types of elements were changed within the claimed range. The influence of each additive element on the temperature coefficient of elastic modulus is different, but in any case, the temperature coefficient of elastic modulus has a value of -15 × 10 ^-5 to +25 × 10 ^-5 in the concentration range of the alloy of the present invention. In particular, even if about 10% of elements such as B, Al, Be, and Cr are added, the temperature coefficient of elastic modulus hardly changes, so other properties such as corrosion resistance and heat resistance , is extremely advantageous in improving oxidation resistance and the like. Next, the reason for limiting the composition of the alloy of the present invention will be described. Regarding the alloy described in claim 1 or 2: If the Zr content is less than 8%, it is difficult to turn it into an amorphous state even if it is ultra-quenched, and if it is more than 14%, the crystallization temperature will be low. 8 to 14% because it decreases and it is difficult to obtain a stable amorphous alloy.
and Zr should be within the range of 8.5 to 13
Within this range, an amorphous alloy with a stable elastic modulus and a small temperature coefficient can be obtained. Regarding the amount of Ni and Co, as can be seen from Figure 3 a and b, by adding up to about 40%, the temperature coefficient of elastic modulus becomes -
It can be adjusted within the range of 15 × 10 ^-5 to +25 × 10 ^-5 , and as shown in Figure 6, it has the effect of increasing the Curie temperature, so it is possible to expand the temperature range where the temperature coefficient of elastic modulus is small. can. but,
When Co and Ni are added in excess of 40%, Figure 3a,
As shown in b, the temperature coefficient of elasticity becomes more negative than -15 x 10 ^-5 , so it needs to be 40% or less.
Furthermore, within the range of 4 to 35%, the temperature coefficient of elastic modulus near room temperature can be obtained as small as -10 × 10 ^-5 to +20 × 10 ^-5 , and furthermore, within the range of 10 to 30%, it is possible to obtain a smaller value of the temperature coefficient of elasticity at room temperature. The temperature coefficient of elastic modulus in the vicinity is -5×10 ^-5 ~ +
Values as small as 10×10 ^-5 can be obtained. Regarding the alloy according to claim 5 of the present invention: P, B, C or Be, Al, Si, Ge, Sn,
Sb and In have the effect of facilitating the amorphization of the alloy and increasing the Tc of the Fe-Zr binary amorphous alloy, but
8% or more for P, B, C, Be, Al, Si,
When Ge, Sn, Sb, and In are added in an amount exceeding 25%, the temperature coefficient of elastic modulus near room temperature decreases by -10×
10 ^-5 , so less than 8% and 25
% or less. Furthermore, in the case of the alloy according to claim 6 of the present invention, the above semimetal has the effect of facilitating the amorphization of the alloy and expanding the temperature range in which the temperature coefficient of elastic modulus has a constant small value. but 20% for P, B, and C, Be,
For Al, Si, Ge, Sn, Sb, and In, if they exceed 25%, the temperature coefficient of elastic modulus near room temperature increases significantly negatively, so they must be kept at 20% or less and 25% or less, respectively. They should preferably be less than 13% and 20% or less, respectively. Furthermore, for P, B, and C, less than 8%;
For Be, Al, Si, Ge, Sn, Sb, and In, it is advantageous to reduce the temperature coefficient of elasticity to 15% or less in order to obtain an alloy with a smaller temperature coefficient of elasticity. It is an element of groups B and VB of the periodic table,
Cr, Mo, W, V, Nb, and Ta have the effect of increasing the crystallization temperature and improving the heat resistance of the alloy, but 20%
If it increases, the temperature coefficient of elastic modulus increases negatively, so it needs to be 20% or less. Mn and Cu improve the corrosion resistance of the alloy, but by 15%
If the amount is increased, the temperature coefficient of the elastic modulus will increase negatively, so it needs to be 15% or less. Tc, Ru, Rh, Pd, Pt, Os, and Ir are all elements that easily make the alloy amorphous, but if at least one selected from these exceeds 15%, the temperature of the elastic modulus Since it significantly increases the coefficient negatively, it is necessary to keep it below 15%. Ti, Hf, Sc, Y, and lanthanide elements are all
Adding less than 10% has the effect of promoting amorphization of the alloy, but adding more than 10% makes the alloy susceptible to oxidation, so it is necessary to keep it below 10%. In addition, adding elements of groups (a) to (f) promotes the amorphization of the alloy, so a stable amorphous alloy can be obtained with a Zr content in the range of 6 to 15%, but - 15×
In order to obtain a temperature coefficient of elasticity of 10 ^-5 to ⁺²⁵ It is necessary that the total of By adding up to about 40% of Ni and Co, the temperature coefficient of elastic modulus can be adjusted within the range of -15 x 10 ^-5 to +25 x 10 ^-5 , and the Curie temperature can be adjusted as shown in Figure 6. Since it has the effect of increasing the temperature, the temperature range in which the temperature coefficient of elastic modulus is small can be expanded. However, if Co or Ni is added in excess of 40%, the temperature coefficient of elastic modulus will negatively increase to -15 x 10 ^-5 or less, so it must be kept below 40%, and further within the range of 4 to 35%. In this case, the temperature coefficient of elastic modulus near room temperature can be obtained as small as -10 × 10 ^-5 to +20 × 10 ^-5 , and furthermore, in the range of 10 to 30%, the temperature coefficient of elastic modulus is −5×10 ^-5 ~+10×10 ^-5
It is possible to obtain a smaller value. Next, the present invention will be explained with reference to examples. Example 1 In the alloy of the present invention, Zr was kept constant at 10%, Fe,
For alloys with different composition ratios of Co and Ni, the dependence of the temperature coefficient of elastic modulus on the composition ratios of Fe, Co and Ni near room temperature was investigated and is shown in FIG. The numbers written on each side of the triangle in the figure represent the proportion of each element among the iron group elements contained in the alloy, and when the total number of iron group elements in the alloy is 1, Fe (X), The values of CO (Y) and Ni (Z) are shown, respectively. Further, the numbers written on the curves in the figure each indicate the value of the temperature coefficient of elastic modulus (×10 ⁻⁵ /° C.). As is clear from the figure, an alloy with a small temperature coefficient of elastic modulus can be obtained over an extremely wide composition range. Example 2 The temperature coefficient t of delay time in an ultrasonic delay line is given by the following equation. t=-1/2(α+e) where α is the coefficient of thermal expansion and e is the temperature coefficient of elastic modulus. Therefore, in order to obtain a good delay time temperature coefficient, α and e of the delay line must be examined. That is, the smaller the absolute value of (α+e), the better the delay line. Most of the amorphous alloys of the present invention having a small temperature coefficient of elastic modulus exhibit so-called invar characteristics in which the coefficient of thermal expansion α is approximately zero. For example, all the alloys having the compositions shown in Table 3 have α of approximately zero, and the temperature coefficient of delay time is as small as within ±10×10 ^-6 , making these alloys suitable for ultrasonic delay lines.

[Table] As can be seen from the above research data and examples of the alloy of the present invention, the amorphous alloy of the present invention exhibits the so-called Elinbar characteristic in which the temperature coefficient of elastic modulus is small over a wide composition range, and most of them have a coefficient of thermal expansion. shows small invar characteristics at the same time. On the other hand, the coefficient of thermal expansion of the conventional crystalline Elinvar type alloy is several times to several tens of times larger than that of the alloy of the present invention. Such characteristics have not been known at all, except for the Fe-B amorphous invar alloy for which one of the inventors has already applied for a patent. The amorphous alloy of the present invention also has a high crystallization temperature and a high embrittlement temperature, and has excellent heat resistance compared to conventionally known Fe-B-based amorphous alloys. Furthermore, the tensile strength and hardness are 2 to 3 times higher than that of crystalline Elinvar type alloys, making it suitable for applications that require mechanical strength, and the above properties remain almost constant even after processing or applying tension. It is unchanging, ie insensitive to external stresses. Furthermore, since the alloy of the present invention becomes amorphous during production, it must be ultra-rapidly cooled at a cooling rate of at least 10 ⁴ °C/sec or higher, and therefore it can be easily obtained in the form of a thin plate or film. The ease of machining such as cutting, punching, and etching is extremely advantageous compared to conventional crystalline Elinvar alloys, which require complicated manufacturing processes. The amorphous alloy in the rapidly cooled state of the present invention has its Elinbar properties further improved by low-temperature annealing, and its properties are stabilized against repeated heating and cooling, with a temperature coefficient of elasticity of 0 x 10 ^-5 . You can also get something with . As described above, the alloy of the present invention can be very suitably used as an electromagnetic material, a precision measurement material, a control equipment material, etc.

[Brief explanation of the drawing]

Figures 1a and b are longitudinal cross-sectional explanatory diagrams of the equipment used to ultra _- quench the alloy of the present invention from a molten state, respectively, and _Figure 2a is a Fe ₇₂ Co _13.5 Ni _4.5 Zr ₁₀ amorphous Figure 2b shows the relationship between the elastic modulus of alloys and temperature, and Figure 3 shows the relationship between the elastic modulus and temperature of various (Fe-Co-Ni) ₉₀ Zr ₁₀ amorphous alloys. a and b show the relationship between the temperature coefficient of elastic modulus of (Fe-Co) ₉₀ Zr ₁₀ and (Fe-Ni) ₉₀ Zr _10- based amorphous alloys and the composition ratio of Fe-Co or Fe-Ni, respectively. Figure 4 shows (Fe _{0.8 Co 0.2 ) 100 -x Zr x} and (Fe _0.8 Ni _0.2 ) _100-x Z
r _x
Figure 5 shows the dependence of the elastic modulus on the Zr content on the temperature coefficient of the Fe-Co-Zr ternary amorphous alloy. Figure 6 shows _{the relationship between temperature} coefficient _{and addition amount .} A diagram showing the dependence of the composition ratio of Ni. Figure 7 is a diagram showing the dependence of the temperature coefficient of elastic modulus of the (Fe _x Co _Y Ni _Z ) ₉₀ Zr ₁₀ series amorphous alloy on the composition ratio of Fe, Co, and Ni. It is. 1... Molten metal, 2... Amorphous ribbon, 3... Cooling drum, 4... Cooling roll.

Claims (1)

[Claims] Contains 8 to 14% of Zr in 1 atomic %, and the remainder is substantially Fe.
The temperature coefficient of elasticity is -15×10 ^-5 ~ +25
An amorphous alloy with a small temperature coefficient of elastic modulus within the range of ×10 ^-5 . 2 Contains 8 to 14% of Zr in atomic %, 40% or less of at least one of Ni and Co, the remainder substantially consists of Fe, and the temperature coefficient of elastic modulus is -15 × 10 ^-5 to +25 ×
An amorphous alloy with a small temperature coefficient of elastic modulus in the range of 10 ^-5 . 3 Contains 8.5 to 13% Zr in atomic %, 4 to 35% of at least one of Ni and Co, the remainder substantially consists of Fe, and has a temperature coefficient of elasticity of -10×10 ^-5 to +20×
10 ^-5 . 4 Contains 9 to 12% Zr in atomic %, 10 to 30% of at least one of Ni and Co, the remainder substantially consists of Fe, and has a temperature coefficient of elasticity of -5 × 10 ^-5 to +10 ×
The alloy according to claim 2 or 3, which is within the range of 10 ^-5 . 5 Zr6 to 15% in atomic%, the following (a) (b) (c) (d) (e) (f)
) 25% of any one or more groups selected from the group
Contains the following, provided that the total of one or more elements selected from the following groups (a), (b), (c), (d), (e), and (f) and Zr is 10 to 35 %, and the remainder is substantially
Made of Fe, the temperature coefficient of elasticity is -15×10 ^-5 ~
An amorphous alloy with a small temperature coefficient of elastic modulus within the range of +25×10 ^-5 . (a) Any one or two or more selected from P, B, and C up to 8% (b) Any one selected from Be, Al, Si, Ge, Sn, Sb, and In or 2 or more types and 25% or less (c) any one selected from Cr, Mo, W, V, Nb, and Ta, or 2 or more and 20% or less (d) any selected from Mn, Cu One or two types 15% or less (e) Any one or more selected from Tc, Ru, Rh, Pt, Pd, Os, Ir 15% or less (f) Ti, Hf, Sc, Y , any one or more selected from the lanthanide elements, up to 10% 6 atoms, Zr 6 to 15%, at least one of Ni, Co, up to 40%, the following (a) (b) (c) Contains 25% or less of any one or more groups selected from the groups (d), (e), and (f), provided that the following (a), (b), (c), (d), (e), (f) The total of one or more elements selected from the group and Zr is 10~
35%, the remainder is essentially Fe, and the temperature coefficient of elastic modulus is -15×10 ^-5 to +25×10 ^-5
An amorphous alloy with a small temperature coefficient of elastic modulus within the range of . (a) Any one or more selected from P, B, and C up to 20% (b) One or more selected from Be, Al, Si, Ge, Sn, Sb, and In. 2 types or more and 25% or less (c) Any one selected from Cr, Mo, W, V, Nb, Ta, or 2 or more and 20% or less (d) Any one selected from Mn, Cu Species or two species 15% or less (e) Any one or more selected from Tc, Ru, Rh, Pd, Pt, Os, Ir 15% or less (f) Ti, Hf, Sc, Y, Any one or more selected from the lanthanide elements, up to 10% 7 Zr6-15% at atomic percent, 4-35% of at least one of Ni and Co, the following (a), (b), (ha) ) (d) (e) (f) Contains 20% or more of any one or two selected from the following (a) (b) (c) (d) (e) (f) Any one
The total amount of the species or two or more elements and Zr is within the range of 10 to 30%, the remainder is substantially composed of Fe, and the temperature coefficient of elastic modulus is -10 × 10 ^-5 to +20 × 10 ^-5 . An alloy according to claim 6 within the scope of claim 6. (a) One or more selected from P, B, and C, less than 13% (b) One or more selected from Be, Al, Si, Ge, Sn, Sb, and In. 2 or more and 20% or less (c) Any one selected from Cr, Mo, W, V, Nb, and Ta, or 2 or more and 15% or less (d) Any 1 selected from Mn and Cu Species or two species 10% or less (e) Any one or more selected from Tc, Ru, Rh, Pd, Pt, Os, Ir 10% or less (f) Ti, Hf, Sc, Y, Any one or more selected from the lanthanide elements up to 10% 8 atomic% Zr 6-15%, at least one of Ni and Co 10-30%, the following (a) (b) (ha) ) (d) (e) (f) Contains 20% or more of any one or two selected from the following (a) (b) (c) (d) (e) (f) Any one
The total amount of the species or two or more elements and Zr is within the range of 10 to 25%, the remainder is substantially composed of Fe, and the temperature coefficient of elastic modulus is -5 × 10 ^-5 to +10 × 10 ^-5 . An alloy according to claim 6 or 7 within the scope of the present invention. (a) One or more selected from P, B, and C, less than 8% (b) One or more selected from Be, Al, Si, Ge, Sn, Sb, and In 2 or more types and 15% or less (c) Any one selected from Cr, Mo, W, V, Nb, and Ta, or 2 or more and 15% or less (d) Any one selected from Mn and Cu 10% or less of one or more species or 2 or more species (e) Tc, Ru, Rh, Pd, Pt, Os, Ir (f) Ti, Hf, Sc, Y , any one or more selected from the lanthanide elements, 10% or less