A precision resistance alloy material for electronic components and a method for manufacturing the same

Abstract

The application discloses a precision resistance alloy material for electronic components and a preparation method thereof. The precision resistance alloy material comprises refractory metal elements and non-refractory metal elements. The refractory metal elements are Hf, Nb, Ta and Re. The non-refractory metal elements are Co and Ni. The precision resistance alloy material is in an amorphous state. The precision resistance alloy material has a low resistance temperature coefficient in a wide temperature range and has good thermal stability.

Description

Technical Field

[0001] This invention belongs to the field of electronic component technology, specifically relating to a precision resistance alloy material for electronic components and its preparation method. Background Technology

[0002] As electronic components evolve towards higher precision, the demand for resistors with low resistance change rates and high accuracy is increasing. Precision resistance alloys have thus become crucial materials in electronic components. Their unique high resistivity, low temperature coefficient of resistance (TCR), stable resistance values, and uniform alloy composition give them an irreplaceable position in electronic components. Precision resistance alloys have extremely wide applications, playing a vital role in the development of cutting-edge technologies such as electronic computers, missile technology, nuclear energy, and aerospace. As the precision requirements in these fields continue to increase, the performance requirements for precision resistance alloys—key materials used in electronic measurement and control instruments—are also rising. Therefore, developing precision resistance alloy materials with wide temperature adaptability, small temperature coefficient of resistance, and extremely low annual resistance change rate has become particularly important.

[0003] Existing precision resistance alloys can be classified according to their alloy system, covering Cu-Mn, Cu-Ni, Ni-Cr, Fe-Cr-Al, and other series. These alloys exhibit low temperature coefficients of resistance within a temperature range of -60℃ to 100℃. However, recent research on these alloys has been limited, especially regarding the preparation and heat treatment processes of blanks for precision resistance alloys with specific crystal structures; detailed techniques remain unclear. During long-term use, the inhomogeneous microstructure of crystalline precision resistance alloys can lead to localized overheating, severely impacting their service life. Furthermore, the forging and heat treatment processes during sample preparation can cause uneven heating and internal stress accumulation, making the material prone to deformation during use and consequently affecting the stability of the resistance.

[0004] Due to the inhomogeneity of the microstructure of crystalline resistance alloys and their complex heat treatment processes, these alloys are difficult to maintain long-term stability. Their temperature coefficient of resistance varies over a wide range, typically between ±10 and 210 ppm / K, and the temperature range is relatively narrow.

[0005] Amorphous alloys, also known as "metallic glasses," were first proposed by Professor Duwez in the 1960s. These alloys exhibit short-range order and long-range disorder in their atomic structure, resulting in significantly superior mechanical, physical, and chemical properties compared to traditional crystalline alloys. Amorphous alloys maintain their stability over long-term use, and their preparation process is simple, requiring no complex post-processing. Therefore, developing a precision resistance alloy that combines a low temperature coefficient of resistance with a wide temperature range is crucial. By integrating the advantages of high-entropy alloys, refractory alloys, and amorphous alloys, this invention aims to develop a new precision resistance alloy material with ultra-high precision and a wide temperature range. However, in the preparation of such ultra-precision, wide-temperature-range precision resistance alloys, the large differences in atomic size of refractory elements lead to lattice distortion, making it difficult to form an amorphous state, thus increasing the difficulty of alloy preparation. Summary of the Invention

[0006] This invention provides a precision resistance alloy material for electronic components, which has a low temperature coefficient of resistance over a wide temperature range and excellent thermal stability.

[0007] This invention provides a precision resistance alloy material for electronic components. The precision resistance alloy material includes refractory metal elements and non-refractory metal elements. The refractory metal elements are Hf, Nb, Ta and Re, and the non-refractory metal elements are Co and Ni. The precision resistance alloy material has an amorphous structure.

[0008] This invention combines refractory high-entropy alloy materials with amorphous structures to form precision resistance alloy materials. The precision resistance alloy materials have a uniform composition distribution, thus possessing the characteristics of both refractory high-entropy alloy materials and amorphous materials. They exhibit a low temperature coefficient of resistance over a wide temperature range and have excellent thermal stability.

[0009] Preferably, the chemical formula of the precision resistance alloy material is Hf a Ni b Ta c Co d Nb e Re f Where a, b, c, d, e, and f represent atomic fractions, and a, b, c, d, e, and f are all between 1 and 35, and a + b + c + d + e + f = 100.

[0010] When the atomic fraction is not specified, the precision resistance alloy material is represented as Hf-Ni-Ta-Co-Nb-Re.

[0011] Preferably, the atomic fraction of Hf is 5%-35%, the atomic fraction of Ni is 5%-35%, the atomic fraction of Ta is 5%-35%, the atomic fraction of Co is 5%-35%, the atomic fraction of Nb is 5%-35%, and the atomic fraction of Re is 1%-10%.

[0012] The precision resistance alloy material contains refractory elements as the main atomic fraction, exceeding 20%. These refractory elements have high melting points above 1800℃ and combine with non-refractory elements Co and Ni commonly used in high-temperature alloys to form the precision resistance alloy material. This invention facilitates the formation of amorphous alloys by controlling the content of Hf, Ni, Ta, Co, Nb, and Re. Re has a melting point of 3180℃. Excessive Re content leads to excessive viscosity and poor melt flow, making it impossible to prepare an amorphous alloy. Insufficient Re content results in a large temperature coefficient of resistance. By doping with an appropriate amount of Re, the material exhibits stable resistivity over a wide temperature range.

[0013] Preferably, the temperature coefficient of resistance of the precision resistance alloy material is ±(0.4-78)ppm / K in the temperature range of 4-900K.

[0014] Preferably, the Re atomic fraction is 1%-4%, and the temperature coefficient of resistance is ±(20-78)ppm / K in the temperature range of 4-780K.

[0015] Preferably, the Re atomic fraction is 5%, the temperature coefficient of resistance is ±(0.4-10)ppm / K in the temperature range of 4-400K, and the temperature coefficient of resistance is ±(10-79)ppm / K in the temperature range of 400-820K.

[0016] Preferably, the Re atomic fraction is 6%-10%, and the temperature coefficient of resistance is ±(27-56)ppm / K in the temperature range of 4-900K.

[0017] On the other hand, the present invention also provides a method for preparing the aforementioned precision resistance alloy material for electronic components, comprising:

[0018] (1) The materials are batched according to the atomic fraction of the precision resistance alloy material used for electronic components, and the mixture is melted evenly to obtain the master alloy ingot.

[0019] (2) After melting the master alloy ingot, it is sprayed onto the surface of a rotating copper roller to obtain a resistance alloy strip for electronic components.

[0020] This invention selects refractory and non-refractory metal elements that easily form eutectic points, and rapidly cools them on copper roller quenching technology to form an amorphous structure. This results in a disordered distribution of metal atoms, eliminating local structural inhomogeneities such as grain boundaries, dislocations, and segregation present in crystalline metals. As a result, the precision resistance alloy strips produced have a low temperature coefficient of resistance over a wide temperature range and exhibit excellent thermal stability.

[0021] In step (1):

[0022] Preferably, the elements and their atomic fractions in the precision resistance alloy material are as follows: Hf atomic fraction 5%-35%, Ni atomic fraction 5%-35%, Ta atomic fraction 5%-35%, Co atomic fraction 5%-35%, Nb atomic fraction 5%-35%, and Re atomic fraction 1%-10%.

[0023] Preferably, before the melting is homogenized, each element of the precision resistance alloy material is ultrasonically cleaned and sanded.

[0024] More preferably, the ultrasonic cleaning and sanding steps are as follows: ultrasonic cleaning is performed for 10-20 minutes with alcohol or acetone, the cleaning is repeated twice, and then sanding is performed before ultrasonic cleaning is performed again for 10-20 minutes with alcohol or acetone.

[0025] Since the surface of metal elements is easily oxidized, affecting the purity of the alloy, it is necessary to remove the oxide scale on the surface of the raw material particles before smelting until the metal itself is exposed.

[0026] Preferably, the melting step is as follows: under a vacuum degree of 4.0 × 10⁻⁶ -3 -5.0×10 -3 Pa, with an applied current of 80-400A, for 4-6 minutes of arc melting.

[0027] More preferably, the precision resistance alloy material is repeatedly melted for each element at least six times to ensure the uniformity of the composition of the master alloy ingot.

[0028] Preferably, the density of the master alloy ingot is ≤13.0 g / cm³. 3 Existing refractory alloys have a high density, which does not meet the requirements of lightweight product design. However, the precision resistance alloy material provided by this invention has a lower density than existing refractory materials and has better lightweight characteristics.

[0029] In step (2):

[0030] Preferably, the molten master alloy ingot is sprayed onto the surface of a copper roller at a vacuum degree of less than 10 Pa, and the linear velocity of the copper roller surface is greater than 20 m / s.

[0031] Excessive linear velocity on the copper roller surface can lead to poor material forming quality, while lower linear velocity means a lower cooling rate, preventing the formation of an amorphous structure. Because refractory metals have high melting points, high viscosity, poor fluidity, and large atomic size differences easily cause lattice distortion, resulting in poor amorphous formation ability, the selection of the material system is crucial during material preparation. To form well-formed amorphous precision resistance alloy materials, a copper roller surface linear velocity greater than 20 m / s is required, and the alloy system must possess good amorphous formation ability.

[0032] Preferably, the thickness of the precision resistance alloy strip is 18-70μm and the width is 0.2-50mm.

[0033] This invention utilizes a vacuum strip spinning machine for preparing amorphous materials. In addition to possessing all the features of an induction melting furnace, this equipment also has the function of spray casting to prepare bulk amorphous materials and metal strips. To maximize the amorphization of the alloy and obtain a precision resistance alloy strip with a fully amorphous structure, a rapid-cooling vacuum single-roller spin quenching strip spinning technique is employed to prepare Hf-Ni-Ta-Co-Nb-Re precision resistance alloy strips.

[0034] The aforementioned precision resistance alloy material is used in electronic components under high temperature, extremely low temperature or various harsh environments, especially in industries such as electronic communications and instrumentation.

[0035] Preferably, the constantan and manganin alloys in existing resistors are replaced with the precision resistance alloy materials used in electronic components, and the resulting resistors are applied to electronic components, such as digital multimeters, temperature sensors for aerospace equipment, electronic balances, strain gauges, precision bridges, and standard resistors.

[0036] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0037] 1. The precision resistance alloy material obtained by this invention has a completely amorphous structure and exhibits the combined effects of refractory high-entropy alloys and amorphous alloys in terms of composition. The precision resistance alloy material provided by this invention has both equal atomic ratio designs and non-equal atomic ratio designs for its constituent elements, which increases the atomic radius difference of the alloy while maintaining its high mixing entropy, thereby improving the amorphous forming ability of the material.

[0038] The precision resistance alloy material obtained by this invention achieves a low temperature coefficient of resistance in the temperature range of 4-900K, which is more than one order of magnitude higher than the temperature coefficient of resistance of the most stable Cu-Mn crystalline resistance alloy in the past. It also achieves a very low temperature coefficient of resistance over an extremely wide temperature range, while the material also has excellent thermal stability and high-temperature oxidation resistance.

[0039] 2. This invention provides a method for preparing precision resistance alloy materials, which utilizes a single-roll rapid quenching method to rapidly cool a refractory alloy with a high degree of eutecticness to form a precision resistance alloy material. This method is simple and efficient. Attached Figure Description

[0040] Figure 1 The images shown are XRD patterns of precision resistance alloy strips for electronic components prepared in Examples 1, 2, 3, and 4 of this invention. Figure 1 The curve a is Hf 19.8 Ni 19.8 Ta 19.8 Co 19.8 Nb 19.8 XRD pattern of Re1 Figure 1 The curve b is Hf 19.4 Ni 19.4 Ta 19.4 Co 19.4 Nb 19.4 XRD pattern of Re3. Figure 1 The curve c is Hf 19 Ni 19 Ta 19 Co 19 Nb 19 XRD pattern of Re5 Figure 1 The curve d is Hf 18.6 Ni 18.6 Ta 18.6 Co 18.6 Nb 18.6 XRD pattern of Re7.

[0041] Figure 2 The DSC curves of precision resistance alloy strips for electronic components prepared in Examples 1, 2, 3, and 4 of this invention are shown below. Figure 2 The curve (a) is Hf 19.8 Ni 19.8 Ta 19.8 Co 19.8 Nb 19.8 DSC curve of Re1 Figure 2 The curve (b) is Hf 19.4 Ni 19.4 Ta 19.4 Co 19.4 Nb 19.4 DSC curve of Re3. Figure 2 The curve (c) is Hf 19 Ni 19 Ta 19 Co 19 Nb 19 DSC curve of Re5 Figure 2 The curve (d) is Hf18.6 Ni 18.6 Ta 18.6 Co 18.6 Nb 18.6 DSC curve of Re7.

[0042] Figure 3 The resistance change rate of the precision resistance alloy strips for electronic components prepared in Examples 1, 2, 3, and 4 of this invention is shown as a function of temperature from 4K to 400K. Figure 3 The curve (a) is Hf 19.8 Ni 19.8 Ta 19.8 Co 19.8 Nb 19.8 Re1 relationship curve, Figure 3 The curve (b) is Hf 19.4 Ni 19.4 Ta 19.4 Co 19.4 Nb 19.4 Re3 relationship curve. Figure 3 The curve (c) is Hf 19 Ni 19 Ta 19 Co 19 Nb 19 Re5 relationship curve graph Figure 3 The curve (d) is Hf 18.6 Ni 18.6 Ta 18.6 Co 18.6 Nb 18.6 Re7 relationship curve.

[0043] Figure 4 The resistance change rate of the precision resistance alloy strip for electronic components prepared in Example 3 of the present invention is shown as a function of temperature.

[0044] Figure 5 Thermogravimetric curve of the precision resistance alloy strip for electronic components prepared in Example 3 of the present invention in high-purity oxygen.

[0045] Figure 6 The resistance change rate of the precision resistance alloy strip provided for Comparative Example 1 is a curve showing the change in resistance with temperature.

[0046] Figure 7 The resistance change rate of the precision resistance alloy strip provided for Comparative Example 2 is a curve showing the change in resistance with temperature. Detailed Implementation

[0047] In view of the deficiencies of the prior art, the inventors of this case, through long-term research and extensive practice, have proposed the technical solution of this invention. The technical solution of this invention will be clearly and completely described below. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0048] In specific embodiments of the present invention, the Hf, Ta, Nb, Re, Ni and Co granular or bulk raw materials used to prepare the alloy ingots are all commercially available raw materials with a purity higher than 99.9%.

[0049] The electric arc melting furnace used in this invention is the DHL-300 vacuum copper mold suction casting melting system developed by Shenyang Scientific Instruments Co., Ltd. of the Chinese Academy of Sciences.

[0050] The vacuum belt spinning machine used in this invention is a VF-RQB20 type single-roll spinning casting equipment.

[0051] Example 1

[0052] Hf 19.8 Ni 19.8 Ta 19.8 Co 19.8 Nb 19.8 Preparation and property testing of Re1 precision resistance alloy material.

[0053] Based on the atomic fraction of the precision resistance alloy material, it was weighed as a mass percentage. High-purity Hf particles, Ni particles, Ta blocks, Co blocks, Nb particles, and Re particles (purity not less than 99.9%) were selected as raw materials. After removing the oxide scale, the materials were ultrasonically cleaned twice with alcohol for 10 minutes each time. The mass of the smelted alloy ingot was 24.350g, and the masses of each element were w(Hf) = 7.502g, w(Ni) = 2.467g, w(Ta) = 7.605g, w(Co) = 2.477g, w(Nb) = 3.905g, and w(Re) = 0.395g.

[0054] The master alloy ingot was prepared by arc melting under a vacuum and argon protective atmosphere, and the vacuum was repeatedly evacuated and purged three times until the vacuum degree reached 5×10⁻⁶. -3 High-purity argon gas (99.999% purity) was introduced into the vacuum chamber to a pressure of -0.05 MPa. The mixture was homogeneously mixed and melted in the chamber under the argon atmosphere adsorbed by titanium. The melting process required at least six remelting cycles to ensure the uniformity of the alloy ingot composition. After cooling, the master alloy ingot Hf-Ni-Ta-Co-Nb-Re hexa-element alloy was obtained. 19.8 Ni 19.8 Ta 19.8 Co 19.8Nb 19.8 Re1; The actual density of the alloy, determined by the water displacement method using a Mettler electronic analytical balance, is 11.956 g / cm³. 3 .

[0055] Hf 19.8 Ni 19.8 Ta 19.8 Co 19.8 Nb 19.8 The Re1 master alloy ingot is broken, and a suitable amount of master alloy is placed inside a quartz tube. The quartz tube is fixed inside an induction coil, with the nozzle diameter of the quartz tube being approximately 1.5 mm and the nozzle height from the copper roller being 1.2 mm. The vacuum is evacuated to below 10 Pa, and high-purity argon gas is injected to maintain the gas pressure in the spinning machine cavity at -0.09 MPa, with the pressure difference between the gas pressure inside the quartz tube and the cavity maintained at 0.04 MPa. The liquid alloy is then sprayed onto a high-speed rotating copper roller to obtain an alloy strip, with the surface linear velocity of the copper roller being 45 m / s. In this embodiment, the strip width is approximately 2 mm, and the strip thickness is approximately 23 μm.

[0056] For the prepared Hf 19.8 Ni 19.8 Ta 19.8 Co 19.8 Nb 19.8 The properties of Re1 precision resistance alloy strips were determined.

[0057] The above-mentioned band Hf 19.8 Ni 19.8 Ta 19.8 Co 19.8 Nb 19.8 The X-ray diffraction (XRD) image of the Re1 sample is as follows: Figure 1 As shown in the a-curve, it exhibits a single diffuse scattering peak, proving that the strip sample is a completely amorphous alloy.

[0058] Differential scanning calorimetry (DSC) experiments were performed on the above-mentioned amorphous alloy strips, and the DSC curves are shown below. Figure 2 As shown in curve (a), the glass transition and crystallization process of this precision resistance alloy are reflected. It can be seen that Hf 19.8 Ni 19.8 Ta 19.8 Co 19.8 Nb 19.8 The glass transition temperature T of Re1 precision resistance alloy g The crystallization temperature is 890K, and the crystallization temperature is T. x The K value is 1008 K. A supercooled liquid phase region ΔT exists at 118 K. This indicates that the aforementioned refractory high-entropy amorphous material possesses good amorphous forming ability and thermal stability.

[0059] The resistivity of the aforementioned precision resistance alloy strip was tested using the PPMS-DynaCool system from Quantum Design, USA. The results are as follows: Figure 3 As shown in curve (a), Hf 19.8 Ni 19.8 Ta 19.8 Co 19.8 Nb 19.8 The temperature coefficient of resistance of Re1 precision resistance alloy is -20ppm / K in the temperature range of 4-400K.

[0060] Example 2

[0061] Hf 19.4 Ni 19.4 Ta 19.4 Co 19.4 Nb 19.4 Preparation and property determination of Re3 precision resistance alloy material.

[0062] Based on the atomic fraction of the precision resistance alloy material, it was weighed as a mass percentage. High-purity Hf particles, Ni particles, Ta blocks, Co blocks, Nb particles, and Re particles (purity not less than 99.9%) were selected as raw materials. After removing the oxide scale, the materials were ultrasonically cleaned twice with alcohol for 10 minutes each. The mass of the smelted alloy ingot was 22.650g, and the masses of each element were w(Hf) = 6.752g, w(Ni) = 2.220g, w(Ta) = 6.845g, w(Co) = 2.229g, w(Nb) = 3.514g, and w(Re) = 1.089g.

[0063] The master alloy ingot was prepared by arc melting under a vacuum and argon protective atmosphere, and the vacuum was repeatedly evacuated and purged three times until the vacuum degree reached 5×10⁻⁶. -3 High-purity argon gas (99.999% purity) was introduced into the vacuum chamber to a pressure of -0.05 MPa. The mixture was homogeneously mixed and melted in the chamber under the argon atmosphere adsorbed by titanium. The melting process required at least six remelting cycles to ensure the uniformity of the alloy ingot composition. After cooling, the master alloy ingot Hf-Ni-Ta-Co-Nb-Re hexa-element alloy was obtained. 19.4 Ni 19.4 Ta 19.4 Co 19.4 Nb 19.4 Re3; The actual density of the alloy, determined by the water displacement method using a Mettler electronic analytical balance, was 11.994 g / cm³. 3 .

[0064] Hf 19.4 Ni 19.4 Ta 19.4 Co 19.4 Nb19.4 The Re3 master alloy ingot is broken, and a suitable amount of master alloy is placed inside a quartz tube. The quartz tube is fixed inside an induction coil. The nozzle diameter of the quartz tube is approximately 1.2 mm, and the height of the nozzle from the copper roller is 1.5 mm. The vacuum is evacuated to below 10 Pa, and high-purity argon gas is injected to maintain the gas pressure in the spinning machine cavity at -0.09 MPa, with the pressure difference between the gas pressure inside the quartz tube and the cavity maintained at 0.05 MPa. Subsequently, the liquid alloy liquid is sprayed onto a high-speed rotating copper roller to obtain an alloy strip, where the surface linear velocity of the copper roller is 40 m / s. In this embodiment, the strip width is approximately 1.5 mm, and the strip thickness is approximately 30 μm.

[0065] For the prepared Hf 19.4 Ni 19.4 Ta 19.4 Co 19.4 Nb 19.4 The properties of Re3 precision resistance alloy strips were determined.

[0066] The above-mentioned band Hf 19.4 Ni 19.4 Ta 19.4 Co 19.4 Nb 19.4 The X-ray diffraction (XRD) images of the Re3 samples are as follows: Figure 1 As shown in the b-curve, it exhibits a single diffuse scattering peak, proving that the strip sample is a completely amorphous alloy.

[0067] Differential scanning calorimetry (DSC) experiments were performed on the above-mentioned amorphous alloy strips, and the DSC curves are shown below. Figure 2 As shown in curve (b), the glass transition and crystallization process of this precision resistance alloy are reflected. It can be seen that Hf 19.4 Ni 19.4 Ta 19.4 Co 19.4 Nb 19.4 The glass transition temperature T of Re3 precision resistance alloy g The crystallization temperature is 951K, and the crystallization temperature is T. x The K value is 1030 K. A supercooled liquid phase region ΔT exists at 79 K. This indicates that the aforementioned refractory high-entropy amorphous material possesses good amorphous forming ability and thermal stability.

[0068] The resistivity of the aforementioned precision resistance alloy strip was tested using the PPMS-DynaCool system from Quantum Design, USA. The results are as follows: Figure 3 As shown in curve (b), Hf 19.4 Ni 19.4 Ta 19.4 Co 19.4 Nb 19.4The temperature coefficient of resistance of Re3 precision resistance alloy is -78ppm / K in the temperature range of 4-400K.

[0069] Example 3

[0070] Hf 19 Ni 19 Ta 19 Co 19 Nb 19 Preparation and property determination of Re5 precision resistance alloy material.

[0071] Based on the atomic fraction of the precision resistance alloy material converted to mass percentage and weighing, high-purity Hf particles, Ni particles, Ta blocks, Co blocks, Nb particles, and Re particles (purity not less than 99.9%) were selected as raw materials. After removing the oxide scale, the materials were ultrasonically cleaned twice with alcohol for 10 minutes each time. The mass of the smelted alloy ingot was 22.750g, and the masses of each element were w(Hf) = 6.560g, w(Ni) = 2.157g, w(Ta) = 6.651g, w(Co) = 2.166g, w(Nb) = 3.415g, and w(Re) = 1.801g.

[0072] The master alloy ingot was prepared by arc melting under a vacuum and argon protective atmosphere, and the vacuum was repeatedly evacuated and purged three times until the vacuum degree reached 5×10⁻⁶. -3 High-purity argon gas (99.999% purity) was introduced into the vacuum chamber to a pressure of -0.05 MPa. The mixture was homogeneously mixed and melted in the chamber under the argon atmosphere adsorbed by titanium. The melting process required at least six remelting cycles to ensure the uniformity of the alloy ingot composition. After cooling, the master alloy ingot Hf-Ni-Ta-Co-Nb-Re hexa-element alloy was obtained. 19 Ni 19 Ta 19 Co 19 Nb 19 Re5; The actual density of the alloy, determined by the water displacement method using a Mettler electronic analytical balance, is 12.221 g / cm³. 3 .

[0073] Hf 19 Ni 19 Ta 19 Co 19 Nb 19The Re5 master alloy ingot is broken, and a suitable amount of master alloy is placed inside a quartz tube. The quartz tube is fixed inside an induction coil, with the nozzle diameter of the quartz tube being approximately 1.2 mm and the nozzle height from the copper roller being 1.5 mm. The vacuum is evacuated to below 10 Pa, and high-purity argon gas is injected to maintain the gas pressure in the spinning machine cavity at -0.09 MPa, with the pressure difference between the gas pressure inside the quartz tube and the cavity maintained at 0.05 MPa. The liquid alloy is then sprayed onto a high-speed rotating copper roller to obtain an alloy strip, with the surface linear velocity of the copper roller being 45 m / s. In this embodiment, the strip width is approximately 1.4 mm, and the strip thickness is approximately 38 μm.

[0074] For the prepared Hf 19 Ni 19 Ta 19 Co 19 Nb 19 The properties of Re5 precision resistance alloy strips were determined.

[0075] The above-mentioned band Hf 19 Ni 19 Ta 19 Co 19 Nb 19 The X-ray diffraction (XRD) images of the Re5 sample are as follows: Figure 1 The c-curve shows a single diffuse scattering peak, proving that the strip sample is a completely amorphous alloy.

[0076] Differential scanning calorimetry (DSC) experiments were performed on the above-mentioned amorphous alloy strips, and the DSC curves are shown below. Figure 2 As shown in curve (c), the glass transition and crystallization process of this precision resistance alloy are reflected. It can be seen that Hf 19 Ni 19 Ta 19 Co 19 Nb 19 The glass transition temperature T of Re5 precision resistance alloy g The crystallization temperature is 879K, and the crystallization temperature is T. x The K value is 1029 K. A supercooled liquid phase region ΔT exists at 150 K. This indicates that the aforementioned refractory high-entropy amorphous material possesses good amorphous forming ability and thermal stability.

[0077] The resistivity of the aforementioned precision resistance alloy strip was tested using the PPMS-DynaCool system from Quantum Design, USA. The results are as follows: Figure 3 As shown in curve (c), Hf 19 Ni 19 Ta 19 Co 19 Nb 19The temperature coefficient of resistance of Re5 precision resistance alloy is 0.4 ppm / K in the temperature range of 4-400K, and 35 ppm / K in the high-temperature range of 400-800K.

[0078] Example 4

[0079] Hf 18.6 Ni 18.6 Ta 18.6 Co 18.6 Nb 18.6 Preparation and property determination of Re7 precision resistance alloy material.

[0080] Based on the atomic fraction of the precision resistance alloy material, it was weighed as a mass percentage. High-purity Hf particles, Ni particles, Ta blocks, Co blocks, Nb particles, and Re particles (purity not less than 99.9%) were selected as raw materials. After removing the oxide scale, the materials were ultrasonically cleaned twice with alcohol for 10 minutes each time. The mass of the smelted alloy ingot was 23.780g, and the masses of each element were w(Hf) = 6.632g, w(Ni) = 2.181g, w(Ta) = 6.723g, w(Co) = 2.190g, w(Nb) = 3.452g, and w(Re) = 2.605g.

[0081] The master alloy ingot was prepared by arc melting under a vacuum and argon protective atmosphere, and the vacuum was repeatedly evacuated and purged three times until the vacuum degree reached 5×10⁻⁶. -3 High-purity argon gas (99.999% purity) was introduced into the vacuum chamber to a pressure of -0.05 MPa. The mixture was homogeneously mixed and melted in the chamber under the argon atmosphere adsorbed by titanium. The melting process required at least six remelting cycles to ensure the uniformity of the alloy ingot composition. After cooling, the master alloy ingot Hf-Ni-Ta-Co-Nb-Re hexa-element alloy was obtained. 18.6 Ni 18.6 Ta 18.6 Co 18.6 Nb 18.6 Re7; The actual density of the alloy, determined by the water displacement method using a Mettler electronic analytical balance, was 12.246 g / cm³. 3 .

[0082] Hf 18.6 Ni 18.6 Ta 18.6 Co 18.6 Nb 18.6The Re7 master alloy ingot is broken, and a suitable amount of master alloy is placed inside a quartz tube. The quartz tube is fixed inside an induction coil, with the nozzle diameter of the quartz tube being approximately 1.2 mm and the nozzle height from the copper roller being 1.5 mm. The vacuum is evacuated to below 10 Pa, and high-purity argon gas is injected to maintain the gas pressure in the spinning machine cavity at -0.09 MPa, with the pressure difference between the gas pressure inside the quartz tube and the cavity maintained at 0.05 MPa. The liquid alloy is then sprayed onto a high-speed rotating copper roller to obtain an alloy strip, with the surface linear velocity of the copper roller being 48 m / s. In this embodiment, the strip width is approximately 1.7 mm, and the strip thickness is approximately 52 μm.

[0083] For the prepared Hf 18.6 Ni 18.6 Ta 18.6 Co 18.6 Nb 18.6 The properties of Re7 precision resistance alloy strips were determined.

[0084] The above-mentioned band Hf 18.6 Ni 18.6 Ta 18.6 Co 18.6 Nb 18.6 The X-ray diffraction (XRD) images of the Re7 sample are as follows: Figure 1 The c-curve shows a single diffuse scattering peak, proving that the strip sample is a completely amorphous alloy.

[0085] Differential scanning calorimetry (DSC) experiments were performed on the above-mentioned amorphous alloy strips, and the DSC curves are shown below. Figure 2 As shown in curve (c), the glass transition and crystallization process of this precision resistance alloy are reflected. It can be seen that Hf 18.6 Ni 18.6 Ta 18.6 Co 18.6 Nb 18.6 The glass transition temperature T of Re7 precision resistance alloy g The crystallization temperature is 881K, and the crystallization temperature is T. x The K value is 1033 K. A supercooled liquid phase region ΔT exists at 152 K. This indicates that the aforementioned refractory high-entropy amorphous material possesses good amorphous forming ability and thermal stability.

[0086] The resistivity of the aforementioned precision resistance alloy strip was tested using the PPMS-DynaCool system from Quantum Design, USA. The results are as follows: Figure 3 As shown in (d), Hf 18.6 Ni 18.6 Ta 18.6 Co 18.6 Nb 18.6The temperature coefficient of resistance of Re7 precision resistance alloy is -42ppm / K in the temperature range of 4-400K.

[0087] Examples 5-28

[0088] The molecular formulas of the precision resistance alloys in Examples 5 to 28 are shown in Table 1 below.

[0089] The preparation methods of the precision resistance alloys in Examples 5 to 28 are basically the same as those in Examples 1, 2, 3 and 4, except that the raw materials are prepared according to the molar ratios described in the molecular formulas in Table 1.

[0090] Similar to Examples 1, 2, 3 and 4, the XRD and DSC images of the precision resistance alloys in Examples 5 to 28 show that these alloys are amorphous alloys.

[0091] In addition, the precision resistance alloy materials prepared in Examples 1-28 and the Hf material without Re doping in Comparative Example 1 were compared. 20 Ni 20 Ta 20 Co 20 Nb 20 Amorphous alloy, Comparative Example 2: Crystalline Hf 19 Ni 19 Ta 19 Co 19 Nb 19 The Re5, as well as Comparative Examples 3 and 4, are compared with commercially available MANGANIN and ZERANIN resistance alloys.

[0092] Hf 20 Ni 20 Ta 20 Co 20 Nb 20 The resistivity change rate of amorphous alloys is as follows Figure 6 As shown. Crystalline Hf 19 Ni 19 Ta 19 Co 19 Nb 19 The rate of change of resistance of Re5 is as follows Figure 7 As shown. The application temperature range and temperature coefficient of resistance of commercially available MANGANIN and ZERANIN resistance alloys can be obtained from the Isabellenhutte website (https: / / www.isabellenhuette.cn / ). Table 1 shows the Hf values ​​of the precision resistance alloy materials prepared in Examples 1-28 and those without Re doping. 20 Ni 20 Ta 20 Co 20 Nb 20 Amorphous alloys, crystalline Hf19 Ni 19 Ta 19 Co 19 Nb 19 Re5 and commercially available MANGANIN and ZERANIN resistance alloys have high resistivity and temperature coefficient of resistance.

[0093] Table 1. Performance parameters of different resistance alloys

[0094]

[0095]

[0096] In Examples 1-28, the resistors maintained stable resistance values ​​under different ambient temperatures, thus ensuring the accuracy of measurement results. This high stability prevents performance drift during long-term use, ensuring measurement repeatability and reliability. Combined with... Figure 3 , Figure 4 As shown in Table 1, the precision resistance alloy achieves a ppm-level variation in temperature coefficient of resistance (TCR) over a wide temperature range and maintains stable resistivity even at extremely low temperatures. This significantly expands the temperature range and achieves a much lower TCR compared to currently commercially available precision resistance alloys. Precise resistance control meets the stringent requirements of high-precision measuring instruments, ensuring the high accuracy of the measurement system. Figure 5 As we can see, the components of Example 3 only undergo rapid oxidation at a high temperature close to 1200K, indicating that this type of precision resistance alloy has extremely excellent high-temperature oxidation resistance, and can still serve stably for many years under harsh working conditions.

[0097] This invention discloses a precision resistance alloy material for electronic components that combines the characteristics of amorphous alloys, high-entropy alloys, and refractory elements. This material is designed and fabricated to significantly improve the narrow temperature range and high temperature coefficient of resistance of existing commercial resistance alloys. The raw materials used in this invention are of moderate cost, the manufacturing process is simple and easy to control, and it yields a precision resistance alloy material with uniform composition, a low temperature coefficient of resistance over a wide temperature range, and excellent resistance to high-temperature oxidation. This facilitates its widespread application and large-scale mass production.

[0098] The embodiments described above are merely illustrative of several implementations of the present invention and should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and any modifications, additions, or similar method substitutions made within the scope of the principles of the present invention are all within the protection scope of the present invention. Therefore, the protection scope of this patent should be determined by the appended claims.

Claims

1. A precision resistance alloy material for electronic components, characterized in that, The precision resistance alloy material includes refractory metal elements and non-refractory metal elements. The refractory metal elements are Hf, Nb, Ta and Re, and the non-refractory metal elements are Co and Ni. The precision resistance alloy material has an amorphous structure. The chemical formula of the precision resistance alloy material is Hf a Ni b Ta c Co d Nb e Re f Where a, b, c, d, e, and f represent the atomic fractions, and a + b + c + d + e + f = 100; The atomic fractions of Hf, Ni, Ta, Co, Nb, and Re are 5%-35%, 5%-35%, 5%-35%, and 1%-4%, respectively. The temperature coefficient of resistance in the temperature range of 4-780 K is ± (20-78) ppm / K.

2. A method for preparing a precision resistance alloy material for electronic components according to claim 1, characterized in that, include: (1) The materials are batched according to the atomic fraction of the precision resistance alloy material for electronic components as described in claim 1, and the mixture is melted evenly to obtain a master alloy ingot. (2) After melting the master alloy ingot, it is sprayed onto the surface of a rotating copper roller to obtain a resistance alloy strip for electronic components.

3. The method for preparing precision resistance alloy material for electronic components according to claim 2, characterized in that, The density of the master alloy ingot is ≤13.0 g / cm³. 3 .

4. The method for preparing precision resistance alloy material for electronic components according to claim 2, characterized in that, The molten master alloy ingot is sprayed onto the surface of a copper roller at a vacuum of less than 10 Pa, and the linear velocity of the copper roller surface is greater than 20 m / s.

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