KR101693122B1 - METHOD FOR FABRICATING NANO-POWDERS USING Al-BASED AMORPHOUS ALLOY - Google Patents

Abstract

The present invention relates to a method of manufacturing a nano powder using an aluminum-based amorphous alloy, comprising the steps of preparing an aluminum-based amorphous alloy containing 80-99 at% of Al, 0.5-10 at% of Ni and 0.5-10 at% of Y, And a step of heating the prepared aluminum-based amorphous alloy to deposit vaporized material on the substrate at a temperature ranging from room temperature to 2/3 of the melting temperature of the aluminum-based amorphous alloy, whereby the strength, abrasion resistance, And a nano powder excellent in resistance to corrosion can be produced.

Description

METHOD FOR FABRICATING NANO-POWDERS USING AL-BASED AMORPHOUS ALLOY BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention provides an amorphous alloy which is capable of producing a nanopowder having excellent strength, abrasion resistance, magnetic properties, and corrosion resistance at a low temperature by providing an amorphous alloy in which weight reduction due to evaporation occurs at a low temperature during a heat treatment, The present invention relates to a method for producing a nano powder using an alloy.

As is well known, an amorphous alloy is not a crystalline metal in which atoms are in a regular lattice arrangement, but rather a solid material having an atomic arrangement similar to that having an atomic arrangement in a liquid phase, , Which are composed of two or more metals (including semimetals).

In general, amorphous alloys have a wide range of application because they have mechanical and chemical properties such as high strength, excellent abrasion resistance and corrosion resistance that can not be obtained from a crystalline material.

The amorphous alloy is a rapid solidification method (RSP) in which constituent elements are added at a specific ratio, and the added constituent elements are not separated into two or more crystalline phases, but the quantitative ratio of the added elements is maintained as they are Process, rapid solidification method).

This rapid solidification method includes a gas spraying method in which a high-pressure gas or high-pressure water is sprayed on a molten alloy, a centrifugal separation method in which a powder is prepared by using a disk rotating rapidly with molten metal, Spinning method, and the like, through which a bulk amorphous alloy such as powder or ribbon can be produced.

On the other hand, an amorphous alloy such as a metal glass has an amorphous portion formed by rapid solidification of two or more kinds of metals (including a semi-metal). The amorphous portion formed when the liquid is in a high temperature state can be maintained at room temperature. Here, the amorphous portion may be included in an amount of about 50-100 vol% in the total volume of the metal glass.

Such a metal glass may be softened at a glass transition temperature (Tg) or higher to exhibit liquid-like behavior, which is a function of the glass transition temperature (Tg) and the crystallization temperature (Tx) of the metallic glass And this temperature interval is referred to as a supercooled liquid region (DELTA Tx).

In addition, amorphous alloy nanoparticles such as metallic glass can be produced by a gas condensing method, which is produced by homogeneous nucleation and condensation in a gas phase, a physical manufacturing method such as a mechanical grinding method in which bulk metals or ceramics are pulverized and finely milled, Or a liquid phase reduction method in which a metal or an oxide powder is produced in an aqueous solution.

Another manufacturing method is a high energy ball milling method, which is a method in which crystalline metals forming each amorphous alloy composition are added, and then alloyed by mechanical grinding using a high energy ball mill.

As described above, the nano powder can be made of an amorphous alloy such as a metal glass. The research and development of an amorphous alloy having excellent strength, abrasion resistance, magnetic properties and corrosion resistance as applications for producing nano powder actively It is progressing.

1. A crystalline alloy having amorphous forming ability, a method for producing the same, an alloy target for sputtering, and a method for manufacturing the same are disclosed in Japanese Patent Application Laid-Open No. 10-1376074 (Mar. 31, 2014) 2. Open Patent Publication No. 10-2013-0048224 (published on May 3, 2013): tin-containing amorphous alloy 3. Published Japanese Patent Application No. 10-2013-0121098 (published Nov. 11, 2013): Methods for producing carbon graphene and other nanomaterials

The present invention provides an amorphous alloy in which a weight loss due to evaporation occurs at a low temperature during a heat treatment and a weight loss of at most 1% relative to the total weight occurs between room temperature and 2/3 Tm, The present invention provides a method of manufacturing a nano powder using an aluminum-based amorphous alloy capable of manufacturing nano powder excellent in characteristics and corrosion resistance at a relatively low temperature.

The present invention also provides an amorphous alloy based on Al-Ni-Y as an aluminum-based amorphous alloy, which provides an amorphous alloy containing 80-99 at% Al, 0.5-10 at% Ni, and 0.5-10 at% The present invention also provides a method for manufacturing a nano powder using an aluminum-based amorphous alloy capable of producing nano powder having higher abrasion resistance, magnetic properties, and resistance to corrosion at a relatively low temperature.

The present invention also provides an amorphous alloy based on Al-Ni-Y and optionally containing at least one of Co and La in an amount of 0.1-5at%, thereby providing strength, abrasion resistance, magnetic properties and resistance to corrosion And a method for manufacturing a nano powder using an aluminum-based amorphous alloy capable of manufacturing a more excellent nano powder at a relatively low temperature.

The objects of the embodiments of the present invention are not limited to the above-mentioned objects, and other objects not mentioned can be clearly understood by those skilled in the art from the following description .

According to an embodiment of the present invention, an aluminum-based amorphous alloy containing 80-99 at% of Al, 0.5-10 at% of Ni, and 0.5-10 at% of Y is prepared, and the prepared aluminum- And depositing a vaporized material on the substrate at a temperature ranging from room temperature to 2/3 of the melting temperature of the aluminum-based amorphous alloy on the substrate.

The present invention provides an amorphous alloy in which a weight loss due to evaporation occurs at a low temperature during a heat treatment and a weight loss of at most 1% relative to the total weight occurs between room temperature and 2/3 Tm, Nanocrystalline powder excellent in characteristics and corrosion resistance can be produced at a relatively low temperature.

The present invention also provides an amorphous alloy based on Al-Ni-Y as an aluminum-based amorphous alloy, which provides an amorphous alloy containing 80-99 at% Al, 0.5-10 at% Ni, and 0.5-10 at% Nano powders with better abrasion resistance, magnetic properties and corrosion resistance can be produced at relatively low temperatures.

The present invention also provides an amorphous alloy based on Al-Ni-Y and optionally containing at least one of Co and La in an amount of 0.1-5at%, thereby providing strength, abrasion resistance, magnetic properties and resistance to corrosion More superior nanopowders can be produced at relatively low temperatures.

1 shows a TGA result of an aluminum-based amorphous alloy according to an embodiment of the present invention,
2 is a view showing a DSC result of an aluminum-based amorphous alloy according to an embodiment of the present invention,
FIG. 3 is a flow chart showing a process of manufacturing a nano powder using an aluminum-based amorphous alloy according to another embodiment of the present invention.
4 is a diagram showing a crystallization state of an aluminum-based amorphous alloy according to another embodiment of the present invention.

Advantages and features of embodiments of the present invention and methods of achieving them will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. The following terms are defined in consideration of the functions in the embodiments of the present invention, which may vary depending on the intention of the user, the intention or the custom of the operator. Therefore, the definition should be based on the contents throughout this specification.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

FIG. 1 is a view showing a TGA result of an aluminum-based amorphous alloy according to an embodiment of the present invention, and FIG. 2 is a diagram showing DSC results of an aluminum-based amorphous alloy according to an embodiment of the present invention.

Referring to FIGS. 1 and 2, the amorphous alloy for nano powder according to the embodiment of the present invention may have a weight reduction of at most 1% with respect to the total weight between room temperature and 2/3 Tm (Tm: melting temperature) have.

The amorphous alloy for nano powder production may increase in weight due to the formation of oxides after 2/3 Tm, endothermic reaction occurs in supercooled liquid region (SCLR), crystallization temperature (Tx) Reactions can occur. The endothermic reaction and the exothermic reaction are caused by the sublimation and evaporation that occur during the heat treatment of the amorphous alloy, and the weight of the amorphous alloy may be reduced due to sublimation and evaporation.

In more detail, since the amorphous alloy is in an amorphous solid state prior to the supercooling liquid region (SCLR), weight reduction occurs due to sublimation. In the supercooling liquid region (SCLR), the amorphous alloy exhibits liquid behavior, have.

The amorphous alloy for preparing nano powder according to the embodiment of the present invention is based on Al-Ni-Y as an aluminum-based amorphous alloy, and is composed of 80-99at% Al, 0.5-10at% Ni and 0.5-10at% Y, and may further include at least one of Co and La by 0.1 to 5 at%.

For example, the amorphous alloy for preparing a nano powder according to an embodiment of the present invention may include any one selected from Al _84.5 Y ₁₀ Ni _5.5 , Al ₈₅ Y ₈ Ni ₅ Co _2, and Al ₈₆ Ni ₆ Y _4.5 Co ₂ La _1.5 Based amorphous alloy.

The aluminum-based amorphous alloy as described above has a glass transition temperature (Tg) suitable for the firing temperature in an amorphous alloy based on any one selected from Ca, Mg, Al, Cu, Ti, Fe and Ni, Lt; RTI ID = 0.0 > conductivity < / RTI >

The Al-Ni-Y-based amorphous alloy selected from the above-described aluminum-based amorphous alloys may be subjected to a heat treatment while being heated to a temperature of from about 0.01 to about 0.5 in terms of the total weight before and after the subcooling liquid region (SCLR) % Weight reduction is observed. This weight reduction can occur up to 1%.

Referring to the graph of the analysis result using a thermogravimetric analyzer (TGA) shown in FIG. 1, it can be seen that, in the case of ANY (for example, Al _84.5 Y ₁₀ Ni _5.5 ), 0.01% After a weight reduction with a gentle slope of 0.07%, weight reduction may occur with a steep slope of up to about 0.5% of the total weight up to approximately 400 ° C.

And, in the case of ANYC (for example, Al ₈₅ Y ₈ Ni ₅ Co ₂ ), a weight reduction can be shown at a gentle slope of about 0.01% -0.15% relative to the total weight up to about 400 ° C.

Further, in the case of ANYCL (for example, Al ₈₆ Ni ₆ Y _4.5 Co ₂ La _1.5 ), weight reduction was observed at a gentle slope of about 0.01% -0.05% relative to the total weight up to about 200 ° C., Weight reduction may occur with a relatively steep slope as much as 0.2%.

As shown in Fig. 1, this weight reduction can be seen from about room temperature to about 400 占 폚 which is two thirds of the melting temperature (Tm: about 660 占 폚) of the Al-Ni-Y based amorphous alloy.

On the other hand, the weight reduction described above disappears at approximately 400 DEG C, which is 2/3 of the melting temperature (Tm: approximately 660 DEG C) of the Al-Ni-Y based amorphous alloy as shown in FIG. 1, The weight of the Ni-Y-based amorphous alloy is increased because the oxides are formed due to the oxidizing action after the crystallization of the amorphous alloy and the weight is increased.

2, the axis of abscissas is temperature (° C), which is the heat treatment temperature, and the axis of ordinate is Heat Flow Endo Down (m / s), which is the internal heat flow lowering value, in the DSC (Differential Scanning Calorimetry) W), the peak in the upward direction shows an exothermic reaction, and the peak in the downward direction shows an endothermic reaction.

2, the Al-Ni-Y based amorphous alloy has a peak (endothermic reaction) slightly oriented in the downward direction at approximately 270 ° C., and immediately followed by a peak toward the upward direction ) Are observed, and it can be seen that the peaks oriented in the lower direction and the upward direction alternately appear relatively gently.

Accordingly, in the present invention, weight reduction due to evaporation occurs at a low temperature during the heat treatment, and a weight reduction of 1% at maximum is caused between the room temperature and 2/3 Tm. The aluminum- Y, and can provide an amorphous alloy containing 80-99 at% of Al, 0.5-10 at% of Ni, and 0.5-10 at% of Y. [

The present invention also provides an amorphous alloy based on Al-Ni-Y and optionally containing at least one of Co and La by 0.1-5at%.

Next, another embodiment of the present invention for producing a nano powder using the above-described aluminum-based amorphous alloy will be described in detail.

FIG. 3 is a flow chart showing a process of manufacturing a nano powder using an aluminum-based amorphous alloy according to another embodiment of the present invention. FIG. 4 is a view illustrating a crystallization state of an aluminum- Fig.

Referring to FIGS. 3 and 4, an aluminum-based amorphous alloy is prepared (step 302). Such an aluminum-based amorphous alloy can be prepared and prepared in various forms such as powders, ribbons, foils, rods, etc. after heating to a temperature above the melting temperature and metal cooling. A detailed description thereof will be omitted.

Here, the aluminum-based amorphous alloy is based on Al-Ni-Y, which may include 80-99at% Al, 0.5-10at% Ni and 0.5-10at% Y, and at least one of Co and La 0.1 to < RTI ID = 0.0 > 5at%. ≪ / RTI >

For example, the aluminum-based amorphous alloy may be any one selected from Al _84.5 Y ₁₀ Ni _5.5 , Al ₈₅ Y ₈ Ni ₅ Co _2, and Al ₈₆ Ni ₆ Y _4.5 Co ₂ La _1.5 .

Next, the prepared aluminum-based amorphous alloy is heated to deposit vaporized material on the substrate at a temperature ranging from room temperature to 2/3 (approximately 400 ° C) of the melting temperature (Tm: approximately 660 ° C) of the aluminum-based amorphous alloy A nano powder is prepared (step 304).

Here, when the aluminum-based amorphous alloy is heat-treated at an elevated temperature, a weight loss occurs before and after a supercooled liquid region (SCLR) of about 260 ° C to about 290 ° C from a normal temperature, and about 400 ° C 3), a weight loss of 0.01-1.0% relative to the total weight appears, which can occur up to 2%.

The weight loss disappears at about 400 占 폚, which is two thirds of the melting temperature (Tm: about 660 占 폚) of the aluminum-based amorphous alloy, and when the temperature rises above 400 占 폚, the weight of the aluminum- This is because oxides are formed due to the oxidizing action after the crystallization of the amorphous alloy and the weight is increased.

On the other hand, the melting temperature of the aluminum-based amorphous alloy is a differential thermal analysis (DTA: differential thermal analysis), or differential scanning calorimetry (DSC) can be measured using an instrument, such analysis equipment Ar and N ₂ inert gas by using a By raising the temperature of the amorphous alloy to 5-15 K / min in the atmosphere, it is possible to measure the temperature difference corresponding to the reference sample or the temperature indicating the difference in the heat absorption amount.

The aluminum-based amorphous alloy as described above is heated at a heating rate of 5-15 K / min up to 2/3 of the melting temperature (liquidifying temperature) measured by DSC and DTA, or the aluminum-based amorphous alloy is heated at room temperature The weight loss per area may be less than about 0.001-0.005 kg / m < 2 > when maintained at a predetermined temperature (e.g., 300 DEG C, etc.) in a temperature range of up to 2/3 of the melting temperature.

Here, the aluminum-based amorphous alloy can be evaporated for about 10-20 minutes when it is evaporated in such a manner as to raise the temperature and maintain the predetermined temperature.

In addition, the decrease in the weight during the isothermal annealing of the aluminum-based amorphous alloy in the temperature range of 200-300 ° C is similar to that in the isothermal annealing in the temperature range of 550-660 ° C of the crystalline Al.

The nanopowder produced through the above-described process can control the amount and size of the nanopowder prepared by controlling the heating temperature and the heating time, and can be heat-treated in air or in an inert gas atmosphere. An atmosphere such as an Ar gas atmosphere or an N ₂ gas atmosphere or the like in the air while controlling the heat treatment conditions such as a temperature range from room temperature to 2/3 of the melting temperature and a time range of 10 to 20 minutes while raising the temperature at a heating rate Nano powder can be prepared by adjusting the conditions.

The produced nanopowder may be composed of at least one element (for example, Al, Ni, Y or the like) among the elements constituting the amorphous alloy when heat-treated in an Ar atmosphere, or may be formed by heat treatment in air or in an N ₂ atmosphere (For example, Al ₂ O ₃ , NiO, Y ₂ O _3, etc.) among the elements constituting the amorphous alloy, or when the heat treatment is performed in air or in an N ₂ atmosphere, the amorphous alloy (E.g., AlN, Ni ₄ N, Ni ₃ N, NiN ₆ , YN, etc.) of at least one element among the elements.

For example, referring to the crystallization state image shown in FIG. 4, after a powder prepared using an Al-Ni-Y based amorphous alloy is mixed with an alcohol solution, several drops of the mixed solution are dropped on a Cu substrate, After evaporating the alcohol solution, a process of placing a Cu substrate on a hot plate set at 300 ° C and heating the substrate was performed. As a result, nanoparticles were formed on the Cu substrate around the amorphous powder.

These nanoparticles are formed by depositing nanoparticles made of Al-Ni-Y based amorphous alloy through sublimation and evaporation during heat treatment, and the weight reduction in the TGA graph may be caused by such sublimation and evaporation .

Here, the Al-Ni-Y based amorphous alloy powder may be disposed on the Cu substrate by spraying, printing, spin coating, or the like.

Accordingly, the present invention provides an amorphous alloy in which a weight loss due to evaporation occurs at a low temperature during a heat treatment, and a weight reduction of at most 1% relative to the total weight is generated between room temperature and 2/3 Tm, Nanoparticles having excellent magnetic properties and corrosion resistance can be produced at relatively low temperatures.

The present invention also provides an amorphous alloy based on Al-Ni-Y as an aluminum-based amorphous alloy, which provides an amorphous alloy containing 80-99 at% Al, 0.5-10 at% Ni, and 0.5-10 at% Nano powders with better abrasion resistance, magnetic properties and corrosion resistance can be produced at relatively low temperatures.

The present invention also provides an amorphous alloy based on Al-Ni-Y and optionally containing at least one of Co and La in an amount of 0.1-5at%, thereby providing strength, abrasion resistance, magnetic properties and resistance to corrosion More superior nanopowders can be produced at relatively low temperatures.

In the meantime, in the embodiments of the present invention as described above, the process of manufacturing nano powder is described. However, by using an aluminum-based amorphous alloy, the nanostructured film can be formed in a low temperature range from room temperature to 2/3 of the melting temperature Ceramics or polymer powders in a low temperature range from room temperature to 2/3 of the melting temperature, or in a low temperature range from room temperature to 2/3 of the melting temperature It is of course possible to use the adhesive as an adhesive for bonding the dissimilar materials.

In addition, the aluminum-based amorphous alloy includes Al, transition metal Ni, and rare-earth metal Y. In the transition metal, Co, Cu, Fe, or the like may be used, Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Yb, etc.).

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be readily apparent that such substitutions, modifications, and alterations are possible.

Claims (10)

Preparing an aluminum-based amorphous alloy containing 80-99 at% of Al, 0.5-10 at% of Ni, and 0.5-10 at% of Y,
Heating the prepared aluminum-based amorphous alloy to deposit vaporized material on the substrate at a temperature ranging from room temperature to 2/3 of the melting temperature of the aluminum-based amorphous alloy
Wherein the amorphous alloy is an aluminum alloy.
The method according to claim 1,
Wherein the aluminum-based amorphous alloy is an aluminum-based amorphous alloy produced in a form selected from powder, ribbon, foil, and rods.
3. The method of claim 2,
Wherein the aluminum-based amorphous alloy further comprises at least one of Co and La in an amount of 0.1-5 at%.
3. The method of claim 2,
_Wherein the aluminum-based amorphous alloy is any one selected from Al _84.5 Y ₁₀ Ni _5.5 , Al ₈₅ Y ₈ Ni ₅ Co _2, and Al ₈₆ Ni ₆ Y _4.5 Co ₂ La _1.5 .
The method according to claim 1,
Wherein the aluminum-based amorphous alloy is heated at a rate of 5-15 K / min to be evaporated or maintained at a predetermined temperature in the low temperature range to be evaporated.
6. The method of claim 5,
Wherein the nano powder is composed of at least one element selected from among elements constituting the aluminum-based amorphous alloy when heat-treated in an Ar atmosphere.
6. The method of claim 5,
Wherein the nano powder is composed of an oxide of at least one element among the elements constituting the aluminum-based amorphous alloy when heat-treated in air or in an N ₂ atmosphere.
6. The method of claim 5,
Wherein the nano powder is composed of a nitride of at least one element among elements constituting the aluminum-based amorphous alloy when heat-treated in air or in an N ₂ atmosphere.
9. The method according to any one of claims 1 to 8,
Wherein the aluminum-based amorphous alloy is subjected to endothermic reaction and exothermic reaction to cause a reduction of 0.01-2% of the total weight of the aluminum-based amorphous alloy.
9. The method according to any one of claims 1 to 8,
Wherein the aluminum-based amorphous alloy is an aluminum-based amorphous alloy whose weight increases at or above the melting temperature.

Images