TWI444481B - A mixture of aluminum-nickel pre-alloyed powders and an alni target made from the same - Google Patents

Description

Aluminum-nickel prealloyed powder composition and aluminum-nickel alloy target thereof

The present invention relates to an aluminum-nickel prealloyed powder composition, and more particularly to an aluminum-nickel prealloyed powder composition for preparing an aluminum-nickel alloy target. The invention also relates to an aluminum-nickel alloy target.

Cathodic arc evaporation (CAE) is widely used in the hard coating market due to its high ionization rate, fast coating rate and good adhesion of prepared films, such as aerospace industry, cutting tools, molds, communication industry, and defense. Corrosion industry, machinery manufacturing industry, etc. However, not all targets can be smoothly coated by arc ion plating process technology. Because the arc generates high temperature during the coating process, if the target has multiple individual elemental phases, it will be due to high temperature. The reaction between the elements causes the exotherm to cause the target to burn, which causes the machine to be damaged and the quality of the coating to be greatly reduced. Therefore, it is necessary to select a suitable target for the arc ion plating, but it is also necessary to consider whether the target is easy to prepare. To meet industrial applicability.

Referring to FIG. 7, an Al-Ni intermetallic compound, such as the AlNi compound in FIG. 7, has a nickel content of between 45 and 59 atomic percent, and the existing preparation of an aluminum-nickel intermetallic compound. The technology of the Al-Ni intermetallic compound aluminum alloy target includes a smelting casting method and a powder metallurgy method. Referring to FIG. 7 again, when the above-mentioned aluminum-nickel alloy target is prepared by the smelting casting method, since aluminum and nickel are composed of an atomic percentage of z:(100-z), an aluminum-nickel intermetallic compound is formed. Between 41 and 55, the melting point of the aluminum-nickel intermetallic compound is very high, about 1580 ° C, which causes the crucible of the melting furnace to have a puncture wind during the smelting process. Risk, which in turn leads to equipment damage, so the risk of preparing an aluminum-nickel alloy target in this way is high and the yield is low.

In the case of powder metallurgy, pure aluminum powder and pure nickel powder are used as starting materials. If the process temperature is high, it is easy to produce different alloy phases after sintering, such as aluminum phase, nickel phase and Al ₃ Ni. An intermetallic compound phase such as Al ₃ Ni ₂ , AlNi, Al ₃ Ni ₅ or AlNi ₃ , so that the microstructure of the aluminum-nickel alloy target is not uniform, which leads to easy generation of voids during processing and does not apply to the aforementioned arc ion. There are many disadvantages such as coating and sputtering of the target, which tends to generate a large amount of fine particles and deteriorate the quality of the film. However, if the process temperature is too low, the intermetallic compound phase produced by the Al-Ni alloy target can be reduced, but the relative density of the Al-Ni alloy target is lowered, and the quality of the Al-Ni alloy target is lowered.

Further, in order to generate a homogeneous microstructure consisting of aluminum-nickel alloy target, by using an aerosol device (gas atomizer) directly to the aluminum to nickel is 1: 1 the aerosol powder composition ratio, as will Al ₅₀ Ni ₅₀ Compound The melting point is too high (about 1638 ° C), causing the nozzle of the aerosol machine to be clogged, causing the powder to fail, so that the subsequent target process cannot be performed.

In order to solve the above-mentioned prior art, an aluminum-nickel alloy target containing an Al-Ni intermetallic compound is difficult to fabricate and its structure is not uniform, so it cannot be applied to an arc ion plating film. The present invention provides an aluminum nickel. a prealloyed powder composition comprising: an Al _x Ni _100-x prealloyed powder consisting of aluminum and nickel, wherein the atomic percentages of aluminum and nickel are x% and (100-x)%, respectively; An Al _y Ni _100-y prealloyed powder consisting of aluminum and nickel, wherein the atomic percentages of aluminum and nickel are y% and (100-y)%, respectively; wherein x is between 1 and 41, The y series is between 55 and 99; and the aluminum-nickel prealloyed powder composition has an atomic percentage of aluminum to nickel of z: (100-z) and a z-system between 41 and 55.

According to the present invention, the aluminum-nickel prealloyed powder composition is composed of the aluminum-nickel prealloyed powder by adjusting the content of the Al _y Ni _100-y prealloyed powder and the content of the Al _x Ni _100-x prealloyed powder. The atomic percentage of aluminum to nickel is z: (100-z), and the z-system is between 41 and 55.

According to the present invention, the Al _x Ni _100-x prealloyed powder of the present invention is obtained by first mixing aluminum and nickel to obtain an aluminum nickel atomized precursor material which accounts for the aluminum nickel atomization precursor. The x at% of the total atomic percentage (at%) of the material, which accounts for (100-x)at% of the total atomic percentage of the aluminum-nickel atomized precursor material, and then atomizes the aluminum-nickel precursor by atomization manufacturing method. The material was atomized to obtain an Al _x Ni _100-x prealloyed powder. Since the x series is between 1 and 41, the aluminum-nickel atomized precursor material can effectively reduce the melting point of the aluminum-nickel atomized precursor material in the process of the atomization manufacturing method, thereby greatly increasing the probability of successful atomization. Further, the Al _x Ni _100-x prealloyed powder is easily produced.

According to the present invention, the Al _y Ni _100-y prealloyed powder of the present invention is obtained by first mixing aluminum and nickel to obtain an aluminum nickel atomized precursor material which accounts for the aluminum nickel atomization precursor. The y at% of the overall atomic percentage (at%) of the material, which accounts for (100-y) at% of the total atomic percentage of the aluminum-nickel atomized precursor material, and then atomizes the aluminum-nickel precursor by atomization manufacturing The material was atomized to obtain an Al _y Ni _100-y prealloyed powder. As described above, since the y system is between 55 and 99, the aluminum-nickel atomized precursor material can effectively reduce the melting point of the aluminum-nickel atomized precursor material in the process of the atomization manufacturing method, thereby greatly increasing the fog. The chance of success is improved, and the Al _y Ni _100-y prealloyed powder is easily prepared.

According to the present invention, the aluminum of the present invention is not limited to any form, such as aluminum block or aluminum powder, and the purity of the aluminum is, for example but not limited to, greater than 99.9% (3N).

According to the present invention, the nickel of the present invention is not limited to any form, such as a nickel block or a nickel powder, and the purity of the nickel is, for example but not limited to, greater than 99.9% (3N).

According to the present invention, the atomization manufacturing method of the present invention is, for example but not limited to, an aerosol method or a water mist method.

Preferably, the x series is between 1 and 34; preferably, the y is between 64 and 99.

Preferably, the x series is between 20 and 30.

Preferably, the Al _x Ni _100-x prealloyed powder has an oxygen content of less than 1000 ppm.

Preferably, the Al _y Ni _100-y prealloyed powder has an oxygen content of less than 1000 ppm.

The present invention also provides an aluminum-nickel alloy target made of the aforementioned aluminum-nickel prealloy powder composition.

According to the present invention, the aluminum-nickel alloy target of the present invention is an aluminum-nickel alloy target of an Al-Ni intermetallic compound, and the aluminum-nickel intermetallic compound is non-stoichiometric (non- Stoichiometric) compound.

According to the present invention, the aluminum-nickel alloy target of the present invention is suitable for use in an arc ion plating process technology. The aluminum-nickel alloy target is produced by any powder metallurgy method using the aforementioned aluminum-nickel prealloy composition. More Preferably, it is produced directly by hot pressing (HP). More preferably, it is produced by means of sealing and heat equalization.

Preferably, the aluminum-nickel alloy target has a flexural strength greater than 200 megapascals (MPa).

Preferably, the aluminum-nickel alloy target has a flexural strength of between 200 MPa and 400 MPa.

In accordance with the present invention, the flexural strength of the present invention is measured using a universal testing machine (INSTRON, 3365) and tested in accordance with ASTM C1161-02c (2008) e1.

Preferably, the aluminum-nickel alloy target has an oxygen content of less than 1000 ppm.

Preferably, the aluminum-nickel alloy target is used in an arc ion plating process.

An advantage of the present invention is that the aluminum-nickel prealloy powder composition of the present invention comprises an Al _x Ni _100-x prealloyed powder and an Al _y Ni _100-y prealloyed powder, and the x series is between 1 and 41. The y series is between 55 and 99. Because the melting point is effectively reduced during the preparation of each prealloyed powder, and the probability of preparing each prealloyed powder is improved, the aluminum nickel prealloyed powder composition is easily prepared, and the aluminum nickel is easily obtained. The prealloyed powder composition is used in the preparation of an aluminum-nickel alloy target of an Al-Ni intermetallic compound, and the failure rate of the target is greatly reduced, thereby improving industrial utilization.

Further, since the Al _x Ni _100-x prealloyed powder has an oxygen content of less than 1000 ppm and the Al _y Ni _100-y prealloyed powder has an oxygen content of less than 1000 ppm, the aluminum nickel prealloyed powder composition of the present invention is formed. When the aluminum-nickel alloy target is used, the aluminum-nickel alloy target can be effectively controlled to have an oxygen content of less than 1000 ppm.

In addition, the microstructure of the aluminum-nickel alloy target of the present invention is very uniform, the relative density is close to 100%, has excellent flexural strength, and the appearance is very The aluminum-nickel alloy target of the present invention has excellent quality, and is not easy to generate a large amount of particles when applied to the coating, so that the quality of the film is greatly improved, and the aluminum-nickel alloy target of the present invention has a very small microstructure. Uniform, no single-phase phase of pure aluminum or pure nickel, so it is very suitable for arc ion plating process technology, does not cause the reaction between elements due to the high temperature generated by arc during the coating process, so avoid the phenomenon of target burning, Therefore, the industrial utilization is greatly improved.

Further, since the aluminum-nickel alloy target of the present invention has an oxygen content of less than 1000 ppm, the probability of forming an oxide of the target is lowered, so that the arc source is more stable and uniform during coating.

In order to understand the technical features and practical functions of the present invention in detail, and in accordance with the contents of the specification, the drawings and preferred embodiments are further described to illustrate the technical means for the purpose of the present invention.

The source and composition ratios of the samples described in the experimental preparation schemes of the following examples are as follows; aluminum: purity is greater than 3N.

Nickel: Purity is greater than 3N.

X-ray diffractometer: Model: Ultima IV (made by Rigaku).

Example 1

In this embodiment, an aluminum-nickel prealloy powder composition is prepared by an aerosol method and a uniform mixing method, and the detailed preparation method is as follows: preparing aluminum and nickel to obtain an aluminum-nickel atomized precursor material, and the aluminum And accounting for 30 at% of the total atomic percentage (at%) of the aluminum-nickel atomized precursor material, the nickel accounting for 70 at% of the total at% of the aluminum-nickel atomized precursor material, and then using the following conditions Aluminium-nickel atomized precursor material for aerosol spraying: nozzle diameter is 5.5 mm (mm), atomization pressure is 15.5 kg/cm 2 (kg/cm ² ), and vacuum degree is 2.4×10 ^-2 Torr (Torr) ), melting temperature of 1660 deg.] C, to obtain a Al ₃₀ Ni ₇₀ prealloyed powder, the Al ₃₀ Ni ₇₀ alloy powder pre-purity greater than 99.95%, an oxygen content less than 800 ppm.

Next, aluminum and nickel are prepared to obtain another aluminum-nickel atomized precursor material, and the aluminum accounts for 70 at% of the total at% of the aluminum-nickel atomized precursor material, and the nickel accounts for the whole of the aluminum-nickel atomized precursor material. at% of 30 at%, then the following conditions using the aluminum-nickel powder aerosol atomized precursor material: nozzle diameter of 5.5 mm, the atomization pressure of 15.5 kg / cm2 kg / cm ^2, the degree of vacuum of 2.2 × 10 ^-2 Torr, the melt temperature was 1487 ℃, Al ₇₀ Ni ₃₀ to obtain a pre-alloy powder, the Al ₇₀ Ni ₃₀ alloy powder pre-purity greater than 99.95%, an oxygen content less than 500 ppm.

The Al ₃₀ Ni ₇₀ prealloyed powder and the Al ₇₀ Ni ₃₀ prealloyed powder were successively mixed to obtain an aluminum nickel prealloy powder composition.

Example 2

In this embodiment, an aluminum-nickel alloy target is prepared by sealing and hot-pressing, and the detailed preparation method is as follows: the aluminum-nickel prealloy powder composition of the first embodiment is prepared; the aluminum-nickel prealloy powder composition is prepared. The material is subjected to a canning treatment to obtain a sealed aluminum-nickel prealloyed powder composition; the aluminum-nickel prealloyed powder composition after the sealing is successively subjected to heat equalization treatment at a temperature of 1250 ° C and a pressure of 25,000 psi, after 3 After an hour, and after processing, an aluminum-nickel alloy target is obtained, the purity of the aluminum-nickel alloy target is greater than 99.95%, the relative density is approximately 100%, and the Rockwell Hardness (HRC) is 49.5. The strength is 310 MPa and the oxygen content is 650-700 ppm. Referring to FIG. 1 to FIG. 2 , the aluminum-nickel alloy target of the embodiment is made of two different atomic percentages of pre-alloyed powder, but the microstructure of the aluminum-nickel alloy target is very uniform, and The aluminum-nickel alloy target was randomly sampled and analyzed by an energy dispersive analyzer. The atomic percentage of aluminum was 49.3%, the atomic percentage of nickel was 50.7%, and the atomic percentage of aluminum to nickel was 49.3:50.7. Referring to FIG. 3, the aluminum-nickel alloy target of the present embodiment is compared with the Al ₅₀ Ni ₅₀ calibration material (JCPDS card number 65-0431), and the positions of 2θ are all stable, thereby knowing the aluminum-nickel alloy target. It is an Al-Ni intermetallic compound, that is, the Al-Ni alloy target does not have a single aluminum phase or a nickel phase, and only a single Al-Ni intermetallic compound. Therefore, when the aluminum-nickel alloy target is used for the arc ion plating process, aluminum or nickel is not reacted due to excessive arc temperature, so it is very suitable for the arc ion plating process. Further, the aluminum-nickel alloy target has no pores and a very flat surface, so that the aluminum-nickel alloy target has good workability.

Comparative example 1

In this comparative example, an aluminum-nickel alloy target is prepared by a vacuum induction melting method, and the detailed preparation method is as follows: First, an aluminum block and a nickel block are prepared to obtain an aluminum-aluminum smelting precursor material, and the aluminum block and the nickel block. The atomic percentage of the block is 1:1; the aluminum-aluminum smelting precursor material is subjected to vacuum induction melting, and the process conditions are as follows: the melting temperature is 1900 ° C, the melting time is 20 minutes, the casting temperature is 1880 ° C; after processing, An aluminum-nickel alloy target having a purity greater than 99.95%, a relative density of approximately 100%, and a flexural strength of 105 MPa. The Rockwell Hardness (HRC) system is 43.5. Referring to FIG. 4, the aluminum-nickel alloy target has a uniform microstructure and is a single Al-Ni intermetallic compound, and the aluminum-nickel alloy target is randomly sampled by an energy dispersive analyzer. The atomic percentage of aluminum is 49.8%, the atomic percentage of nickel is 50.2%, and the atomic percentage of aluminum to nickel is close to 1:1. In addition, the surface of the aluminum-nickel alloy target has many pores and the crystal grains are removed, which is caused by the processing, so the aluminum-nickel alloy target has poor processability.

Comparative example 2

This comparative example prepares an aluminum-nickel alloy target by powder metallurgy. The detailed preparation method is as follows: First, aluminum and nickel are mixed to obtain an aluminum-nickel mixture, and the atomic percentage of aluminum to nickel is 1:1. .

The aluminum-nickel mixture was subjected to a canning treatment to obtain a sealed aluminum-nickel mixture.

Subsequently, the sealed aluminum-nickel mixture is subjected to hot-pressure treatment at a temperature of 500 ° C and a pressure of 14,000 psi, and after one hour, and processed, an aluminum-nickel alloy target is obtained, and the purity of the aluminum-nickel alloy target is obtained. The system is greater than 99.9%, the relative density is approximately 90%, the Rockwell Hardness (HRC) system is 25.6, and the oxygen content is 1500 ppm. Referring to FIG. 5 to FIG. 6 , it can be seen from the figure that the microstructure of the aluminum-nickel alloy target is very uneven, and has many compound phases, wherein the aluminum phase and the nickel phase are dominant, and the aluminum-nickel intermetallic compound phase is partially formed. Since the nature of the compound phase is hard and brittle, pores are easily formed on the surface of the aluminum-nickel alloy target after processing, and the local compound tends to generate a large amount of particles during the sputtering process, and the quality of the film is degraded.

Comparative example 3

In this comparative example, an aluminum-nickel prealloyed powder having an atomic percentage of aluminum and nickel of 1:1 is directly prepared by aerosol spraying, and an aluminum-nickel alloy target is prepared by subsequent sealing, heat equalizing and processing. The detailed preparation method of the aluminum-nickel prealloyed powder in which the atomic percentage of nickel and aluminum is 1:1 is as follows: First, the aluminum block and the nickel block are mixed to obtain an aluminum-nickel atomized precursor material, and aluminum and nickel. The atomic percentage is 1:1, and then the aluminum-nickel atomized precursor material is subjected to aerosol dusting using the following conditions: the nozzle diameter is 5.5 mm, the vacuum degree is 8.0×10 ^-2 Torr, and the melting temperature is 1880 °C. However, since the melting temperature is too high, the fluidity of the aluminum-aluminum atomized precursor material after each smelting is not good, resulting in failure of atomization, so that the pre-alloyed powder of aluminum-nickel cannot be obtained, so the aluminum-nickel alloy target is not obtained in the comparative example.

in conclusion

The aluminum-nickel alloy target of the second embodiment has a significantly higher flexural strength than the aluminum-nickel alloy target of the comparative example 1, so that the mechanical strength is excellent, and the appearance of the target is complete without voids, so the workability is superior to the comparative example. 1 aluminum-nickel alloy target.

Compared with the aluminum-nickel alloy target of Comparative Example 2, the aluminum-nickel alloy target of Example 2 has a relatively high relative density, a low oxygen content, and a uniform microstructure, and no single aluminum phase or nickel phase is produced. Therefore, it is very suitable for the arc ion plating process, and the sputtering process does not generate a large amount of particles, so the quality of the film is improved.

Fig. 1 is a scanning electron microscope image of 50 times of an aluminum-nickel alloy target according to a second embodiment of the present invention.

2 is 100 times of the aluminum-nickel alloy target of Example 2 of the present invention. Scanning electron microscope image map.

Fig. 3 is an X-ray diffraction diagram of an aluminum-nickel alloy target of Example 2 of the present invention.

4 is a scanning electron microscope image of an aluminum-nickel alloy target of Comparative Example 1.

Fig. 5 is a scanning electron microscope image of 200 times the aluminum-nickel alloy target of Comparative Example 2.

Fig. 6 is a scanning electron microscope image of 500 times the aluminum-nickel alloy target of Comparative Example 2.

Figure 7 is a phase diagram of an aluminum-nickel binary alloy.

Claims (13)

An aluminum-nickel prealloyed powder composition comprising: an Al _x Ni _100-x prealloyed powder consisting of aluminum and nickel, wherein the atomic percentages of aluminum and nickel are respectively x% and (100-x) And an Al _y Ni _100-y prealloyed powder consisting of aluminum and nickel, wherein the atomic percentages of aluminum and nickel are y% and (100-y)%, respectively; wherein x is between 1 and 41 The y series is between 55 and 99; and the aluminum-nickel prealloy powder composition has an atomic percentage of aluminum to nickel of z: (100-z) and a z-system between 41 and 55. The aluminum-nickel prealloyed powder composition of claim 1, wherein the x series is between 1 and 34. The aluminum-nickel prealloyed powder composition of claim 2, wherein the x series is between 20 and 30. The aluminum-nickel prealloyed powder composition according to any one of claims 1 to 3, wherein the y is between 64 and 99. The aluminum-nickel prealloyed powder composition of claim 4, wherein the Al _x Ni _100-x prealloyed powder has an oxygen content of less than 1000 ppm. The aluminum-nickel prealloyed powder composition of claim 5, wherein the Al _y Ni _100-y prealloyed powder has an oxygen content of less than 1000 ppm. The aluminum-nickel prealloyed powder composition according to any one of claims 1 to 3, wherein the Al _y Ni _100-y prealloyed powder has an oxygen content of less than 1000 ppm. An aluminum-nickel alloy target produced by the aluminum-nickel prealloy powder composition according to any one of claims 1 to 7. The aluminum-nickel alloy target according to claim 8 has a flexural strength of more than 200 MPa. The aluminum-nickel alloy target according to claim 9 has a flexural strength of between 200 MPa and 400 MPa. The aluminum-nickel alloy target according to any one of claims 8 to 10, which has an oxygen content of less than 1000 ppm. The aluminum-nickel alloy target according to claim 11 is for use in a cathodic arc evaporation (CAE) process. The aluminum-nickel alloy target according to any one of claims 8 to 10, which is for use in a cathodic arc evaporation (CAE) process.