KR20180092011A - Titanium amorphos alloys with anti-wear and high-performance lubrication - Google Patents

Abstract

The present invention relates to an amorphous alloy to have small friction resistance and improve wear resistance, a target composed of the amorphous alloy, and a compressor having a layer of the alloy as a lubricating layer. According to the present invention, a Ti-Cu-Ni-X quaternary amorphous alloy comprises Ti, Cu, Ni, and further, a quaternary element (X) to form a process point in all of a Ti-X binary system, a Cu-X binary system, and a Ni-X binary system. The amorphous alloy is used to control amorphous fine tissue as a main phase to secure high hardness and a low elastic coefficient of a lubricating layer. Therefore, reliability or durability of the compressor can be improved by restricting the lubricating layer to be peeled or broken from a base.

Description

[0001] TITANIUM AMORPHOS ALLOYS WITH ANTI-WEAR AND HIGH PERFORMANCE LUBRICATION [0002]

The present invention relates to a sputtering target for forming a lubricating layer composed of an amorphous alloy and an amorphous alloy capable of reducing friction resistance and improving abrasion resistance, and a compressor including the lubricating layer.

Generally, air conditioners such as air conditioners and refrigerators generally include mechanical devices such as compressors. Such a compressor utilizes a principle of applying mechanical energy to a fluid by compressing the fluid, so that reciprocating motion or rotational motion is essential for compressing the fluid.

The operation of such compressors necessarily involves friction or vibration between the mechanical components of the compressor. For example, in a compressor that operates based on rotation, such as a rotary compressor or a scroll compressor, friction of the rotary shaft can not be avoided.

In general, to improve friction in a compressor, first use a separate mechanical component, such as a bearing, to reduce frictional resistance. Further, a lubricating layer is formed to reduce frictional resistance between the rotating shaft and the bearing.

Conventionally, a lubricating film of a liquid phase is mainly used as a lubricating layer. However, in recent years efforts have been made to reduce friction and / or wear, primarily by using solid lubricant films as coating bearings.

As a method of applying such a solid lubricant film, a solid material having excellent friction and abrasion characteristics is coated on one or both of the components, which are in contact with each other and are relatively moving, and on one side or both sides of the friction surface to form a friction surface tribology ) Properties are known.

Examples of the components of the solid lubricant film include solid lubricants such as PTFE, MoS ₂ , WS ₂ and graphite, ceramic fillers, and organic material-based lubricants including a mixed material such as a silane coupling material Based coating composition comprising a carbide or nitride such as cBN, TiC, TiN or the like, or a lubricating coating composition based on a low melting point metal such as Sn-Bi alloy, or a lubricating coating composition based on a lubrite layer A composite lubricating coating composition comprising a solid lubricant such as PTFE, MoS ₂ , WS ₂ , and graphite impregnated on the surface of the base material, or a carbon-based lubricating coating composition such as DLC (Diamond like carbon).

On the other hand, in recent years, as the size of home appliances has become smaller, compressors are rapidly increasing in speed and miniaturization. The miniaturization and speeding up of the compressor means that the conditions under which the compressor is operated become increasingly severe. In particular, a compressor designed for high-speed and small-sized conditions must not deteriorate under severe operating conditions in order to exhibit efficiency equal to or higher than that of a large-sized compressor. Therefore, friction and wear reduction methods using solid lubricant films are becoming more important.

However, the conventional solid lubricant film components have technical limitations because they are used in compact and high-speed compressors. For example, the manganese-based coating has a low friction property due to self-exhaustion, and thus has limitations in improving reliability and efficiency in abrasion resistance under severe operating conditions. In addition, DLC has been reported to have improved abrasion loss in comparison with the Lubrite coating, but it lacks affinity with the additives of the oil used in the compressor, so there is a limit to the improvement of characteristics at low speed operation.

Therefore, there is a growing demand for a new solid lubricant film that can replace the conventional solid lubricant film and a compressor using the same.

A related prior art is Korean Patent Laid-Open Publication No. 10-2014-0145219, which discloses a Zr-based amorphous alloy composition having amorphous forming ability.

An object of the present invention is to provide a lubricating layer having a new component and a microstructure in a lubricating layer used in a compressor of an air-conditioning equipment such as an air conditioner and a refrigerator, in order to improve friction characteristics and wear resistance of the lubricating layer.

Specifically, the present invention provides a new composition range of Ti-Cu-Ni-X quaternary alloys as a new lubricant layer to provide a new amorphous coating with reduced friction resistance between components constituting the compressor Layer. ≪ / RTI >

More specifically, it provides a new composition range Ti-Cu-Ni-X quaternary alloy capable of forming amorphous in a Ti rich region capable of precipitating a high-hardness phase capable of reducing frictional resistance, thereby improving friction resistance and durability And a lubricating layer having a new amorphous coating.

Further, the present invention provides a crystalline sputtering target comprising a Ti-Cu-Ni-X quaternary alloy having a specific composition range having amorphous ability to form the amorphous coating layer and having thermal stability remarkably superior to amorphous The purpose

In addition, it is an object of the present invention to provide a compressor having a lubricating layer of improved frictional resistance, wear resistance, and tame characteristics than conventional ones by forming a lubricating layer using the sputtering target.

According to one aspect of the present invention, there is provided a method of manufacturing a semiconductor device including Ti, Cu, and Ni, Ti-Cu-Ni-X quaternary amorphous alloy characterized in that it further comprises a fourth element (X) capable of forming an eutectic point.

Preferably, the atomic radius of the fourth element (X) is a Ti-Cu-Ni-X quaternary amorphous alloy having a difference of 12% or more from the atomic radius of each of Ti, Cu and Ni.

Preferably, the fourth element X is a Ti-Cu-Ni-X quaternary amorphous alloy having a large negative heat of mixing when mixed with Ti, Cu, and Ni, respectively.

Preferably, the fourth element (X) is a Ti-Cu-Ni-X quaternary amorphous alloy which is Si.

At this time, the alloy is preferably a Ti-Cu-Cu alloy having a composition range of 65 to 80% of Ti, 5 to 20% of Cu, 5 to 25% of Ni, and 9% or less of Si (excluding 0) Ni-X quaternary amorphous alloy.

Particularly, the alloy contains Ti-Cu-Ni having a composition range of 65 to 80% Ti, 5 to 15% of Cu, 10 to 20% of Ni and 9% or less of Si (excluding 0) -X is a quaternary amorphous alloy.

In particular, the Ti is a Ti-Cu-Ni-X quaternary amorphous alloy which forms an intermetallic compound with Cu and / or Ni.

The Si is a Ti-Cu-Ni-X quaternary amorphous alloy which forms Ti and titanium silicide.

According to another aspect of the present invention, there is provided a sputtering target comprising any one of the Ti-Cu-Ni-X tetravalent elements described above.

Preferably, the target microstructure is a crystalline sputtering target.

Preferably, the average grain size of the target is in the range of 0.1 to 10 mu m.

According to another aspect of the present invention, there is provided a compressor comprising a lubricating layer of any one of the Ti-Cu-Ni-X quaternary amorphous alloys.

Preferably, the lubricating layer is a compressor coated on a base material comprising at least one of a steel material, a cast alloy, an alloy containing aluminum, and an alloy containing magnesium.

According to the present invention, since the composition of the Ti-Cu-Ni-X quaternary alloy has an amorphous forming ability, it may contain amorphous or further have a microstructure in which the amorphous phase is a main phase. As a result, the amorphous microstructure with respect to the crystalline microstructure can secure not only the inherent low elastic modulus but also the hardness through the hardness precipitation phase.

Further, the Ti-Cu-Ni-X quaternary amorphous alloy of the present invention can be obtained by a conventional Ti-Cu binary amorphous alloy or a Ti-Cu-Ni ternary amorphous alloy (TiO2), TiO2 (TiO2), TiO2 (TiO2), TiO2 (TiO2), and Ti Layer can be formed.

In addition, the sputtering target of the present invention significantly improves the thermal / mechanical stability of the target, so that the destruction of the target during the sputtering process can be significantly suppressed, and the stabilization of the sputtering process can be improved. In addition, since it has a very uniform microstructure, the compositional deviation between the target composition and the thin film composition, which may be caused by the difference in the sputtering yield of each component derived from the quaternary multi-component constituting the target, .

Further, the compressor of the present invention has an amorphous lubricating layer coated with the alloy of the quaternary composition. As a result, it is possible to obtain an advantageous effect on the wear resistance and the friction characteristics of the compressor from the relatively high hardness of the amorphous microstructure. In addition, since the modulus of elasticity of the amorphous microstructure is similar to that of the matrix metal, it is possible to prevent the lubricating layer from being peeled or broken from the matrix, thereby improving the reliability or durability of the compressor.

FIG. 1 is a conceptual diagram for explaining an amorphous alloy or a lubricant layer of the present invention having an amorphous structure and a nanocrystalline structure.
2 is a stress-strain curve diagram comparing an amorphous metal with a metal nitride and a crystalline metal.
3 is a phase balance diagram of a binary alloy of Ti and Cu.
Fig. 4 shows an example of an equilibrium state diagram of a ternary alloy.
5 is a phase balance diagram of a binary alloy of Ti and Si.
6 is a phase balance diagram of a binary alloy of Cu and Si.
7 is a phase balance diagram of a binary alloy of Ni and Si.
Fig. 8 shows the radial difference and the mixing column between the constituent elements of the Ti-Cu-Ni-Si quaternary alloy.
9 shows a Ti-Cu-Ni ternary Gibbs triangle marking a composition region irradiated with amorphous forming ability.
10 is an XRD pattern showing an amorphous forming ability of an alloy having a composition range of Ti 65% -Cu 15% -Ni 20%.
11 is XRD patterns showing amorphous formability of ternary alloys having a composition range of 70% -Cu x% -Ni y% (x + y = 30) of Ti.
FIG. 12 shows XRD patterns in which amorphous forming ability of a quaternary alloy added with Si 3% to the Ti 70 line of FIG. 9 is observed.
13 is XRD patterns showing amorphous forming ability of ternary alloys having a composition range of Ti 75% -Cu x% -Ni y% (x + y = 25).
14 is XRD patterns showing the amorphous forming ability of a quaternary alloy added with 5% Si to the Ti 75 line of FIG.
FIG. 15 shows XRD patterns of the amorphous forming ability of a quaternary alloy added with 7% Si in the Ti 80 line of FIG.
16 shows the total composition range of a Ti-Cu-Ni-Si quaternary alloy irradiated with amorphous forming ability.
Fig. 17 shows a compressor 10 of any type, using a rotating shaft 11 and bearings 12, 13, to which the lubricant layer of the present invention is applied.

Hereinafter, a titanium amorphous alloy according to a preferred embodiment of the present invention, a sputtering target for forming a lubricating layer made of the amorphous alloy, and a compressor including the lubricating layer will be described in detail with reference to the accompanying drawings.

It is to be understood that the present invention is not limited to the disclosed embodiments, but may 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, It is provided to inform. Also, for convenience of explanation, the components may be exaggerated or reduced in size.

Most solid materials are aggregates of microcrystals. In the three-dimensional space, each atom has a long range translational periodicity and is located in a defined crystal lattice. Alternatively, the liquid material has a disordered structure that lacks translational periodicity due to thermal vibrations.

In terms of atomic structure, the amorphous metal is a crystalline solid in that it does not have long-range order patterns, which are typical atomic structures of crystalline alloys, and is a solid that exists in a disordered state with a liquid structure. It is a concept compared with alloy.

In the present invention, the term amorphous refers generally to an amorphous structure in which the general concept of the amorphous structure is a microstructure and the X-ray diffraction pattern is a diffuse halo, Lt; RTI ID = 0.0 > amorphous < / RTI >

Furthermore, in the present invention, the term amorphous refers not only to the case where the composition of the composition is 100% amorphous, but also to the case where the amorphous state exists in the main phase and does not lose the property of the amorphous state, . Specifically, in the case where a part is present as crystalline (or nanocrystalline) in the amorphous structure, some nitride and / or carbide precipitates are present, some intermetallic compound exists, or some silicide exists . Here, the nanocrystalline means a metal alloy having an average size of crystal grains of nano size (when it is several hundreds nm or less).

The glass forming ability (GFA) in the present invention indicates how easily an alloy of a specific composition can be amorphized. Generally, the amorphous formability of metals and / or alloys depends largely on their composition, and this ability to form amorphous from continuous cooling transformation diagrams or time-temperature-transformation diagrams The critical cooling rate (hereinafter referred to as Rc), which can be measured, can be directly evaluated. However, in reality, it is not easy to obtain Rc by experiments or calculations because the physical properties such as melt viscosity and latent heat of fusion are different depending on the composition of each alloy.

In order to form amorphous alloys through the most common and common method of casting, a higher cooling rate above a certain level of Rc is required. If a casting method in which the solidification rate is relatively slow (for example, a mold casting method) is used, the composition range of the amorphous formation is reduced. Alternatively, the rapid solidification method, such as melt spinning, in which a molten alloy is dropped on a rotating copper roll to solidify the alloy with a ribbon or wire rod, is usually carried out using a maximized cooling rate of 10 ⁴ to 10 ⁶ K / sec or more An amorphous ribbon having a thickness of several tens of micrometers can be obtained, thereby widening the composition range capable of forming amorphous. Therefore, the evaluation of the degree of amorphous formability of a particular composition is generally characterized by a relative value depending on the cooling rate of a given cooling process.

In consideration of the relative characteristics of amorphous forming ability, the alloy having amorphous forming ability in the present invention means an alloy capable of obtaining an amorphous ribbon when casting using a melt spinning method.

The amorphous alloy of the present invention can be applied to a compressor, more specifically, a lubricating layer formed at a friction portion of a rotating shaft or a rotating shaft and a bearing. The lubricating layer in the present invention can improve the durability, the low friction property, the heat resistance, and the tame property.

Ti -Cu- Ni -X Quaternary  Amorphous alloy

1 is a conceptual diagram for explaining an amorphous alloy or solid lubricant layer of the present invention.

The lubricating layer in the present invention shown in Fig. 1 shows an example in which the lubricating layer is formed at the friction portion between the rotating shaft and the bearing. 1 shows the lubrication layer 20 and the base materials 11, 12 and 13 on which the lubricating layer 20 is formed. The base material 11, 12, 13 to which the lubricating layer 20 is coated may comprise any material that can be used as a structural material. However, metals are more preferable than other materials because rapid cooling due to inherent high thermal conductivity of the metal is possible, which can promote amorphous formation of the lubricating layer 20. [

The lubricating layer 20 in the present invention may be composed of only the amorphous material 21 or may have a composite structure in which the main phase is amorphous or the amorphous material 21 and the nano-sized crystalline material 22 are mixed.

FIG. 2 is a stress-strain curve obtained by comparing an amorphous metal with a metal nitride and a crystalline metal. Here, the stress refers to the resistance generated in the material when an external force is applied to the material. Strain rate refers to the ratio of deformation to material and the original length of material. The slope in the stress-strain curve corresponds to the modulus of elasticity.

In general, the durability (reliability against abrasion resistance) of the lubricating layer can be evaluated by the ratio (H / E) between the hardness (H) and the elastic modulus (E). The relatively large value of the ratio of hardness to elastic modulus means that the durability of the lubricating layer is high and the possibility of peeling or fracture is low.

12 and 13 due to the influence of residual stress during deformation when the interface elasticity characteristics (or mechanical characteristics) between the base materials 11, 12 and 13 and the lubricating layer 20 are not similar, Or the lubricant layer 20 may be broken. The fact that the elastic characteristics do not coincide means that the elastic modulus difference between the base material 11, 12, 13 and the lubricating layer 20 is large. Conventional lubricating materials generally have a high modulus of elasticity due to the high hardness ceramic phase. Accordingly, even though the conventional lubricating materials deposit a soft crystalline phase, since they have a large elastic modulus difference with the base materials 11, 12 and 13, they exhibit low interfacial stability even when the initial lubrication performance is excellent. As a result, conventional lubricant materials are not readily sustainable because they are easily peeled or broken from the base material. The occurrence of peeling or fracture of the lubricating layer 20 means that the durability (reliability against abrasion resistance) of the lubricating layer 20 is low.

The metal nitride has a very high hardness. However, the metal nitride has a high modulus of elasticity, as can be seen from the slope of the graph shown in Fig. Also, the metal nitride has a low elastic strain of 0.5% or less. As a result, the metal nitride can form a hardness lubricating layer due to its relatively high hardness, but it is difficult to secure durability due to a relatively high elastic modulus.

On the other hand, the crystalline metal has a very low modulus of elasticity, as can be seen from the slope of the graph shown in Fig. However, the crystalline metal has a low elastic strain of 0.5% or less like a metal nitride. The elastic strain of the crystalline metal is so small that a plastic deformation typically occurs from a strain of 0.2% or more (0.2% Offset yield strain). Further, the hardness of the crystalline metal has a much lower hardness than the metal nitride. As a result, it is difficult to form a high hardness lubricant layer due to the relatively low hardness, while the crystalline metal has a certain degree of durability of the lubricant layer due to a low elastic modulus.

On the other hand, as can be seen from the above results of the metal nitride and the crystalline metal, the elastic modulus tends to increase as the hardness increases. On the contrary, when the elastic modulus is lowered, the hardness also tends to be lowered. Therefore, it is very difficult to simultaneously improve the ratio of hardness and modulus of elasticity. This means that it is difficult to ensure the durability of the high hardness lubricant layer through high hardness and low modulus of elasticity.

However, the present invention can achieve high hardness and low elastic modulus through the microstructure of a composite structure composed of amorphous and nanocrystalline. The hardness of the amorphous metal is lower than that of the metal nitride, but has a higher hardness than the crystalline metal. Referring to FIG. 2, the modulus of elasticity of the amorphous metal is much lower than that of the crystalline metal or metal nitride. Since the elastic deformation limit of the amorphous metal is more than 1.5%, the amorphous metal exhibits a wide elastic limit and serves as a buffer between the lubricating layer and the friction material.

Therefore, unlike the general tendency in the metal materials described above, the amorphous metal has a high hardness, a low elastic modulus and a large elastic strain. Accordingly, the ratio (H / E) between the hardness of the amorphous metal and the modulus of elasticity is larger than that of the crystalline metal or the metal nitride.

As a result, the lubricating layer utilizing the amorphous metal has an advantage that it has not only abrasion resistance caused by amorphous hardness but also reliability (durability). More specifically, since the lubricating layer 20 of the present invention shown in FIG. 1 is made of a material and composition having amorphous (21) forming ability, it is possible to form a composite structure composed of amorphous material 21 and nanocrystal material 22 . As described above, peeling or fracture of the lubricating layer 20 occurs due to mismatch of the interface elastic properties (or mechanical properties) between the base materials 11, 12, 13 and the lubricating layer 20. However, since the lubricating layer 20 including the amorphous material 21 according to the present invention has a hardness and a low elastic modulus value as compared with the crystalline alloy, the nitride and / or carbide precipitation phase and / or the intermetallic compound and / Peeling or fracture of the lubricating layer 20 can be minimized even if a hard coating is formed through precipitation. Accordingly, the lubricating layer 20 of the present invention has higher durability (reliability against abrasion resistance) than conventional lubricating materials.

The amorphous alloy in the present invention is a Ti-Cu-Ni (Ni-X) alloy further comprising a fourth element (X) capable of forming process points in both Ti-X binary system, Cu- -X 4 It is an elemental alloy. In the present invention, in particular, a quaternary alloy having amorphous forming ability in a higher Ti content (so-called Ti rich) composition region than a Ti-Cu binary alloy or a Ti-Cu-Ni ternary alloy is invented.

The reason why the Ti-Cu-Ni-X quaternary alloy having the Ti rich composition is adopted is that the hardness of the whole alloy increases as the content of Ti increases. Particularly, the higher the content of Ti, the easier it is for Ti to form an inter-metallic compound or a silicide which is advantageous for realizing other alloying elements and ultrahigh hardness characteristics. However, even if it has a high hardness, if there is a discrepancy in interfacial elasticity properties with the base material, breakage or peeling of the lubricating layer may occur. Therefore, in the present invention, a Ti-Cu-Ni-X quaternary alloy is designed to have an amorphous microstructure capable of forming amorphous microstructure, that is, a composition capable of forming excellent amorphous properties, in order to resemble elastic properties of a base material and a lubricant layer

Similar to common metals, Ti alloys are generally made of crystalline alloys in general compositions and manufacturing processes, so that compositions with amorphous forming ability generally have a narrow range. However, an excessively narrow composition range may not have sufficient amorphous forming ability, but also limits the improvement of various characteristics depending on the composition.

Therefore, in the present invention, in order to develop an alloy having amorphous forming ability over a wide composition range, it is possible to lower the melting point based on the existing ternary Ti-Cu-Ni alloy and further to form a high hardness phase with Ti Ti-Cu-Ni-X quaternary alloys were designed

In general, the state diagram of a binary alloy, for example a Ti-Cu alloy, can be expressed in a two-dimensional plane (Fig. 3). The bimodal state diagram quantitatively shows the equilibrium phase (s) and the fraction of each phase thermodynamically most stable under certain conditions (e.g., composition or temperature).

However, the state diagram of the ternary alloy, for example, the A-B-C alloy, is a three-dimensional triangular pole (Fig. 4). At this time, a triangle in the xy plane of the triangular pillar (commonly referred to as a Gibbs triangle) represents the composition range of the three components and the z direction represents the temperature. Therefore, unlike binary alloys, it is extremely difficult to measure and evaluate metallurgical information because the equilibrium state of the ternary alloy becomes a three-dimensional solid rather than a two-dimensional plane due to the addition of the third element.

In addition, in order to understand the equilibrium phase and microstructure of Ti-Cu-Ni-X quaternary amorphous alloy to be invented in the present invention under specific conditions (for example, composition or temperature), four ternary phase diagrams are basically required (Ti-Cu-Ni, Ti-Cu-X, Ti-Ni-X and Cu-Ni-X ternary phase diagrams) When the X component is added to the Ti- Should be determined.

However, the above information is difficult to be practically tested or evaluated. Therefore, in the present invention, the present inventors have found out that Ti, Cu and Ni, which are constituent components of a ternary Ti-Cu-Ni amorphous alloy, and binary alloys of Ti-X, Cu-X and Ni- The fourth element (X) capable of lowering the melting point of the binary alloys was first investigated.

In general, metals with low melting points have the following advantages in amorphous formability.

First, in general, the transfer phenomenon of a substance is classified into a thermal activation process in both convection in a liquid phase and diffusion in a solid phase. Therefore, as the melting point is lower, the liquid phase may be present at a low temperature, and therefore, when the liquid phase is phase-transformed into a solid phase, the movement of the material is slowed, so that the possibility of formation of an equilibrium crystal is further lowered.

Next, the phase transformation from liquid phase to solid phase always requires under-cooling due to the energy barrier of solid-liquid interface energy generated in the nucleation process of solid phase. This means that the liquid phase is also present at a temperature substantially lower than the equilibrium temperature, which is thermodynamic.

Therefore, in the present invention, the elements of Ti, Cu, and Ni and the fourth element (X) capable of forming an eutectic point were firstly searched to find a component capable of minimizing the melting point. As the term eutectic indicates, the process point is the temperature at which the liquid phase can be maintained at the lowest temperature in any alloy system. As a result, the composition near the process point corresponds to a composition that can exist at the lowest temperature of the liquid phase in terms of thermodynamics. In addition, in terms of kinetics, larger undercooling As a result, it is the most favorable composition which can secure the amorphous forming ability in the Ti-Cu-Ni-X quaternary alloy.

Figs. 5 to 7 are binary state equilibrium diagrams of Ti-Si, Cu-Si and Ni-Si, respectively. As shown in the above state diagrams, it can be seen that Si forms both process points with Ti, Cu and Ni. For example, when Si is added to Ti, the melting point of the Ti-Si alloy decreases as the amount of Si added increases to about 13 at.% (Hereinafter referred to as%) Si, which is a process point composition. Therefore, in the present invention, Si is selected as one of the alloying elements capable of greatly lowering the melting point of the Ti-Cu-Ni ternary alloy in terms of the lowering of the melting point.

In general, in order for metals to have amorphous formability, it is known that several rules of experience must be met. In the present invention, it is understood that among these empirical laws, there must be a large difference in atomic radius of 12% or more between the main constituent atoms and a large negative heat of mixing between the constituent atoms. .

FIG. 8 is a diagram showing the radial difference between the constituent elements of the Ti-Cu-Ni-Si quaternary alloy to be invented in the present invention and the heat of mixing. As shown in FIG. 8, it can be seen that the atomic radius of Si is at least 12% different from the atomic radius of Ti, Cu and Ni. The present inventors have also found that the mixed heat of Si and Ti, Cu and Ni is higher than the mixed heat of the respective components in the Ti-Cu-Ni ternary amorphous alloy invented in another invention, Respectively.

Due to the characteristics of Si, the present inventors have selected Si as the fourth element in order to secure the amorphous forming ability in the Ti rich composition region of the Ti-Cu-Ni ternary amorphous alloy.

However, the best Si content capable of securing the amorphous forming ability does not correspond to a structure that can be easily predicted or easily derived by an ordinary technician. 5 to 7, the degree of the lowering of the melting point with respect to the addition amount of Si when Si is added to Ti, Cu and Ni varies depending on each element, and the composition for forming the silicide is also Ti, Cu and Ni .

In addition, it is advantageous in terms of the lowering of the melting point of the alloy to increase the Si addition amount before the process point, but as the Si content increases, there arises another side effect that the fraction of the silicide increases. For example, as shown in FIG. 5, the addition of about 5% or more Si in the Ti matrix causes the formation of silicide. However, since some of the silicides have a melting point higher than the melting point of pure Ti and Si, not only the amorphous ability of the alloy is deteriorated, but excessive silicide precipitation may also have undesirable mechanical characteristics.

Therefore, it is very important to derive the Si content which can simultaneously obtain the melting point lowering and the suppression of excessive precipitation of the silicide. In the present invention, the following amorphous alloys were prepared and amorphous formability evaluation methods were used for inventing a Ti-Cu-Ni-Si quaternary amorphous alloy.

First, the Ti-based amorphous alloy composition of the desired component is implemented with an amorphous alloy casting material, an amorphous alloy powder, and an amorphous alloy ribbon in the form of a foil. Methods for implementing this method are widely known in the art to which the present invention belongs, and examples thereof include a rapid solidification method, a die casting method, a high-pressure casting method, an atomizing method, and a melt spinning method.

In the present invention, first, an alloy button having a desired composition is prepared using a vacuum arc remelting method. The alloy of the button shape was then re-dissolved again to prepare an alloy melt, and the molten alloy was injected into the surface of a copper roll rotating at a high speed through a nozzle to rapidly solidify the alloy melt.

Whether or not the ribbon-like amorphous body produced by the melt spinning method as described above is discriminated by X-ray diffraction (XRD) method widely known in the art to which the present invention belongs.

Fig. 9 shows a Ti-Cu-Ni ternary Gibbs triangle showing a composition region irradiated with an amorphous forming ability in the present invention. As shown in Fig. 9, the ternary alloy has two ternary system process points in the composition range (indicated in Fig. 9); One is the Ti 73.2% -Ni 17.7% -Cu 9.1% process point named E4 and the other is the Ti 65.1% -Ni 21.8% -Cu 12.9% process point named E5. In the present invention, the amorphous formability of a Ti-Cu-Ni-Si quaternary alloy in a wide range from a Ti content (Ti lean) having a Ti content lower than that of the E5 content to a Ti content richer than a Ti content Respectively.

10 shows the XRD results of a Ti 65% -Cu 15% -Ni 20% ternary alloy near the E 5 composition. FIG. 10 shows a typical diffraction halo form, which is a typical XRD pattern of amorphous phases, indicating that almost all of the microstructure of the ternary alloy of the above composition is amorphous.

11 and 12 are XRD results of investigating the amorphous forming ability of Ti-Cu-Ni ternary alloy and Ti-Cu-Ni-Si ternary alloy each containing 70% Ti.

First, in a composition region where the content of Cu + Ni in the Ti-Cu-Ni ternary alloy is 30%, the content of Cu is 20 to 10% and the content of Ni is 10 to 20%, the main phase is amorphous. (Fig. 11). Furthermore, when the Ni content in the composition range is increased from 10% to 20%, weak diffraction peaks on Ti ₂ Ni are observed in the XRD results. This means that the Ti-Cu 10% -Ni 20% ternary alloy has a complex microstructure in which the Ti ₂ Ni phase coexists within the amorphous matrix.

On the other hand, a Ti-Cu-Ni-Si quaternary alloy containing 3% Si added to the Ti-Cu-Ni ternary alloy has a Cu + Ni content of 30%, a Cu content of 20 to 10% and a Ni content of 10 To 20% in the composition range (FIG. 12). However, in the Ti-10% Cu-20% Ni ternary alloy, a part of the microstructure has a Ti ₂ Ni phase which is a crystalline phase (FIG. 11), whereas (Ti-Cu 10% -Ni 20%) ₉₇ Si ₃ 4 It can be seen from FIG. 12 that the pure alloy only forms a substantially pure amorphous phase substantially free of crystalline Ti ₂ Ni phase. These results directly indicate that the addition of 3% Si greatly improves the amorphous formability of the Ti-Cu-Ni-Si quaternary alloy.

13 and 14 are XRD results of examining the amorphous forming ability of Ti-Cu-Ni ternary alloy and Ti-Cu-Ni-Si ternary alloy each containing 75% of Ti.

First, in the Ti-Cu-Ni ternary alloy, it was confirmed that there was no amorphous forming ability in the irradiated ternary system total composition region where Ti was 75%. This means that the T-Cu-Ni ternary alloy system in which Ti is contained more than the E4 composition substantially lacks amorphous forming ability.

However, in the T-Cu-Ni-Si quaternary alloy system in which 5% of Si is contained in the Ti-Cu-Ni ternary alloy system, unlike the ternary system, the content of Cu + Ni is 25% (Composition satisfying Ti + Cu + Ni = 95%) was found to be amorphous in a wide composition range of 5 to 15% and a Ni content of 10 to 20%. It was also found that the quaternary alloy exists only in a substantially pure amorphous phase substantially free of an intermetallic compound or a silicide.

15 is an XRD result of examining the amorphous forming ability of a Ti-Cu-Ni-Si quaternary alloy containing 80% of Ti.

As a result of experiments conducted by the inventors of the present invention, it was confirmed that the T-Cu-Ni ternary alloy system to which Ti was added in an amount of 80% or more had no amorphous forming ability in the entire irradiated composition range. However, in the T-Cu-Ni-Si quaternary alloy system containing 7% of Si, unlike the ternary system, the content of Cu + Ni is 20%, the content of Cu is 5 to 10% and the content of Ni is 10 (In which Ti + Cu + Ni = 95% is satisfied) in the composition range of 25% to 25%. It was also found that this quaternary alloy also exists only in a substantially pure amorphous phase substantially containing no intermetallic compound or silicide.

FIG. 16 summarizes the amorphous forming ability of the Ti-Cu-Ni-Si quaternary alloy tested in the entire composition range irradiated. First, in FIG. 16, the XRD pattern experiment results show that the composition region on the dotted arrows extending from the lower left to the upper right shows amorphous formation ability and microstructure is almost entirely formed by amorphous. On the other hand, the XRD pattern results show that the shaded composition region on the left side of the arrow has amorphous ability to form and the main phase is amorphous and contains some intermetallic compounds in terms of microstructure. On the other hand, the shaded composition region on the right side of the arrow has an amorphous forming ability, and in the microstructure side, a composition region containing amorphous phase and containing some silicide in the main phase is shown.

From the above experimental results, Ti-Cu-Ni-X 4 having a composition range of 65 to 80% of Ti, 5 to 20% of Cu, 5 to 25% of Ni and 9% It was confirmed that the amorphous formability of the alloy was stable.

Sputtering target

Hereinafter, the sputtering target proposed in the present invention will be described.

The sputtering process is widely used in semiconductor manufacturing fields, microelectronic devices such as MEMS, and motors, and coatings for improving wear resistance in compressors and the like.

When a thin film of amorphous phase or a complex amorphous thin film containing nanocrystalline is produced using a sputtering process, the sputtering target to be used may be a crystalline or amorphous target. However, in amorphous targets, the target surface is locally increased in temperature due to the collision of plasma ions during the sputtering process, and this temperature increase can again cause microstructure change of the target surface.

More specifically, since amorphous is a thermodynamically unstable phase, an increase in the temperature of the target causes crystallization that transforms the thermodynamically unstable amorphous material to the thermodynamically stable crystalline material at the target surface. However, such localized crystallization can lead to volume change and structural relaxation of the target, which increases the brittleness of the target, resulting in even extreme results in which the target is destroyed during the sputtering process.

Therefore, in order to improve the thermal stability of the sputtering target and the process reliability of the sputtering process, a sputtering target having a microstructure in a composition range having amorphous forming ability was produced. More specifically, a quaternary Ti amorphous alloy in the present invention was used to produce a sputtering target having a crystalline microstructure.

In the present invention, a Ti-Cu-Ni-X quaternary alloy having a composition which is found to have an amorphous forming ability in the above embodiments is dissolved by vacuum arc melting, and then melt-spinning is performed to form a ribbon or a foil- Amorphous alloy was obtained. Then, a plurality of the ribbons were stacked, and then a sputtering target having a crystalline quality was obtained by heating at a temperature higher than the crystallization initiation temperature in the composition of the ribbons and lower than the melting temperature.

The amorphous alloy ribbons during the heat pressing process are crystallized by progress of bonding due to interdiffusion among the ribbons, and grain growth also occurs when the time of holding the heat pressure after crystallization is prolonged. Also in this process, the lamination interface between the deposited alloy ribbons can be destroyed by interdiffusion of atoms.

It is preferable that the grain size of the sputtering target of the microstructure finally crystallized or grain-grown has a range of 0.1 to 10 탆. When the grain size is smaller than 0.1 탆, sufficient crystallization can not be ensured, which is not preferable from the viewpoint of ensuring the thermal stability of the target. On the other hand, when the grain size is larger than 10 탆, crystallization can be sufficiently secured, but it is disadvantageous in terms of stability and uniformity of the plasma process and uniformity of the composition of the final coating layer.

Meanwhile, as another method, a crystalline sputtering target can be produced using the amorphous alloy powder having the Ti-Cu-Ni-X quaternary amorphous alloy composition of the present invention. In this case, a crystalline sputtering target can be produced by bonding aggregates of amorphous alloy powders produced by atomization or the like by high-temperature sintering or high-temperature sintering. In this case, the sintering temperature is higher than the crystallization start temperature in the composition of the alloy powder and is lower than the melting temperature.

As another example, a molten metal is injected into a copper mold through a nozzle and rapidly solidified in a mold such as copper having a high cooling ability such as a copper mold casting method using a pressure difference between the inside and the outside of the mold, Of the amorphous alloy casting material can be produced. Thereafter, a crystalline alloy target may be obtained through annealing.

Lubricating layer  Compressor including

Hereinafter, the lubricant layer proposed by the present invention and a compressor including the lubricant layer will be described.

The lubricant layer of the present invention is applicable to all moving parts or components, but in the present invention, as a simplest example, a compressor having a structure utilizing the rotation of the rotating shaft is illustrated.

17 is a partial cross-sectional view of a compressor according to the present invention. Fig. 17 shows a compressor 100 of any type using a rotary shaft 111 and bearings 112, 113. Fig.

The rotating shaft 111 rotates to compress the gas during the operation of the compressor 100. The bearings 112 and 113 are configured so as to surround at least a part of the rotating shaft 111. The bearings 112 and 113 are fixed to rotate relative to the rotary shaft 111. [ The bearings 112 and 113 may include a main bearing 112 (or a first bearing) and a sub bearing 113 (or a second bearing).

When the compressor 100 operates, gas flows from one side of the rotating shaft 111 while the rotating shaft 111 rotates. And a reaction force F is formed in a direction opposite to the gas force G due to the introduced gas. Therefore, the rotating shaft 111 is in constant contact with the bearings 112 and 113 while the rotating shaft 111 rotates.

The lubricant layer is formed in the friction portions 112a and 113a of the rotating shaft 111 and the bearings 112 and 113 to realize wear resistance and low friction. The lubricant layer may be deposited on at least one of the rotating shaft 111 and the bearings 112, 113. Here, the lubricating layer is a Ti-Cu-Ni-X 4 element alloy having the above-described amorphous forming ability.

The lubricant layer in the present invention is not applied only to the contact portion of the rotating shaft 111 and the bearings 112 and 113. [ For example, it may be applied to other components that the rotating shaft can contact, for example, a contact portion with a frame or a subframe. The lubrication layer of the present invention can also be applied to compressor components other than the rotating shaft and the bearing. For example, it can be applied to a friction portion of a cylinder, a rolling piston, a vane, and the like in a rotary compressor. Finally, the lubricant layer of the present invention can be applied to all parts, tools, and apparatuses other than the compressor in which friction or abrasion may occur.

On the other hand, the base material of the lubricating layer, such as the rotating shaft on which the lubricating layer is formed, is not particularly limited. However, it is preferable to include at least any one of steel, cast iron, aluminum-containing alloy, and magnesium-containing alloy, which are currently commercially available and widely used. This is because metals such as the above-mentioned steels, castings, aluminum-containing alloys, magnesium-containing alloys and the like have a side effect of promoting the amorphous forming ability of the lubricating layer due to high heat conduction.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the scope of the invention is not limited to the disclosed exemplary embodiments. It is obvious that a transformation can be made. Although the embodiments of the present invention have been described in detail above, the effects of the present invention are not explicitly described and described, but it is needless to say that the effects that can be predicted by the configurations should also be recognized.

Claims (13)

Ti, Cu and Ni,
Further comprising a fourth element (X) capable of forming process points in both the Ti-X binary system, the Cu-X binary system, and the Ni-X binary system.
Ti-Cu-Ni-X quaternary amorphous alloy.
The method according to claim 1,
Wherein the atomic radius of the fourth element (X) is at least 12% different from the atomic radius of each of Ti, Cu and Ni.
The method according to claim 1,
Wherein the fourth element X has a negative heat of mixing when mixed with Ti, Cu and Ni, respectively. 2. The Ti-Cu-Ni-X based amorphous alloy according to claim 1,
The method according to claim 1,
And the fourth element (X) is Si. The Ti-Cu-Ni-X quaternary amorphous alloy.
5. The method of claim 4,
Wherein the alloy has a composition range of 65 to 80% of Ti, 5 to 20% of Cu, 5 to 25% of Ni, and 9% or less of Si (excluding 0) -Ni-X 4-quaternary amorphous alloy.
6. The method of claim 5,
Wherein the alloy has a composition range of 65 to 80% of Ti, 5 to 15% of Cu, 10 to 20% of Ni, and 9% or less of Si (excluding 0) in atomic% -Ni-X 4-quaternary amorphous alloy.
The method according to claim 6,
Wherein the Ti forms an intermetallic compound with Cu and / or Ni. The Ti-Cu-Ni-X quaternary amorphous alloy is characterized in that the Ti forms an intermetallic compound with Cu and / or Ni.
The method according to claim 6,
Wherein said Si forms Ti and Titanium silicide. ≪ RTI ID = 0.0 > 15. < / RTI >
A sputtering target comprising the Ti-Cu-Ni-X tetravalent composition according to any one of claims 1 to 8.
The sputtering target according to claim 9, wherein the microstructure of the target is crystalline.
11. The sputtering target according to claim 10, wherein an average grain size of the target ranges from 0.1 to 10 mu m.
A compressor comprising a lubricating layer of a Ti-Cu-Ni-X quaternary amorphous alloy according to any one of claims 1 to 8.
13. The method of claim 12,
Wherein the lubricating layer is coated on a base material comprising at least one of a steel material, a cast alloy, an alloy containing aluminum, and an alloy containing magnesium.

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