JPS58126964A - Amorphous iron alloy containing carbon with high strength, high hardness, high crystallization temperature and high embrittlement temperature - Google Patents

Abstract

PURPOSE:To obtain an amorphous Fe alloy contg. C with high strength, high hardness, a high crystallization temp. and a high embrittlement temp. by restricting the composition of an alloy consisting of Fe, Cr, Mo and/or W, and C and by rapidly cooling the alloy from a liq. state. CONSTITUTION:This alloy has a composition represented by the formula (where M is Mo and/or W, Q is C, a is 28-82 atomic%, b is <=20 atomic%, c is 4- 26 atomic% and d is 15-26 atomic%). The alloy is melted, sprayed on an opposite coppr plate for cooling by means of highly pressurized N2, Ar or other gas, and solidified by rapid cooling in the form of fine powder to manufacture amorphous alloy powder.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a carbon-based amorphous iron alloy that has high strength, high hardness, high crystallization temperature, and excellent embrittlement resistance.

Normally, solid metals and alloys are in a crystalline state, but they are cooled much more rapidly than liquids (the cooling rate depends on the composition of the alloy, but approximately 1
0 to 10° C./sec), a solid with an amorphous structure similar to a liquid without a periodic atomic arrangement can be obtained.3 Such metals are called amorphous metals or amorphous metals. Generally, this type of metal is an alloy of two or more elements, usually a combination of both transition metal elements and nonmetal elements, with the metalloid being about 15 to 80 atoms.

In addition, the present inventors had previously invented an amorphous iron alloy with high strength, fatigue resistance, general corrosion resistance, pitting corrosion resistance, crevice corrosion resistance, stress corrosion cracking resistance, and hydrogen embrittlement resistance (Japanese Patent Laid-Open No. 51-4017). A patent application was filed. This alloy has the following composition.

Contains as a main component Qrl-40% and 7 to 85% of any one of p, c, and B, and as a subcomponent (1111 of any one of Li N1 and co: t is g@0.01-40%, (2) Mo, Zr, Ti, Si, Mut, Pt
, any one of Mn and Pd 111 [or 2 or more 0
．． 01-20chi, (8) V, Mb, Ta
, W, any one or two or more of Ge and B9 0.01 to 10%, (4) Au, Ou, Zn,
Cd, Sn, As,! 9b, B soil or S 1m
or one group selected from the group of 0.01 to 59 $1 over 2 m, or the Fia group or above, is loaded with a combined device of 0.01 to 75 inches, and the remainder is substantially F
An amorphous iron alloy with high strength, fatigue resistance, general corrosion resistance, pitting corrosion resistance, crevice corrosion resistance, stress corrosion resistance, cracking-1 hydrogen embrittlement resistance, which is derived from the composition of e.

The amorphous alloy disclosed in JP-A No. 51-4017 was a new alloy that had improved strength and heat resistance through the addition of chromium, and was also endowed with excellent corrosion resistance. Also worth mentioning is that these alloys have novel properties in terms of corrosion resistance, and are not only resistant to general corrosion, but also resistant to pitting corrosion that cannot be avoided with modern stainless steels (804 steel, 816 steel, etc.). It had excellent characteristics such as high resistance to crevice corrosion and stress corrosion cracking. However, because these alloys have a wide range of compositions,
A component composition range that is easy to manufacture and inexpensive within a range that maintains various properties such as high heat resistance, high hardness and strength, and high embrittlement temperature for practical and new uses. Fortunately, this was not previously known.

The purpose of the present invention is to provide a carbon-based amorphous iron alloy that is easy to manufacture and inexpensive while having various properties such as high strength, high hardness, high crystallization temperature, and high embrittlement temperature. It is something to do. That is, the present invention provides a carbon-based high strength, high hardness,
It is an amorphous iron alloy with high crystallization temperature and high embrittlement temperature.

1. F e a Or bM c Q d (in the formula F
e means that Fe contains aJli -1OrbFiOr contains b atoms, Mo contains 0 atoms of one or more selected from cr, No, and lj, and Qd contains d atoms of C. , a is 28 to 82, b is 20 or less (not including zero), cll: t4 to 26, dFi1
The sum of a, b, c and d is substantially 100. However, when M consists only of W, b is within the range of 4 to 2o. )2, Fea
McQd (In the formula, Fe is all (Chi, Mo is MO, lj
Which one selected from among 111 or 2 indicates that C atoms are abundant, Qa ti O contains djl child child rearing, and aFis! 8-82, C is 4-26, d is 16-2
6, and the sum of a, C and d is substantially 100
It is. However, M is never greater than just W. ) The present inventors have newly discovered that an iron alloy containing only carbon as a nonmetallic element easily becomes amorphous over a wide composition range and has excellent properties in terms of strength, hardness, corrosion resistance, and heat resistance. Based on this knowledge, the present invention was created.

Next, the present invention will be explained in detail.

Among the well-known amorphous alloys, inexpensive ones are mainly iron-based, such as FeP.
Fe B, Fe8oP□, B8, so s
io ~ 80 20Fe Si B
FeSiP,,Fe8oP18C7FB1510'761!110hiko How was the combination of iron and the nonmetallic elements P, B, Si, and C?

However, the present inventors have discovered that these metalloid elements, which are necessary additives for amorphousization, each have advantages and disadvantages. The effects are summarized in Table 1. In the same table, the characteristics are evaluated by ◎ (excellent), ○ (good), and × (town).

From the same table, G6 is preferable in all respects.P is good in raw material cost, amorphous formation ability, and corrosion resistance, but other properties are not preferable. In particular, it is a problematic element because it generates harmful gases during melting and promotes thickening of the material during heating. In the same table, Si and B are undesirable because they have the effect of reducing corrosion resistance, and B has the disadvantage of high raw material cost. As is clear from the table, C was found to be an element having preferable properties in all respects with respect to the above-mentioned elements.

Thus, the present inventors completed the present invention through detailed research on amorphous iron alloys containing only 0 among the metalloids that contribute to amorphization.

Generally, amorphous alloys are obtained by rapid cooling from a liquid state, and various cooling methods have been considered for this purpose. For example, on the outer peripheral surface of a disk rotating at high speed (
Figure 1 (a)) or at high speed, liquid metal is continuously jetted between two counter-rotating rolls (Figure 1 (b)) onto the surface of a rotating disk or twin rolls. 10-1
A method of rapid solidification at a rate of about 0° C./second is known. In addition, the present inventor has recently invented a method for directly manufacturing wide thin strips from molten metal, and its manufacturing equipment at (%).
Kaisho 58-1252518, 5B-15152!9
(No.) can be used.

The amorphous iron alloy of the present invention can also be obtained by rapid cooling from a liquid state, and the amorphous alloy of the present invention in the form of a wire or plate can be produced by the above-mentioned method. Also, high pressure gas (1! element, argon gas, etc.)
By blowing off the liquid metal and rapidly solidifying it into a fine powder on an opposing cooling copper plate, for example, using an atomizer, it is possible to produce an amorphous alloy powder with a diameter of several μm to several lθμ. The carbon-based amorphous iron alloy of the present invention is suitable for powders and wires because it is not only cheaper but also easier to manufacture than conventional amorphous alloys. It is extremely advantageous in that plates can be manufactured on an industrial scale. It should be noted that the alloy of the present invention contains impurities present in ordinary industrial materials, such as P, Si, As, 8. Sb, Zn, (u,
The purpose of the present invention can be achieved even if a small amount is included.
, Kn, or five atoms or less of Nb, Ti, or Zr can also achieve the object of the present invention.

The amorphous iron alloy of the present invention can be roughly classified into the following groups based on its composition.

(a) Fe-0r-C (b) Fe-No-0 (c) Fe-0r-No-0 (d) Fe-0r-W-C (e) Fe-Mo-W-0 (f) Fe -0r-No-W-0 Next, the reason for limiting the component composition in the present invention will be explained.

Is ye 28 atoms chiyoshi Shohiko or 811 atoms -
If the amount is larger, it is difficult to easily obtain an amorphous alloy, so the amount of Fe needs to be within the range of 28 to 8 g atoms.

If Q is less than 15 atoms or more than 26 atoms, it is difficult to easily obtain an amorphous alloy, so Q
must be within the range of 15 to 26 atoms.

OrbMo's b is 0~! Since it is difficult to obtain an amorphous alloy when 0 and C are outside the range of 4 to 26, ・Orb'c and c must be within the range of θ~20.4 to 116, respectively! There is. Also, when the father-in-law consists of only W, the character deteriorates if B is less than the number, and on the other hand! If it is more than 0, it is difficult to make it amorphous, so b needs to be within the range of 4 to SO.

Also, when replacing a part of the father with V, Ta, In, y, T
Either a, In, 111t& is more than g@ (if there are more than 10 atoms, or a part of M is Nb).

When substituting with 〒i, Zr, it is difficult to obtain an amorphous alloy when there are more than 111 or 3 or more of Nb, Ti, and Zr than 5 atoms, so V, TIL is used.

MrLC) Group Fi 10 atoms or less, 11b, Ti,
The Zr group! IJI child - It is preferred to do each of the following.

In addition, when replacing a part of Q with N, if there are more than 4 atoms of N, N will precipitate as bubbles in the alloy structure during rapid solidification, deteriorating the shape of the alloy and reducing mechanical strength.
It is advantageous to have an IL-7-1 or lower.

Next, the composition of the amorphous iron alloy of the present invention and the crystallization source [Tx
(℃), hardness Hy (DPI) and breaking strength 6r (kp
/s votes) are shown in Table 2. The sample amorphous alloy was made to a thickness of 0.06 mm% by the single roll method shown in Figure 1(a).
It is made into a ribbon shape of $1 lsua. However, the crystallization source [Tx is the first exothermic peak start temperature in the differential calorimetry curve heated at 5° C./min, and Hv is the measured value of a 50 f load small Vickers hardness meter. - in the table means not measured.

! In general, amorphous alloys crystallize when heated and lose their characteristic ductility and toughness, as well as deteriorating other excellent properties. This is practically advantageous.

As shown in Table 3, the Tx of the amorphous alloy of the present invention is mostly within the range of 850 to 650°C, (ir, MO.

Judgment 9 shows that the TX tends to increase as the content of W + V + Ta and an increases. Therefore, it can be seen that the alloy of the present invention has a high TX and is a heat-stable alloy. Also, hardness Hv) and fracture strength (σf
) welfare 800~1100 DPN and 280~ respectively
Rashi, Or, MO, W, V, at 400 ky/am.
Ta.

) (Both increase as the n content increases. These values are the highest values conventionally known (for Fe-B alloys, Hv = 1100 DPN, σf = = 880
It is found that it has excellent hardness and strength, which is equivalent to or higher than K47 m-). In other words, in the first table of contents (c
) Hardness is 10'00 DPN in Fe-MO-0 system
There are some which have a crystallization temperature of over 600°C and a breaking strength 7 of 400 k4/wtm.

In addition, a part of the above alloy composition is Ta of less than loN,
Any one or three or more elements selected from the group consisting of In, y, or Wb or less than 5N atoms, Ti
An alloy containing at least one element selected from the group consisting of , Zr, or a combination of at least one element from each of the three groups mentioned above also has high strength and high hardness. , was found to have a high crystallization temperature.

Furthermore, it is generally known that amorphous iron alloys have the disadvantage of becoming brittle even at temperatures lower than the crystallization temperature. According to the research of the present inventors, the embrittlement phenomenon of the amorphous iron alloy is caused by the content of metalloid elements contained in the alloy.
We found that it depends greatly on The results of comparing the embrittlement temperatures of an amorphous iron alloy containing 1!1 metalloid elements and an amorphous iron alloy containing 0 of the present invention are shown in No. 8*.

The embrittlement temperature shown in the table is 1 when heated for 80 minutes at each temperature.
80° bending indicates the temperature at which it is flexible, and the higher the temperature, the less the tendency to embrittle. As shown in the same table, most of the alloys of the present invention are l. Pg.

Fe8oB, which has a higher embrittlement temperature than alloys and is less likely to become brittle, is conventionally known as an alloy that does not easily become brittle.

It has a embrittlement temperature almost comparable to alloys. These properties allow the alloy of the present invention to be used as tool materials such as knives and saws, hard wire materials such as tire cords and wire lobes, composite materials with synthetic resins such as vinyl and rubber, and composite materials with low melting point metals such as aluminum. This is advantageous because it does not become brittle even when subjected to unavoidable heat treatment or temperature rise during production when used in hazardous conditions.

As mentioned above, the alloy of the present invention is a high-strength material with amazing hardness and strength, and has a hardness of 700 to 800 DPN and a breaking strength of 2
50 to 800 kg/mttt". In addition, it is generally difficult to make high-strength steel into wire or plate, and requires a complex manufacturing process (melting → casting → soaking → forging, rolling → However, the alloy of the present invention has the great advantage that it is possible to manufacture final products such as wires and temporary wires directly after melting. Therefore, the amorphous iron alloy of the present invention can be used for cutting tools and Tool materials such as saw teeth, hard wire materials such as tire buds and wire ropes, composite materials with organic and inorganic materials (reinforced materials such as vinyl, plastic, rubber, aluminum, and concrete), blended materials (safety work clothes, security tents,
It has many uses, including ultra-high frequency protective clothing, microwave absorbing plates, shield sheets, conductive tape, surgical gowns, training socks, carpets, belts, etc.), pollution prevention filters, and screens.

Next, an example of physical property testing for an application example of the amorphous alloy of the present invention will be shown.

Example 1 Carbon steel, hard stainless steel, and low-alloy steel are widely used for conventional cutlery, such as razors and paper cutters, and these have characteristics suitable for cutlery materials.

As such, it is required to have high hardness, corrosion resistance, high elasticity, and good wear resistance. It has been found that the alloy of the present invention fully has the above-mentioned characteristics and is extremely excellent. Table 4 shows hardness and 1oB on emery paper (#400)
The weight reduction, that is, the amount of wear when abrasion was performed for 10 minutes with 2 loads applied, is shown in comparison with a commercially available product. The amount of wear in the table shows the results obtained by adding up the two mouth sides of the same sample.

From the same table, this alloy material is approximately 100% lower than commercially available razor blade materials.
It can be seen that the amount of wear is less than one-fold.

Example 2 Properties of the alloy of the present invention as a reinforcing material Table 5 shows the results of using the alloy as a reinforcing material in comparison with existing reinforcing materials such as piano steel wire, glass fiber, and nylon wire.

According to the same table, the tensile strength required as a reinforcing material is that of piano wire)
It has a high tensile strength of 50 to 100 kg/wm-, and has excellent high-temperature tensile strength and bending fatigue limit. Adhesion, which is another important property, was good when used as a reinforcing material for rubber and plastics.

Traditionally, steel wire, synthetic fibers, and glass fibers have been used as reinforcing materials in rubber structures, but it is difficult to further increase the fatigue strength currently obtained with steel wires, and synthetic fibers and glass It is well known that it is nearly impossible to make fibers have fatigue strength greater than that of steel wires. Furthermore, in order to reinforce synthetic resins, mat-like reinforcing materials mainly made of processed glass fibers have conventionally been used, and although this reinforcing material has good corrosion resistance, it is brittle and therefore does not have sufficient bending strength.

Concrete structures include PC concrete, which uses steel wires or cables as reinforcement materials, and concrete, which is made by randomly mixing steel wires cut into short pieces.
Falling also has drawbacks in terms of corrosion resistance.

However, if the alloy of the present invention is used as a reinforcing material, it can be used extremely advantageously as a reinforcing material for the above-mentioned rubber, synthetic resin, concrete, etc. A few examples will be explained below.

CA) Fell5Ori16C18 and F6
a * Or 1s M OB Os s Using the apparatus shown in Figure 1(a), form amorphous alloy into lines of @0.06 tuts and thickness of 0.04 wsa, and then form a mesh into tire rubber. It was embedded in the material and used as a test piece.

The mesh spacing is 1 wsa, and the specimen is 8 x 20 x 1.
It was a 00II fable board. Approximately 1 sample is used when vulcanizing rubber.
Humidity was raised at 50-180° for about 1 hour.

A long-term fatigue test (amplitude elongation l cps) was conducted using a tensile fatigue testing machine using a specimen of the same. the result,
It did not break even after 10 cycles, and peeling between the rubber and the wire was observed, which was dangerous. This result is Fe6fiOrlf
fiM08CI8 alloy has high destructive strength [(81110ume/-1
m ), crystallization temperature (565°C), fatigue strength (85Ik
id/ss).

Rubber alloys must also resist corrosion by sulfur. Therefore, the above-mentioned alloy wire was embedded in excessively vulcanized rubber and left at 80° C. for about one year to be removed.The surface and strength of the alloy wire were examined, but there was almost no change.

CB) Fe Cjr (3Fe M
o066 2618' 14 818%
An amorphous alloy of Fe, Orl, No8C□808m was made into a wire of approximately 0.05 m11%φ using the apparatus shown in Fig. 1(a), and this was cut into a certain length and cut into a certain shape. Only resin mixed into concrete. The test piece shape is 15×
It is a 15 x 152 cyn prism, and the specimen support distance is 4' CIl + % load loading point is 15 cII from each fulcrum.
It was K's 21i1 location. The table below shows the results of the bending test.

As shown in the table, the fiber reinforcement material is about 14% of the unreinforced material.
It can be seen that it has twice the maximum load and approximately three times the deflection. That is, the strength and deflection of fiber-reinforced concrete is expected to be 1.5 to 1.5 g, o times as strong as that of general reinforcing concrete.

As described above, the alloy of the present invention has high hardness and strength, excellent fatigue limit, and excellent corrosion resistance, and moreover, compared to conventional amorphous alloys,
It has many characteristics such as being inexpensive and easy to manufacture, and is expected to be used in many fields.

The alloy of the present invention can be made into powder, wire or plate depending on the purpose.

[Brief explanation of the drawing]

FIGS. 1(a) and 1(t) are diagrams showing the principle of an apparatus for producing an amorphous alloy by rapidly cooling a bath alloy. DESCRIPTION OF SYMBOLS 1... Bath molten metal, 2... Rapidly solidified amorphous alloy wire or plate, 8... Cooling disc, 4... Roll. Patent applicant: Director, Research Institute for Metals, Tohoku University Figure 1 <a> cb) 37 -

Claims (1)

[Scope of Claims] L A carbon-based amorphous iron alloy having high strength, high hardness, high crystallization temperature, and high embrittlement temperature due to the component composition represented by the following formula. F8aOrbMcQd (In the formula, Fea means Fe is a atom, Crb means cr is brf
lA child, Mo is cr, to, wo, any one or more of the selected ones is C atom, Qd is C is dJj
j Indicates that the child contains a uterus, a is 28-8B, b
is 20 or less (not including zero), c H4 to 26, d is in the range 15 to 26, and the sum of a, b, c and d is substantially 1003, provided that M is only W , b is within the range of 4 to 20. )λ A carbon-based amorphous iron alloy with the composition shown by the formula below. F e a M c Q d (In the formula, Fea means Fe is an atom, Mo is M., any one or two selected from W is a C atom, and Qd is C is dw, containing a child. a is 88~
B! , C is in the range of 4 to 26, d is in the range of 15 to 26,
The sum of a, C and d is substantially 100. However, M is W
There is nothing better than that. )