JPS597773B2 - Titanium-beryllium-based amorphous alloy - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to high strength, low density compositions of non-quality alloys, particularly in the beryllium-titanium-zirconium system.

Research has shown that solid non-quality materials can be obtained from certain metal alloy compositions.

Amorphous materials lack virtually any length range order and are characterized by an X-ray diffraction pattern whose intensity varies slowly with diffraction angle.

Such an X-ray diagram is qualitatively similar to the diffraction pattern of a liquid or an ordinary window glass.

This is in contrast to crystalline materials, which give an X-ray pattern in which the intensity of the diffraction pattern changes rapidly with the diffraction angle.

These non-quality metals are in a metastable state.

When heated to a sufficiently high temperature, it crystallizes while generating heat of crystallization, and its X-ray diffraction pattern changes from having amorphous characteristics to having crystalline characteristics.

A new non-quality alloy is disclosed by H. S. Chen and D. E.
Disclosed and claimed by Polk.

These amorphous alloys have the formula MaYbZc, where M
is at least one metal selected from the group consisting of iron, nickel, cobalt, chromium and vanadine, Y is at least one element selected from the group consisting of phosphorus, boron and carbon, and Z is aluminum , antimony, beryllium,
Kelma? At least one element selected from the group consisting of aluminum, indium, tin, and silicon, and a is about 60 to
b is in the range of about 10 to 30 atoms, and C is in the range of about 0.1 to 15 atoms.

These amorphous alloys have been found to be suitable for a wide variety of applications including ribbons, layers, wires, powders, and the like.

Also disclosed and claimed are amorphous alloys having the formula T i X j , where T is at least one transition metal,
is at least one element selected from the group consisting of aluminum, antimony, beryllium, boron, germanium, carbon, indium, phosphorus, silicon, and soot, i is about 70 to 87 atoms, and j is about It is in the range of 13 to 30 atoms.

These metals have been found suitable for wire applications.

At the time these alloys were discovered, they exhibited superior mechanical properties to polycrystalline alloys that were known at the time.

These excellent mechanical properties include an ultimate tensile strength of up to 350,000 psi and a hardness value (D
PH) and good ductility.

Nevertheless, new applications requiring improved magnetic, physical and mechanical properties and higher thermal stability require efforts to develop alternative compositions.

More specifically, there remains a need for high strength, low density materials suitable for structural applications.

According to the present invention, a high-strength, low-density non-quality alloy has the formula BeaTi
is formed from the composition of bzro , at least one additional alloying element selected from the group consisting of the metalloid elements consisting of soot, germanium, indium and antimony, where a changes from 30 to 52 atoms, and b
is 0 to 68 atoms, C is 0 to 70 atoms, d is 0 to 10
Change to atomic staff.

The two alloys included in this formula are (I) titanium from about 48 to
68 atoms, beryllium about 32-52 atoms, and beryllium
Up to about 10 atoms of J IJum are listed in I of the periodic table.
B~■ Transition metals displayed in the 4th, 5th, and 6th columns of Group B and Group ■, as well as phosphorus, boron, carbon, aluminum, silicon,
It is formed from a composition replaced by at least one additional alloying element selected from the group consisting of metalloid elements: soot, germanium, indium and antimony.

Preferably, the amorphous titanium-beryllium-based alloy contains about 50 to 61 atoms of titanium, about 37 to 41 atoms of beryllium, and at least one member selected from the group consisting of aluminum, boron, tantalum, and zirconium. element of about 2-1
Formed from a composition with zero atomic ratio.

Also suitable are amorphous titanium-beryllium binary alloys formed from compositions having about 58-68 atoms of titanium and about 32-42 atoms of beryllium.

The second type of composition according to the present invention is a composition that is limited to a region on a ternary diagram having the atomic coordinates of Be, Ti, and Zr as coordinates; (a) 30%Be, O%Ti, 70%Zr(b
)50%Be, 0%Ti, 50%Zr(c)5
0%Be, 40%Ti, 10%Zr(d)42%B
e,56%Ti, 2%Zr(e)36%Be,62
It is defined by a polygon with five corner points determined by %Ti, 2%Zr.

The alloys of the present invention exhibit specific strengths of about 28-60 x 105c77Z.

The alloys of the invention are also at least 50 amorphous, as measured by X-ray diffraction, and are preferably substantially amorphous, i.e.
They are both 80% amorphous, and most preferably about 100% amorphous.

Non-quality alloys are made by forming a melt of the desired composition and quenching the molten alloy at a rate of about 105-106 °C/sec by pouring it onto a quench wheel in an inert atmosphere or partial vacuum. It will be done.

According to the present invention, a high-strength, low-density amorphous alloy with the formula BeaT
It is made from a composition called ibZroXd.

Here, X is a transition metal shown in the 4.5th and 6th columns of Group IB to Group ■B and Group ■B of the periodic table, as well as phosphorus, boron,
at least one additional alloying element selected from the group consisting of metalloid elements carbon, aluminum, silicon, soot, germanium, indium and antimony, where a is 30
Changed to -52 atom, b is O to 68 atom, C is O-7
0 atoms, d changes to O-10 atoms.

The non-quality alloys of the present invention contain about 30-52 atoms of Be, about 68 atoms of titanium, about 70 atoms of ZrO, and up to about 1 selected from the group consisting of transition metal elements and metalloids.
Contains up to 0 atoms of one additional alloying element.

Transition elements are Group IB-■B of the periodic table, Group 8, Group 4,
These are displayed in columns 5 and 6.

Metalloid elements include phosphorus, boron, carbon, aluminum, silicon, soot, germanium, indium and antimony.

Examples of preferred additional alloying elements include boron, aluminum, tantalum and zirconium.

In a preferred type, the amorphous alloy consists essentially of titanium.
It has a composition of 0 to 61 atoms, beryllium 37 to 41 atoms, and about 2 to 10 atoms of at least one element selected from the group consisting of aluminum, tantalum, and zirconium.

The purity of all elements is as found in normal industry practice.

FIG. 1 is a ternary composition phase diagram showing the glass forming region that conforms to this type.

This region, designated by the polygon a-b-c-da, encompasses a glass-forming composition with high strength, good malleability, and low density.

Specifically, the first type of amorphous alloy has an essentially binary composition of about 58-68 atoms of titanium and about 32=42 atoms of beryllium.

Such preferred alloys exhibit high strength and low density, thus resulting in high strength-to-weight ratios.

In Figures 1 and 2, the preferred range is represented by the line a-e.

As a result of the high strength-to-weight ratio achieved for the binary system, it is preferred that any additional alloying elements added be of relatively low density to maintain this preferred strength-to-weight ratio.

The second type (b) of the alloy considered in the above formula is B as a coordinate.
It is limited to one area on the ternary diagram with e atom group, Ti atom group and Zr atom group, and the area is (a) 30%Be, 0%Ti, 70%Zr (b
)50%Be, 0%Ti, 50%Zr(c)5
0%Be, 40%Ti, 10%Zr(d)42%
Be, 56%Ti, 2%Zr(e)36%Be
, 62% Ti, and 2% Zr.

FIG. 3 is a ternary composition phase diagram, which represents the glass forming region of the second type (company) of the present invention.

This region, designated by the polygon a-b-c-d-ea, encompasses a glass-forming composition with high strength, low density, and good malleability.

A non-quality alloy that exhibits a substantial improvement in strength-to-weight ratio is represented by the formula Be4oTi6o-XZrx, where X is about 2
~60 atoms.

These alloys are represented by line f--g in the figure and are suitable.

For low values of X, i.e. from about 2 to about 10 atoms, about 63
Hardness value of 0-720 kf/1 and approx. 3.8-4
, 1? A density of lcrd is achieved.

Although this hardness value is within the range of prior art non-quality alloys, the density is considerably reduced by a reduction rate of approximately 2.

Since hardness is related to strength, a substantial improvement in strength to weight ratio is realized for low values of X.

Therefore, such a composition is particularly preferred.

For higher values of X, the hardness remains virtually unchanged, but the density is approximately 5.4? /cJ, yet still well below that of prior art amorphous alloys.

A high strength-to-weight ratio is therefore maintained over this range of compositions.

The specific strength of non-quality alloys is calculated by dividing the hardness value (in rot/cA) by a dimensionless factor of approximately 3.2 and the density (k/cA).

The basis for this dimensionless factor is in Scripta Metaradica, Volume 9, pages 431-436 (1
975).

The high strength-to-weight properties of the alloy according to the invention are then compared with those of other prior art non-quality alloys.

For example, Pd30Si20 has a specific strength (in 10 cm) of 15.1 and Ti50Cu5,) has a specific strength of 29.1.
Has 6.

In contrast, Be40Ti50Zr10, one of the typically preferred alloys of the present invention, has a specific strength of 54.8, which is lower than that of the prior art amorphous alloys. considerably higher than that.

Generally speaking, non-quality alloys of the present invention have a specific strength of about 28 to
60X105c77Z is shown.

An example of an alloy of the present invention exhibiting high specific strength is represented by the formula Be Ti Zr above: 40 60 --X X .

Alloys within the scope of the invention which exhibit the same or higher hardness values at lower densities have correspondingly higher specific strengths.

A typical non-grade alloy of the present invention exhibiting good strength-to-weight ratio and exceptional ease of glass forming behavior has the formula B e y Z
It is represented by r 1 ()oy, where y is in the range of about 30-50 atoms.

These compositions are represented by line a--b in Figure 3 and are also preferred.

This non-quality alloy produces melts of the desired composition approximately 105 to 10
It is formed by cooling at a rate of 6°C/sec.

The purity of all compositions is that found in normal industry practice.

splat quenched foils and ultra-quenched continuous ribbons;
A variety of techniques are available for making wires, layers, powders, etc., as are well known in the art today.

Typically, a specific composition is selected, a desired amount of powder or granules of the desired element is melted and homogenized, and the molten alloy is rapidly transferred onto a cold surface such as a rotating wheel. is rapidly cooled.

Because of the high reactivity of these compositions, it is preferred that the alloys be made in an inert atmosphere or partial vacuum.

Non-quality alloys were previously defined as being at least 50% amorphous, with more amorphous yielding higher malleability.

Therefore, amorphous alloys that are substantially amorphous, ie, at least 80% amorphous, are preferred.

Generally preferred are alloys that are of poor overall quality.

Because of the strength of these alloys, their hardness data and low density make them useful in applications requiring high strength-to-weight ratios, such as structural materials in spaceflight applications and fibers in composite materials. The amorphous alloy of the invention is 4
It exhibits a crystallization temperature exceeding 00°C.

It is therefore suitable for applications involving fairly high temperatures of up to about 400°C.

Example 1 A single arc-splat device was used to melt and liquid quench a high temperature reactive alloy.

The apparatus was a conventional electric arc melting button furnace modified to provide "hammer and anvil" splat quenching of alloys under an inert atmosphere, but with a vacuum chamber coupled to a pump system.

Quenching was accomplished by providing a smooth-surfaced water-cooled copper grate on the floor of the chamber and a pressure-driven copper block hammer positioned above the molten metal.

Conventionally, electric arc melting was accomplished by negatively biasing a copper shaft with a non-consumable tungsten tip inserted through the top of the chamber and positively biasing the bottom of the chamber.

All alloys are created directly by repeated electric arc melting of the constituent elements.

Single alloy button (approx. 200mg)? is remelted and then cut to a thickness of approximately 0 by a hammer located directly above the melt pool.
．． 0.004 inch foil was shock quenched.

The cooling rate obtained with this method was approximately 105-106°C/sec.

The shock-quenched foil just below the hammer will have undergone plastic deformation after solidification.

However, the portion of the foil formed from the melt that protrudes from the hammer is undeformed and is therefore suitable for hardness and other related tests.

Hardness was measured by the diamond pyramid method using a Vickers-type Oji made of square-based pyramid-shaped diamond with a narrow angle of 136° between opposing surfaces.

Various compositions were made using the electric arc flattening apparatus described above.

A non-reactive atmosphere of argon was used. Non-quality was measured by X-ray diffraction.

Beryllium-rich compositions such as Ti4oBeao and T'i50Be50 formed poorly amorphous alloys at very extreme quench rates (much greater than about 106 ht).

Eutectic composition Ti63Be37 and supereutectic composition T i6
0 Be40 readily forms a wholly amorphous alloy at quenching speeds in the range of about 105-106° C./sec.

The Ti63Be3 composition has two crystallization peaks at about 460°C as determined by differential thermal analysis (DTA, scan rate 20°C/min).
and 545℃, hardness approximately 4 as measured by diamond pyramid method.
50-550 DPH, and a density of 3.83 g/ctd.

The Ti60Be40 composition has a crystallization peak of 423° C., a hardness of 630 DPH, and a density of 3.76 g/min as measured by DTA.
showed crti.

Titanium and aluminum with one or more additional elements of aluminum, boron, tantalum and zirconium
Other amorphous alloys of Jum were made in the manner described above.

Its composition, observed crystallization temperature (Tc), hardness value (
DPH) and density (j'/cr!) are shown in Table 1.

The strength of these alloys based on this hardness data and their low density make these alloys useful in structural applications in space engineering and applications requiring high strength-to-weight ratios such as fibers in composite materials.

Example 2 An electric arc and plate apparatus was used to melt and liquid quench a high temperature reactive alloy.

The apparatus was a conventional electric arc melting button furnace modified to provide "hammer and anvil" splat quenching of alloys under an inert atmosphere, but with a vacuum chamber coupled to a pump system.

Quenching was accomplished by providing a smooth-surfaced water-cooled copper grate on the floor of the chamber and a pressure-driven copper block hammer positioned above the molten metal.

Conventionally, electric arc melting was accomplished by negatively biasing a copper shaft with a non-consumable tungsten tip inserted through the top of the chamber and positively biasing the bottom of the chamber.

All alloys are made directly by repeated electric arc melting of the constituent elements.

A single alloy button (approximately 2007y) was remelted and then "impacted" into approximately 0.004 inch thick foil with a hammer located directly above the melt pool.

The cooling rate obtained with this method was approximately 105-106°C/sec.

The hardness (DPH) was measured by the diamond pyramid method using a Vickers type diamond made of pyramidal diamond with a square base with an included angle of 136° between opposing surfaces, and a load of 50 g was applied.

The crystallization temperature was determined by differential thermal analysis (DT) at a scanning speed of approximately 20°C/min.
Measured in A).

Typically, amorphous alloys exhibited crystallization temperatures ranging from about 412° to 455°C.

Various alloys were made using the electric arc flattening apparatus described above.

A non-reactive atmosphere of argon was used. Non-quality was measured by X-ray diffraction.

The composition, measured hardness value and density, and calculated specific strength are
Shown in the table.

Other ribbons of various compositions were made in vacuum using a quartz crucible and extruding the molten material onto a quench wheel with overpressure of argon.

Approximately 200μmH? using a partial vacuum.

Be4(,Ti,Zr6,Be4oTi52Zr8
, Be4(, Ti50Zr10) were made in this way.

[Brief explanation of drawings]

Figure 1 is a ternary compositional phase diagram in terms of atoms for the Ti-Be-X system of type 1 (I), where X represents at least one additional alloying element and indicates the glass-forming region. There is. FIG. 2 is a binary composition phase diagram in terms of atoms of the Ti-Be system in the first type (I), showing the glass forming region. FIG. 3 is a ternary composition phase diagram in the atomic relationship of the Be-Ti-Zr system in type 2 0, showing the glass forming region.

Claims (1)

[Claims] 1. essentially titanium with 48 to 68 atoms and 32 to 52 atoms
A substantially non-quality, high-strength, low-density alloy characterized by consisting of the atomic elements beryllium and beryllium. 2 Formula BeaTibXd [wherein X is at least one additional alloying element selected from the group consisting of aluminum, boron, and tantalum, a is 32 to 52 atoms, b is 48 to 68 atoms and d is less than or equal to 10 atoms. ] A substantially amorphous, high-strength, low-density alloy characterized by having a composition represented by: 3 Formula B e a T ibZ r c [In the formula, a has a ratio of 30 to 50 atoms, b has a ratio of 5 to 58 atoms, and C has a ratio of 2 to 55 atoms. A substantially non-quality, high-strength, low-density alloy characterized by having the composition represented by: