Gypsum-based dielectric material and preparation method thereof
Through the ball milling-calcination combined method and the method of adding doped source powder, gypsum-based dielectric material was prepared, which solved the problem of insufficient dielectric performance of gypsum, achieved the effect of low dielectric constant and excellent dielectric performance, and simplified the Process and reduce costs.
Patent Information
- Application Number
- CN202411562495.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-05
- Publication Date
- 2025-02-14
AI Technical Summary
The prior art is difficult to effectively improve the dielectric properties of gypsum, which limits its application in electronic devices and materials.
By mixing gypsum pulverization with dispersion, adding doped source powder for ball milling, then suction filtering, drying, grinding and calcining, a gypsum-based dielectric material with low polarization ability and very low dielectric constant was prepared. Doping source powder contains metal elements such as strontium, copper, manganese, and magnesium.
The low dielectric constant and excellent dielectric properties of gypsum-based dielectric materials are achieved, the process flow is simplified, the cost is reduced, and the possibility of comprehensive utilization of gypsum and high value-added utilization is expanded.
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Figure CN119430259A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of dielectric materials, and in particular to a gypsum-based dielectric material and a preparation method thereof. Background Art
[0002] By-product gypsum is a by-product or waste generated during the industrial production process. Its main component is calcium sulfate, including desulfurized gypsum, phosphogypsum, citric acid gypsum, fluorinated gypsum, copper gypsum and titanium gypsum. At present, the main treatment methods for by-product gypsum are stacking and landfill, which not only occupies land resources, but also causes serious pollution to the environment and destroys the ecological balance. However, by-product gypsum that has been properly treated has been widely used in the fields of building materials and cement, and has gradually been used to prepare other products. However, limited by a variety of objective factors, its comprehensive utilization is still mainly based on traditional building materials and cement.
[0003] Natural gypsum is an important non-metallic mineral whose main component is hydrated calcium sulfate. Its utilization is mainly based on traditional building materials and cement.
[0004] Whether it is by-product gypsum or natural gypsum, it has a low dielectric constant, which may give it certain application prospects in electronic devices and materials that need to reduce the dielectric constant. However, there is currently no efficient and effective method to develop gypsum and improve its dielectric properties. Summary of the invention
[0005] The object of the present invention is to provide a gypsum-based dielectric material and a preparation method thereof in view of the above-mentioned deficiencies in the prior art.
[0006] A method for preparing a gypsum-based dielectric material of the present invention comprises the following steps:
[0007] The gypsum is crushed and mixed with a dispersion liquid to form a slurry, and then the doping source powder is added and ball milled. After the ball milling is completed, the mixed solution is filtered to remove the dispersion liquid, and then dried, ground and calcined to obtain a gypsum dielectric material;
[0008] The doping source powder contains one or more metal elements selected from the group consisting of strontium, copper, manganese, magnesium, zinc, titanium and barium.
[0009] Furthermore, the doping source powder is one or more of copper oxide, manganese oxide, magnesium oxide, zinc oxide, titanium dioxide, barium carbonate, magnesium carbonate, and strontium carbonate.
[0010] Furthermore, the mass volume ratio of the gypsum to the dispersion is 1 g: (1-100) mL.
[0011] Furthermore, the mass ratio of the gypsum to the doping source powder is 100:(50-100).
[0012] Furthermore, the gypsum is by-product gypsum or natural gypsum; the by-product gypsum includes any one of desulfurized gypsum, phosphogypsum, citric acid gypsum, fluorinated gypsum, copper gypsum and titanium gypsum.
[0013] Furthermore, the dispersion liquid is one or more of water, ethanol, n-hexane, ammonium sulfate solution, ammonium nitrate solution, ammonium carbonate solution, methanol, and formic acid.
[0014] Furthermore, the ball milling speed is 100-800 rpm, and the ball milling time is 5-20 hours.
[0015] Furthermore, the drying temperature is 50-180° C., and the drying time is 1-10 hours.
[0016] Furthermore, the calcination temperature is 200-1200° C., and the calcination time is 1-20 hours.
[0017] A gypsum-based dielectric material prepared by the above-mentioned preparation method.
[0018] Compared with the prior art, the present invention has the following beneficial effects:
[0019] (1) The present invention uses gypsum as a raw material to prepare a gypsum-based dielectric material through a ball milling-calcination combined method. The gypsum-based dielectric material has a CaSO4 phase and a crystalline phase structure containing doped elements. The prepared gypsum-based dielectric material has low polarization ability, presents an extremely low dielectric constant, and has excellent dielectric properties.
[0020] (2) The preparation method of the present invention has a simple process flow, is easy to operate, and has broad practical application prospects. It provides technical support for the comprehensive utilization and high value-added utilization of gypsum, and also has a certain guiding role in the development and industrial production of new dielectric materials.
[0021] (3) The main component of gypsum is calcium sulfate, which has a low dielectric constant. This makes it exhibit excellent electrical properties in electronic devices and materials that need to reduce the dielectric constant. Secondly, gypsum resources are abundant, low-cost, easy to obtain and process, which gives it an economic advantage in the application of dielectric materials. In addition, the lightweight characteristics of gypsum materials and their easy molding and processing properties enable them to adapt to the needs of different shapes and sizes. They can be widely used in fields that require low dielectric properties, such as microelectronic packaging and antenna substrates. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1a is the X-ray diffraction pattern of AH dielectric material;
[0023] Figure 1b It is the X-ray diffraction pattern of Sr-AH-M10 dielectric material;
[0024] Figure 1cIt is the X-ray diffraction pattern of Sr-AH-M18 dielectric material;
[0025] Figure 2a This is the SEM image of AH dielectric material;
[0026] Figure 2b This is the SEM image of Sr-AH-M10 dielectric material;
[0027] Figure 3a It is the hysteresis loop spectrum of AH dielectric material;
[0028] Figure 3b This is the hysteresis loop spectrum of Sr-AH-M10 dielectric material;
[0029] Figure 4a For AH dielectric materials at 10 3 -10 7 Dielectric constant and dielectric loss in the Hz range;
[0030] Figure 4b For Sr-AH-M10 dielectric material, 3 -10 7 Dielectric constant and dielectric loss in the Hz range;
[0031] Figure 4c For Sr-AH-M18 dielectric material at 10 3 -10 7 Dielectric constant and dielectric loss in the Hz range;
[0032] Figure 4d For Sr-AH-M14 dielectric material at 10 3 -10 7 Dielectric constant and dielectric loss in the Hz range;
[0033] Figure 4e For Sr-AH-M18 dielectric material at 10 3 -10 7 Dielectric constant and dielectric loss in the Hz range;
[0034] Figure 4f For Sr-AH-1200 dielectric material in 10 3 -10 7 Dielectric constant and dielectric loss in the Hz range. DETAILED DESCRIPTION
[0035] The following are specific embodiments of the present invention and the accompanying drawings to further describe the technical solution of the present invention, but the present invention is not limited to these embodiments.
[0036] Comparative Example 1
[0037] This embodiment provides a method for preparing phosphogypsum ore AH dielectric material.
[0038] Step S1, crushing the phosphogypsum ore for 15 minutes to obtain phosphogypsum powder;
[0039] Step S2, mixing the phosphogypsum powder obtained in step S1 with water in a mass ratio of 1g:15g to form a slurry, ball milling at a rotation speed of 500rpm for 8h, and after the reaction is completed, filtering the mixed solution to remove the dispersion liquid, drying at 70°C to obtain a doped powder filter cake, grinding it for 15min, and then calcining it at 1000°C for 5h to obtain the phosphogypsum AH material.
[0040] Example 1
[0041] This embodiment provides a method for preparing phosphogypsum ore Sr-AH-M8 dielectric material.
[0042] Step S1, crushing the phosphogypsum ore for 15 minutes to obtain phosphogypsum powder;
[0043] Step S2, mixing the phosphogypsum powder obtained in step S1 with water in a mass ratio of 1g:15g to form a slurry, and adding a certain mass of strontium carbonate, wherein the mass ratio of strontium carbonate to phosphogypsum powder is 1:5, and ball milling at a speed of 500rpm for 8h. After the reaction is completed, the mixed solution is filtered to remove the dispersion liquid, and dried at 70°C to obtain a doped powder filter cake, which is ground for 15min and then calcined at 1000°C for 3h to obtain the phosphogypsum Sr-AH-M8 material.
[0044] Example 2
[0045] This embodiment provides a method for preparing phosphogypsum ore Sr-AH-M10 dielectric material.
[0046] The ball milling time was 10 h, and the others were the same as in Example 1.
[0047] Example 3
[0048] This embodiment provides a method for preparing phosphogypsum ore Sr-AH-M14 dielectric material.
[0049] The ball milling time was 14 h, and the others were the same as in Example 1.
[0050] Example 4
[0051] This embodiment provides a method for preparing phosphogypsum ore Sr-AH-M18 dielectric material.
[0052] The ball milling time was 18 h, and the others were the same as in Example 1.
[0053] Example 5
[0054] This embodiment provides a method for preparing phosphogypsum raw ore Sr-AH-1200 dielectric material.
[0055] The calcination temperature is 1200° C., and the rest is the same as in Example 1.
[0056] Figure 1a This is the X-ray diffraction spectrum of the AH dielectric material. It can be seen from the figure that the main phase in the material is CaSO4, and the characteristic peak of the anhydrous gypsum phase is sharp and has high intensity, indicating that the synthesized anhydrous gypsum has good crystallinity and high crystal order, and no other impurity phases are observed.
[0057] Figure 1b is the X-ray diffraction spectrum of Sr-AH-M10 dielectric material. It can be seen from the figure that: Figure 1a Similarly, the main phase in this material is CaSO4, and the characteristic peak of anhydrous gypsum phase is sharp and obvious, and obvious Ca 0.7 Sr 0.3 SO4 crystal structure.
[0058] Figure 1c is the X-ray diffraction spectrum of Sr-AH-M18 dielectric material. It can be seen from the figure that: Figure 1b Similarly, the main phase in this material is CaSO4, and the characteristic peak of anhydrous gypsum phase is sharp and obvious, and obvious Ca 0.7 Sr 0.3 SO4 crystal structure.
[0059] Figure 2a This is the SEM spectrum of the AH dielectric material. It can be observed that the material is mainly an irregular granular structure with an average particle size of about 1.13μm.
[0060] Figure 2b This is the SEM spectrum of the Sr-AH-M10 dielectric material. It can be observed that the material is mainly an irregular granular structure with an average particle size of about 1.17μm.
[0061] Figure 3a This is the hysteresis loop spectrum of the AH dielectric material. It can be observed that the residual polarization strength of the material is about 6.27×10 -2 μC / cm 2 .
[0062] Figure 3b This is the hysteresis loop spectrum of Sr-AH-M10 dielectric material. It can be observed that the residual polarization strength of this material is about 2.75×10 -2 μC / cm 2 , which is significantly smaller than that of the AH sample, meaning that during the electric field polarization process, Sr-AH-M10 is more difficult to polarize than AH, resulting in a lower dielectric constant and dielectric loss.
[0063] Figure 4a For AH dielectric materials at 10 3 -10 7 The dielectric constant and dielectric loss in the Hz range show lower dielectric constant and dielectric loss, for example, at 10 3 At 18 GHz, the dielectric constant and dielectric loss of the material are 3.92 and 0.014 respectively.
[0064] Figure 4b For Sr-AH-M8 dielectric material in 10 3 -10 7 The dielectric constant and dielectric loss in the Hz range show lower dielectric constant and dielectric loss, for example, at 10 3 At Hz, the dielectric constant and dielectric loss of the material are 7.66 and 0.33 respectively.
[0065] Figure 4c For Sr-AH-M10 dielectric material, 3 -10 7 The dielectric constant and dielectric loss in the Hz range show lower dielectric constant and dielectric loss than AH materials. For example, 3 At 18 GHz, the dielectric constant and dielectric loss of the material are 3.81 and 0.013 respectively.
[0066] Figure 4d For Sr-AH-M14 dielectric material at 10 3 -10 7 The dielectric constant and dielectric loss in the Hz range show lower dielectric constant and dielectric loss, for example, at 10 3 At Hz, the dielectric constant and dielectric loss of the material are 7.42 and 0.27 respectively.
[0067] Figure 4e For Sr-AH-M18 dielectric material at 10 3 -10 7 The dielectric constant and dielectric loss in the Hz range are lower than those of AH materials, such as Sr-AH-M10, for example, at 10 3 At 10 Hz, the dielectric constant and dielectric loss of the material are 4.05 and 0.19 respectively. It shows a low dielectric constant and dielectric loss, for example, at 10 3 At Hz, the dielectric constant and dielectric loss of the material are 5.78 and 0.15 respectively.
[0068] According to the above XRD, SEM, hysteresis loop and dielectric tests, it is found that the Sr-doped anhydrous gypsum AH has more significant dielectric properties than the undoped AH. This is mainly because: after Sr is doped into AH, the doped area has a stronger lattice tensile strain. This distortion regulates the surrounding coordination environment and forces the undoped area to be compressed. This compression effect weakens the bell effect of the [CaO8] polyhedron, thereby reducing the ionic polarizability of the structure and weakening the polarization ability, so that the Sr-AH material exhibits excellent dielectric properties. At the same time, the material has low density, low preparation cost, a wide range of raw materials and can be recycled and reused, which is suitable for replacing traditional inorganic dielectric materials.
[0069] The ball milling time also affects the dielectric properties of dielectric materials, which may also be related to the proportion of doped and undoped regions in the material.
[0070] For matters not mentioned above, the prior art applies.
[0071] Although some specific embodiments of the present invention have been described in detail through examples, those skilled in the art should understand that the above examples are for illustration only and are not intended to limit the scope of the present invention. Those skilled in the art to which the present invention belongs may make various modifications or supplements to the specific embodiments described or replace them in a similar manner, but they will not deviate from the direction of the present invention or exceed the scope defined by the attached claims. Those skilled in the art should understand that any modifications, equivalent substitutions, improvements, etc. made to the above embodiments based on the technical essence of the present invention should be included in the protection scope of the present invention.
Claims
1. A method for preparing a gypsum-based dielectric material, characterized in that: The steps include: The gypsum is crushed and mixed with a dispersion liquid to form a slurry, and then the doping source powder is added and ball milled. After the ball milling is completed, the mixed solution is filtered to remove the dispersion liquid, and then dried, ground and calcined to obtain a gypsum dielectric material; The doping source powder contains one or more metal elements selected from the group consisting of strontium, copper, manganese, magnesium, zinc, titanium and barium.
2. The preparation method according to claim 1, characterized in that: The doping source powder is one or more of copper oxide, manganese oxide, magnesium oxide, zinc oxide, titanium dioxide, barium carbonate, magnesium carbonate, and strontium carbonate.
3. The preparation method according to claim 1, characterized in that: The mass volume ratio of the gypsum to the dispersion liquid is 1 g: (1-100) mL.
4. The preparation method according to claim 1, characterized in that: The mass ratio of the gypsum to the doping source powder is 2:(1-2).
5. The preparation method according to claim 1, characterized in that: The gypsum is by-product gypsum or natural gypsum; the by-product gypsum includes any one of desulfurized gypsum, phosphogypsum, citric acid gypsum, fluorinated gypsum, copper gypsum and titanium gypsum.
6. The preparation method according to claim 1, characterized in that: The dispersion liquid is one or more of water, ethanol, n-hexane, ammonium sulfate solution, ammonium nitrate solution, ammonium carbonate solution, methanol, and formic acid.
7. The preparation method according to claim 1, characterized in that: The ball milling speed is 100-800 rpm, and the ball milling time is 5-20 hours.
8. The preparation method according to claim 1, characterized in that: The drying temperature is 50-180° C., and the drying time is 1-10 hours.
9. The preparation method according to claim 1, characterized in that: The calcination temperature is 200-1200° C., and the calcination time is 1-20 hours.
10. A gypsum-based dielectric material prepared by the preparation method according to any one of claims 1 to 9.