CN114956165A - Material for special insulated cable and preparation method thereof - Google Patents
Material for special insulated cable and preparation method thereof Download PDFInfo
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- CN114956165A CN114956165A CN202210652224.5A CN202210652224A CN114956165A CN 114956165 A CN114956165 A CN 114956165A CN 202210652224 A CN202210652224 A CN 202210652224A CN 114956165 A CN114956165 A CN 114956165A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/002—Compounds containing, besides titanium, two or more other elements, with the exception of oxygen or hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/60—Arrangements for transfer of electric power between AC networks or generators via a high voltage DC link [HVCD]
Abstract
The invention discloses a material for a special insulated cable, which is selected from cerium-doped calcium copper titanate with a molecular formula of Ca (1‑3x/2) Ce x Cu 3 Ti 4 (ii) a Wherein x = 0.10-0.30. In addition, a preparation method of the material is also disclosed, which comprises the following steps: preparing cerium-doped calcium copper titanate sol; preparing crystal cerium-doped copper calcium titanate powder; the materials were prepared according to the above. Compared with the prior art, the dielectric property and the volt-ampere characteristic of the material for the special insulated cable are better.
Description
Technical Field
The invention belongs to the technical field of special cables, and particularly relates to a material for a special insulated cable and a preparation method thereof.
Background
With the continuous development of the ultra-high voltage technology in China, high-voltage direct current transmission has been widely regarded and developed. Compared with alternating current transmission, the high-voltage direct current transmission has the advantages of large transmission capacity, low line loss, no reactive power, convenience in power supply connection, easiness in control and adjustment and the like; the capacity of short-circuit current of an original power system is not increased, the system stability is not limited, a direct-current cable line is not similar to an alternating-current cable line, the capacity and current faults are avoided, magnetic loss and dielectric loss are avoided, only core wire insulation resistance loss is basically achieved, and the characteristics of relatively low insulation voltage, high reliability and the like are achieved.
The high-voltage direct-current cable accessory is important connecting equipment for ensuring the reliable operation of a power transmission line. Because the cable accessories are of a multilayer composite insulation structure, the cable accessories easily generate the defects of bulges, air gaps, impurities and the like, and bear complex working conditions and laying modes, the cable accessories also become the weakest link of a direct current transmission system.
The research on the reasons of the cable accessory faults finds that the fault positions are concentrated on the root of a semi-conductive stress cone in the accessory and the interface between main insulation (XLPE) of the cable and stress cone reinforced insulation. This is due to the fact that the electric field distribution inside the accessory under direct voltage is related to the conductivity of the respective insulating layer material. In order to improve the electric field distribution in the high-voltage direct-current cable accessory, the specific insulation structure is optimized, and the direct-current dielectric property of the material can be adjusted and controlled.
Chinese patent application CN103080237A discloses a composition and material having varistor properties and suitable for use in electrical stress control devices and surge arrester devices. The compositions and materials include a polymeric material and a calcined calcium copper titanate filler material, and have reversible nonlinear current-voltage characteristics. As filler material, the non-linear current-voltage characteristics of calcium copper titanate play a decisive role in the composition. However, for special insulated cables, the dielectric properties and the current-voltage characteristics of the materials used are still unsatisfactory.
In view of the above-mentioned drawbacks of the prior art, there is still a need to find a material for special insulated cables with better dielectric properties and voltammetric properties and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a material for a special insulated cable and a preparation method thereof. Compared with the prior art, the dielectric property and the volt-ampere characteristic of the material for the special insulated cable are better.
In order to solve the technical problem, on one hand, the invention adopts the following technical scheme: a material for special insulated cables is characterized in that the material is selected from cerium-doped calcium copper titanate with a molecular formula of Ca (1 - 3x/2) Ce x Cu 3 Ti 4 (ii) a Wherein x is 0.10-0.30.
The material according to the invention, wherein x is 0.15-0.25.
The material according to the invention, wherein x is 0.18-0.22.
In another aspect, the present invention provides a method for preparing the material according to the present invention, comprising:
(1) preparing cerium-doped copper calcium titanate sol from raw materials of calcium nitrate tetrahydrate, cerium nitrate hexahydrate, copper nitrate trihydrate, tetrabutyl titanate and ethylene glycol monomethyl ether;
(2) preparing crystallized cerium-doped copper calcium titanate powder from the cerium-doped copper calcium titanate sol;
(3) the material according to the invention was prepared from a crystalline cerium-doped copper calcium titanate powder.
According to the preparation method, raw materials of calcium nitrate tetrahydrate, cerium nitrate hexahydrate, copper nitrate trihydrate, tetrabutyl titanate and ethylene glycol monomethyl ether are in a molar ratio of (1-3x/2) x:3:4: 16.
The preparation method provided by the invention is characterized in that the step (1) specifically comprises the following steps: firstly, placing calcium nitrate tetrahydrate, cerous nitrate hexahydrate and copper nitrate trihydrate into ethylene glycol monomethyl ether, and stirring until the calcium nitrate tetrahydrate, the cerous nitrate hexahydrate and the copper nitrate trihydrate are completely dissolved; dripping a plurality of drops of inorganic acid, and stirring to uniformly mix the inorganic acid and the inorganic acid; slowly adding tetrabutyl titanate, stirring until the tetrabutyl titanate is completely dissolved, and continuously reacting for 2-8h after the tetrabutyl titanate is added; and after the reaction is finished, standing for 8-48h in a dark place.
The preparation method according to the invention, wherein the inorganic acid is selected from concentrated nitric acid.
The preparation method provided by the invention, wherein the step (2) specifically comprises the following steps: heating the cerium-doped calcium copper titanate sol dry powder to 200 ℃ and 400 ℃ at the speed of 3-7 ℃/min, and preserving the heat for 1-4 h; then the temperature is raised to 1000 ℃ and 1100 ℃, and the temperature is kept for 4-12 h.
The preparation method provided by the invention, wherein the step (3) is specifically as follows: adding the crystallized cerium-doped copper calcium titanate powder into a dispersion medium for wet milling, and then drying to remove the dispersion medium.
The preparation method according to the present invention, wherein the dispersion medium is absolute ethanol.
Compared with the prior art, the dielectric property and the volt-ampere characteristic of the material for the special insulated cable are better.
Drawings
FIG. 1 is a graph of dielectric constant (right ordinate) and dielectric loss (left ordinate) of samples of examples and comparative examples.
Detailed Description
The invention will be further illustrated with reference to specific embodiments.
It should be understood that the detailed description of the invention is merely illustrative of the spirit and principles of the invention and is not intended to limit the scope of the invention. Furthermore, it should be understood that various changes, substitutions, deletions, modifications or adjustments may be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents are also within the scope of the invention as defined in the appended claims.
In the present invention, all percentages are by weight, as otherwise indicated.
Comparative example 1
Raw materials of calcium nitrate tetrahydrate, copper nitrate trihydrate, tetrabutyl titanate and ethylene glycol monomethyl ether are prepared according to a molar ratio of 1:3:4: 16. Firstly, placing calcium nitrate tetrahydrate and copper nitrate trihydrate into ethylene glycol monomethyl ether, and stirring until the calcium nitrate tetrahydrate and the copper nitrate trihydrate are completely dissolved; then, several drops of concentrated nitric acid (68% by mass) were added dropwise and stirred to mix them uniformly. Then slowly adding tetrabutyl titanate, stirring until the tetrabutyl titanate is completely dissolved, and continuously reacting for 4 hours after the tetrabutyl titanate is added. And after the reaction is finished, standing for 24 hours in a dark place to obtain the copper calcium titanate sol.
The calcium copper titanate sol was dried at 80 ℃ for 48h and ground to give a powder. Then raising the temperature to 300 ℃ at a speed of 5 ℃/min, and preserving the temperature for 2 h; then heating to 1050 ℃, and preserving the temperature for 8 hours to obtain the crystalline copper calcium titanate powder. Adding absolute ethyl alcohol as a dispersion medium, and wet-grinding for 12 h; and drying for 48 hours at the temperature of 80 ℃ to obtain the copper calcium titanate product.
Example 1
Raw materials of calcium nitrate tetrahydrate, cerium nitrate hexahydrate, copper nitrate trihydrate, tetrabutyl titanate and ethylene glycol monomethyl ether are prepared according to a molar ratio of 0.7:0.2:3:4: 16. Firstly, placing calcium nitrate tetrahydrate, cerous nitrate hexahydrate and copper nitrate trihydrate into ethylene glycol monomethyl ether, and stirring until the calcium nitrate tetrahydrate, the cerous nitrate hexahydrate and the copper nitrate trihydrate are completely dissolved; then, several drops of concentrated nitric acid (68% by mass) were added dropwise and stirred to mix them uniformly. Then slowly adding tetrabutyl titanate, stirring until the tetrabutyl titanate is completely dissolved, and continuously reacting for 4 hours after the tetrabutyl titanate is added. And standing for 24h in a dark place after the reaction is finished to obtain the cerium-doped calcium copper titanate sol.
The cerium-doped calcium copper titanate sol is dried for 48 hours at the temperature of 80 ℃ and ground to obtain powder. Then raising the temperature to 300 ℃ at a speed of 5 ℃/min, and preserving the temperature for 2 h; then heating to 1050 ℃, and preserving the temperature for 8 hours to obtain the crystallized cerium-doped copper calcium titanate powder. Adding absolute ethyl alcohol as a dispersion medium, and wet-grinding for 12 h; and drying for 48 hours at the temperature of 80 ℃ to obtain the cerium-doped calcium copper titanate product.
Performance testing
Respectively adding 5 wt% of PVA into the products of comparative example 1 and example 1 to be used as a binder for granulation; pressing the granulated sample into a sample with the diameter of 20mm and the thickness of 2mm under the pressure of 10 MPa; and directly sintering the obtained sample at 1050 ℃ and preserving the temperature for 10 hours to obtain a test sample.
The test sample adopts an X-ray diffractometer to test the crystal phase and the crystal structure of the sample by using a copper target, the 2 theta angle test range is 20-90 degrees, the scanning step length is 0.02 degree, and the scanning time of each step is 0.3 second. The results show that the crystal phase structure is assigned to JCPDS card # 075-.
The dielectric property of the sample is measured by a 4284A network impedance analyzer produced by Agilent, the measuring frequency range is 600Hz-1MHz, and the result is shown in figure 1. As can be seen from FIG. 1, in the frequency range of 600Hz to 1000kHz, in both example 1 and comparative example 1, the change of the dielectric constant with the frequency is small, which indicates that the dielectric property is relatively stable in the frequency range; however, the dielectric constant of example 1 was significantly higher than that of comparative example 1. From the viewpoint of dielectric loss, example 1 is also superior to comparative example 1 as a whole.
The voltammetric characteristics (I-V) of the sample were measured by Agilent 1505B until the sample broke down. The voltage-current characteristic curve satisfies that I is KV α . Alpha is a nonlinear coefficient of the voltammetry characteristic; in addition, on the voltammogram, the current density J was 1mA/cm 2 The electric field strength at that time was considered as the breakdown strength (kV/cm).
See table 1 for results.
TABLE 1
| Breakdown strength | Coefficient of non-linearity | |
| Comparative example 1 | 3.06 | 6.17 |
| Example 1 | 2.73 | 5.38 |
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. A material for special insulated cables is characterized in that the material is selected from cerium-doped calcium copper titanate with a molecular formula of Ca (1-3x/2) Ce x Cu 3 Ti 4 (ii) a Wherein x = 0.10-0.30.
2. The material of claim 1, wherein x = 0.15-0.25.
3. The material of claim 2, wherein x = 0.18-0.22.
4. A method of preparing a material according to any one of claims 1 to 3, comprising:
(1) preparing cerium-doped copper calcium titanate sol from raw materials of calcium nitrate tetrahydrate, cerium nitrate hexahydrate, copper nitrate trihydrate, tetrabutyl titanate and ethylene glycol monomethyl ether;
(2) preparing crystallized cerium-doped copper calcium titanate powder from the cerium-doped copper calcium titanate sol;
(3) the material according to any one of claims 1-3 prepared from a crystalline cerium-doped calcium copper titanate powder.
5. The production method according to claim 4, wherein the raw materials of calcium nitrate tetrahydrate, cerium nitrate hexahydrate, copper nitrate trihydrate, tetrabutyl titanate and ethylene glycol monomethyl ether are in a molar ratio of (1-3x/2) x:3:4: 16.
6. The production method according to claim 4 or 5, wherein the step (1) is specifically: firstly, calcium nitrate tetrahydrate, cerium nitrate hexahydrate and copper nitrate trihydrate are placed in ethylene glycol monomethyl ether and stirred until the calcium nitrate tetrahydrate, the cerium nitrate hexahydrate and the copper nitrate trihydrate are completely dissolved; dripping a plurality of drops of inorganic acid, and stirring to uniformly mix the inorganic acid and the inorganic acid; slowly adding tetrabutyl titanate, stirring until the tetrabutyl titanate is completely dissolved, and continuously reacting for 2-8h after the tetrabutyl titanate is added; and after the reaction is finished, standing for 8-48h in a dark place.
7. The method of claim 6, wherein the mineral acid is selected from concentrated nitric acid.
8. The production method according to claim 4 or 5, wherein the step (2) is specifically: heating the cerium-doped calcium copper titanate sol dry powder to 200 ℃ and 400 ℃ at the temperature of 3-7 ℃/min, and preserving heat for 1-4 h; then the temperature is raised to 1000 ℃ and 1100 ℃, and the temperature is kept for 4 to 12 hours.
9. The production method according to claim 4 or 5, wherein the step (3) is specifically: adding the crystallized cerium-doped copper calcium titanate powder into a dispersion medium for wet grinding, and then drying to remove the dispersion medium.
10. The production method according to claim 9, wherein the dispersion medium is absolute ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202210652224.5A CN114956165A (en) | 2022-06-10 | 2022-06-10 | Material for special insulated cable and preparation method thereof |
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| CN202210652224.5A CN114956165A (en) | 2022-06-10 | 2022-06-10 | Material for special insulated cable and preparation method thereof |
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Citations (7)
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| CN101891460A (en) * | 2010-07-08 | 2010-11-24 | 桂林理工大学 | Method for preparing calcium copper titanium oxide powder by sol-gel method |
| US20100317502A1 (en) * | 2009-06-12 | 2010-12-16 | Snu R&Db Foundation | Sintered material for dielectric substance and process for preparing the same |
| CN102173780A (en) * | 2011-01-11 | 2011-09-07 | 桂林理工大学 | Preparation method of rare earth modified pressure-sensitive material |
| CN104860673A (en) * | 2015-05-12 | 2015-08-26 | 太原理工大学 | Method for manufacturing low dielectric loss CaCu3Ti4O12 ceramic |
| CN105073683A (en) * | 2012-12-07 | 2015-11-18 | 法商圣高拜欧洲实验及研究中心 | Product comprising an oriented function and process for obtaining same |
| CN109704396A (en) * | 2019-01-28 | 2019-05-03 | 广东朗研科技有限公司 | A kind of preparation method of CaCu 3 Ti 4 O |
| CN114835978A (en) * | 2022-06-10 | 2022-08-02 | 浙江冠明电力新材股份有限公司 | Composite material of special insulated cable |
-
2022
- 2022-06-10 CN CN202210652224.5A patent/CN114956165A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100317502A1 (en) * | 2009-06-12 | 2010-12-16 | Snu R&Db Foundation | Sintered material for dielectric substance and process for preparing the same |
| CN101891460A (en) * | 2010-07-08 | 2010-11-24 | 桂林理工大学 | Method for preparing calcium copper titanium oxide powder by sol-gel method |
| CN102173780A (en) * | 2011-01-11 | 2011-09-07 | 桂林理工大学 | Preparation method of rare earth modified pressure-sensitive material |
| CN105073683A (en) * | 2012-12-07 | 2015-11-18 | 法商圣高拜欧洲实验及研究中心 | Product comprising an oriented function and process for obtaining same |
| US20150329431A1 (en) * | 2012-12-07 | 2015-11-19 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Product comprising an oriented function and process for obtaining same |
| CN104860673A (en) * | 2015-05-12 | 2015-08-26 | 太原理工大学 | Method for manufacturing low dielectric loss CaCu3Ti4O12 ceramic |
| CN109704396A (en) * | 2019-01-28 | 2019-05-03 | 广东朗研科技有限公司 | A kind of preparation method of CaCu 3 Ti 4 O |
| CN114835978A (en) * | 2022-06-10 | 2022-08-02 | 浙江冠明电力新材股份有限公司 | Composite material of special insulated cable |
Non-Patent Citations (2)
| Title |
|---|
| LULU REN ET AL.: ""Effect of CeO2 and ZrO2 doping on the dielectric characteristics of CCTO ceramics"", 《2017 ELECTRICAL INSULATION CONFERENCE》, pages 148 * |
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