JPH0153332B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is an alloy consisting of iron and tungsten, or an alloy containing these as the main component, with subcomponents of vanadium, niobium, chromium, molybdenum, tantalum, nickel, copper, cobalt, titanium, zirconium,
Square hysteresis consisting of 0.01 to 60% of one or more of silicon, aluminum, germanium, tin, antimony, beryllium, manganese, rare earth elements (yttrium, lanthanum elements), and carbon, and containing a small amount of impurities. The present invention relates to a method for manufacturing a magnetic alloy, and its purpose is to obtain a square hysteresis magnetic alloy that has a large residual magnetic flux density, good square hysteresis characteristics, and is easy to forge and process. Currently, prismatic magnetic materials are used as magnetic materials for memory elements, ferrites, and latching relays in electromagnetic equipment. They have a large residual magnetic flux density, exhibit angular hysteresis, and have coercive forces ranging from several Oersteds to several 100 Oersteds depending on the application. alloy is used. Some of these products require advanced processing or require work such as glass sealing, so they are highly processable and their magnetic properties change when heated at high temperatures (approximately 800°C). It is hoped that it will remain stable over time. Conventionally, magnetic materials having such characteristics include Fe-C alloys, Fe-Mn alloys, Fe-Co alloys, and Fe-Ni alloys. However, Fe-C
Although these alloys are inexpensive and have excellent workability, they have the disadvantage that their magnetic properties deteriorate significantly when heated to high temperatures, and Fe-Co and Fe-Ni alloys have Since it contains a large amount of expensive cobalt or nickel and requires advanced processing technology, it is difficult to say that it is fully satisfactory industrially. As a result of numerous studies, the present inventors found that tungsten 1
Alloys consisting of ~20% and the balance iron, with this as the main component, and additional subcomponents of vanadium 10% or less, niobium 0.5% or less, chromium 15% or less, molybdenum 10% or less, tantalum 0.5% or less, and nickel 15
% or less, Copper 10% or less, Cobalt 50% or less, Titanium 5% or less, Zirconium 5% or less, Silicon 5% or less, Aluminum 5% or less, Germanium 5% or less, Tin 5% or less, Antimony 5% or less, Beryllium 3 % or less, manganese 15% or less, rare earth elements 2%
An alloy consisting of 0.01 to 60% in total of one or more of the following and 1.5% or less of carbon and a small amount of impurities has a large residual magnetic flux density, exhibits excellent square hysteresis, and has a coercive force of 2 oersted or more. We discovered that it is a magnetic alloy that is easy to process and has stable magnetic properties even when heated at high temperatures, and we investigated a method for producing it. That is, the present invention provides a method for manufacturing a prismatic hysteresis magnetic alloy that has a large residual magnetic flux density, exhibits prismatic hysteresis, has a coercive force of 2 oersted or more, and is easy to forge and form. The alloy obtained by this method is suitable as a magnetic material for the above-mentioned electromagnetic equipment requiring square hysteresis characteristics. To make an alloy using the manufacturing method of the present invention, first 1 to 20% of tungsten as the main component and the balance iron;
Vanadium 10% or less, niobium 0.5% as secondary components
less than 15% chromium, less than 10% molybdenum, less than 0.5% tantalum, less than 15% nickel, less than 10% copper, less than 50% cobalt, less than 5% titanium, less than 5% zirconium, less than 5% silicon, less than 5% aluminum
% or less, germanium 5% or less, tin 5% or less, antimony 5% or less, beryllium 3% or less, manganese 15% or less, rare earth elements 2% or less, and carbon
1.5% or less of one or more types total 0.01-60
% in air, preferably in a non-oxidizing atmosphere or in vacuum using a suitable melting furnace, manganese, silicon, aluminum, titanium, calcium alloys, magnesium alloys, and other deoxidizers, Add a small amount (1% or less) of a desulfurizing agent to remove as much impurity as possible, and stir thoroughly to obtain a compositionally uniform molten alloy. Next, this is poured into a mold of an appropriate shape and size to obtain a sound ingot, which is further heated to approximately 800℃~
It is forged or hot-worked and cold-worked at a high temperature of 1200°C to form a suitable shape, such as a bar or plate, and then annealed or solution-treated by heating at a high temperature of about 900°C or higher for an appropriate time. give
This is then subjected to cold working at a processing rate of 50% or more using methods such as swaging, wire drawing, or rolling to form the desired shape, such as a thin wire or thin plate. Furthermore, by heating these cold-worked products in air, preferably in a non-oxidizing atmosphere or in vacuum at a temperature of 400°C to 1000°C, excellent rectangular hysteresis magnetism with a coercive force of 2 oersted or more can be obtained. An alloy is obtained. The above annealing or solution treatment is selected as appropriate depending on the composition of the alloy, but annealing is necessary to remove processing strain and homogenize the structure by heating. In addition, solution treatment uses high-temperature heating to form a supersaturated structure, and during the heating performed after cold working, fine intermetallic compounds are precipitated and the coercive force is increased. is necessary. The above-mentioned cold working has the effect of aligning the dominant direction of the crystals of the alloy, and this effect is particularly noticeable when processing is performed at a working rate of 50% or more. Furthermore, the heating performed after the above-mentioned cold working improves the squareness characteristics and coercive force through removal of processing strain, recrystallization, transformation, precipitation, etc., but this effect is especially effective when heated from 400℃ to about 1000℃. is large. Next, examples of the present invention will be described. Example 1 Production of alloy with alloy number 8 (composition Fe = 87.8%, W = 12.2%) The raw materials are 99.9% pure electrolytic iron and 99.8% pure
High purity tungsten was used. To prepare the sample, raw materials were placed in an alumina crucible with a total weight of 700 g, melted in air in a high-frequency induction electric furnace, and then thoroughly stirred to form a homogeneous molten alloy. Next, add this to diameter 25
The resulting ingot was forged at approximately 1000℃ to form a round bar with a diameter of 4mm, heated at 1000℃ for 1 hour, cooled in water, and then cold drawn. It was made into a wire with a diameter of 0.5 mm. The processing rate (area reduction rate) in this case is 98%. Further, a 20 cm length was cut from this line as a sample, and after various heat treatments, the squareness ratio Br/B 100 expressed as the ratio of the residual magnetic flux density Br to the magnetic flux density B ₁₀₀ at a magnetic field of ₁₀₀ oersted was obtained. Measure the value of coercive force Hc,
The properties shown in Table 1 were obtained.

[Table] Example 2 Alloy number 52 (composition Fe = 85.7%, W = 11.3%, Cr
3%) The raw materials used were iron and tungsten with the same purity as in Example 1, and chromium with a purity of 99.8%. The method of manufacturing the sample was the same as in Example 1. The samples were subjected to various heat treatments to obtain the properties shown in Table 2.

[Table] Example 3 Alloy number 120 (composition Fe = 85.2%, W = 11.6%, Ge
3.2%) The raw materials used were iron and tungsten of the same purity as in Example 1, and germanium of 99.8% purity. The method of manufacturing the sample was the same as in Example 1. The samples were subjected to various heat treatments to obtain the properties shown in Table 3.

【table】 The magnetic properties of typical alloys are shown in Table 4.

[Table] Example 4 Alloy number 180 (composition Fe = 67.5%, W = 9.8%, Cr
2%, Mo=0.7%, Co=20%) The raw materials used were iron and tungsten of the same purity as in Example 1, and chromium, molybdenum, and cobalt of 99.8% purity. The method of manufacturing the sample was the same as in Example 1. The samples were subjected to various heat treatments to obtain the properties shown in Table 4.

[Table] Example 5 Alloy number 228 (composition Fe = 66.7%, W = 12%, Be
1%, Co=20%, C=0.3%) The raw materials used were iron and tungsten of the same purity as in Example 1, and beryllium, cobalt, and carbon of 99.8% purity. The method of manufacturing the sample was the same as in Example 1. The samples were subjected to various heat treatments to obtain the properties shown in Table 5.

[Table] Figure 1 shows Fe containing various amounts of tungsten.
- Coercive force HC when a W-based alloy is heated at 1000°C for 1 hour, water-cooled, and then cold-worked at a processing rate of 98% and heated in a vacuum at 700°C,
The residual magnetic flux density Br and the squareness Br/B ₁₀₀ are shown. As shown in the figure, as the amount of tungsten increases, the coercive force HC increases significantly, and the residual magnetic flux density
Although Br gradually decreases, the squareness ratio Br/B ₁₀₀ shows excellent properties of 80% or more regardless of the amount of tungsten. However, if tungsten is less than 1%, the coercive force HC
is less than 2 oersted, and tungsten
If it exceeds 20%, processing becomes difficult. Figure 2 shows the coercive force HC and residual magnetic flux density Br when an alloy containing 12.2% tungsten was similarly cold worked at a processing rate of 98% and then heated at various temperatures.
and the squareness ratio Br/B ₁₀₀ are shown. As shown in the figure, when heated at a temperature of 400°C or higher, the squareness ratio is 80% or more, but when heated at a temperature of 400°C or lower, the squareness ratio becomes less than 80%, making it unsuitable as a square hysteresis magnetic alloy. It is a major feature of the alloy of the present invention that this squareness ratio remains 80% or more even when heated at high temperatures. Figure 3 shows Fe-12.7%W-22.0%Co alloys heated at various high temperatures for 1 hour, cooled with water, and then processed at various processing rates.
FIG. 2 is a characteristic diagram showing the magnetic properties of an alloy obtained by the manufacturing method of the present invention, which was subjected to 98% cold working and then heated at 750°C. As is clear from the figure, the high temperature
In solution treatment by water cooling after heating, the coercive force, residual magnetic flux density, and squareness are all high over a wide range of water cooling start temperatures, showing excellent magnetic properties. Figure 4 shows Fe-12.2%W alloy with Cr, Ni or
This is a characteristic diagram showing the magnetic properties of an alloy obtained by the manufacturing method of the present invention in which Co is added and similarly cold worked and heat treated.
Alternatively, when Co is added, both the coercive force and the squareness increase. The residual magnetic flux density increases when Co is added, but it decreases when Cr is 15% or more and Ni is 15% or more, which is not preferable. Moreover, if Co exceeds 50%, processing becomes difficult, which is not preferable. Figure 5 is a characteristic diagram showing the magnetic characteristics of an alloy obtained by the manufacturing method of the present invention in which V, Mo, or Mn is added to the Fe-12.2% W alloy and similarly cold-worked and heat-treated. As is clear from the figure, coercive force and squareness increase when any of V, Mo, or Mn is added, but V10% or more, Mo10% or more,
If Mn exceeds 15%, the residual magnetic flux density decreases, which is not preferable. Figure 6 shows Ta, Cu, and Fe-12.2%W alloy.
This is a characteristic diagram showing the magnetic properties of an alloy obtained by the manufacturing method of the present invention in which Al, Ti, Zr, or Si is added and similarly subjected to cold working and heat treatment. 12.2% W alloy with Ta, Cu, Al,
Coercive force and squareness will increase if any of Ti, Zr, or Si is added, but if Ta is 10% or more, Cu is 10% or more,
If Al is 5% or more, Ti is 5% or more, Zr is 5% or more, or Si is 5% or more, the residual magnetic flux density decreases and is not desirable.
Also, Al5% or more, Ti5% or more, Zr5% or more, Si5%
If it is more than that, it becomes difficult to process, which is not preferable. Figure 7 shows the Fe-12.2%W alloy with Ge, Sn,
This is a characteristic diagram showing the magnetic properties of an alloy obtained by the manufacturing method of the present invention in which Sb, Be, C, Ce, or Nb is added and similarly subjected to cold working and heat treatment. Ge, Sn, Sb, Be, C, Ce
If any of these is added, the coercive force and squareness will increase, but if it is more than 5% Sn, 5% Sb, or 3% Be, the residual magnetic flux density will decrease and processing will become difficult, which is not preferable. .5% or more, Ce
(Rare earth element) If it exceeds 2%, processing becomes difficult, which is not preferable. Adding Nb increases coercive force and residual magnetic flux density, but Nb of 0.5% or more impairs workability, which is not preferable. Also, Figures 8, 9, 10 and 11
The figure shows Fe-5%W alloy with Cr, Ni, Co, Mn, V,
Mo, Cu, Ti, Zr, Si, Al, Ge, Sn, Sb, Be,
FIG. 2 is a characteristic diagram showing the magnetic properties of an alloy obtained by the manufacturing method of the present invention in which Ce, Nb, Ta, or C is added and similarly subjected to cold working and heat treatment. As is clear from these figures, the addition of these elements increases both the coercive force and the squareness. Although the residual magnetic flux density increases with the addition of Co and decreases with the addition of other elements, it still shows a large value of 10 kilogauss or more. Furthermore, Fig. 12, Fig. 13, Fig. 14, and Fig. 15 show that Cr, Ni, Co, Mn,
V, Mo, Cu, Ti, Zr, Si, Al, Ge, Sn, Sb,
This is a characteristic diagram showing the magnetic properties of an alloy obtained by the manufacturing method of the present invention in which Be, Ce, Nb, Ta or C is added and similarly subjected to cold working and heat treatment. When these elements are added, both the coercive force and the squareness increase. Although the residual magnetic flux density increases with the addition of Co and decreases with the addition of other elements, it still shows a large value of 10 kilogauss or more. Furthermore, as can be seen from the above examples and Table 4, Fe-W alloys and Fe-W alloys containing this as the main component, V, Nb, Cr, Mo, Ta, Ni, Cu,
Co, Ti, Zr, Si, Al, Ge, Sn, Sb, Be, Mn,
The alloy produced by the manufacturing method of the present invention obtained by adding a total of 0.01 to 60% of one or more of rare earth elements and C has a processing rate of 50% after annealing or solution treatment.
After the above cold working, by heating at 400℃ or higher, the coercive force becomes 2 oersted or higher.
A magnetic alloy having a large residual magnetic flux density and excellent square hysteresis characteristics can be obtained. In addition, in the manufacturing method of the present invention, the alloy is given a
It has the feature that the squareness does not deteriorate easily even if the alloy is further heated or cold worked after it has been cold-worked by 50% or more and given squareness by heating to 400℃ or higher. . Therefore, the alloy obtained by the production method of the present invention is advantageous in producing products that require glass sealing or further processing after final heat treatment. As mentioned above, in the manufacturing method of the present invention, the properties of the alloy can be obtained by performing cold working with a loading rate of 50% or more and then heating at a temperature of 400°C or higher. Even if I go over and over again,
Naturally, good squareness characteristics can be obtained. The alloys listed in the drawings, examples, and Table 4 include relatively pure metals Nb, Cr, Mo, W,
Mn, V, Ti, Al, Si, rare earth elements, C, etc. were used, but it is also possible to use economically advantageous general commercially available ferro or master alloys and Mitsushi metal instead of these materials without deoxidizing and desulfurizing during melting. If you do it enough,
Almost the same magnetic properties and workability as when using these metals can be obtained. As described above, according to the manufacturing method of the present invention, by annealing or solution treatment of a given alloy, cold working it, and then heating it at 400°C or higher, an alloy with excellent squareness characteristics and a large coercive force can be obtained. .

[Brief explanation of drawings]

Figure 1 is a curve diagram showing the magnetic properties when Fe-W alloy is heated at 1000℃ for 1 hour, cooled, then cold worked at a working rate of 98%, and then heated at 700℃. The figure shows a Fe-W alloy containing 12.2% tungsten after being cold-worked at a processing rate of 98%.
Curve diagrams showing magnetic properties when heated at various temperatures. Figure 3 shows Fe-12.7%W-22.0%Co alloys heated at various high temperatures for 1 hour, water-cooled, and then processed at a processing rate of 98.
% cold working and then heating at 750°C. Figure 4 shows the magnetic properties when Cr, Ni or Co is added to the Fe-12.2% W alloy and cold worked and heat treated in the same way. Figure 5 is a curve diagram showing the magnetic properties when V and Mo are applied to the Fe-12.2%W alloy.
Alternatively, a curve diagram showing the magnetic properties when Mn is added and similarly subjected to cold working and heat treatment. Figure 6 shows the same Fe-12.2% W alloy with Ta, Cu, Al, Ti,
Alternatively, Figure 7 is a curve diagram showing the magnetic properties when Si is added and similarly subjected to cold working and heat treatment.
Figure 8 is a curve diagram showing the magnetic properties when Ge, Sn, Sb, Be, C, Ce, or Nb is added to Fe-12.2% W alloy and similarly subjected to cold working and heat treatment.
A curve diagram showing the magnetic properties when Cr, Ni, Co, or Mn is added to Fe5%W alloy and similarly subjected to cold working and heat treatment. Figure 9 shows the magnetic properties of Fe-5%W alloy with V, Mo, A curve diagram showing the magnetic properties when Cu, Ti, Zr or Si is added and subjected to cold working and heat treatment in the same way.
A curve diagram showing the magnetic properties when Sn, Sb, Be or Ce is added and similarly cold worked and heat treated. Similarly, a curve diagram showing the magnetic properties when subjected to cold working and heat treatment, Figure 12 is Fe17
%W alloy by adding Cr, Ni, Co or Mn,
Similarly, a curve diagram showing the magnetic properties when subjected to cold working and heat treatment, Figure 13 shows V,
A curve diagram showing the magnetic properties when Mo, Cu, Ti, Zr or Si is added and subjected to cold working and heat treatment in the same way.
A curve diagram showing the magnetic properties when Sn, Sb, Be or Ce is added and similarly cold worked and heat treated. It is a curve diagram showing magnetic properties when cold working and heat treatment are similarly performed.

Claims (1)

[Claims] 1 An alloy consisting of 1 to 20% tungsten by weight, the balance iron, and a small amount of impurities is annealed or solution treated, then cold worked at a working rate of 50% or more, and then A method for producing a rectangular hysteresis magnetic alloy, which exhibits a coercive force of 2 oersted or more by heating at 400°C or more. 2 The main components are 1 to 20% tungsten and the balance iron by weight, and the subcomponents are less than 10% vanadium, less than 0.5% niobium, less than 15% chromium, less than 10% molybdenum, less than 0.5% tantalum, and nickel 15.
% or less, Copper 10% or less, Cobalt 50% or less, Titanium 5% or less, Zirconium 5% or less, Silicon 5% or less, Aluminum 5% or less, Germanium 5% or less, Tin 5% or less, Antimony 5% or less, Beryllium 3 % or less, manganese 15% or less, rare earth elements 2%
An alloy consisting of the following and carbon 1.5% or less, a total of 0.01 to 60% of one or more types, and a small amount of impurities, is annealed or solution treated, then cold worked at a processing rate of 50% or more, and then 1. A method for producing a rectangular hysteresis magnetic alloy, which exhibits a coercive force of 2 oersted or more by heating it at 400°C or more.