Copper calcium titanate nanoflower and preparation method thereof
Copper-calcium titanate nanoflowers were prepared by a hydrothermal method. Phenolic compounds were used to attach copper and calcium ions to the surface of the titanium dioxide nanoflowers, which solved the problem of poor compatibility between copper-calcium titanate and the polymer matrix, and realized the preparation of high dielectric composite materials with low dielectric loss.
Patent Information
- Application Number
- CN202511429266.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-08
- Publication Date
- 2026-02-24
AI Technical Summary
The poor compatibility between calcium copper titanate and the polymer matrix results in high dielectric loss in the prepared composite material.
Titanium dioxide nanoflowers were synthesized via a hydrothermal method as templates. Phenolic compounds were used to attach copper and calcium ions to the surface of the titanium dioxide nanoflowers. Subsequently, they were reacted with copper nitrate trihydrate and calcium nitrate tetrahydrate to prepare petal-shaped copper-calcium titanate nanoflowers, increasing their contact area with the polymer.
The compatibility of calcium copper titanate nanoflowers with polymers has been improved, dielectric loss has been reduced, and they are suitable for industrial production.
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Figure CN121553980A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a copper calcium titanate nanoflower and its preparation method, belonging to the field of high dielectric constant inorganic ceramic materials. Background Technology
[0002] High dielectric constant materials are significant for improving capacitor storage capacity, reducing electronic device size, and enhancing communication system performance due to their ability to store more charge under an electric field. They have broad application prospects in electronics, electrical engineering, energy conversion, and dielectric energy storage. Furthermore, the application of high dielectric constant materials in semiconductor memory devices is currently a hot research topic in the microelectronics industry. The application of these materials helps solve the gate oxide layer thickness limit problem caused by the miniaturization of semiconductor devices and can realize novel devices with special properties. In the microelectronics field, by selecting a suitable polymer matrix, high-capacitance embedded microcapacitors can be rapidly and massively fabricated on printed circuit boards. These high-capacitance microcapacitors can ensure the high-speed and safe operation of integrated circuits.
[0003] Calcium copper titanate (CaCu3Ti4O) 12 Calcium copper titanate (CCTO) is a lead-free perovskite dielectric ceramic material that exhibits neither ferroelectric nor relaxation properties. It possesses an extremely high dielectric constant (~10⁻¹⁰). 5 The giant dielectric constant of calcium copper titanate has attracted widespread attention. This can be attributed to the Maxwell-Wagner effect, also known as the inner-layer blocking capacitance effect, that occurs between crystal interfaces during crystal growth. Furthermore, the giant dielectric constant of calcium copper titanate is remarkably stable over a wide frequency (100 Hz-1 MHz) and temperature (100-600 K) range. Due to its dielectric properties, materials based on calcium copper titanate hold promise for manufacturing dielectric composites and microcapacitors. Although calcium copper titanate exhibits a high dielectric constant and good stability, like most inorganic fillers, it suffers from poor compatibility with polymer matrices, leading to high dielectric losses in the prepared composites. To address these issues, this invention provides calcium copper titanate nanoflowers and their preparation method. By increasing the contact area between the calcium copper titanate nanoflowers and the polymer, their compatibility with the polymer is improved, facilitating the acquisition of high-dielectric composites with low dielectric losses. Summary of the Invention
[0004] The purpose of this invention is to address the problem of poor compatibility between calcium copper titanate and polymer matrices, which leads to high dielectric loss in the prepared composite materials. This invention provides calcium copper titanate nanoflowers and their preparation method to improve their compatibility with polymers, facilitating the acquisition of high-dielectric composite materials with low dielectric loss. Specifically, tetrabutyl titanate and hydrochloric acid are first synthesized into titanium dioxide nanoflowers via a hydrothermal method; then, using the titanium dioxide nanoflowers as templates, copper nitrate trihydrate and calcium nitrate tetrahydrate as raw materials, and phenolic compounds as additives, calcium copper titanate nanoflowers are synthesized via a hydrothermal method.
[0005] The technical solution adopted by this invention to solve the above problems, a method for preparing calcium copper titanate nanoflowers, includes the following steps:
[0006] (1) Preparation of titanium dioxide nanoflowers: Tetrabutyl titanate and hydrochloric acid were stirred evenly at room temperature, and then hydrothermal reaction was carried out. After filtration, washing and drying, titanium dioxide nanoflowers were obtained.
[0007] (2) Preparation of copper titanate calcium nanoflowers: Copper nitrate trihydrate, calcium nitrate tetrahydrate, phenolic compounds and titanium dioxide nanoflowers were placed in a beaker and stirred evenly, and then subjected to hydrothermal reaction. After the reaction was completed, the mixture was filtered, washed, dried and sintered to obtain copper titanate calcium nanoflowers.
[0008] Furthermore, in the preparation of the above-mentioned titanium dioxide nanoflowers, the volume ratio of tetrabutyl titanate to hydrochloric acid is 1:20-50, and the concentration of hydrochloric acid is 2-8 mol / L.
[0009] Furthermore, in the preparation of the above-mentioned titanium dioxide nanoflowers, the hydrothermal reaction temperature is 150-200 ℃ and the hydrothermal reaction time is 1-5 h.
[0010] Furthermore, in the preparation of the above-mentioned titanium dioxide nanoflowers, the washing is performed using anhydrous ethanol and deionized water in a ratio of 1:0.5-2 until neutral, the drying temperature is 50-100 ℃, and the drying time is 10-24 h.
[0011] Furthermore, in the preparation of the above-mentioned copper titanate calcium nanoflowers, the molar ratio of copper, calcium and titanium among the copper nitrate trihydrate, calcium nitrate tetrahydrate and titanium dioxide nanoflowers is 1:1:1.
[0012] Furthermore, in the preparation of the above-mentioned copper titanate calcium nanoflowers, the phenolic compound is one of phenol, resorcinol, catechol, and trichlorophenol, and the molar ratio of phenolic hydroxyl groups in the phenolic compound to titanium dioxide nanoflowers is 1:0.1-1.
[0013] The further beneficial effect of the above-mentioned method is that, during the use of phenolic compounds, copper ions and calcium ions can be better attached to the surface of titanium dioxide nanoflowers.
[0014] Furthermore, in the preparation of the above-mentioned calcium copper titanate nanoflowers, the hydrothermal reaction temperature is 140-200 ℃ and the hydrothermal reaction time is 12-36 h.
[0015] Furthermore, in the preparation of the above-mentioned copper titanate calcium nanoflowers, the washing is performed using anhydrous ethanol and deionized water in a ratio of 1:0.5-2 until neutral, and the drying temperature is 50-100 ℃, with a drying time of 10-24 h.
[0016] Furthermore, in the preparation of the above-mentioned calcium copper titanate nanoflowers, the sintering temperature is 600-1000 ℃ and the sintering time is 1-5 h.
[0017] The further beneficial effects of the above-mentioned method are that excessively high sintering temperature and excessively long holding time will lead to uneven local heating, shrinkage of the preform and cracking; excessively low sintering temperature and excessively short holding time will lead to insufficient solid-phase reaction, thereby inhibiting the complete growth of grains and increasing intergranular voids.
[0018] The beneficial effects of this invention are as follows: The copper-calcium titanate nanoflowers of this invention have a size of 100-500 nm, a petal-like morphology, and a three-dimensional structure. Compared with copper-calcium titanate nanoparticles, nanorods, and nanofibers, their compatibility with polymers can be improved by increasing the contact area between the copper-calcium titanate nanoflowers and the polymer. This invention prepares copper-calcium titanate nanoflowers by adding phenolic compounds to allow calcium and copper ions to attach to the surface of the titanium dioxide nanoflowers. The method for preparing copper-calcium titanate nanoflowers in this invention is simple to operate, environmentally friendly, avoids raw material waste, has low equipment requirements, and low cost, making it suitable for continuous and large-scale industrial production. Attached Figure Description
[0019] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.
[0020] Figure 1 Scanning electron microscope image of the calcium copper titanate nanoflowers prepared in Example 1.
[0021] Figure 2 The image shows the X-ray diffraction pattern of the calcium copper titanate nanoflowers prepared in Example 1.
[0022] Figure 3 The graph shows the dielectric constant of the calcium copper titanate nanoflowers prepared in Example 1 as a function of frequency. Detailed Implementation
[0023] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0024] Example 1
[0025] (1) Preparation of titanium dioxide nanoflowers: Tetrabutyl titanate and 5 mol / L hydrochloric acid solution were added to the reactor at a ratio of 1:30 and hydrothermally reacted at 180 °C for 2 h; the reaction product was filtered and then the filter cake was washed with 1:1 anhydrous ethanol and deionized water until neutral; finally, it was dried in an oven at 60 °C for 12 h to obtain titanium dioxide nanoflowers.
[0026] (2) Preparation of copper titanate calcium nanoflowers: 1.09 g of copper nitrate trihydrate, 0.35 g of calcium nitrate tetrahydrate, 0.48 g of titanium dioxide nanoflowers and 0.19 g of phenol were weighed and stirred evenly at room temperature. The homogeneous mixture was added to a high-pressure reactor and reacted at 155 °C for 24 h. The product after reaction was filtered and washed with 1:1 anhydrous ethanol and deionized water until neutral. Then it was dried in an oven at 60 °C for 12 h. Finally, the dried product was placed in a muffle furnace and sintered at 800 °C for 2 h to obtain copper titanate calcium nanoflowers.
[0027] The prepared calcium copper titanate nanoflowers have a diameter of 400 nm, and their scanning electron microscope images are attached. Figure 1 As shown; the XRD diffraction pattern is attached. Figure 2 As shown, its crystal structure is proven to be calcium copper titanate; the dielectric constant of the calcium copper titanate nanoflowers as a function of frequency is shown in the attached figure. Figure 3 As shown, the dielectric constant at 100 Hz is 2 × 10⁻⁶. 4 .
[0028] Example 2
[0029] (1) Preparation of titanium dioxide nanoflowers: Tetrabutyl titanate and 8 mol / L hydrochloric acid solution were added to the reactor at a ratio of 1:50 and hydrothermally reacted at 200 °C for 2 h; the reaction product was filtered and then the filter cake was washed with anhydrous ethanol and deionized water at a ratio of 1:2 until neutral; finally, it was dried in an oven at 60 °C for 12 h to obtain titanium dioxide nanoflowers.
[0030] (2) Preparation of copper titanate calcium nanoflowers: 1.09 g of copper nitrate trihydrate, 0.35 g of calcium nitrate tetrahydrate, 0.48 g of titanium dioxide nanoflowers and 0.19 g of phenol were weighed and stirred evenly at room temperature. The homogeneous mixture was added to a high-pressure reactor and reacted at 155 °C for 24 h. The product after reaction was filtered and washed with 1:1 anhydrous ethanol and deionized water until neutral. Then it was dried in an oven at 60 °C for 12 h. Finally, the dried product was placed in a muffle furnace and sintered at 800 °C for 2 h to obtain copper titanate calcium nanoflowers.
[0031] The prepared calcium copper titanate nanoflowers have a diameter of 230 nm and a dielectric constant of 3 × 10⁻⁶ at 100 Hz. 4 .
[0032] Example 3
[0033] (1) Preparation of titanium dioxide nanoflowers: Tetrabutyl titanate and 3 mol / L hydrochloric acid solution were added to the reactor at a ratio of 1:20 and hydrothermally reacted at 160 °C for 2 h; the reaction product was filtered and then the filter cake was washed with 1:1 anhydrous ethanol and deionized water until neutral; finally, it was dried in an oven at 80 °C for 12 h to obtain titanium dioxide nanoflowers.
[0034] (2) Preparation of copper titanate calcium nanoflowers: 1.09 g of copper nitrate trihydrate, 0.35 g of calcium nitrate tetrahydrate, 0.48 g of titanium dioxide nanoflowers and 0.19 g of phenol were weighed and stirred evenly at room temperature. The homogeneous mixture was added to a high-pressure reactor and reacted at 155 °C for 24 h. The product after reaction was filtered and washed with 1:1 anhydrous ethanol and deionized water until neutral. Then it was dried in an oven at 60 °C for 12 h. Finally, the dried product was placed in a muffle furnace and sintered at 800 °C for 2 h to obtain copper titanate calcium nanoflowers.
[0035] The prepared calcium copper titanate nanoflowers have a diameter of 312 nm and a dielectric constant of 5 × 10⁻⁶ at 100 Hz. 4 .
[0036] Example 4
[0037] (1) Preparation of titanium dioxide nanoflowers: Tetrabutyl titanate and 5 mol / L hydrochloric acid solution were added to the reactor at a ratio of 1:30 and hydrothermally reacted at 180 °C for 2 h; the reaction product was filtered and then the filter cake was washed with 1:1 anhydrous ethanol and deionized water until neutral; finally, it was dried in an oven at 60 °C for 12 h to obtain titanium dioxide nanoflowers.
[0038] (2) Preparation of copper titanate calcium nanoflowers: 1.09 g of copper nitrate trihydrate, 0.35 g of calcium nitrate tetrahydrate, 0.48 g of titanium dioxide nanoflowers and 0.28 g of phenol were weighed and stirred evenly at room temperature. The homogeneous mixture was added to a high-pressure reactor and reacted at 160 °C for 12 h. The product after reaction was filtered and washed with 1:0.5 anhydrous ethanol and deionized water until neutral. Then it was dried in an oven at 60 °C for 12 h. Finally, the dried product was placed in a muffle furnace and sintered at 800 °C for 2 h to obtain copper titanate calcium nanoflowers.
[0039] The prepared calcium copper titanate nanoflowers have a diameter of 195 nm and a dielectric constant of 5 × 10⁻⁶ at 100 Hz. 5 .
[0040] Example 5
[0041] (1) Preparation of titanium dioxide nanoflowers: Tetrabutyl titanate and 5 mol / L hydrochloric acid solution were added to the reactor at a ratio of 1:30 and hydrothermally reacted at 180 °C for 2 h; the reaction product was filtered and then the filter cake was washed with 1:1 anhydrous ethanol and deionized water until neutral; finally, it was dried in an oven at 80 °C for 12 h to obtain titanium dioxide nanoflowers.
[0042] (2) Preparation of copper titanate calcium nanoflowers: 1.09 g of copper nitrate trihydrate, 0.35 g of calcium nitrate tetrahydrate, 0.48 g of titanium dioxide nanoflowers and 0.38 g of resorcinol were weighed and stirred evenly at room temperature. The homogeneous mixture was added to a high-pressure reactor and reacted at 180 °C for 24 h. The product after reaction was filtered and washed with 1:1 anhydrous ethanol and deionized water until neutral. Then it was dried in an oven at 60 °C for 12 h. Finally, the dried product was placed in a muffle furnace and sintered at 1000 °C for 1 h to obtain copper titanate calcium nanoflowers.
[0043] The prepared calcium copper titanate nanoflowers have a diameter of 226 nm and a dielectric constant of 4 × 10⁻⁶ at 100 Hz. 5 .
[0044] Example 6
[0045] (1) Preparation of titanium dioxide nanoflowers: Tetrabutyl titanate and 2 mol / L hydrochloric acid solution were added to the reactor at a ratio of 1:20 and hydrothermally reacted at 160 °C for 2 h; the reaction product was filtered and then the filter cake was washed with 1:1 anhydrous ethanol and deionized water until neutral; finally, it was dried in an oven at 80 °C for 12 h to obtain titanium dioxide nanoflowers.
[0046] (2) Preparation of copper titanate calcium nanoflowers: 1.09 g of copper nitrate trihydrate, 0.35 g of calcium nitrate tetrahydrate, 0.48 g of titanium dioxide nanoflowers and 0.38 g of resorcinol were weighed and stirred evenly at room temperature. The homogeneous mixture was added to a high-pressure reactor and reacted at 180 °C for 12 h. The product after reaction was filtered and washed with 1:1 anhydrous ethanol and deionized water until neutral. Then it was dried in an oven at 70 °C for 12 h. Finally, the dried product was placed in a muffle furnace and sintered at 600 °C for 5 h to obtain copper titanate calcium nanoflowers.
[0047] The prepared calcium copper titanate nanoflowers have a diameter of 243 nm and a dielectric constant of 1 × 10⁻⁶ at 100 Hz. 5 .
[0048] Example 7
[0049] (1) Preparation of titanium dioxide nanoflowers: Tetrabutyl titanate and 5 mol / L hydrochloric acid solution were added to the reactor at a ratio of 1:30 and hydrothermally reacted at 180 °C for 2 h; the reaction product was filtered and then the filter cake was washed with 1:1 anhydrous ethanol and deionized water until neutral; finally, it was dried in an oven at 80 °C for 12 h to obtain titanium dioxide nanoflowers.
[0050] (2) Preparation of copper titanate calcium nanoflowers: 1.09 g of copper nitrate trihydrate, 0.35 g of calcium nitrate tetrahydrate, 0.48 g of titanium dioxide nanoflowers and 0.24 g of catechol were weighed and stirred evenly at room temperature. The homogeneous mixture was added to a high-pressure reactor and reacted at 160 °C for 36 h. The product after reaction was filtered and washed with 1:1 anhydrous ethanol and deionized water until neutral. Then it was dried in an oven at 80 °C for 12 h. Finally, the dried product was placed in a muffle furnace and sintered at 700 °C for 2 h to obtain copper titanate calcium nanoflowers.
[0051] The prepared calcium copper titanate nanoflowers have a diameter of 294 nm and a dielectric constant of 8 × 10⁻⁶ at 100 Hz. 4 .
[0052] Example 8
[0053] (1) Preparation of titanium dioxide nanoflowers: Tetrabutyl titanate and 5 mol / L hydrochloric acid solution were added to the reactor at a ratio of 1:30 and hydrothermally reacted at 180 °C for 2 h; the reaction product was filtered and then the filter cake was washed with anhydrous ethanol and deionized water at a ratio of 1:2 until neutral; finally, it was dried in an oven at 60 °C for 12 h to obtain titanium dioxide nanoflowers.
[0054] (2) Preparation of copper titanate calcium nanoflowers: 1.09 g of copper nitrate trihydrate, 0.35 g of calcium nitrate tetrahydrate, 0.48 g of titanium dioxide nanoflowers and 0.32 g of trichlorophenol were weighed and stirred evenly at room temperature. The homogeneous mixture was added to a high-pressure reactor and reacted at 160 °C for 12 h. The product after reaction was filtered and washed with 1:1 anhydrous ethanol and deionized water until neutral. Then it was dried in an oven at 80 °C for 12 h. Finally, the dried product was placed in a muffle furnace and sintered at 800 °C for 2 h to obtain copper titanate calcium nanoflowers.
[0055] The prepared calcium copper titanate nanoflowers have a diameter of 335 nm and a dielectric constant of 6 × 10⁻⁶ at 100 Hz. 5 .
Claims
1. A copper titanate calcium nanoflower, characterized in that: The described copper titanate calcium nanoflowers have a size of 100-500 nm, a petal-like morphology, and a dielectric constant of 2 × 10⁻⁶ at 100 Hz. 4 -8×10 5 .
2. The copper titanate calcium nanoflower according to claim 1, characterized in that: The preparation steps of the calcium copper titanate nanoflowers are as follows: (1) Preparation of titanium dioxide nanoflowers: Tetrabutyl titanate and hydrochloric acid were stirred evenly at room temperature, and then hydrothermal reaction was carried out. After filtration, washing and drying, titanium dioxide nanoflowers were obtained. (2) Preparation of copper titanate calcium nanoflowers: Copper nitrate trihydrate, calcium nitrate tetrahydrate, phenolic compounds and titanium dioxide nanoflowers were placed in a beaker and stirred evenly, and then subjected to hydrothermal reaction. After the reaction was completed, the mixture was filtered, washed, dried and sintered to obtain copper titanate calcium nanoflowers.
3. The method for preparing titanium dioxide nanoflowers according to claim 2, characterized in that: The volume ratio of tetrabutyl titanate to hydrochloric acid is 1:20-50, and the concentration of hydrochloric acid is 2-8 mol / L.
4. The method for preparing titanium dioxide nanoflowers according to claim 2, characterized in that: The hydrothermal reaction temperature is 150-200 ℃, and the hydrothermal reaction time is 1-5 h.
5. The method for preparing titanium dioxide nanoflowers according to claim 2, characterized in that: The washing process involves using anhydrous ethanol and deionized water in a 1:0.5-2 ratio until neutral. The drying temperature is 50-100 °C, and the drying time is 10-24 h.
6. The method for preparing calcium copper titanate nanoflowers according to claim 2, characterized in that: The molar ratio of copper, calcium, and titanium among the copper trihydrate, calcium tetrahydrate, and titanium dioxide nanoflowers is 1:1:
1.
7. The method for preparing calcium copper titanate nanoflowers according to claim 2, characterized in that: The phenolic compound is one of phenol, resorcinol, catechol, and trichlorophenol, and the molar ratio of phenolic hydroxyl groups to titanium dioxide nanoflowers in the phenolic compound is 1:0.1-1.
8. The method for preparing calcium copper titanate nanoflowers according to claim 2, characterized in that: The hydrothermal reaction temperature is 140-200 ℃, and the hydrothermal reaction time is 12-36 h.
9. The method for preparing calcium copper titanate nanoflowers according to claim 2, characterized in that: The washing process involves using anhydrous ethanol and deionized water in a 1:0.5-2 ratio until neutral. The drying temperature is 50-100 °C, and the drying time is 10-24 h.
10. The method for preparing calcium copper titanate nanoflowers according to claim 2, characterized in that: The sintering temperature is 600-1000 ℃, and the sintering time is 1-5 h.