JPS6059032A - Fine wire of amorphous pd alloy with superior corrosion resistance - Google Patents

Abstract

PURPOSE:To manufacture a fine wire of an amorphous alloy with superior corrosion resistance by solidifying a molten Pd alloy contg. specified amounts of Ni and Si or P in the form of a fine wire having a circular cross-section by rapid cooling. CONSTITUTION:A molten Pd alloy consisting of 4-62 atomic% Ni, 15-25 atomic% Si or P and the balance Pd is spouted from a spinning nozzle into a water film formed on the inner wall of a rotating drum by centrifugal force. The molten alloy is rapidly cooled in the water film, and a fine wire of an amorphous Pd alloy with superior corrosion resistance is obtd. The wire has a circular cross-section.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a Pd-based amorphous metal thin wire having a circular cross section and excellent corrosion resistance.

Traditionally, noble metal elements such as Ild, Pt, and ΔU have been widely used in ornaments, etc., but in the petrochemical industry in particular, they are used in hydrogenation reactions during crude oil refining.

+1t, Pd, etc. are very important catalysts, and in recent years, it has been found that they are also catalysts that can be used to synthesize methane and methanol for 2-coal liquefaction.

In addition, as hard soldering material #[, Pd2oCr
Kan35i5BI2Ni50 (atomic %, the same applies hereinafter) and P
d32 Nip Aus and the like are increasingly being used in fields that require corrosion resistance and oxidation resistance, particularly in aircraft and missiles. It is also used as a dental material due to its high corrosion resistance, and its industrial value has doubled in recent years.

Moreover, using an alloy with a composition containing noble metal elements.

Pd-B is an alloy that has an amorphous state by liquid quenching.

Pd-5i+Pd-M-5i (M = Ni, (:u
+ Pe, Co, 8g+ At') +Pd-N1-P
, Pt-N1-P and other base metal threads.

In addition, most of the samples in these cases all have a thickness of 10~
The thin strips were about 30 μm thick, and the single roll method, piston-anvil method, etc., which were the easiest to prepare samples among the liquid quenching methods, were used. Research on Pd-based amorphous metals, which has been particularly well-researched, is mainly concerned with basic research such as the critical cooling rate required to become amorphous, and the formation and stability of the amorphous phase. There are no reports on its industrial usefulness. This is as mentioned earlier.

This is because research on Pd-based amorphous metals has mainly been conducted on ribbon materials with a thickness of about 10 to 30 μm.

On the other hand, recently, industrially extremely useful fine wire abrasives have been developed using the rotating liquid spinning method (Japanese Patent Laid-Open No. 56-1650), which is a liquid quenching method that reduces manufacturing costs through ultra-high-speed direct production and also saves energy.
(see Publication No. 16). According to this rotating liquid spinning method, high-quality fine metal wire (with a roundness of 90%) can be produced.
As described above, it has a very uniform shape with 1-wire diameter unevenness of 4% or less. ) are produced continuously. Thin 11! The superiority of thin wire material compared to shape material is that first, '4+++ wire material can be knitted or woven into a wire mesh, whereas thin strip material cannot. In addition, the thin line +A interest is
Although it has a good circular cross section, it can be further cold drawn to dramatically improve the smoothness of the two surfaces, □=J-method onness, etc. Furthermore, the thin wire material has high rigidity and is very easy to handle.

The ribbon-like material is extremely thin5 and therefore very difficult to handle.

In view of these circumstances, the inventors of the present invention have devised the following.

With the aim of providing an industrially useful P4 amorphous metal thin wire with a circular cross section, we have conducted extensive research and found that when a Pd-based alloy with a specific composition is rapidly solidified into a thin wire from a molten state, it becomes thin. The present invention was completed based on the discovery that it is possible to obtain a Pd-based amorphous metal thin wire with a circular cross section that has better corrosion resistance than band-shaped materials.

In other words, in the present invention, Ni is 4 to 62 atomic % and S
It is a Pd-based amorphous metal fine wire with excellent corrosion resistance, which is made of an alloy in which t or P is 15 to 25 atomic %, and the remainder is substantially Pd, and has a circular cross section.

To explain the thin wire of the present invention, the Ni content is 4
It is necessary that the content is 62 atomic %, and preferably 4 to 5 atomic %. Further, it is necessary that +S+ or P is 15 to 25 atomic %, and 5i15 to 20 atomic %8P is preferably 18 to 25 atomic %. When the amount of Nl exceeds 62 atomic %.

When manufacturing thin wires by the industrially most effective spinning method in a rotating liquid, wire forming ability (the ability to form a uniform continuous thin wire with a circular cross section and very small irregularities in wire diameter when rapidly solidified in a cooling liquid) !&′) decreases, making it difficult to manufacture continuous thin wires. Also, the amount of Ni.

If it is less than 4 atomic %, corrosion resistance and breaking strength will also decrease, which is not preferable. Moreover, when Si or P is outside the range of 15 to 25 at %, the ability to form an amorphous state is extremely low, and the material becomes brittle. Further, the remainder is substantially Pd-based, but may contain impurities to the extent that they are present in ordinary Pd materials.

The above alloy composition is used to manufacture the thin wire of the present invention,
As a manufacturing method, it may be rapidly solidified by spinning in a rotating liquid, which is particularly preferable. As a spinning method in a rotating liquid, Japanese Patent Application Laid-open No. 56
-teso1e'; Public (as described in the memorial service, water is poured into a rotating drum once, a water film is formed on the inner wall of the drum 11 by centrifugal force, and the molten alloy in the water film is spun into a spinning nozzle. One method is to obtain a thin wire with a circular cross section by ejecting it from the spinning nozzle.In particular, to obtain a uniform continuous thin wire, the circumferential speed of the drum should be adjusted to the speed of the spinning nozzle. It is desirable that the peripheral speed of the rotating drum be the same or higher, and it is particularly preferable that the circumferential speed of the rotating drum is 5 to 30% faster than the speed of the molten metal flow jetted from the spinning nozzle. The angle between the molten metal flow jetted out and the water film formed on the inner wall of the drum is preferably 20° or more.

The thin wire of the present invention has 60% or more, preferably 80% or more,
Particularly preferably, the circularity is 90% or more, and the wire diameter unevenness is 4.
It is a thin line with a uniform shape of less than %.

The thin wire of the present invention can be subjected to continuous cold working.
In order to further improve dimensional accuracy and mechanical properties, rolling and
It can be subjected to wire drawing, and if necessary, it can also be subjected to heat treatment such as annealing. The high speed and simplicity of this liquid quenching method makes it possible to produce the thin wire of the present invention.

This has the effect of reducing manufacturing costs and saving energy.

The thin wire of the present invention has excellent corrosion resistance.

Additionally, it exhibits high strength. For example, high-quality (PdO,9-Ni 01 ) 82-5i1 with a circular cross section
8 Amorphous alloy thin wire in 1ONH2SO4,
0.52mm/year, 1.96m of pure Pd wire
m/year and 1.02mm of ribbon material of the same composition
/ year, the corrosion resistance is significantly improved. Moreover, (Pd0.9 NiO,1) of the present invention 82
The breaking strength of Si18 is 172 kg/mm2, and the strength is further improved by cold drawing.It was measured for 194 crocodile diameter irregularities, and the results are summarized in Table 1. Here, the roundness is 1 in the length direction of the continuous thin line.
0 points are selected, and the ratio of the major axis (R) to the minor axis (r) of each point is determined by the average value of r/11 x 100 (%). The 1111 line was run 1 (10 m) using a measuring machine.

By continuously measuring the average wire diameter, (4) the variation of the average wire diameter was achieved.

As is clear from Table ■, Examples 1 to 3 had N1, Si, and P contents within appropriate ranges, and the obtained 11) quality (high roundness and very small wire diameter unevenness) was 1. It has excellent corrosion resistance and high breaking strength. However, the pure Pd thin wire of Comparative Example 1 has low breaking strength and poor corrosion resistance.

In addition, in Comparative Examples 2 and 3.8, N1(i) is 0 or a small amount, so although it is amorphous, no improvement in corrosion resistance is observed and the breaking strength is low.Comparative Example 5.IO is the total amount of Ni. exceeds the appropriate amount, and one-turn submerged spinning method is used.

When producing an amorphous thin wire material, the wire forming ability was significantly reduced, and the wire diameter became extremely uneven, making it impossible to obtain a continuous thin wire.

Further, Comparative Example 4.9 has the same composition as Example 2.5, but since it is a thin strip material, the breaking strength and corrosion resistance are inferior when comparing the thin wire materials. this is.

While the thin wire material has a protruding surface with almost no irregularities, the ribbon material has many irregularities due to entrainment of gas etc. during manufacturing, and this is thought to be a factor in the deterioration of corrosion resistance.

Comparative example 6. 7. 11.12, the content of Si and P is out of the appropriate composition range, and it becomes crystalline instead of amorphous, so it is brittle (not practical).
child.

Agent: Yuzo Sales (self-proposal) February 1, 1980, Patent Application No. 168730/1982, Name of the invention: PD-based amorphous metal thin wire with excellent corrosion resistance 3, Relationship with the case of the person making the amendment Patent applicant 4, agent 5, subject of amendment Column 6 of detailed explanation of the invention in Book 1a, contents of amendment (11 Specification, page 2, line 8, "Thread" to "Alloy"
I am corrected.

(2) Correct "formation state-1" in line 15, L1 of the same page of the circular, to "formability."

(3) On page 6, line 15 of the same book, “Alloy fine wire is ION
In H2SO4, the alloy thin wire was heated at 80°C for 1
"In ON+12504" is corrected.

(4) Same +, l+ /m at l-1, 58 at the beginning of the second line of page 7
m2j is stopped at +58 J/mm2J.

(5) “Erosion dust ION II□S” in Table 1, page 10 of the same book
O, room temperature” to “erosion dust ION II□SOa tiO℃
Correct it with J.

(6) Same as above 2) Continuation of Table 1 on page 11 1-11 Food intake 1O
N +12so4 room temperature" to "l acceptance degree ION II
+) 480℃”.

Claims (1)

[Claims] fllNi is 4 to 62 atom%-7', Si or 1] is 1
I'd-based non-matrix crystalline metal fine with excellent corrosion resistance, consisting of an alloy of 5 to 25 atomic % and the remainder being substantially PD, and having a circular cross section.