JPH0258334B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an Mn-Ge based multi-component hexagonal lattice type antiferromagnetic invar alloy with a small linear thermal expansion coefficient of -8x10 ^-6 to +8x10 ^-6 at -50°C to +100°C. Conventionally, many iron-based ferromagnetic face-centered cubic lattice alloys have been found as invar-type alloys. However, since these alloys have a large positive spontaneous bulk magnetostriction below their magnetic transformation point, their coefficient of thermal expansion is less than a fraction of that of general alloys, and they are ferromagnetic, so their applications are limited. There is. In particular, these invar-type alloys can be used, for example, in the head support of video tape recorders, the shadow mask of television receivers, the specimen support of electron microscopes, and the balance wheel of watches that are required to vibrate in a non-uniform magnetic field generated due to motorization. It is difficult to apply it to , escapes, pallets, etc., gravity pendulums, nuclear reactors, and various control equipment, and non-ferromagnetic invar type alloys are required for these applications. As a non-ferromagnetic invar type alloy, there is already a hexagonal lattice type Mn-Ge alloy invented by the present inventors, but although this alloy exhibits excellent invar type properties, it is hard and brittle. In general, grinding with a whetstone is used to form the material.
Therefore, there has been a demand for improvement in its workability. The present inventors have conducted numerous experiments and studies to improve the workability of the above Mn-Ge alloy without impairing the invar-type characteristics, and have found that Ge is the main component in a weight ratio of 20 to 33%, preferably 23 to 32%, 0.01 to 11% of any of Cr, W, or V as subcomponents, Mo, Ti,
Zr, Nb, Ta, Ag, Au, Re, platinum group elements (Pd,
Pt, Rh, Ir, Ru, Os) 0.01 to 10%,
Any of Zn, Cd, Al, Ga, In, Tl, Sn, Pb
0.01~9%, Co, Ni, Si, As, Sb, Bi, Se,
Te, rare earth elements (Sc, Y and lanthanum elements)
Any of 0.01 to 8%, Be, Mg, Ca, B
0.01 to 6%, 0.01 to 1% of C, P, and S, total amount of 0.01 to 11% of one or more of them, unavoidable impurities of 1% or less, and the balance Mn (however, the subcomponents are Co,
By applying ^a specific heat treatment to the alloy ^consisting of It was discovered that a hexagonal lattice type antiferromagnetic invar type alloy can be obtained. The Mn-Ge based multi-component alloy according to the present invention has approximately 500
The high temperature phase is the ε phase with a hexagonal structure, and the low temperature phase is the ε ₁ phase with a face-centered square structure, and the invar characteristics are ε
It is exhibited in alloys with a phase structure. One of its features is that the rate of transformation to the ε ₁ phase is much slower than that of the ε phase. The present inventors confirmed the special characteristics of the antiferromagnetic (non-ferromagnetic) invar type alloy as described above, and as a result of numerous studies on how to manufacture it, they found that it is possible to combine Mn with purity of 99% obtained by ordinary electrolysis. Has a purity of ~99.9%
By adding a third or fourth element selected from the above-mentioned subcomponents to an alloy consisting of Ge, an antiferromagnetic invar type alloy was successfully manufactured. As Ge20~33
%, any of Cr, W, or V as subcomponents 0.01 to 11
%, Mo, Ti, Zr, Nb, Ta, Ag, Au, Re, any of the platinum group elements 0.01-10%, Zn, Cd, Al,
0.01 to 9% of Ga, In, Tl, Sn, Pb, Co,
0.01-8% of any of Ni, Cu, Si, As, Sb, Bi, Se, Te, rare earth elements, 0.01-6% of any of Be, Mg, Ca, B, 0.01 of any of C, P, S A composition consisting of one or more of ~1% in a total amount of 0.01 to 11%, unavoidable impurities of 1% or less, and the remainder Mn (excluding cases where the only subsidiary components are Co and Ni).
After melting at a high temperature of 870°C (liquidus) or higher, it is cast to form a product in a specified shape, and then heated at a temperature of at least 500°C or higher and below the melting point for an appropriate period of time (for example, 1 minute or more).
500 hours)) and then subjected to homogenization treatment and then cooled at a rate of 0.7°C/hour or more from the temperature of (A), or (B) rapidly cooled from that temperature at a cooling rate of 0.7°C/hour or more, Furthermore, at an appropriate temperature of 500℃ or less and 300℃ or more for an appropriate time (for example, 1 minute to 500 hours)
By reheating and cooling at a rate faster than 0.7°C/hour, or by any heat treatment method, it is given a hexagonal lattice crystal structure and the linear thermal expansion coefficient at -50°C to +100°C is -8 × 10 ^-6 ~ The purpose is to produce a high-performance invar-type alloy within the range of +8×10 ^-6 . Next, the method for producing the alloy of the present invention will be explained in detail. In order to make the alloy of the present invention, first the main component is
Ge20~33%, any of Cr, W, or V as subcomponents
0.01~11%, Mo, Ti, Zr, Nb, Ta, Ag, Au,
Re, 0.01-10% of any platinum group element, Zn, Cd,
0.01 to 9% of Al, Ga, In, Tl, Sn, Pb,
Co, Ni, Cu, Si, As, Sb, Bi, Se, Te, any rare earth element 0.01-8%, Be, Mg, Ca, B any 0.01-6%, any C, P, S or 0.01~1
Total amount of any one or two or more of the following: 0.01 to 11%
and the remaining Mn (excluding when the subcomponents are only Co and Ni) in air or in a non-oxidizing atmosphere (e.g. hydrogen, nitrogen, argon, etc.) or in vacuum in a suitable melting furnace. at least 870℃
(liquidus line) or higher and melted with sufficient stirring to create a compositionally uniform molten alloy. Next, this is poured into a suitable mold such as a sand mold or a metal mold to obtain an ingot with a shape suitable for the desired use, or this ingot is processed by an appropriate processing method such as cutting, grinding, or cutting. Then cut out the desired shape. In order to make the thus obtained molded body an antiferromagnetic material with a hexagonal structure, the molded body must be heated at a temperature of at least 500°C or higher and lower than its melting point in normal argon, other non-oxidizing atmosphere, or vacuum. Homogenization treatment is performed by heating at a temperature for an appropriate time (for example, 1 minute or more and 500 hours or less). Alloys homogenized in this way, regardless of their composition, are
If it is cooled at a faster rate of 0.7°C/hour or more than the temperature above ℃ or below the melting point, an antiferromagnetic invar-type alloy in the ε phase can be obtained at room temperature because the transformation rate from the ε phase to the ε ₁ phase is extremely slow. . Furthermore, if a cast compact is homogenized at a temperature of 500°C or higher and lower than its melting point and then rapidly cooled, quenching distortion may remain, and in this case, it is necessary to reheat the product at a temperature below 500°C. At this time, the holding time for reheating is 50 hours or less when the reheating temperature is 450℃, and 400℃
Then, it must be more than 50 hours and less than 120 hours.
This time increases rapidly as the reheating temperature decreases. Therefore, the reheating temperature for tempering treatment is less than 500℃.
It is better to keep it above ℃. A desired product can be obtained by performing the above tempering treatment. Next, the present invention will be explained with reference to examples. Example 1 Alloy No. 1 (27% Ge, 1% Cr, remainder Mn) As raw materials, 99.9% pure Ge, electrolytic Cr, and 99.8% pure electrolytic Mn were used. To make the sample, first, raw materials with a total weight of 30 g were melted in an alumina crucible in a Tammann furnace while blowing argon gas onto the surface, and the molten metal was stirred well and heated to 300℃.
A round bar with a diameter of 3 mm was obtained by casting into a sand mold heated to . At this time, the cooling rate of the casting was controlled to 0.7° C./hour or more. Next, an alloy rod with a length of 10 cm and an alloy ingot of 500 mg were cut out from this and used as samples for measuring thermal expansion and magnetic susceptibility. Finally these
After heating to 850℃ for 10 hours, 100℃/hour and 0.3
Experiments were conducted for an annealed state cooled at a rate of °C/hour and a state cooled in water from 850°C. The coefficient of thermal expansion was determined using a precision vertical dilatometer and a horizontal dilatometer, and the magnetic susceptibility was determined using a magnetic balance in a magnetic field of 10 KOe in an argon atmosphere. The measurement results are shown in Table 1.

[Table] As is clear from Table 1, the Mn alloy containing 27% Ge and 1% Cr has the critical cooling rate to obtain the ε phase.
It can be seen that the desired small coefficient of thermal expansion can be obtained by cooling at a rate exceeding 0.7/hour. It also has a small magnetic susceptibility of about 4.5×10 ^-5 emu/g and is antiferromagnetic. FIG. 1 shows thermal expansion curves under various conditions shown in Table 1. From Figure 1, curves A and B cooled at a rate exceeding 0.7°C/hour exhibit invar characteristics over a wide temperature range, while curve C cooled at a rate of 0.3/hour, which is slower than 0.7°C/hour, exhibits invar characteristics. You can see that it is not shown. Example 2 Alloy number 4 (Ge27%, Mo2%, balance Mn) The raw materials were Ge and Mn of the same purity as in Example 1.
Electrolytic Mo with a purity of 99.8% was used. sample manufacturing method;
The heat treatment method and measurement method are the same as in Example 1.
The results obtained are shown in Table 2. The magnetic susceptibility is
It is 3.9×10 ⁻⁵ emu/g.

[Table] Example 3 Alloy number 17 (27% Ge, 1% Zn, balance Mn) The raw materials were Ge and Mn of the same purity as in Example 1.
Zn with a purity of 99.9% was used. After the sample was melted using the method of Example 1, the molten metal was thoroughly stirred and poured into a mold cooled to 15°C to obtain a round bar with a diameter of 3 mm. From this, an alloy bar with a length of 10 cm and a diameter of 2.5 mm and a 500 mg The alloy ingot was cut out and made into a chill cast state. This was then heated at 400°C for 110 and 130 hours, and at 450°C for 45 and 55 hours.
It was heated for each time and cooled at a rate of 100° C./hour to obtain a reheated state at a temperature of less than 500° C. The measurement method was the same as in Example 1 above. The properties of the obtained molded product are shown in Table 3.

[Table] From Table 3, 27%Ge-1%Zn-Mn alloy is heated to 500℃.
It can be seen that when reheating to a temperature lower than that, there is a natural limit to the heating time depending on the heating temperature in order to maintain the Invar characteristics. In addition, the magnetic susceptibility was 2.9
10 ^-5 emu/g at 400℃ for 130 hours and
18× when reheated at 450°C for 55 hours
10 ^-2 emu/g. That is, the former is antiferromagnetic, while the latter is strongly ferrimagnetic. FIG. 2 shows the expansion curves of the various heating conditions shown in Table 3 after reheating at 400 DEG C. for 110 hours and 130 hours, in comparison with the chill casting condition. As shown in curve F in Figure 2,
It can be seen that those heated at 400° C. for 130 hours do not exhibit Invar properties, but those subjected to other treatments (curves D and E) exhibit excellent Invar properties. Example 4 Alloy number 56 (27% Ge, 1% Si, 1% Al, balance Mn) The raw materials are Ge and Mn of the same purity as in Example 1,
99.9% pure Si and Al were used. Samples were manufactured by the methods of Examples 1 and 3 and were heat treated. The measurement method was the same as in Example 1 above.
The properties of the obtained molded product are shown in Table 4. The magnetic susceptibility is 3.6×10 ⁻⁵ emu/g.

[Table] Example 5 Figures 3 to 8 show the measurement results of linear thermal expansion when various subcomponents were added to a Mn-27%Ge binary alloy with Ge constant at 27%. In this case, the raw materials are Ge and Mn with the same purity as in Example 1, and 99.8% purity.
Cr, W, V, Mo, Ti, Zr, Nb, Ta and 99.9% purity Ag, Au, Re, platinum group elements, Zn, Cd, Al,
Ga, In, Tl, Sn, Pb, Cu, Si, As, Sb, Bi,
Se, Te, rare earth elements, Be, Mg, Ca, B, C,
A sample was produced using P and S in the same manner as in Example 1. Next, this was heated at 850°C for 10 hours and then gradually cooled at a rate of 100°C/hour to obtain an annealed state. The measurement method was as described in Example 1 above. Figures 3 to 8 show -50℃~
The coefficient of thermal expansion α (10 ⁻⁶ ) at +100°C is plotted against the concentration of added elements (%). As shown in each figure, the coefficient of linear thermal expansion α is -8×
It was found that it takes a value of 10 ^-6 to +8×10 ^-6 . However, it has been confirmed that when the upper limit (dotted line in the figure) described in the claims is exceeded, the coefficient of linear thermal expansion suddenly increases, which is not preferable. Example 6 Next, FIGS. 9 to 35 show examples of measuring linear thermal expansion of Mn-Ge groups when Cr, W, V, Al, In, Co, and Si among the subcomponents are fixed at 1%. A range in which the linear thermal expansion coefficient of the multi-component alloy is −8×10 ⁻⁶ to +8×10 ⁻⁶ is depicted. The raw materials, manufacturing method, heat treatment method, and measurement method in this case are the same as in Example 1. As shown in each figure, it was found that the linear thermal expansion coefficient formed an excellent invar region over a wide composition range in various combinations of elements. Finally, typical properties of the alloy of the present invention are shown in Table 5. In this case, the raw materials are Ge of the same purity as in Example 1,
Mn, 99.8℃ purity Co, Ni, Cr, W, V, Mo,
Ti, Zr, Nb, Ta and 99.9% purity Ag, Au, Re,
Platinum group elements, Zn, Cd, Al, Ga, In, Tl, Sn,
Using Pb, Cu, Si, As, Sb, Bi, Se, Te, rare earth elements, Bi, Mg, Ca, B, C, P and S,
Samples were manufactured by the same method as in Example 1. Next, this was heated at 850°C for 10 hours and then cooled at a rate of 100°C/hour to obtain an annealed state. The measurement method was as described in Example 1 above, and the hardness was measured using a Vickers hardness meter, and the machinability was measured using a normal lathe.

【table】

【table】

[Table] Note: ◎Very good, ○Good As is clear from Table 5, the present alloy has a small coefficient of linear thermal expansion over a wide composition and temperature range;
It can be seen that it is far superior to conventional non-ferromagnetic Invar alloys. The magnetic susceptibility is on the order of 2.5 to 5.9×10 ⁻⁵ emu/g even in a high magnetic field, and the magnetism is so small that it can be ignored. Furthermore, it can be seen that by using a multi-component alloy, the hardness is reduced and the machinability is improved accordingly. In short, the alloy of the present invention has Ge20~
33%, any of Cr, W, or V as subcomponents 0.01 to 11
%, Mo, Ti, Zr, Nb, Ta, Ag, Au, Re, any of the platinum group elements 0.01-10%, Zn, Cd, Al,
0.01 to 9% of Ga, In, Tl, Sn, Pb, Co,
0.01-8% of any of Ni, Cu, Si, As, Sb, Bi, Se, Te, rare earth elements, 0.01-6% of any of Be, Mg, Ca, B, 0.01 of any of C, P, S ~1% of the total amount of any one or two or more types of 0.01~11%, unavoidable impurities of 1% or less, and the balance Mn (however, the subcomponent is
It is a multi-component alloy consisting of (excluding cases where only Co and Ni are used), and by simple heat treatment, it becomes hexagonal lattice type anti(non)ferromagnetic, and has a magnetic field of -8×10 ^-6 to +8×
It is an excellent non-ferromagnetic invar type alloy with a coefficient of linear thermal expansion anywhere in the range of ^10-6 . Therefore, the present invention is very suitable as a member of precision equipment or control equipment. Finally, in the alloy of the present invention, the amount of Ge is 20 to 33%,
0.01 to 11% of Cr, W, V, Mo, Ti, Zr,
Nb, Ta, Ag, Au, Re, any platinum group element
0.01~10%, Zn, Cd, Al, Ga, In, Tl, Sn,
Any 0.01 to 9% of Pb, Co, Ni, Cu, Si, As,
0.01 to 8% of Sb, Bi, Se, or rare earth elements,
0.01-6% of Be, Mg, Ca, B, C, P,
0.01 to 1% of any S (however, the total amount of subcomponents is 0.01 to 11
The reason for limiting it to %) is whether the Ge amount exceeds 33%.
Less than 20% and subcomponents Cr, W, V more than 11%, Mo, Ti, Zr, Nb, Ta, Ag, Au, Re, platinum group elements more than 10%, Zn, Cd, Al, Ga ,In,
Tl, Sn, Pb exceeds 9%, Co, Ni, Cu, Si,
As, Sb, Bi, Se, Te rare earth elements exceed 8%,
If Be, Mg, Ca, and B exceed 6% and C, P, and S exceed 1%, the antiferromagnetic hexagonal structure required by the alloy of the present invention cannot be obtained no matter what treatment is performed, and the wire This is because the coefficient of thermal expansion exceeds ±8×10 ^-6 . Additionally, if 0.01% or more of additional elements are included as subcomponents, machinability will be significantly improved;
Since machinability is not improved at all if it is less than 0.01%, the lower limit is set to 0.01% or more.

[Brief explanation of the drawing]

Figure 1 is a characteristic curve diagram showing temperature changes in linear thermal expansion coefficient of 27%Ge-1%Cr-Mn alloy subjected to various heat treatments.
-Characteristic curve diagrams showing temperature changes in linear thermal expansion coefficient when Mn alloy is chilled cast and heated at 400℃ for 110 and 130 hours, Figures 3 to 8 are
Characteristic curve diagrams showing temperature changes in linear thermal expansion coefficient α from -50℃ to +100℃ when various subcomponents are added to Mn-27%Ge alloy, Figures 9 to 35 are Mn-27%Ge alloy It is a characteristic curve diagram showing a range in which a multi-component alloy has a coefficient of linear thermal expansion α=+8×10 ⁻⁶ or less when 1% of a third element is added and fixed, and a fourth element is further added.

Claims (1)

[Claims] 1 Ge as the main component 20 to 33% by weight, any of Cr, W, or V as subcomponents 0.01 to 11%, Mo,
Ti, Zr, Nb, Ta, Ag, Au, Re, 0.01-10% of any platinum group element, Zn, Cd, Al, Ga, In,
0.01 to 9% of Tl, Sn, Pb, Cu, Si, As,
Any of Sb, Bi, Se, Te, or rare earth elements 0.01 to 8
%, Be, Mg, Ca, 0.01 to 6% of any of B, C,
Consisting of 0.01 to 1% of either P or S, the total amount of one or more subcomponents of 0.01 to 11%, unavoidable impurities of 1% or less, and the balance Mn, -50℃ to +100℃
Linear thermal expansion coefficient at °C is -8×10 ^-6 ~+8×
A hexagonal lattice type antiferromagnetic invar alloy characterized by a magnetic flux in the range of 10 ^-6 . 2 Contains 20 to 33% of Ge as the main component, 0.01 to 8% of Co or Ni as a subcomponent, and further 0.01 to 11% of any of Cr, W, or V as a subcomponent by weight
%, Mo, Ti, Zr, Nb, Ta, Ag, Au, Re, any of the platinum group elements 0.01-10%, Zn, Cd, Al,
0.01 to 9% of Ga, In, Tl, Sn, Pb, Cu,
Any of Si, As, Sb, Bi, Se, Te, rare earth elements
0.01~8%, any of Be, Mg, Ca, B 0.01~6
%, consisting of 0.01 to 1% of any one of C, P, and S, the total amount of any one or two or more subcomponents of 0.01 to 11%, unavoidable impurities of 1% or less, and the balance Mn, -50
Linear thermal expansion coefficient between ℃ and +100℃ is -8×10 ^-6
The hexagonal lattice type antiferromagnetic invar alloy according to claim 1, characterized in that the hexagonal lattice type antiferromagnetic invar type alloy has a magnetic flux in the range of ~+8×10 ^-6 . 3 Ge 20-33% as main component by weight, 0.01-11% of any of Cr, W, V as subcomponents, Mo,
Ti, Zr, Nb, Ta, Ag, Au, Re, 0.01-10% of any platinum group element, Zn, Cd, Al, Ga, In,
0.01 to 9% of Tl, Sn, Pb, Cu, Si, As,
Any of Sb, Bi, Se, Te, or rare earth elements 0.01 to 8
%, Be, Mg, Ca, 0.01 to 6% of any of B, C,
A composition consisting of 0.01 to 1% of either P or S in a total amount of 0.01 to 11% of one or more of the subcomponents, unavoidable impurities of 1% or less, and the balance Mn was heated at 870°C.
Melt at a high temperature of 500°C or higher, cast it to form a molded product in a specified shape, and heat it for 1 minute to 500°C at a temperature of 500°C or higher and lower than the melting point.
After applying homogenization treatment by heating for an appropriate period of time, cooling from a temperature of 500°C or more and less than the melting point at a rate of 0.7°C/hour or more to form a hexagonal lattice crystal phase,
A method for producing a hexagonal lattice type antiferromagnetic invar alloy, which exhibits a linear thermal expansion coefficient in the range of -8×10 ^-6 to +8×10 ^-6 . 4 Ge20 to 33% as main component by weight, 0.01 to 11% of any of Cr, W, or V as subcomponents, Mo,
Ti, Zr, Nb, Ta, Ag, Au, Re, 0.01-10% of any platinum group element, Zn, Cd, Al, Ga, In,
0.01 to 9% of Tl, Sn, Pb, Cu, Si, As,
Any of Sb, Bi, Se, Te, or rare earth elements 0.01 to 8
%, Be, Mg, Ca, 0.01 to 6% of any of B, C,
0.01 to 1% of either P or S, one or two
A composition consisting of a total amount of 0.01 to 11% of the total amount of subcomponents above, 1% or less of unavoidable impurities, and the balance Mn is melted and cast at a high temperature of 870°C or higher to form a molded product of a specified shape, and the melting point is 500°C or higher and below the melting point. A step of homogenizing the product by heating it at a temperature of 1 minute to 500 hours for an appropriate period of time, and then cooling it at a rate of 0.7 °C/hour or more from a temperature of 500 °C or more and below the melting point, and the obtained molded product. is further reheated at a temperature of 300°C or more and less than 500°C for 1 minute to 500 hours, and cooled at a rate of 0.7°C/hour or more to form a hexagonal lattice crystal phase, -8×10 ^-6 to +8×
A method for producing a hexagonal lattice antiferromagnetic invar alloy characterized by exhibiting a linear thermal expansion coefficient in the range of 10 ^-6 .