JPH049622B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for manufacturing metal ribbons or wires, and in particular to manufacturing ribbons or wires of high melting point metals, highly active metals, or alloys containing a large amount of these metals. Regarding preferred methods. [Prior art] In recent years, research and development of magnetic materials, brazing filler metals, reinforcing wire rods, and corrosion-resistant thin plates has become active.
The applications of quenched thin sheets and wires of metals or alloys are expanding, and in recent years in particular, thin strips and wires of alloys containing a large amount of active metal have been put into practical use, and the demand for them has been increasing. A thin plate or wire of metal or alloy (hereinafter, metals and alloys are collectively referred to as "metal" in this specification) is generally produced using a nozzle having a slit-shaped or dot-shaped molten metal spout. It is manufactured by spouting molten metal from a molten metal and rapidly cooling it on rolls or in oil or water. Conventionally, the material for this molten metal spouting nozzle has been SiO ₂ , Al ₂ O ₃ , ZrO ₂ , or non-oxide ceramics such as Si ₃ N ₄ , SiC, BN, and BC. For example, JP-A No. 56-163093 describes a method for producing thin sheets of brazing filler metal used for joining ceramics and metals, using a quartz tube (SiO ₂ nozzle) with a slit-shaped opening to inject molten metal. A method for cooling a rotating copper cylinder by jetting it onto the surface of a rotating copper cylinder is disclosed. [Problems to be solved by the invention] However, when a nozzle made of SiO ₂ -based, Al ₂ O ₃ -based, or ZrO ₂ -based refractory material is used in the production of metal ribbons or wires, the metal is highly active. If the metal is a metal or an alloy containing a large amount of the metal, there is a problem that the molten metal passing through the nozzle reacts with the refractory material of the nozzle, resulting in oxygen contamination, contaminating the molten metal, and making it difficult to obtain a high-quality product. I can't. Further, continuous production may not be possible due to damage such as erosion of the nozzle due to reaction with the molten metal and change in the shape of the molten metal outlet. In addition, nozzles made of non-oxide ceramics such as Si ₃ N ₄ , SiC, BN, BC, etc. are expensive and prone to cracking due to thermal shock, and problems of molten metal contamination and nozzle damage are unavoidable. [Means for Solving the Problems] The present invention has been made to solve the above-mentioned conventional problems, and in manufacturing a metal ribbon or wire, a molten metal having a composition of 98% or more CaO is used. ,
It is ejected into an inert atmosphere by inert gas pressure from a nozzle made of high-purity CaO refractory material containing 0.1% or less of SiO ₂ , 0.2% or less of Fe ₂ O ₃ , and 0.5% or less of other metal oxides. It is used to rapidly cool the liquid. The present invention will be explained in detail below. In addition, in this specification, "%" represents "weight %". In the present invention, first, a molten master alloy is created. A preferred method for producing the master alloy is to put each component element into a CaO crucible and melt it in the crucible. Each component element is melted in a water-cooled Cu crucible by arc melting or the like. Although several methods can be mentioned, it is particularly preferable to employ a method because a homogeneous alloy can be obtained. Next, the obtained molten metal is poured into a CaO nozzle, or the master alloy ingot is charged into the nozzle and heated and melted. and an inert gas (e.g. nitrogen,
Applying pressure (argon, helium, etc.) to the molten metal surface,
Spray molten metal from a nozzle. In the present invention, when spouting this molten metal,
A nozzle made of high-purity CaO refractory material with a specific composition is used. The CaO refractory material that makes up the nozzle has a very high CaO content of 98% or more. Such calcia furnace materials with a high CaO content are thermodynamically stable, have high stability against highly active metals, and can be melted at high temperatures. In addition, it easily absorbs oxides and sulfides, absorbs oxides and sulfides in the molten metal, and can significantly reduce the amount of oxide and sulfide-based nonmetallic inclusions. In particular, in the present invention, CaO 98% or more,
Because we use a nozzle made of high-purity CaO refractory material containing 0.1% or less of SiO ₂ , 0.2% or less of Fe ₂ O ₃ , and 0.5% or less of other metal oxides (e.g., Al ₂ O ₃ , MgO, TiO _{2 ,} etc.), It is also suitable for injection of molten metal containing a large amount of highly active metals such as Ti and Zr. CaO raw materials for CaO-based refractories include refractories containing CaO as their main component, such as calcia (CaO), but among CaO, fused calcia is particularly dense and has a high activity when it comes into contact with molten metals or alloys. Even in this case, it is preferable because there is little contamination to the molten metal. The CaO-based refractory material nozzle used in the present invention is not limited in shape, size, hole diameter, etc., except that it is made of such a CaO-based refractory material, and is selected depending on the purpose of use. In order to manufacture the nozzle according to the present invention, a calcia raw material such as fused calcia is powdered with a predetermined particle size, and if necessary, high melting point metal oxide such as ZrO ₂ , MgO, Y ₂ O ₃ etc. and other additives for improving properties are mixed in appropriate proportions to form the main raw material. Then, an appropriate binder is added to this main raw material as necessary, the material is molded into the shape of a nozzle, and the material is fired to form a nozzle. The nozzle hole may be finished by laser, electric discharge machining using a non-aqueous liquid, ultrasonic machining, drilling with diamond, or the like. Moreover, as this binder, a non-aqueous one is used. The non-aqueous binder may be either liquid or solid. Liquid types include alcohol (monohydric or polyhydric alcohol) in which anhydrous calcium chloride or gum arabic are dissolved, oleic acid dissolved in toluene,
Preferably, oleic acid dissolved in alcohol, oleic acid dissolved in oil, beeswax dissolved in carbon tetrachloride, or isobutyl acetate, mineral oil such as tar or pitch, or animal oil. Any non-aqueous liquid that does not cause calcia to be digested can be used, such as vegetable oil. As the solid binder, thermoplastic resins such as polyethylene, polypropylene, cellulose acetate, acrylic resins, polyvinyl alcohol, thermosetting resins such as novolac, paraffin, etc. can be suitably used, but they can impart moldability. Other materials may also be used. As the molding method, various methods such as mold molding, slip casting, rubber pressing, injection molding, warm pressing, stamping, etc. are used. Alternatively, a molded body may be produced by mixing with a nonaqueous solvent such as n-hexane to form a slurry, and pouring the slurry into a mold. The molded body or stamped nozzle is dried if necessary, then preferably calcined at a temperature lower than the main firing temperature, and then main fired and sintered. This firing temperature is over 1100℃, especially 1300~
A temperature of about 1800°C is suitable. Of course, the nozzle according to the present invention can also be manufactured by a method such as hot pressing. It can also be manufactured by carving a fired calcia body into a desired shape. The molten metal spouted from such a nozzle is sprayed onto the surface of a single roll, twin rolls, or
Supplied in oil or non-aqueous liquids and rapidly cooled under an inert atmosphere. In the present invention, all kinds of metal ribbons or wires can be manufactured by appropriately selecting and setting the shape or size of the nozzle or the molten metal spout, the type of quenching means, and the degree of quenching. Such a method of the present invention can be carried out using high melting point metals, highly active metals, such as Ti, Zr, Hf, Sc, Y, La, lanthanoid elements such as Ce and Pr having atomic numbers of 58 to 71,
Alkali metals, alkaline earth metals such as Mg, V,
Nb, Ta, Cr, Mo, W, Mn, Al, Tc, Re,
1 of the elements Ru, Os, Co, Ni, Rh, Pd, Ir, Pt
It is extremely suitable for manufacturing ribbons or wires of alloys containing a large number of species or two or more species. In particular, when the present invention is applied to molten metal containing deoxidizing elements such as Al, Si, Zr, and Ti, excellent scouring effects such as deoxidation, desulfurization, denitrification, and removal of inclusions can be obtained, and extremely It's advantageous. [Function] CaO refractory materials are extremely stable in vacuum or inert gas, have a low dissociated oxygen pressure, and can be used even at high temperatures. Furthermore, it is inexpensive and has excellent thermal shock resistance. In the present invention, CaO with a particularly high CaO content is used.
Since refractory materials are used, even highly active metals or alloy molten metals are hardly contaminated, and the refractory materials are not damaged by these molten metals. Furthermore, when the molten metal contains a deoxidizing element, a scouring action is also performed. Therefore, according to the present invention, damage to the nozzle is also prevented, and highly pure metal ribbon or wire can be stably produced continuously for a long period of time. [Examples] The present invention will be described in more detail with reference to Examples and Comparative Examples below, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. Example 1 The main raw material was fused calcia (CaO purity 98%) crushed and classified to 0.2 mm or less, to which 3 parts by weight of heavy oil pitch was added, heated to 150°C and mixed well, and then mixed with gold. Mold molded. After calcining this molded body at 650℃ for 3 hours,
Sintering was performed at ℃ for 2 hours. The sintered body thus obtained had the shape and dimensions shown in FIG. (In addition, in Figure 1,
2 is a molten metal spouting port of the nozzle 1. ) Using this nozzle, pour a molten alloy with the following composition into the second
At the temperature shown in the table and argon gas pressure (1.2 atm),
The mixture was jetted onto the surface of a single roll (250 mm diameter, made of Cu) and rapidly cooled to continuously produce alloy ribbons with a width of 13 mm and a thickness of 40 μm. No.1 Co-60%Zr alloy No.2 Ag-30%Cu-40%Ti alloy No.3 Cu-50%Ti alloy No.4 Cu-40%Nb alloy As a result, the long-term Continuous production over many years was possible. Further, the results of oxygen analysis of the obtained alloy ribbon are shown in Table 2. Comparative Example 1 An alloy ribbon was produced in the same manner as in Example 1, except that a SiO ₂ -based refractory nozzle having the composition shown in Table 1 (the shape and dimensions are the same as those used in Example 1) was used. I did this. The results of impurity analysis of the obtained alloy are shown in Table 2. As production continued, it took 3 seconds for No. 1 alloy, 10 seconds for No. 2 alloy, 4 seconds for No. 3 alloy, and 4 seconds for No. 4 alloy. On the other hand, because the shape of the nozzle outlet changed or was damaged during melting and holding, it became impossible to produce a ribbon of a certain standard.

【table】

[Table] Comparative Examples 2 to 4 An alloy ribbon was produced in the same manner as in Example 1 except that a CaO-based nozzle having the composition shown in Table 3 was used. The impurity analysis results of the obtained alloy are shown in Table 4 together with the results of Example 1. From Table 4, even if the CaO content is 98% or more, if the Fe ₂ O ₃ , SiO ₂ , Al ₂ O ₃ content exceeds the range of the present invention, a highly clean alloy ribbon cannot be obtained. is clear.

【table】

〔Effect of the invention〕

As is clear from the above examples, the nozzle used in the present invention is extremely stable and can be used satisfactorily at high temperatures. Even when used for discharging molten metal or alloy with a high melting point and high activity, there is little contamination from the nozzle to the molten metal. Therefore, the nozzle is hardly eroded and damaged by the molten metal. It also has excellent thermal shock resistance. It has the following advantages. Therefore, according to the method for manufacturing a metal ribbon or wire of the present invention using such a nozzle, it is possible to stably and continuously produce a high-purity metal ribbon or wire with almost no molten metal contamination over a long period of time. It becomes possible.

[Brief explanation of drawings]

FIGS. 1a and 1b are views showing the nozzles used in Example 1 and Comparative Example 1, in which a is a sectional view and b is a bottom view. 1... Nozzle, 2... Outlet.

Claims (1)

[Claims] 1 Molten metal with a composition of 98% or more CaO and 0.1% SiO ₂
% or less, Fe ₂ O ₃ 0.2% or less, other metal oxides
A method for manufacturing a metal ribbon or wire, characterized by ejecting it with inert gas pressure from a nozzle made of a high-purity CaO refractory material having a content of 0.5% or less and rapidly cooling it in an inert atmosphere.