JP2010174350A - High elastic and constant-modulus alloy, method for producing the same, and precise mechanical equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a constant-modulus alloy which has a high Young's modulus, and in which the temperature coefficient thereof is low, and further to provide precision mechanical equipment using the same. <P>SOLUTION: An alloy having a composition containing, by mass, 20 to 40% Co, 10 to 20% Ni, 5 to 15% Cr, the IIa group metals of Ca, Sr and Ba of each at most 2%, and one or more kinds selected from the fluorine compounds of the IIa group elements of each at most 1% and of the total of 0.0001 to 5%, and the balance Fe is annealed at 900°C to less than the melting point, is thereafter cooled, and is next subjected to wire drawing at a working ratio of at least 50% so as to be a wire rod or a fine wire with a desired thickness, and thereafter, the wire rod or fine wire is heated at 550 to 720°C so as to obtain a high elastic and constant-modulus alloy having a Young's modulus of at least 190 GP a, and in which the temperature coefficient of the Young's modulus at 0 to 40°C is (-5 to 5)x10<SP>-5</SP>. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an improvement in an Fe—Co—Ni—Cr alloy generally referred to as a coelin bar. More specifically, the present invention relates to an I Ia group element of Ca, Sr, Ba and fluorine of the I Ia group element. The present invention relates to a highly elastic / constant elastic alloy in which the Young's modulus itself is increased while maintaining the characteristics of the Coelin bar that the temperature coefficient of Young's modulus is small by adding one or more compounds. Further, the present invention provides Mo, W, V, Nb, Ta, Cu, Mn, Ti, Zr, Hf, Au, Ag, platinum group elements, Al, Si, rare earth elements, Be, B, C as subcomponents. The present invention relates to a highly elastic / constant elastic alloy containing one or more of the above. In addition, the present invention relates to a method for producing a highly elastic / constant elastic alloy capable of producing the alloy of the present invention with high productivity and improving the reproducibility of the characteristics, and a precision instrument using the alloy. .

Patent Document No. 135850 (Japanese Patent Publication No. 16-5622), which is the inventor of the applicant and the foundation of the foundation, relates to the coelin bar. It is as follows. “1-74.9% Co, 2-17% Cr, 16-68% Fe, 0.1-38% Ni, except that an alloy containing 25-75% of the total of Ni and Co is processed at room temperature or high temperature into a predetermined shape. This is an elastic working body which has been subjected to an appropriate heat treatment and has a substantially invariant frequency or invariant bias with respect to a temperature change in a normal range. Therefore, the manufacturing process of the coelin bar disclosed in Patent Document 1 includes hot or cold working and subsequent heat treatment.

Since the publication of Patent Document 1, Coelin Bar has been used mainly for watches, but was the director of the applicant and incorporated foundation regarding the composition and properties of Coelin Bar that had been put into practical use about 17 years after Patent Document 1. Saito et al., Non-Patent Document 1: “New Magnetic Materials” published on June 10, 1983, 2nd edition, pages 258-264. It is (1) 43.6% Co, 34.6% Fe, 12.7% Cr, 9.1% Ni, thermal expansion coefficient (10-50 ° C) 7.4 × 10 ^-6 , transverse elastic modulus 7080 kg / mm ² , transverse elastic modulus temperature Coefficient (20-50 ° C) 0.0, and (2) 27.7% Co, 39.2% Fe, 10.0% Cr, 23.1% Ni, thermal expansion coefficient (10-50 ° C) 8.1 × 10 ^-6 , transverse elastic modulus 6610kg / mm ² 、 Temperature coefficient of transverse elastic modulus (20 ~ 50 ℃) -0.2 × 10 ^-5 . Non-Patent Document 1 describes that a coelin bar is hardened by processing and heat treatment and becomes highly elastic, and that oxidation of an alloy element affects the reproducibility of characteristics.

Furthermore, the composition and characteristics of the new Coelin bar are published in Non-Patent Document 2: “Revised 4th Edition Metal Data Book” edited by the Japan Institute of Metals, February 29, 2004, page 249. Quote.

  Conventionally, Fe-Co-Ni-Cr-based alloys (coelin bar) have constant elastic properties with a small Young's modulus temperature coefficient, so they are used for suspension wires, coil springs, leaf springs, and balance springs. In addition, the suspension line, coil spring, leaf spring, and hairspring are used in precision instruments such as surveying instruments, seismometers, tachometers, and watches.

Various constant elastic alloys in which Cr of the coelin bar proposed in Non-Patent Document 1 is replaced with Mo, W, V, or Mn have been proposed. On the other hand, the above-mentioned non-patent literature does not show an announcement that attempts to improve the characteristics while maintaining the Fe—Co—Ni—Cr alloy component, which is the basic component of the coelin bar. Since the present applicant has manufactured a coelin bar from the time when the patent of Patent Document 1 was established to the present, it can be evaluated that it was difficult to achieve good characteristics other than the compositions published in Non-Patent Documents 1 and 2.

Furthermore, when the present inventors manufactured a coelin bar by changing the manufacturing conditions in order to reproduce the characteristics of Non-Patent Document 2, the characteristics can be obtained according to the conditions shown in Table 6 below, while the drawing process is performed. When the ratio and the like are further increased, the temperature coefficient of Young's modulus deteriorates, so the conditions in Table 6 were confirmed to be the best. Therefore, it can be said that the characteristic of Non-Patent Document 2 is the current Coelin Champion data.
As for the manufacturing method, it is difficult for Coelin Bar to obtain a sound ingot, particularly a large ingot, as compared with an Fe—Ni alloy. Furthermore, there is a problem of workability defects peculiar to Co-based alloys. These problems can be dealt with when a small ingot is processed through many processes, but the productivity is significantly reduced. Furthermore, Non-Patent Document 2 describes that it is effective to prevent oxidation during production in order to enhance the reproducibility of characteristics, and although actual vacuum melting or the like is performed, sufficient No results were given.

    Patent Document 1: Japanese Patent Publication No. 16-5622

Non-Patent Document 1: “New Material Magnetic Materials”, published in June 10, 1983, 2nd edition, pp. 258-264 Non-Patent Document 2: “Revised 4th Edition Metal Data Book” edited by the Japan Institute of Metals, 2004 Published February 29, pp. 249

As described above, the conventional coelin bar has a problem that the Young's modulus itself cannot be increased at the same time while keeping the temperature coefficient of Young's modulus at the original low value, and the composition range having a constant elastic property is narrow. It was.
Furthermore, the manufacturing method of the coelin bar disclosed in Patent Document 1 is very simple and is not suitable for actually manufacturing the coelin bar. As described above, coelin bar has a characteristic that it is inferior in reproducibility due to oxidation or the like, and thus it is strongly desired to provide a method for producing in large quantities with good reproducibility.

In view of such a current situation, the present invention adds a Ca, Sr, Ba I Ia group element and a fluorine compound of the I Ia group element to a coelin bar of an Fe—Co—Ni—Cr alloy. It was discovered as a result of earnest research on the temperature coefficient of Young's modulus. As a result, in terms of mass ratio, Co20-40%, Ni10-20%, Cr5-15%, Ca, Sr, Ba and each 2% or less of each of the I Ia group element and the fluorine compound of the I Ia group element are each 1 % Or less, a total of 0.0001 to 5% of one or more, and the balance Fe, or if necessary, Mo and W as subcomponents of 10% or less, V, Nb, Ta, Cu, Mn, Ti, Zr, Hf each 7% or less, Au, Ag, platinum group elements, Al, Si, rare earth elements 5% or less, Be3% or less, B, C 1% or less each 1 or 2 Alloys with a total addition of 0.001-15% above the seed were found.
Further, in the production of the coelin bar, when setting the process conditions consisting of melting, hot forging and rolling, annealing, wire drawing and heat treatment, a predetermined amount of the aforementioned I Ia group element and a fluorine compound of the I Ia group element was added. The improved coelin bar has found that the above production conditions can be advantageously set so that both the temperature coefficient of Young's modulus and Young's modulus are good. Moreover, it discovered that the reproducibility defect with respect to oxidation etc. during manufacture was suppressed.

The features of the present invention are as follows.
(1) According to the first invention, in terms of mass ratio, Co20-40%, Ni10-20%, Cr5-15%, and each of Ca, Sr, Ba and 2% or less of each of the I Ia group elements and the I Ia group elements It consists of 0.0001-5% in total of 1 or 2 or more kinds of fluorine compounds of 1% or less respectively, and the balance Fe and unavoidable impurities. Young's modulus is 190 GPa or more and the temperature coefficient of Young's modulus at 0-40 ° C (-5- 5) relates to a high elastic-constant modulus alloy and having a x10 ^-5.

(2) The second invention relates to a mass ratio of Co20-40%, Ni10-20%, Cr5-15% and Ca, Sr, Ba of 2% or less of each of the I Ia group elements and the I Ia group elements. 1% or less of each fluorine compound, or a total of 0.0001 to 5% of 2 or more types, and Mo and W as subcomponents of 10% or less, V, Nb, Ta, Cu, Mn, Ti, Zr, and Hf, respectively. 7% or less each, Au, Ag, platinum group elements, Al, Si, rare earth elements each 5% or less, Be3% or less, B, C 1% each 1 type or 2 types total 0.001-15% , And the balance Fe and inevitable impurities, and has a Young's modulus of 190 GPa or more and a Young's modulus temperature coefficient of 0 to 40 ° C. (−5 to 5) × 10 ⁻⁵ .

  (3) The third invention relates to a precision instrument using the highly elastic / constant elastic alloy described in the above item (1) or (2) processed into a wire, fine wire, plate or thin plate.

(4) In the fourth invention, the alloy having the composition described in the above (1) or (2) is processed into an appropriate shape by hot forging and hot working, and annealed at a temperature of 900 ° C. or higher and lower than the melting point. After cooling, and then drawing to a processing rate of 50% or more to form a wire or fine wire with a desired thickness, the wire or fine wire is heated at a temperature of 550 to 720 ° C. The present invention relates to a method for producing a highly elastic / constant elastic alloy having a temperature coefficient of Young's modulus (−5 to 5) × 10 ⁻⁵ at 0 to 40 ° C.

(5) In the fifth invention, an alloy having the composition described in (1) or (2) above is processed into an appropriate shape by hot forging and hot working, and annealed at a temperature of 900 ° C. or higher and lower than the melting point. Then, after cooling and then rolling to a reduction ratio of 50% or more to obtain a plate or thin plate with a desired thickness, the plate or thin plate is heated at a temperature of 550 to 720 ° C. The present invention relates to a method for producing a highly elastic / constant elastic alloy having a temperature coefficient of Young's modulus (−5 to 5) × 10 ⁻⁵ at 0 to 40 ° C.

(6) In the sixth invention, an alloy having the composition described in (1) or (2) above is processed into an appropriate shape by hot forging and hot working, and annealed at a temperature of 900 ° C. or higher and lower than the melting point. After cooling, the wire is then drawn to a processing rate of 50% or more to form a wire or fine wire with a desired thickness, and then the wire or thin wire is further rolled to a reduction rate of 30% or more to obtain a desired thickness. After forming the plate or thin plate, the plate or thin plate is heated at a temperature of 550 to 720 ° C., whereby the Young's modulus is 190 GPa or more and the Young's modulus temperature coefficient at 0 to 40 ° C. (−5 to 5) × 10 ^{− The} present invention relates to a method for producing a highly elastic / constant elastic alloy having ⁵ .
Next, the present invention will be described in the order of the composition, characteristics, and manufacturing method of the highly elastic / constant elastic alloy.

Composition The component composition system of the alloy of the present invention is composed of Co 20 to 40%, Ni 10 to 20%, Cr 5 to 15%, the following specific group IIa elements and their fluorine compounds, and the balance Fe and inevitable impurities. . The present inventors increased or decreased the amount of Co, Ni, and Cr, centering on the composition (2) of Non-Patent Document 1 and the composition of Non-Patent Document 2, and added the following specific IIa group elements and their fluorine compounds. The Young's modulus and its temperature coefficient were measured. That, Ca, Sr, respectively fluorine compound 2% or less I Ia group element and the I Ia group element, for example CaF _2, SrF ₂ and respectively one or the sum of two or more of 1% or less of BaF ₂ and Ba 0.0001-5% was added. As a result, it was found that the Young's modulus was 190 GPa or more and the temperature coefficient of Young's modulus at 0 to 40 ° C. was (−5 to 5) × 10 ⁻⁵ in the composition range described above. That is, the composition range can be expanded as compared to the composition (2) of Non-Patent Document 1 and the composition of Non-Patent Document 2, but if this composition range is exceeded, the Young's modulus is 190 GPa or less and the Young's modulus at 0 to 40 ° C. temperature coefficient rate becomes -5X10 ^-5 or less, or 5x10 ^-5 or more can not be obtained high elasticity, constantly elastic alloy.

Fe-Co20-40%, Ni10-20%, Cr5-15% alloy is made of single face (γ phase) polycrystal with homogeneous face centered cubic lattice, and the ingot is subjected to hot and cold working When the heat treatment is performed, almost no cast structure remains and the plastic working structure is recrystallized. 2% or less of each of I, Ia group elements of Ca, Sr, Ba added to the Fe-Co-Ni-Cr alloy, and 1% or less of each of the fluorine compounds of the group I Ia elements, or Two or more kinds (hereinafter sometimes referred to as “Ca” or the like) strengthen the matrix by being dispersed and precipitated in the matrix of the γ phase, and further segregate at the grain boundaries to The Young's modulus and strength are increased by the effect of strengthening and preventing the movement of dislocations at the grain boundaries. In addition, since the constant elastic characteristics are closely related to magnetism, the addition of an appropriate amount such as Ca, which is a nonmagnetic element, lowers the saturation magnetic flux density and the magnetic transformation point, thereby obtaining the constant elastic characteristics.

Ca and the like react well with impurity elements such as phosphorus, oxygen, sulfur and nitrogen contained in a trace amount of Fe-Co-Ni-Cr alloy, and have the effects of dephosphorization, deoxidation, desulfurization and denitrification. Remarkably appear and remove these impurity elements. Therefore, when the Fe-Co-Ni-Cr alloy is poured from the melting furnace through the ladle into the mold, the hot water flow becomes good and solidification occurs in a state where the mold is completely filled, and inclusions in the ingot. And segregation of impurities are reduced. Furthermore, if the ingot or intermediate material contains a large amount of inclusions, hot workability or cold workability is impaired, but these workability are remarkably improved. Table 2 shows impurities usually contained in the Fe—Co—Ni—Cr alloy, and each corresponds to an example described later.

Figure 1 is Koerinba - to Ca, Sr, Ba, the CaF _2, SrF ₂ or BaF ₂ were added each alloy, when heated for one hour at 630 ° C. was subjected to wiredrawing working ratio of 99%, it added The relationship between the quantity, Young's modulus and its temperature coefficient is shown.
The horizontal axis in FIG. 1 indicates the amount of Ca, Ba, Sr, CaF ₂ , SrF ₂ or BaF ₂ (ie, “Ca etc.”) added. 10 ⁻⁴ % on the horizontal axis indicates the limit of analysis by atomic absorption spectrometry. In FIG. 1, the Young's modulus E monotonously increasing with the addition amount of Ca or the like is considered to be related to impurity removal by Ca or the like and grain boundary strengthening. The temperature coefficient e of Young's modulus shows a constant elastic characteristic within the range of FIG. However, the temperature coefficient of Young's modulus becomes small at an addition amount of 10 ⁻¹ % or more, and desirable constant elastic properties are obtained. This is presumably because the saturation magnetic flux density and the magnetic transformation point are lowered because Ca and the like are nonmagnetic elements.

  Further, as subcomponents, Mo and W are each 10% or less, V, Nb, Ta, Cu, Mn, Ti, Zr and Hf are each 7% or less, Au, Ag, platinum group elements, Al, Si, rare earth elements 5% or less, Be 3% or less, B, C 1% or less, or a total of 0.001 to 15% of each of these elements, as shown in FIGS. In addition to the effect of increasing the Young's modulus and strength, these additive elements are non-magnetic, so adding an appropriate amount reduces the saturation magnetic flux density and the magnetic transformation point, and reduces the Young's modulus temperature coefficient. is there. Furthermore, when Mn, Al, Si, Ti and rare earth elements are added, the effect of deoxidation / desulfurization is particularly great.

FIG. 2 shows an alloy obtained by adding subcomponents Mo, W, V, Nb or Ta to Alloy No. 30, and FIG. 3 shows an alloy obtained by adding Cu, Mn, Ti, Zr or Hf to Alloy No. 30. FIG. 4 shows that the alloy No. 30 is added with Au, Ag, Pt, Al, Si, La, Be, Y, B, or C, respectively. The relationship between the added amount, Young's modulus, and temperature coefficient when heated for a period of time is shown.
The rare earth element is composed of Sc, Y and a lanthanum element, but the effect is uniform, and the platinum group element is composed of Pt, Ir, Ru, Rh, Pd, Os, but the effect is also uniform. And can be regarded as a synergistic ingredient.

Characteristics (1) Young's modulus The Young's modulus of the present invention is high elasticity of 190 GPa or more, but was measured by a free resonance method in the case of a wire and a plate, and by a dynamic viscoelastic method in the case of a thin wire and a thin plate.
(2) Temperature coefficient of Young's modulus The temperature coefficient of Young's modulus of the present invention is small (-5 to 5) x ^10-5 in the temperature range of 0 to 40 ° C, and has excellent constant elastic properties. The measurement method is the same as the measurement of Young's modulus.

Production Method (1) Melting In order to produce the alloy of the present invention, the raw materials are metallic cobalt, metallic nickel, metallic chromium and electrolytic iron, and metallic Ca, Sr, Ba, group I Ia elements and fluorine compounds of the group I Ia elements. Are appropriately mixed, and in terms of mass ratio, Co20-40%, Ni10-20%, Cr5-15%, and Ca, Sr, Ba, 2% or less of each of the I Ia group elements and the fluorine compounds of the I Ia group elements The total amount is 0.0001 to 5% of 1 type or 2 types or less, and the balance is Fe. These raw materials can be Fe-Ni prealloys or prealloys of Fe and Ca.
The raw material is melted in air, preferably in a non-oxidizing atmosphere (gas such as hydrogen or argon) or in a vacuum using a suitable melting furnace such as a high-frequency melting furnace. When sub-component elements are contained, Mo and W are each 10% or less, V, Nb, Ta, Cu, Mn, Ti, Zr, and Hf are each 7% or less, Au, Ag, platinum group elements, Al, Si 1% or less of each rare earth element 5% or less, Be 3% or less, and B and C 1% or more. A new molten alloy.

(2) Forging and hot working Next, the molten alloy is poured into a mold having an appropriate shape and size at 1450 to 1550 ° C. to obtain an ingot. The size of the ingot is preferably about 1 to 10 kg. Further, the ingot is heated to 900 ° C. or higher and lower than the melting point, preferably 1000 to 1300 ° C., and the ingot is made into an appropriate shape by hot forging. Thereafter, the forged material is subjected to hot working such as hot rolling or a hot roll for a round bar to obtain an intermediate material having an appropriate shape.

(3) Homogenization heat treatment The precision parts that are used for a constant elastic alloy are very small in weight and are used in large quantities, so it is important that each of the small parts has certain characteristics. A homogenization heat treatment is performed.
The above intermediate material is subjected to homogenization heat treatment. That is, the cast structure is destroyed to some extent by the hot forging process and the subsequent hot process, but the cast structure still remains, so it is necessary to homogenize it. Furthermore, homogenization can be promoted by heat-treating the intermediate material. In the homogenization, heating is performed at a temperature of 900 ° C. or higher and lower than the melting point, preferably 950 to 1300 ° C. for an appropriate time, preferably 0.5 to 5 hours, and then cooled. When the homogenization heat treatment is less than 900 ° C., the compositionally heterogeneous structure generated during solidification cannot be made into a homogeneous structure.

(4) Drawing process or rolling process In order to make a precision part, it is necessary to further reduce the size of the intermediate material. Further, as shown in FIGS. It can harden and increase Young's modulus. Accordingly, drawing or rolling with a processing rate of 50% or more is desirable, but when rolling is performed after drawing with a processing rate of 50% or more, the rolling reduction is preferably 30% or more.

(5) Heat treatment after processing After drawing or rolling, when heat treatment is performed at a temperature range of 550 to 720 ° C., preferably 580 to 700 ° C. for an appropriate time, preferably 0.5 to 20 hours, FIG. As shown, the Young's modulus is kept as large as 190 GPa or more, and the temperature coefficient thereof is also small (-5 to 5) × 10 ⁻⁵ , and constant elastic characteristics can be obtained. However, heating at a temperature of 550 ° C. or lower does not remove the curing due to processing, loses mechanical flexibility, and does not provide constant elastic properties. In addition, when heated at a temperature of 720 ° C. or higher, the structure softens, the Young's modulus decreases, the temperature coefficient increases, and the constant elastic properties are lost.

The highly elastic / constant elastic alloy of the present invention, its production method and application will be further described in terms of effects.
(1) Young's modulus 190 GPa by adding a predetermined amount of Ca and the like to the Fe-Co-Ni-Cr alloy, which is a basic component system of the alloy of the present invention, and adjusting the heat treatment conditions after rolling / drawing and working. A high Young's modulus as described above can be obtained. In other words, Ca and the like strengthen the above-mentioned basic component-based alloy, and rolling and wire drawing can be set under conditions such that the Young's modulus is higher than that of a conventional coelin bar, so that a high Young's modulus can be obtained. Can do. On the other hand, when trying to set such processing conditions for the conventional coelin bar, the temperature coefficient of Young's modulus decreases and the constant elasticity characteristic is lost.
(2) Impact resistance Since the alloy of the present invention can be processed at a high degree of processing as described above, it is highly cured, and therefore has excellent impact resistance under conditions in which precision equipment is used.
(3) Temperature coefficient of Young's modulus The alloy of the present invention has a temperature coefficient of Young's modulus of (-5 to 5) x ^10-5 , and has small and excellent constant elastic properties.
(4) Manufacturing method As shown in Non-Patent Documents 1 and 2, the composition specifically disclosed as a conventional coelin bar was only a few examples. However, according to the present invention, a wide range of compositions can be obtained as shown in the following examples. Desirable characteristics can be obtained for the Fe—Co—Ni—Cr based alloy changed to 1. This is because processing has become much easier by adding Ca or the like.
(5) Applications Suitable for suspension lines, coil springs, leaf springs, and hairsprings, etc. In addition, surveying instruments that use suspension lines, seismometers that use coil springs, tachometers that use leaf springs, and hairsprings are used. It is suitable not only as a highly elastic / constant elastic alloy such as a watch, but also as an elastic material used in general precision equipment that requires high elasticity and constant elastic characteristics and impact resistance.

FIG. 6 is a characteristic diagram showing the relationship between the amount of alloy added with Ca, Sr, Ba, CaF ₂ , SrF _2, or BaF ₂ , the Young's modulus, and the temperature coefficient thereof in coelin bar. It is a characteristic view which shows the relationship between the addition amount of the alloy which added Mo, W, V, Nb, or Ta to the alloy number 30, and Young's modulus and its temperature coefficient, respectively. It is a characteristic view which shows the relationship between the addition amount of the alloy which added Cu, Mn, Ti, Zr, or Hf to the alloy number 30, and Young's modulus and its temperature coefficient, respectively. It is a characteristic view which shows the relationship between the addition amount of the alloy which added Au, Ag, Pt, Al, Si, La, Be, Y, B, or C to the alloy number 30, and Young's modulus and its temperature coefficient. (A) It is a characteristic view which shows the relationship between a drawing rate, a Young's modulus, and its temperature coefficient at the time of heating at 630 degreeC for 1 hour after performing a drawing process to the alloy number 30. FIG. (B) It is a characteristic view which shows the relationship between a heating temperature, a Young's modulus, and its temperature coefficient at the time of heating at various heating temperatures for 1 hour after performing a drawing process with a processing rate of 99% on Alloy No. 30. (A) It is a characteristic view which shows the relationship between a rolling reduction, a Young's modulus, and its temperature coefficient at the time of heating at 650 degreeC for 2 hours after rolling to alloy number 43. FIG. (B) It is a characteristic view which shows the relationship between a heating temperature, a Young's modulus, and its temperature coefficient at the time of heating at various heating temperature for 2 hours after giving rolling processing of 98% of reduction ratio. (A) Alloy No. 126 is drawn at a reduction rate of 95%, rolled at various reduction rates, and further heated at 670 ° C. for 2 hours. It is a characteristic view which shows a relationship. (B) Heating temperature, Young's modulus and temperature coefficient when alloy No. 126 is drawn at a processing rate of 95%, rolled at a reduction rate of 60%, and further heated at various heating temperatures for 2 hours It is a characteristic view which shows the relationship.

Next, examples of the present invention will be described.
Example 1
Production of alloy No. 30 (composition Co = 28.8%, Ni = 16.0%, Cr = 9.5%, Sr = 0.8%, BaF ₂ = 0.10%, Fe = balance).
As raw materials, commercially available 99.9% pure electrolytic iron, electrolytic nickel, electrolytic cobalt, electrolytic chromium, metal strontium, and barium fluorine compound (BaF ₂ ) were used. A total weight of 800 g of the raw material was put in an alumina crucible, melted in a high-frequency induction electric furnace in vacuum, and then stirred well to obtain a homogeneous molten alloy. Subsequently, this was poured into a mold having holes of 25 mm in diameter and 170 mm in height at 1500 ° C., and after completely solidified, the ingot was separated from the mold. Thereafter, the ingot was heated to about 1200 ° C. and forged to obtain a square bar having a diameter of 20 mm. Furthermore, after reheating this square bar to about 1200 ° C., it was hot-worked into a round bar using a hot roll machine for round bars up to a diameter of 10 mm and allowed to cool. Then, the said round bar was heated at 1150 degreeC for 1 hour, and annealed. Next, after cold-drawing at room temperature to obtain a 5 mm wire, the wire was heated in a vacuum of 1050 ° C. for 2 hours and annealed to obtain a wire having an appropriate diameter at various processing rates. Thereafter, heat treatment was performed at an appropriate temperature and time, various characteristics were measured, and characteristic values as shown in Table 3 were obtained.

  Further, FIG. 5 (A) shows the drawing ratio, Young's modulus E, and temperature coefficient e when alloy number 30 is drawn at various working rates and then heated at 630 ° C. for 1 hour. It shows the relationship. FIG. 5B shows the relationship between the heating temperature, Young's modulus E, and temperature coefficient e when the wire is drawn at a working rate of 99% and then heated at various temperatures.

Example 2
Production of alloy No. 43 (composition Co = 31.0%, Ni = 15.0%, Cr = 10.0%, Ca = 0.6%, SrF ₂ = 0.05%, Mo = 7.0%, Fe = balance).
As raw materials, commercially available 99.9% purity electrolytic iron, electrolytic nickel, electrolytic cobalt, electrolytic chromium, metallic calcium, strontium fluorine compound (SrF ₂ ) and molybdenum were used. Subsequently, a 20 mm square bar obtained by melting, ingot forming and forging in the same manner as in Example 1 was made into a plate using a hot rolling mill at about 1150 ° C. to a thickness of 10 mm, and then the plate was made 1100. Heated at ℃ for 2 hours and annealed. Next, after rolling into a 3 mm plate at room temperature using a cold rolling mill, the plate is annealed by heating in a vacuum at 1100 ° C. for 2 hours, and at a suitable thickness at various reduction rates. After forming a thin plate, heat treatment was performed at an appropriate temperature and time, and various characteristics were measured, and characteristic values as shown in Table 4 were obtained.

  Further, FIG. 6 (A) shows the relationship between the rolling reduction ratio, Young's modulus E, and temperature coefficient e when alloy number 43 is rolled at various rolling reduction ratios and heated at 650 ° C. for 2 hours. Is shown. FIG. 6B shows the relationship between the heating temperature, the Young's modulus E, and the temperature coefficient e when heated at various temperatures after rolling with a rolling reduction of 98%.

Example 3
Alloy No. 126 (composition Co = 28.0%, Ni = 14.7%, Cr = 8.8%, Ba = 0.8%, CaF ₂ = 0.12%, W = 6.5%, Nb = 3.5%, Fe = remainder) Manufacturing.
As raw materials, commercially available 99.9% pure electrolytic iron, electrolytic nickel, electrolytic cobalt, electrolytic chromium, barium, calcium fluoride compound, tungsten and niobium were used. Melting and ingot forming were carried out in the same manner as in Example 1, and this was forged at about 1200 ° C. to obtain a round bar having a diameter of 20 mm to carry out the ingot. The forged round bar was heated to about 1150 ° C, then hot worked to a diameter of 10mm using a hot roll machine for round bars, allowed to cool, and the round bar was heated at 1200 ° C for 1 hour and annealed. . Next, after cold drawing at room temperature to form a 5 mm wire, the wire was heated and annealed in a vacuum of 1200 ° C. for 1 hour, and further at various processing rates using a cold drawing machine. After forming a wire having an appropriate diameter, the wire was further rolled to an appropriate thickness using a cold rolling mill to form a thin plate. Subsequently, the thin plate was subjected to heat treatment at an appropriate temperature and time, and various characteristics were measured, and characteristic values as shown in Table 5 were obtained.

  Further, FIG. 7A shows that alloy No. 126 was drawn into a thin wire by performing a drawing process at a processing rate of 95%, and then the thin wire was rolled at various reduction ratios to form a thin plate. 3 shows the relationship between the rolling process rate (rolling rate), Young's modulus E, and temperature coefficient e when heated at 670 ° C. for 2 hours. FIG. 7B shows the heating temperature and Young's modulus E when a thin wire subjected to a drawing process with a processing rate of 95% is further rolled at a reduction rate of 60% and then heated at various temperatures for 2 hours. And the relationship with the temperature coefficient e.

Example 4
Wires and fine wires or plates and thin plates were produced for the alloys shown in Tables 6 and 7 (where the balance of the alloy composition is Fe). That is, in Table 6, an alloy having a processing rate of “−” is manufactured by the manufacturing method of Example 2, an alloy having a rolling reduction of “−” is manufactured by the manufacturing method of Example 1, and the other examples are the examples. According to the production method 3, a wire and a thin wire or a plate and a thin plate were produced.

The alloy of the present invention has a high Young's modulus of 190 GPa or higher, a temperature coefficient of Young's modulus at 0 to 40 ° C. is small (-5 to 5) × 10 ⁻⁵ , and has excellent constant elastic properties. Since it is suitable not only for seismometers, tachometers, and watches, but also as an elastic material for general precision equipment that requires high elasticity and constant elasticity, it makes a great contribution to the industry.

Claims (6)

In terms of mass ratio, Co20-40%, Ni10-20%, Cr5-15% and Ca, Sr, Ba, 2% or less of each of the I Ia group element and 1% or less of the fluorine compound of the I Ia group element. one or more total from 0.0001 to 5%, and the balance being Fe and unavoidable impurities, the temperature coefficient of the Young's modulus at least a Young's modulus 190GPa and 0 to 40 ° C. (-5~5) have a x10 ^-5 Highly elastic and constant elastic alloy characterized by By mass ratio, Co20-40%, Ni10-20%, Cr5-15% and Ca, Sr, Ba each 2% or less I Ia group element and each I Ia group element fluorine compound 1% or less One or two or more total 0.0001-5%, Mo and W as subcomponents 10% or less, V, Nb, Ta, Cu, Mn, Ti, Zr, Hf 7% or less, Au, Ag , Platinum group elements, Al, Si, rare earth elements 5% or less, Be3% or less, B, C 1% or less, total of 0.001-15%, and the balance Fe and inevitable impurities A high-elasticity / constant-elasticity alloy having a Young's modulus of 190 GPa or more and a Young's modulus temperature coefficient of 0 to 40 ° C. (−5 to 5) × 10 ⁻⁵ .   3. A precision instrument using a highly elastic / constant elastic alloy according to claim 1 or 2 processed into a wire, fine wire, plate or thin plate. The ingot of the alloy having the composition according to claim 1 or 2 is processed into an appropriate shape by hot forging and hot working, annealed at a temperature of 900 ° C. or higher and lower than the melting point, cooled, and then processed at a processing rate of 50 % To obtain a wire or thin wire having a desired thickness, and then heating the wire or thin wire at a temperature of 550 to 720 ° C., thereby Young's modulus of 190 GPa or more and Young's modulus at 0 to 40 ° C. A method for producing a highly elastic / constant elastic alloy having a temperature coefficient of (-5 to 5) × 10 ⁻⁵ . The ingot of the alloy having the composition according to claim 1 or 2 is processed into an appropriate shape by hot forging and hot working, annealed at a temperature of 900 ° C. or higher and lower than the melting point, cooled, and then reduced to 50%. % To obtain a plate or thin plate having a desired thickness, and then the plate or thin plate is heated at a temperature of 550 to 720 ° C., whereby a Young's modulus of 190 GPa or more and a Young's modulus at 0 to 40 ° C. A method for producing a highly elastic / constant elastic alloy having a temperature coefficient of (-5 to 5) × 10 ⁻⁵ . The alloy having the composition according to claim 1 or 2 is processed into a suitable shape by hot forging and hot working, annealed at a temperature of 900 ° C. or higher and lower than the melting point, cooled, and then processed at a processing rate of 50% or higher. After drawing into a wire or fine wire with a desired thickness, the wire or fine wire is further rolled to a reduction ratio of 30% or more to obtain a plate or thin plate with a desired thickness, and then the plate Alternatively, a method for producing a highly elastic / constant elastic alloy having a Young's modulus of 190 GPa or more and a Young's modulus temperature coefficient (-5 to 5) × 10 ⁻⁵ at 0 to 40 ° C. by heating the thin plate at a temperature of 550 to 720 ° C. .

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