JPS6077965A - Square hysteresis magnetic alloy and its production - Google Patents

Abstract

PURPOSE:To provide a magnetic alloy which has a large residual magnetic flux density and good square hysteresis characteristic and is easy to forge and work by adding main components and auxiliary components of specific metals to an Fe-W alloy. CONSTITUTION:One or >=2 kinds among a specific amt. of Ag, Au, platinum group elements, Mg, Ca, Sr, Ba, Hf, Zn, Cd, B, Ga, In, Tl, Pb, P, As, Bi, Se, Te are added as main additive components at 0.001-20% in total to an Fe-W alloy contg. 1-20% W. Or 1 or >=2 kinds among V, Nb, Cr, Mo, Ta, Ni, Cu, Co, Ti, Zr, Si, Al, Ge, Sn, Sb, Be, Mn, rare earth elements and C are further incorporated as auxiliary additive components at 0.001-60% in total to said alloy. A casting ingot of such alloy is subjected to an annealing or soln. heat treatment. The treatment ingot is cold worked at >=50% reduction ratio and is then subjected to a heating treatment at >=400 deg.C, by which the magnetic alloy is obtd.

Description

Detailed Description of the Invention The present invention relates to a 1+1 magnetic alloy used in reed switches, memory elements, ferrets, latching relays, etc., and its purpose is to create a rectangular hysteresis with a high residual magnetic flux density and a large square hysteresis. The purpose of the present invention is to obtain a square hysteresis magnetic alloy that is custom-made and easy to forge and process.

Currently, it is used as a magnetic material for reed switches, memory elements, ferreeds, and latching relays in electromagnetic equipment.
The residual magnetic flux density is sharp and shows hysteresis of squareness.
A prismatic magnetic alloy having a coercive force of several Oersteds to several 100 Oersteds is used depending on the application. These products require advanced processing or require work such as glass sealing, etc., and are dusty, easy to process, and have magnetic properties that do not require high-temperature heating.
It is desired that about soo'OJ and -C also be cheap.

Traditionally, Fe has been used as a magnetic material that can handle such special orders.
-C alloy, li'e-14n yarn kettle, b'e-co
There are o alloys, Fe-Ni alloys, etc. However, Fe-
Although C-based alloys and Ff3-Mn-based base metals are inexpensive and have excellent workability, they have the disadvantage that magnetic customization deteriorates markedly when heated at still high temperatures.
The nl-based alloy contains commercially available cobalt or nickel in the child door, and requires high-crystalline engineering techniques, so it is difficult to say that it is industrially fully satisfactory.

Previously, the present inventors disclosed in Japanese Patent Application No. 52-2874.2 that a pe-w alloy is an excellent rectangular magnetic base metal with a coercive force of 2 krusted or more, but since then, numerous studies have been carried out. As a result, tungsten l ~ 20%, silver 10% or less, gold 10% or less, platinum group elements 10% or less, magnesium 3% or less, calcium 3% or less, strontium 10%
Hereinafter, Barium 10T or less, Hafnium) or less,
Zinc 5% or less, cadmium 5% or less, boron 2% or less,
Potassium 10% or less, indium 10% or less, thallium 10% or less, lead 3% or less, phosphorus 2% or less, arsenic 2% or less,
An alloy consisting of a total of 0.001 to 20% of bismuth s9b or less, 3% or less of heptalene, and 5% or less tellurium, and the balance iron, and an alloy containing this as the main component and vanadium 10% or less as a minor component. , niobium 10.0% or less, chromium 25qb or less, molybdenum 10% or less, tantalum 10% or less, nickel 15φ or less, copper 1O% or less,
Cobalt 50% or less, titanium 5% or less, zirconium 5
5% or less of silicon, 5% or less of aluminum, 5% or less of germanium, 5% or less of tin, 5% or less of antimony, 3% or less of beryllium, 15% or less of mankan, rare earth elements 2
% or less, and 1fIII or 2 with less than 1.5% carbon
Alloys with a total of 0.001 or more than 60% and a small amount of impurities have a large residual magnetic flux density, exhibit excellent square hysteresis, have a coercive force of 2 millimeters or more, and are easy to process. We discovered that the magnetic special order is a stable magnetic alloy even when heated at high temperatures, and investigated the manufacturing method.

That is, the present invention has a large residual magnetic flux density, exhibits rectangular hysteresis, has a coercive force of 2 millimeters or more, and is forged,
The present invention provides a method for manufacturing a rectangular hysteresis magnetic alloy that is easy to form, and the alloy obtained by the manufacturing method of the present invention is suitable as a magnetic material for the above-mentioned electromagnetic equipment that requires a rectangular hysteresis characteristic.

To make the alloy according to the manufacturing method of the present invention, the main components are 1 to 20% tungsten, less than 10% silver, less than 10% gold, less than 10% platinum group elements, less than 3% magnesium, and less than 3% calcium. , Strontium 10% or less, Barium 10% or less, Hafnium 10T or less, Zinc 5 or less, Cadmium 5% or less, Boro 72% or less, Gallium 10% or less, Indium 10% or less, Thallium 10% or less, Lead 8
% or less, phosphorus 2% or less, arsenic 2% or less, bismuth 3- or less, selenium 3φ or less, and tellurium 5% or less, total 0.001 to 20%, balance iron, and vanadium as a subcomponent. 10% or less, niobium 10% or less, chromium 25% or less, molybdenum 10% or less, tantalum 10%
Below, nickel 15% or less, copper 10% or less, cobal) 5
0% or less, titanium 5% or less, zirconium 5% or less, silicon 5% or less aluminum 5% or less, dalmanium 5% or less, tin 5% or less, antimony 5% or less, beryllium 3 or less, mankanium 15% or less, rare earths One building or combination of two or more elements with 2φ or less and carbon 1.5% or less; 1
bales, manganese, silicon aluminum, titanium, calcium alloys, magnesium alloys, which are melted using a suitable melting furnace in air, preferably in a non-oxidizing Ti atmosphere or in A air. Add a small amount of other deoxidizing agents and desulfurizing agents! (1 g or less) is added to remove any impurities and thoroughly stirred to obtain a compositionally uniform molten alloy.

Next, this is poured into a mold of an appropriate shape and size to obtain a residual ingot, which is further subjected to forging, hot working, and cold working at a high temperature of approximately 800°C to 1300°C to form a suitable ingot. An object in the form of a rod or plate, for example, is annealed or solution-treated by heating at a stomach temperature of about 900"C or higher for an appropriate period of time. Then, it is subjected to processes such as swaging, wire drawing, rolling, and shaping. Processing rate 5 depending on the method
The material is subjected to cold working of 0% or more and made into a desired shape, such as a thin wire or a thin plate. Furthermore, these cold-worked products are placed in fresh air, preferably in a non-oxidizing atmosphere or in an A
An excellent rectangular hysteresis magnetic alloy having a coercive force of 2 hours or more can be obtained by heating the alloy at a temperature of 4.00'C or more to about 100'A in 2C.

The above-mentioned annealing or solution treatment is selected and applied appropriately depending on the composition of the alloy, but annealing is necessary to remove stress and beads and homogenize the structure by heating. Also, solution treatment causes the formation of a supersaturated structure through high-temperature heating, resulting in the formation of a supersaturated structure after cold working. This heating is necessary to precipitate fine intermetallic compounds and increase the coercive force.

The above cold working has the effect of aligning the dominant direction of the crystals of the alloy, and this effect is remarkable when 71 pieces are worked at a working rate of 50% or more. After the above-mentioned cold working, heating is performed (bow 1, removal of processing distortion.

Recrystallization, transformation, 41 output, etc. can be used to customize square shapes and improve coercive force, especially + o o ”c or more 10
It is highly effective when heated up to about 00°C.

I will briefly describe the 11th generation of the present invention.

Example l D-side type 3 go (iQW F'e T !8.-9
%, -W = 10.5%.

As a raw material for manufacturing a joint name of Ag=1.5φ) ≦)9. Electrolytic iron with a purity of 99.8
Tungsten of high purity was used. To use the sample: Put all the raw materials in an alumina J-1 pot at +t8ooy, melt in a high frequency 6N'S Tt furnace in an argon atmosphere, then add 0.5% Mn and stir well to make a homogeneous molten alloy. And so. Next, this is 25 diameter, warm type] 701.1 m
The resulting ingot was poured into a mold with holes of approximately 1200°C.
It was forged into a round bar with a diameter of 2mm, heated at 1200°C for 1 hour, cooled in oil, and then cold-drawn into a round bar with a diameter of 0.5mm.
The line is mm. In this case, the processing rate (area reduction rate is 97%)
It is. Furthermore, a length of 25 CrrLf was cut from this line as a sample, and the residual magnetic flux density Br was subjected to extensive heat treatment.
and the magnetic flux density B□ when the magnetic field is 100 oersted. .

Squareness ratio Br/B□ expressed as a ratio. . Measurements of the values of coercive force Ha in seconds and coercive force Ha were made as shown in Table 1.

The raw materials for producing the alloy of Table 1 Example 2 were 9jl, 9% purity III P+Ml iron,
Tungsten (ferrotungsten 99 containing 1%, gold of 9% purity and indium of 5φ purity was used. To make a (E), use the original 4) [1f, I'L 800g, j, i for alumina
Pig was placed in the
Stir O.5 well to make a homogeneous bath.
; Dimensions of this are 251 in diameter, l + 11% quotient -
a ] 7 (l Vli+ hole t υj type, a;
After that, I set it to 1-2 #1lllO9, and heated it for 1 hour at 200'e with 11 convex reps and oil cooling.
Next, draw 1 item between '11 ((Therefore, 111i0.5...
+ (W-shape and Shin).

In this case, the processing rate (the tiJ rate) is 9. Kirani Jin's 6 is 1 = 1020 (,m LIJ l) and test J'-(, and after various heat treatments, the residual magnet density Br and the magnetic flux when the magnetic field is 100 Oe ~'
Ly a B. . Square 2GB expressed in equal tangents
r/B,. . and the value of coercive force (C), and the second
Toku 192 as shown in the table was obtained. □Table 2 The magnetic properties of typical alloys are shown in Table 3.

As can be seen from the above examples and Table 3, F19-W
and Ag, Au, platinum group elements, Mg, ca
, sr.

Ba, Hf, Zn, Cd, B, G
a, In, TA*Pb.

An alloy consisting of a total of 0.001 to 20 cycles of one or more of P, As, Bi, Se, and Te, with this as the main component and V, Nb as minor components
, Or.

14o, Ta, Ni, Gu, Go,
Ti, Zr, Si, 11°Ge, Sn
, Sb, Be, Mn, rare earth elements and C 1. The alloy produced by the manufacturing method of the present invention, which is smoked or added with a total of 0.001 to 60 of two or more types, is annealed or solution treated, and then cold worked at a rate of 50% or more, and then heated at 400°. By heating at a temperature of C or more, a magnetic alloy having a coercive force of 2 F or more, a large residual magnetic flux density, and excellent square hysteresis can be obtained.

In addition, in the manufacturing method of the present invention, the alloy is subjected to cold working at a processing rate of 50% or more, and after imparting square characteristics by heating at 400°0 or more, the alloy is further heated or cold worked to the alloy. However, 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 described above, in the manufacturing method of the present invention, the characteristics of the -C alloy are that the processing rate is 5.
As mentioned above, it can be obtained by cold working to a coefficient of 0 or higher and then heating at a temperature of 400°C or higher, but even if this cold working and heating are repeated, good square properties can be obtained. Of course.

In addition, the Q alloys listed in Examples and Table 3 contain relatively high purity tag, ca, B, p, and metal N.
b, Or.

No, W, Mn, V, Ti, Al
1, Si, rare earth elements, C, etc. were used, but instead of these, generally commercially available ferro or metal alloys, which are economically advantageous, and Mitsushi metal can be used, as long as sufficient deoxidation and desulfurization are performed during melting. Is there almost the same magnetic customization and workability as when using these metals? be qed.

Next, in the present invention, the composition of the alloy is set to 1 to 2 tungsten.
0% and less than 10% silver, less than 10% gold, and 10% platinum group elements
Below, magnesium 3% or less, Kavalium 10% or less,
Hafnium 10% or less, zinc 5% or less, cadmium 5%
The following: boron 2 tres or less, gallium 10% or less, indium 10% or less, thallium 10% or less, lead 3% or less, phosphorus 2
Less than 2% arsenic, less than 8% bismuth, 3% selenium
The following and tellurium 5% or less, total of 0.001 to 20% of two or more types and the balance iron, or as a main component and sub-component vanadium 10% or less, anion' 10.0% Below, chromium 25% or less, molybdenum 106 or less, tantalum 10% or less, nickel 1
5% or less, copper 10 parts or less, cobalt 50% or less, titanium 5 parts or less, zirconium 5 parts or less, silicon 5% or less, aluminum 5% or less, germanium 5 parts or less, iron 5 parts or less, antimony 5% or less, beryllium 3% or less, man is 7
15% or less, rare earth elements 2% or less, and carbon 1.5%
The reason why the total of one or more of the following types is limited to 0.001 to 60% is that, as is clear from each example and Table 3, alloys in the composition range have a large residual magnetic flux density and have excellent square shape. It is a magnetic alloy that exhibits hysteresis, has a coercive force of 2 F or more, is easy to process, and has stable magnetic properties even when heated at high temperatures. However, if the composition is outside this range, the magnetic properties deteriorate and the process is difficult. This is because it becomes difficult to use, making it unsuitable as a square hysteresis magnetic alloy.

Here, the main components and Mll components are Ag, Au, platinum group elements, Sr, Ba, Hf, Zn,
Cd, B, Ga, In.

TA, Pb, P, As, Bi, T
e, V, Nb, Or.

Mo, Ta, Ni, Cu, Co,
Ti, Zr, Si, Al.

Ge, Sn, Sb, Be, Mn, rare earth elements and C have a particularly large effect on increasing the coercive force of gold.
CO has a particularly large effect of increasing the residual magnetic flux 'fj degree, and A
g + Au + platinum group element, Mg, Oa, S
r, Ba, Hf, Zn.

Cd, B, Ga, In, Tjl,
V, Nb, Mo, Ta.

N1. Cu, Co, and rare earth elements have the greatest effect on improving the squareness, while Mg, Oa, and S
r, Ba.

B, Ti, Si, A/, G6, B
e, Mn and rare earth elements have a particularly large effect on improving hot and cold workability, and As, (3a,
Bi, Pb, P, B, Se.

Ta and sb are particularly effective in improving free machinability.・
Note that oxygen, nitrogen, and sulfur have the effect of increasing coercive force and free machinability, and may be contained in small amounts as long as they do not impair the customization and workability of the alloy of the present invention.

Patent Applicant: Amendment to the Transfer Procedures for the Research on Electric and Magnetic Materials Corporation, January 12, 1939, 1, Case Description, 1982 Patent Application No. 185842, Manufacturing Method 3, Person making the amendment. +('l:,!:O related Patent applicant foundation 11T
, Old Institute of Magnetic Materials Telephone number (581) 2241 (Representative) 7. Contents of the amendment (as attached) ■ In the specification, No. 1 O, Negative line 19, "[Due to the heating of the high 71 M tug"] was changed to "high temperature". ) by heating and then rapidly cooling (water cooling, oil cooling, air cooling, etc.) gJ pressure.

2, page 12, line 1, “2 mra J to r 3 m
m Correct it as J.

3. In the same page 13, line 9, change ``in an argon atmosphere'' to ``in a vacuum''.

4, page 18, line 14, ``heated at 1200°C for 1116 hours, then cooled in oil'' was changed to ``heated at 100°C for 1 hour, then cooled with water,'' and applied 1J pressure.

5, page 14, line 15, "representative" is changed to "representative, subjected to optimal cold working and heat treatment after solution treatment" (d).

Claims (1)

[Claims] L Mk ratio of 1 to 20 tungsten and silver 1O related to 10% or less of gold, 10% or less of platinum group elements, 3% or less of magnesium, 3% or less of calcium, strontium 10
% or less, barium 10 parts or less, hafnium 10 parts or less,
Zinc 5% or less, cadmium 5% or less, rag 72% or less,
Gallium 10% or less, indium 10% or less, thallium 10 or less, lead 3 or less, phosphorus 2% or less, arsenic 2 or less,
Consisting of 0.001 to 20% in total of one or more of bismuth 3% or less, selenium 8% or less and tellurium 5% or less, the balance being iron and a small amount of impurities, and having a coercive force of 2K or more. A square hysteresis magnetic alloy characterized by: λ Weight ratio of tungsten 1 to 20%, silver 10% or less, gold 10% or less, platinum group elements 10% or less, magnesium 3% or less, calcium 3% or less, strontium 10%
The following: barium 10% or less, hafnium 10% or less, zinc 5% or less, cadmium 5% or less, boro 72% or less, gallium 10% or less, indium 10% or less, thallium 1
Total 0.001 to 20% of one or more of the following: 0% or less, lead 3% or less, phosphorus 2% or less, arsenic 2% or less, bismuth 3% or less, selenium 8% or less, and tellurium 5% or less. The main component is iron, and the subcomponents are less than 10% vanadium, less than 10% niobium, less than 25% chromium, and 1% molybdenum.
0% or less, tank 1° or less, 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 or less, and carbon 1.5 or less. A prismatic hysteresis magnetic alloy consisting of 0.001 to 60% and a small amount of impurities, and having a coercive force of 2 F% or more. & Weight ratio of tungsten 1 to 20%, silver 10% or less, gold lθ% or less, platinum group elements 10% or less, magnesium 3% or less, calcium trifid or less, strontium 10%
The following: barium 10% or less, hafnium 10% or less, zinc 5% or less, cadmium 5% or less, boro 72% or less, gallium 10φ or less, indium 10% or less, thallium 1
0% or less, lead 3% or less, phosphorus 2% or less, arsenic 2qb or more J,
Iha 2f with one type of bismuth less than 3%, selenium less than 3% and tellurium less than 5%! If or more (D total i10.001
An alloy consisting of ~20% iron, the balance iron, and 9 impurities is annealed or solution treated, then cold worked at a processing rate of 50% or more, and then heated at 400°C or higher to produce a 2-mill grade or higher. A method for manufacturing a rectangular hysteresis magnetic alloy characterized by exhibiting a coercive force of . Ton: In terms of weight ratio, tongue 2 fufu 1 ru 20% silver 1 also less than 10%, gold 10% or less, platinum group elements 10% or less, magnesium 3% or less, calcium 3% or less, strontium 10%
The following: barium 10% or less, hafnium 10% or less, zinc 5 or more, cadmium 5 or less, boro 72% or less, gallium 10% or less, indium 10% or less, thallium 10 or less, lead S or less , 2% or less of phosphorus, 2% or less of arsenic, 3% or less of bismuth, 3% or less of selenium, and 5% or less of tellurium @lo, ool~2
The main component is 0% and the balance is iron, with barium 10 as a subcomponent.
% or less, niobium 10% or less, chromium 25% or less, moly 1fufu JO% or less, tantalum 1° or less, nickel 15
Copper 10% or less, ':I H/L/T 5Q% or less, Titanium 5% or less, Zirconium 5% or less, Silicon 5% or less, Aluminum 5% or less, Germanium 5% or less, Tin 5% Total of 0.00 of one or more of the following: 5% or less of antimony, 3% or less of beryllium, 15% or less of manganese, 2x or less of rare earth elements, and 1.5% or less of carbon.
After annealing or solution treatment, an alloy consisting of 1 to 60 mm and a small amount of impurities is subjected to cold working at a working rate of 50 mm or higher, and further heated at 400 degrees Celsius or higher with zero force.
A method for manufacturing a rectangular hysteresis magnetic alloy characterized by exhibiting a coercive force greater than that of a magnetic alloy.