TZO ceramic powder, preparation method and application thereof

Abstract

The application relates to the field of coated ceramic target materials, in particular to a TZO ceramic powder, a preparation method and application thereof, the chemical general formula of the TZO ceramic powder is (1-x)SnO2-xZnO, wherein x=48-52 (wt. %), the TZO ceramic powder is prepared through primary ball milling powder, secondary ball milling powder, primary calcination powder, spray granulation powder and secondary calcination powder, so that the TZO ceramic powder for plasma spraying with high bulk density, high sphericity and high fluidity, which cannot be obtained through a traditional crushing process, has a higher powder feeding rate, and a more effective TZO powder preparation method is formed.

Description

Technical Field

[0001] This invention relates to the field of coated ceramic targets, and particularly to a TZO ceramic powder, its preparation method, and its application. Background Technology

[0002] Various oxide coatings have wide applications in Low-E glass, electronic displays, solar cells, and electronic product decoration. Currently, large-scale industrial coating mainly uses magnetron sputtering, which requires the use of appropriate targets, traditionally metal targets.

[0003] Although metal targets offer advantages such as high conductivity, high power consumption, and high deposition efficiency, the deposition process requires a suitable oxidation reaction to ensure the final coating layer is the desired oxide. Therefore, oxide ceramic targets were developed because oxide ceramic targets do not require as much consideration of oxidation during deposition. Oxide targets were initially prepared using traditional ceramic sintering processes.

[0004] On the one hand, traditional ceramic processes cannot produce ceramic targets of sufficiently large size. Therefore, a target of the required length is made by splicing together multiple sintered bodies, which forms seams. These seams can easily lead to uneven coating during use. On the other hand, ceramic processes are time-consuming and inefficient. Accordingly, people have proposed a spraying process to prepare oxide ceramic targets, which effectively avoids the seam problem of sintered targets.

[0005] Plasma spraying is the most commonly used spraying process, characterized by high deposition efficiency and good uniformity. However, plasma spraying has high requirements for powder. Currently, plasma spraying powders on the market are prepared through a crushing process, which is relatively complex, time-consuming, and results in low powder application rate and poor production efficiency. Summary of the Invention

[0006] The purpose of this invention is to solve the problems of complex preparation methods and low powder application rate of existing plasma spraying powders. This invention proposes a new TZO ceramic powder, its preparation method and application. The preparation method of this TZO ceramic powder is simple and time-saving, and the powder has the advantages of high bulk density, high sphericity and high flowability, thereby improving the powder application rate.

[0007] The technical solution adopted by this invention to solve its technical problem is: a method for preparing TZO ceramic powder, which includes the following steps:

[0008] S1. Weigh and mix SnO2 and ZnO to obtain raw materials;

[0009] S2. The raw material is subjected to primary ball milling, primary sand milling and primary calcination to obtain primary ceramic powder;

[0010] S3. After drying the primary ceramic powder, perform secondary ball milling and secondary sand milling to obtain secondary ceramic powder;

[0011] S4. The secondary ceramic powder is subjected to spray granulation and secondary calcination to obtain TZO ceramic powder;

[0012] The temperature of the secondary calcination in step S4 is 1000-1400℃, the time is 2-24h, the heating rate from room temperature to the secondary calcination temperature is 0.1-10℃ / min, and the furnace is cooled down after the secondary calcination is completed.

[0013] The first-stage and second-stage ball milling are wet ball milling processes using deionized water as the milling medium, and the solid content in the slurry produced by the ball milling is 50-70 wt%.

[0014] In this invention, by optimizing the ball milling / sand milling process conditions, the particle size of the primary powder is made to achieve a reasonable normal distribution. Then, by using a spray granulation process, the density of individual spheres in the granulated powder and the distribution of sphere particle size are increased, thereby improving the loose packing density of the granulated powder. At the same time, optimizing the process improves the sphericity of the granulated powder spheres and enhances their flowability.

[0015] Preferably, the SnO2 in step S1 accounts for 48-52% of the total mass of the raw materials.

[0016] Preferably, the primary and secondary ball milling processes are performed using zirconium balls with a diameter of 1-5 mm, a ball-to-material ratio of (1-3):1, a milling speed of 100-300 rpm, and a milling time of 2-24 h.

[0017] Preferably, the temperature of the first-stage calcination in step S2 is 600-1200℃, the time is 2-24h, the heating rate from room temperature to the first-stage calcination temperature is 0.1-10℃ / min, and the furnace is cooled down after the first-stage calcination is completed.

[0018] Preferably, the temperature of the secondary calcination in step S4 is 1000-1400℃, the time is 2-24h, the heating rate from room temperature to the secondary calcination temperature is 0.1-10℃ / min, and the furnace is cooled down after the secondary calcination is completed.

[0019] Preferably, the primary and secondary sand milling processes are performed using zirconium balls with a diameter of 0.6-0.8 mm, a ball-to-material ratio of (1-3):1, a milling rate of 400-500 rpm, a time of 2-12 h, and a temperature of room temperature.

[0020] Preferably, during the primary ball milling, primary sand milling, secondary ball milling, and secondary sand milling processes, an additive is added to adjust the slurry viscosity to 100-300 cps. The additive accounts for 1-5% of the slurry mass and includes a dispersant, a binder, a thickener, and a plasticizer. Specifically, the dispersant is sodium polyacrylate, the binder is polyvinyl alcohol, the thickener is polyacrylamide, and the plasticizer is selected from one or more of dioctyl phthalate, dibutyl phthalate, and dihexyl adipate.

[0021] Preferably, the inlet temperature of the spray granulation in step S4 is 180-320℃, the outlet temperature is 90-150℃, and the rotation speed is 4000-8000rpm.

[0022] In this invention, the primary and secondary ball milling are preferably performed using zirconium dioxide grinding balls (zirconia balls), the diameter of which is preferably 1-5 mm, more preferably 1 mm; the ball-to-material ratio (mass ratio of grinding balls to raw materials or grinding balls to primary ceramic powder) is preferably (1-3):1, more preferably 2.5:1; the ball milling speed is preferably 100-300 rpm, more preferably 250 rpm; and the ball milling time is preferably 2-24 h, more preferably 8 h.

[0023] In this invention, the primary calcination temperature is preferably 600-1200℃, more preferably 900℃; the primary calcination time is preferably 2-24h, more preferably 4h; and the primary calcination heating rate is preferably 0.1-10℃ / min, more preferably 3℃ / min.

[0024] In this invention, the secondary calcination temperature is preferably 1000-1400℃, more preferably 1200-1300℃, and most preferably 1259℃; the secondary calcination time is preferably 2-24h, more preferably 4h; and the secondary calcination heating rate is preferably 0.1-10℃ / min, more preferably 2℃ / min.

[0025] In this invention, the preferred speeds of the primary and secondary sand milling processes are 400-600 rpm, more preferably 500 rpm; the preferred milling time is 2-12 h, more preferably 8 h; the preferred milling temperature is room temperature; the preferred milling balls are zirconium balls, with a preferred diameter of 0.6-0.8 mm, more preferably 0.6 mm; and the preferred ball-to-material ratio is (1-3):1, more preferably 2:1.

[0026] In this invention, additives are added during the primary ball milling, primary sand milling, secondary ball milling, and secondary sand milling processes, and sand milling is combined to adjust the viscosity of the slurry to 100-300 cps, more preferably 180 cps; the additives include dispersants, binders, thickeners, and plasticizers, wherein the dispersant is preferred, the binder is preferred, the thickener is preferred, and the plasticizer is preferred; the additives preferably account for 1-5% of the slurry mass, more preferably 3%.

[0027] In this invention, the inlet temperature of the spray granulation in step S4 is preferably 180-320℃, more preferably 240℃; the outlet temperature is preferably 90-150℃, more preferably 120℃; and the rotation speed is preferably 4000-8000rpm, more preferably 6500rpm.

[0028] TZO ceramic powder prepared by the above-described method.

[0029] The general chemical formula of the TZO ceramic powder is: (1-x)SnO2-xZnO, where x or (1-x) represents the weight percentage, and x is preferably 48-52 wt%. Its basic composition can be reasonably adjusted according to the specific application.

[0030] An application of the above-described TZO ceramic powder as a TZO ceramic target material prepared by plasma spraying.

[0031] The beneficial effects of this invention are: the method for preparing TZO ceramic powder provided by this invention can not only save labor time, but also improve the powder application rate (≥40%), reduce energy consumption, and improve production efficiency. The prepared TZO ceramic powder has the characteristics of high bulk density, high sphericity, and high flowability. Attached Figure Description

[0032] Figure 1 The images are scanning electron microscope (SEM) images of the TZO ceramic powder prepared in Example 2 at different magnifications.

[0033] Figure 2 The image shows the X-ray diffraction (XRD) pattern of the TZO ceramic powder prepared in Example 2. Detailed Implementation

[0034] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of this application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains.

[0035] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the exemplary embodiments according to this application. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0036] The present invention will now be further illustrated with specific examples. The following embodiments are only for explaining the present invention and do not constitute a limitation thereof. The test samples and test procedures used in the following embodiments include the following (if the specific experimental conditions are not specified in the embodiments, they are usually performed according to conventional conditions or the conditions recommended by the reagent company; the reagents, consumables, etc. used in the following embodiments can be obtained commercially unless otherwise specified).

[0037] Example 1

[0038] A TZO ceramic powder, the composition of which is (1-x)SnO2-xZnO, x = 48 (wt.%), is prepared by the following steps:

[0039] (1) Ingredients: Weigh and mix the tin dioxide and zinc oxide raw materials according to the set ratio to obtain the raw materials;

[0040] (2) First-stage ball milling and sand milling: The raw material is placed in a stainless steel grinding jar with zirconium balls, and then deionized water is added as the ball milling medium. The solid content of the slurry is controlled to be 60%. The slurry is then ball-milled in the stainless steel grinding jar for 8 hours at a ball milling speed of 250 rpm. The diameter of the zirconium balls used in the ball milling is 1 mm. The ball-milled slurry is then transferred to a sand mill for sand milling. The sand milling speed is 500 rpm for 8 hours at room temperature. The diameter of the zirconium balls used in the sand milling is 0.6 mm.

[0041] (3) First-stage calcination: The ground slurry is spray-dried, and the powder obtained after drying is calcined in the first stage. The temperature is raised to 900℃ at a heating rate of 3℃ / min, held for 4 hours, and then cooled down with the furnace.

[0042] (4) Secondary ball milling and sand milling: The powder after primary calcination is put back into a stainless steel mill jar with zirconium balls, and deionized water medium is added to control the solid content of the slurry to 60%. Add 3% of the medium mass of the additive to adjust the viscosity of the slurry to about 180 cps. Then, the slurry is ball milled in the stainless steel mill jar for 8 hours at a ball milling speed of 250 rpm and the zirconium balls used for ball milling have a diameter of 1 mm. The ball-milled slurry is then transferred to a sand mill for sand milling at a speed of 500 rpm for 8 hours at room temperature and the zirconium balls used for sand milling have a diameter of 0.6 mm.

[0043] (5) Granulation: The slurry after sand milling in step (4) is sprayed to obtain granulated powder. The inlet temperature is 240℃, the outlet temperature is 120℃, and the rotation speed is 6500rpm.

[0044] (6) Secondary calcination: The granulated powder from step (5) is subjected to secondary calcination to obtain TZO ceramic powder. The temperature is increased to 1250℃ at a heating rate of 2℃ / min, held for 4 hours, and then cooled down with the furnace.

[0045] Example 2

[0046] A TZO ceramic powder, the composition of which is (1-x)SnO2-xZnO, x = 50 (wt.%), and the specific steps of its preparation method are the same as those in Example 1.

[0047] Example 3

[0048] A TZO ceramic powder, the composition of which is (1-x)SnO2-xZnO, x = 52 (wt.%), and the specific steps of its preparation method are the same as those in Example 1.

[0049] Example 4

[0050] A TZO ceramic powder, the composition of which is the same as that of Example 2, and its preparation method is similar to that of Example 1, except that the calcination temperature in step (6) is 1250℃.

[0051] Example 5

[0052] A TZO ceramic powder, the composition of which is the same as that of Example 2, and its preparation method is similar to that of Example 1, except that the calcination temperature in step (6) is 1300℃.

[0053] Example 6

[0054] A TZO ceramic powder, the composition of which is the same as that of Example 2, and its preparation method is similar to that of Example 1, except that the calcination temperature in step (6) is 1259℃.

[0055] The TZO ceramic powders prepared in Examples 1-5 were analyzed. XRD was used for phase analysis, and SEM was used for particle size and morphology analysis. The loose packing density, flow rate and particle size range of the TZO ceramic powders prepared in Examples 1-5 were compared. The results are shown in Table 1.

[0056] Method for detecting loose packing density: Scott volumetric method.

[0057] Method for detecting flow velocity: gravity flow method.

[0058] Table 1

[0059]

[0060] Depend on Figure 1 It can be seen that the TZO ceramic powder prepared in Example 2 has good sphericity. Figure 2 It can be seen that the TZO ceramic powders prepared in Example 2 have all formed the zinc stannate phase.

[0061] As shown in Table 1, under the same process conditions, the SnO2 and ZnO compositions of TZO ceramic powder are almost identical within the range that meets the spraying requirements; the secondary calcination temperature has a significant impact on the performance of TZO ceramic powder. The calcination temperature is determined by ensuring that the spherical particles of the granulated powder do not stick together, and that the original powder particles within each spherical particle are sufficiently dense; the determined temperature is the optimal calcination temperature.

[0062] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on its differences from other embodiments. Similar or identical parts between embodiments can be referred to interchangeably. For the apparatus disclosed in the embodiments, since it corresponds to the method disclosed in the embodiments, the description is relatively simple; relevant parts can be referred to in the method section.

[0063] The present invention provides a detailed description of a TZO ceramic powder, its preparation method, and its applications. Specific examples have been used to illustrate the principles and implementation methods of the invention. These examples are merely illustrative and are intended to aid in understanding the method and core concepts of the invention. It should be noted that those skilled in the art can make various improvements and modifications to the invention without departing from its principles, and these improvements and modifications also fall within the scope of protection of the claims.

Claims

1. A method for preparing TZO ceramic powder, characterized in that: The preparation method includes the following steps: S1. Weigh and mix SnO2 and ZnO to obtain raw materials, wherein SnO2 accounts for 48-52% of the total mass of the raw materials; S2. The raw material is subjected to primary ball milling, primary sand milling and primary calcination to obtain primary ceramic powder; the temperature of primary calcination is 600-1200℃, the time is 2-24 h, the heating rate from room temperature to primary calcination temperature is 0.1-10℃ / min, and the temperature is cooled down with the furnace after primary calcination is completed. S3. After drying the primary ceramic powder, perform secondary ball milling and secondary sand milling to obtain secondary ceramic powder; during the primary ball milling, primary sand milling, secondary ball milling and secondary sand milling processes, add additives to adjust the slurry viscosity to 100-300 cps, the additives account for 1-5% of the slurry mass, and the additives include dispersants, binders, thickeners and plasticizers; S4. The secondary ceramic powder is subjected to spray granulation and secondary calcination to obtain TZO ceramic powder; The temperature of the secondary calcination in step S4 is 1200-1300℃, the time is 2-24 h, the heating rate from room temperature to the secondary calcination temperature is 0.1-10℃ / min, and the furnace is cooled down after the secondary calcination is completed. The first-stage and second-stage ball milling are wet ball milling processes using deionized water as the milling medium, and the solid content in the slurry produced by the ball milling is 50-70 wt%.

2. The method for preparing TZO ceramic powder according to claim 1, characterized in that: The primary and secondary ball milling processes are performed using zirconium balls with a diameter of 1-5 mm, a ball-to-material ratio of (1-3):1, a milling speed of 100-300 rpm, and a milling time of 2-24 h.

3. The method for preparing TZO ceramic powder according to claim 1, characterized in that: The primary and secondary sand milling processes are performed using zirconium balls with a diameter of 0.6-0.8 mm, a ball-to-material ratio of (1-3):1, a milling rate of 400-500 rpm, a time of 2-12 h, and a temperature of room temperature.

4. The method for preparing TZO ceramic powder according to claim 1, characterized in that: In step S4, the inlet temperature of the spray granulation is 180-320℃, the outlet temperature is 90-150℃, and the rotation speed is 4000-8000 rpm.

5. A TZO ceramic powder prepared by the method of any one of claims 1-4.

6. The application of the TZO ceramic powder according to claim 5 as a TZO ceramic target material prepared by plasma spraying.

Images