TWI910491B - Nickel copper zinc powder and method of making the same - Google Patents

Abstract

Disclosed is a nickel copper zinc powder. The nickel copper zinc powder comprises, based on 100 wt% of a total weight of the nickel copper zinc powder, 60 to 75 wt% iron oxide, 10 to 25 wt% of nickel trioxide, 3 to 10 wt% of copper oxide, and 10 to 20 wt% of zinc oxide. A method of preparing the nickel copper zinc powder is further disclosed.

Description

Nickel-copper-zinc powder and its preparation method

This invention relates to a material for high-frequency microwave communication, and more particularly to a nickel-copper-zinc powder for high-frequency microwave communication.

With technological advancements, microwave communication technology has matured significantly, with magnetic materials serving as a crucial component. Nickel-zinc ferrite (Ni-Znferrite) is a common magnetic material possessing excellent properties such as high permeability, low dielectric constant, and low dielectric loss, making it widely used in the microwave field. For instance, in short-range communication applications like Radio-frequency Identification (RFID), Ni-Znferrite is extensively used to manufacture antennas, enhancing communication range and sensitivity. The high permeability of Ni-Znferrite enhances magnetic flux, thereby increasing the induced voltage of the receiver; its low dielectric constant and low dielectric loss reduce signal loss, preventing transmission delays and improving overall performance.

However, the megahertz (MHz) band used by RFID is insufficient for longer-distance communication needs. Therefore, materials in the gigahertz (GHz) band need to be developed. Their high-frequency microwave signals have shorter wavelengths and can penetrate obstacles more easily, thus enabling longer-distance communication, including satellite communication, radio towers, and mobile communication base stations.

As can be seen from the above, there is a need to improve the materials commonly used in high-frequency microwave communication.

The main purpose of this invention is to provide a nickel-copper-zinc powder that can be used in high-frequency microwave communication.

To achieve the above objectives, in one embodiment of the present invention, a nickel-copper-zinc powder is provided, comprising: 60 to 75 wt% iron oxide ( _Fe₂O₃ ), 10 to 25 wt% nickel oxide ( _Ni₂O₃ ), ₃ to 10 wt% copper oxide ( _CuO ), and 10 to 20 wt% zinc oxide (ZnO) based on 100 wt% of the total weight of the nickel-copper-zinc powder.

In one embodiment of the present invention, the content of the iron oxide is 64 to 67 wt%.

In one embodiment of the present invention, the nickel trioxide content is 13 to 18 wt%.

In one embodiment of the present invention, the content of copper oxide is 6 wt%.

In one embodiment of the present invention, the zinc oxide content is 12 to 15 wt%.

To achieve the above objectives, in another embodiment of the present invention, a method for preparing the nickel-copper-zinc powder as described above is provided, comprising the following steps: wet mixing of iron oxide, nickel oxide, copper oxide, and zinc oxide to form a slurry, wherein, based on a total weight of 100 wt% of the nickel-copper-zinc powder, the content of iron oxide is 60 to 75 wt%, the content of nickel oxide is 10 to 25 wt%, the content of copper oxide is 3 to 10 wt%, and the content of zinc oxide is 10 to 20 wt%. The slurry is dried and then calcined at a temperature of 700 to 900°C for 0.5 to 2 hours. The calcined slurry is then wet-milled. The wet-milled slurry is then dried and pressurized, and sintered at 800 to 1200°C for 0.5 to 2 hours.

In one embodiment of the present invention, a ball mill is used for wet mixing, and the ratio of the total weight of iron oxide, nickel oxide, copper oxide and zinc oxide, the weight of the grinding balls and the weight of water is 4 to 6:30 to 35:5 to 15, and the mixing time is 0.5 to 1.5 hours.

In one embodiment of the present invention, a vibratory grinder and grinding balls are used together for wet grinding, and the ratio of the total weight of iron oxide, nickel oxide, copper oxide and zinc oxide, the weight of the grinding balls and the weight of water is 1:20:2 to 1:40:4, and the grinding time is 1 to 60 minutes.

In one embodiment of the invention, the applied pressure is 1600 to 2000 kgf/ ^cm² .

In one embodiment of the present invention, based on a total weight of 100 wt% of the nickel-copper-zinc powder, the content of iron oxide is 64 to 67 wt%, the content of nickel oxide is 13 to 18 wt%, the content of copper oxide is 6 wt%, and the content of zinc oxide is 12 to 15 wt%.

The beneficial effects of this invention are as follows: by adding copper to nickel-zinc ferrite, the resulting nickel-copper-zinc powder has the characteristics of high saturation magnetization, narrow ferromagnetic resonance linewidth and low dielectric loss, which further optimizes its gyromagnetic properties and makes it more suitable for use in components in the field of high frequency microwaves.

The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Furthermore, to better illustrate the present invention, numerous specific details are given in the detailed embodiments below. Those skilled in the art should understand that the present invention can be implemented without certain specific details.

According to one embodiment of the present invention, a nickel-copper-zinc powder comprises, based on 100 wt% of the total weight of the nickel-copper-zinc powder, 60 to 75 wt% (e.g., 60, ₆₁ , 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75 wt%) of iron oxide ( _Fe₂O₃ ), 10 to 25 wt% (e.g., 10, 11, ₁₂ , 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 wt%) of nickel trioxide ( _Ni₂O₃ ), and 3 to 10 wt% (e.g., 3, 4, 5, 6, 7, 8, 9, 10). The mixture contains 10 to 20 wt% copper oxide (CuO) and 10 to 20 wt% zinc oxide (ZnO), e.g., 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 wt%. In one embodiment, the iron oxide content is 64 to 67 wt%. In one embodiment, the nickel oxide content is 13 to 18 wt%. In one embodiment, the copper oxide content is 6 wt%. In one embodiment, the zinc oxide content is 12 to 15 wt%.

A method for preparing nickel-copper-zinc powder as described above, according to another embodiment of the present invention, comprises the following steps: wet mixing of iron oxide, nickel oxide, copper oxide and zinc oxide to form a slurry, wherein, based on a total weight of 100 wt% of the nickel-copper-zinc powder, the content of iron oxide is 60 to 75 wt%, the content of nickel oxide is 10 to 25 wt%, the content of copper oxide is 3 to 10 wt%, and the content of zinc oxide is 10 to 20 wt%. The slurry is dried and then calcined at a temperature of 700 to 900°C (e.g., 700, 750, 800, 850, 900°C) for 0.5 to 2 hours (e.g., 0.5, 1, 1.5, 2 hours). The calcined slurry is then wet-milled. Finally, the wet-milled slurry is dried and pressurized, and then sintered at 800 to 1200°C (e.g., 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200°C) for 0.5 to 2 hours (e.g., 0.5, 1, 1.5, 2 hours).

In one embodiment, a ball mill is used for wet mixing, and the ratio of the total weight of iron oxide, nickel oxide, copper oxide and zinc oxide, the weight of the grinding balls and the weight of water is 4 to 6:30 to 35:5 to 15, for example 5:32:10, and the mixing time is 0.5 to 1.5 hours, for example 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4 and 1.5 hours.

In one embodiment, a vibratory grinder and grinding balls are used together for wet grinding, and the ratio of the total weight of iron oxide, nickel oxide, copper oxide and zinc oxide, the weight of the grinding balls and the weight of water is 1:20:2 to 1:40:4, and the grinding time is 1 to 60 minutes, for example: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 and 60 minutes.

In one embodiment, the applied pressure is 1600 to 2000 kgf/ ^cm² , for example, 1600, 1650, 1700, 1750, 1800, 1850, 1900, 1950, 2000 kgf/ ^cm² .

The following examples further illustrate the nickel-copper-zinc powder of the present invention, but they are not intended to limit the present invention. Anyone skilled in the art can make various modifications and refinements without departing from the spirit and scope of the present invention.

Implementation Example 1:

First, iron oxide, nickel oxide, copper oxide, and zinc oxide (hereinafter collectively referred to as raw materials) are wet-mixed for 1 hour using a ball mill to form a slurry. The slurry contains 64 wt% iron oxide, 15 wt% nickel oxide, 6 wt% copper oxide, and 15 wt% zinc oxide, based on a total weight of 100 wt% of the raw materials. The ratio of the total weight of the raw materials to the weight of the grinding balls to the weight of the pure water is 250 g: 1600 g: 500 cc.

Next, the mixed slurry is dried and then calcined at 850°C for 2 hours. The calcined slurry is then wet-milled for 30 minutes using a vibratory mill with grinding balls, where the ratio of the total weight of the raw materials to the weight of the grinding balls to the weight of pure water is 250 g: 3000 g: 450 cc. Finally, the wet-milled slurry is dried, pressed into shape at 1800 kgf/ ^cm² , and sintered at 1000°C for 2 hours to obtain the nickel-copper-zinc powder of this invention.

Implementation Example 2:

First, iron oxide, nickel oxide, copper oxide, and zinc oxide (hereinafter collectively referred to as raw materials) are wet-mixed for 1 hour using a ball mill to form a slurry. The slurry contains 64 wt% iron oxide, 18 wt% nickel oxide, 6 wt% copper oxide, and 12 wt% zinc oxide, based on a total weight of 100 wt% of the raw materials. The ratio of the total weight of the raw materials to the weight of the grinding balls to the weight of the pure water is 250 g: 1600 g: 500 c.c.

Next, the mixed slurry is dried and then calcined at 850°C for 2 hours. The calcined slurry is then wet-milled for 30 minutes using a vibratory mill with grinding balls, where the ratio of the total weight of the raw materials to the weight of the grinding balls to the weight of pure water is 250 g: 3000 g: 450 cc. Finally, the wet-milled slurry is dried, pressed into shape at 1800 kgf/ ^cm² , and sintered at 1000°C for 2 hours to obtain the nickel-copper-zinc powder of this invention.

Implementation Example 3:

First, iron oxide, nickel oxide, copper oxide, and zinc oxide (hereinafter collectively referred to as raw materials) are wet-mixed for 1 hour using a ball mill to form a slurry. The slurry contains 65 wt% iron oxide, 14 wt% nickel oxide, 6 wt% copper oxide, and 15 wt% zinc oxide, based on a total weight of 100 wt% of the raw materials. The ratio of the total weight of the raw materials to the weight of the grinding balls to the weight of the pure water is 250 g: 1600 g: 500 c.c.

Next, the mixed slurry is dried and then calcined at 850°C for 2 hours. The calcined slurry is then wet-milled for 30 minutes using a vibratory mill with grinding balls, where the ratio of the total weight of the raw materials to the weight of the grinding balls to the weight of pure water is 250 g: 3000 g: 450 cc. Finally, the wet-milled slurry is dried, pressed into shape at 1800 kgf/ ^cm² , and sintered at 1000°C for 2 hours to obtain the nickel-copper-zinc powder of this invention.

Implementation Example 4:

First, iron oxide, nickel oxide, copper oxide, and zinc oxide (hereinafter collectively referred to as raw materials) are wet-mixed for 1 hour using a ball mill to form a slurry. The slurry contains 67 wt% iron oxide, 13 wt% nickel oxide, 6 wt% copper oxide, and 13 wt% zinc oxide, based on a total weight of 100 wt% of the raw materials. The ratio of the total weight of the raw materials to the weight of the grinding balls to the weight of the pure water is 250 g: 1600 g: 500 c.c.

Next, the mixed slurry is dried and then calcined at 850°C for 2 hours. The calcined slurry is then wet-milled for 30 minutes using a vibratory mill with grinding balls, where the ratio of the total weight of the raw materials to the weight of the grinding balls to the weight of pure water is 250 g: 3000 g: 450 cc. Finally, the wet-milled slurry is dried, pressed into shape at 1800 kgf/ ^cm² , and sintered at 1000°C for 2 hours to obtain the nickel-copper-zinc powder of this invention.

Implementation Example 5:

First, iron oxide, nickel oxide, copper oxide, and zinc oxide (hereinafter collectively referred to as raw materials) are wet-mixed for 1 hour using a ball mill to form a slurry. The slurry contains 67 wt% iron oxide, 13 wt% nickel oxide, 6 wt% copper oxide, and 13 wt% zinc oxide, based on a total weight of 100 wt% of the raw materials. The ratio of the total weight of the raw materials to the weight of the grinding balls to the weight of the pure water is 250 g: 1600 g: 500 c.c.

Next, the mixed slurry is dried and then calcined at 850°C for 2 hours. The calcined slurry is then wet-milled for 30 minutes using a vibratory mill with grinding balls, where the ratio of the total weight of the raw materials to the weight of the grinding balls to the weight of pure water is 250 g: 3000 g: 450 cc. Finally, the wet-milled slurry is dried, pressed into shape at 1800 kgf/ ^cm² , and sintered at 1000°C for 3 hours to obtain the nickel-copper-zinc powder of this invention.

The proportions of the nickel-copper-zinc powders in Examples 1 to 5 are summarized in Table 1 below. The difference between Example 4 and Example 5 is that the nickel-copper-zinc powder in Example 4 was obtained by sintering at 1000°C for 2 hours, while the nickel-copper-zinc powder in Example 5 was obtained by sintering at 1000°C for 3 hours.

[Table 1] Implementation Example 1 Implementation Example 2 Implementation Example 3 Implementation Example 4 Implementation Example 5 _{Fe₂O₃ (} wt%) 64 64 65 67 67 _{Ni₂O₃ (} wt%) 15 18 14 13 13 CuO (wt %) 6 6 6 6 6 ZnO (wt %) 15 12 15 13 13

The nickel-copper-zinc powders from Examples 1 to 5 were analyzed using 4πM_{_s} , ΔH(Oe), and tanδ. The results are shown in Table 2 below.

[Table 2] 4πM _s (Gs) ΔH(Oe) tanδ Implementation Example 1 4480 250 <0.001 Implementation Example 2 4410 220 <0.001 Implementation Example 3 4420 240 <0.001 Implementation Example 4 4200 210 <0.001 Implementation Example 5 4380 220 <0.001

As shown in Table 2, the nickel-copper-zinc powder of this invention has a high saturation magnetization _{of 4πMs} , ranging from 4200 to 4480 Gs, and also has a narrow ferromagnetic resonance linewidth (ΔH < 250 Oe) and low dielectric loss (tanδ < 0.001).

Referring further to Figures 1 and 2, Figure 1 shows the _S11 diagram of the nickel-copper-zinc powder of Examples 1 to 5 at a frequency of 27 to 30 GHz, and Figure 2 shows the _S21 diagram of the nickel-copper-zinc powder of Examples 1 to 5 at a frequency of 27 to 30 GHz. In Figure 1, at 27 GHz, Examples 4, 5, 3, 2, and 1 are shown from top to bottom; in Figure 2, at 29 GHz, Examples 4, 5, 2, 1, and 3 are shown from top to bottom. It can be seen that in the microwave range of 27 to 30 GHz, _S11 is mostly less than -15 dB, indicating that the reflection loss in the transmission process is small, while _S21 is greater than -0.45 dB, indicating that the insertion loss in the transmission process is small.

In summary, by adding copper to nickel-zinc ferrite, the nickel-copper-zinc powder of this invention possesses characteristics such as high saturation magnetization, narrow ferromagnetic resonance linewidth, and low dielectric loss, further optimizing its gyromagnetic properties and making it more suitable for use in components in the high-frequency microwave field.

Although the present invention has been disclosed in a preferred embodiment, it is not intended to limit the present invention. Any person skilled in the art may make various modifications and alterations without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended patent application.

without

Figure 1 shows _S11 diagrams of various nickel-copper-zinc powders at frequencies from 27 to 30 GHz; and Figure 2 shows S21 diagrams of various nickel-copper-zinc powders at frequencies from 27 to 30 GHz.

Claims (9)

A nickel-copper-zinc powder comprising: 60 to 75 wt% iron oxide, 13 to 18 wt% nickel oxide, 3 to 10 wt% copper oxide, and 10 to 20 wt% zinc oxide, based on a total weight of 100 wt% of the nickel-copper-zinc powder. The nickel-copper-zinc powder as described in claim 1, wherein the iron oxide content is 64 to 67 wt%. The nickel-copper-zinc powder as described in claim 1, wherein the copper oxide content is 6 wt%. The nickel-copper-zinc powder as described in claim 1, wherein the zinc oxide content is 12 to 15 wt%. A method for preparing nickel-copper-zinc powder as described in claim 1, comprising the following steps: Wetly mixing iron oxide, nickel oxide, copper oxide, and zinc oxide to form a slurry, wherein, based on a total weight of 100 wt% of the nickel-copper-zinc powder, the content of iron oxide is 60 to 75 wt%, the content of nickel oxide is 10 to 25 wt%, the content of copper oxide is 3 to 10 wt%, and the content of zinc oxide is 10 to 20 wt%; Drying the slurry and then calcining it, wherein the calcination temperature is 700 to 900°C and the calcination time is 0.5 to 2 hours; Wet grinding the calcined slurry; and The wet-milled slurry is dried and pressurized, then sintered at 800 to 1200°C for 0.5 to 2 hours. The method described in claim 5, wherein a ball mill is used for wet mixing, and the ratio of the total weight of iron oxide, nickel oxide, copper oxide and zinc oxide, the weight of the grinding balls and the weight of water is 4 to 6:30 to 35:5 to 15, and the mixing time is 0.5 to 1.5 hours. The method described in claim 5, wherein a vibratory grinder and grinding balls are used for wet grinding, and the ratio of the total weight of iron oxide, nickel oxide, copper oxide and zinc oxide, the weight of the grinding balls and the weight of water is 1:20:2 to 1:40:4, and the grinding time is 1 to 60 minutes. The method described in claim 5, wherein the applied pressure is 1600 to 2000 kgf/ ^cm² . The method described in claim 5, wherein, based on a total weight of 100 wt% of the nickel-copper-zinc powder, the content of iron oxide is 64 to 67 wt%, the content of nickel oxide is 13 to 18 wt%, the content of copper oxide is 6 wt%, and the content of zinc oxide is 12 to 15 wt%.