Glass packaging material for high-temperature-resistant armored cable and preparation method of glass packaging material

Abstract

The invention discloses a glass packaging material for a high-temperature-resistant armored cable, which is prepared from the following components in parts by mole: 15 to 25 parts of BaO, 10 to 20 parts of ZnO, 35 to 15 parts of Al2O3, 10 to 20 parts of La2O3, 3 to 10 parts of B2O3, 0.5 to 4 parts of MgF2 / CaF2 and 0.05 to 0.70 part of Pr6O11 / SrO, the molar ratio of MgF2 to CaF2 is 2: 1, and the molar ratio of Pr6O11 / SrO is 1: 1. According to the glass packaging material for the high-temperature-resistant armored cable and the preparation method of the glass packaging material, the technical problem that the high-temperature-resistant performance of a high-temperature cable end packaging material used in the current aero-engine and nuclear power fields cannot meet working condition requirements is solved; after the material provided by the invention is packaged with a high-temperature armored cable, the armored cable can normally work under harsh working conditions such as high temperature, vibration, damp heat and the like, the interference on signal transmission of the cable is very small, and the packaging glass material has a wide application prospect in the field of the armored cable.

Description

Technical Field

[0001] The invention relates to the technical field of electronic materials, and in particular to a glass packaging material for high-temperature resistant armored cables and a preparation method thereof. Background Art

[0002] Cables are transmission lines for electrical signals and are indispensable transmission media for short-distance communications in various electronic systems. As the "nerves and blood vessels" of electronic devices, they play an irreplaceable role in the transmission of information and are widely used in various fields of electronic technology such as electrical equipment or electronic instruments.

[0003] Aerospace cables include various cables used in aircraft, micro-machines, rockets and other aircraft. These products operate at high altitudes and require small outer diameter, light weight, high temperature resistance, vibration resistance, impact resistance, easy installation, and a comprehensive balance of electrical, thermal and mechanical properties. The aerospace industry has always required a cable that can guarantee high reliability, flexibility and low toxicity in harsh environments with high temperature and high vibration.

[0004] With the development of aerospace technology and nuclear power technology, especially in high temperature environment, high temperature resistant materials and cables are required to have higher performance, higher working temperature and mechanical physical properties and meet higher transmission performance requirements. At present, most of the high temperature resistant cables for aerospace and nuclear reactors under harsh conditions cannot meet the requirements of use under working conditions. The main reason for the performance degradation of armored cables under high temperature is the rapid degradation of the insulation performance of the end packaging material under high temperature.

[0005] Therefore, how to improve the high temperature resistance of high temperature cable end packaging materials has become an urgent problem to be solved. Summary of the invention

[0006] In view of this, the present invention discloses a glass packaging material for a high-temperature resistant armored cable and a preparation method thereof, which can achieve good packaging with the high-temperature armored cable.

[0007] The present invention provides a glass packaging material for high temperature resistant armored cables, which comprises, by mole, 15-25 parts of BaO, 10-20 parts of ZnO, 5-15 parts of Al2O3, 10-20 parts of La2O3, 3-10 parts of B2O3, 0.5-4 parts of MgF2 / CaF2, and 10-20 parts of Pr6O3. 11 / SrO 0.05-0.70 parts, wherein the molar ratio of MgF2 to CaF2 in MgF2 / CaF2 is 2:1, Pr6O 11 Pr6O in SrO 11 The molar ratio of SrO is 1:1.

[0008] Preferably, the composition comprises, by mole, 15-25 parts of BaO, 10-20 parts of ZnO, 5-15 parts of Al2O3, 10-20 parts of La2O3, 3-10 parts of B2O3, 0.5-4 parts of MgF2 / CaF2, and 10-20 parts of Pr6O3. 11 / SrO0.05-0.70 parts, CuO0-1.5 parts, BeO 0-1.5 parts, V2O5 0-1 parts, Y2O3 0-2 parts, Yb2O3 0-1.5 parts, CeO2 0-2 parts, Gd2O3 0-2 parts, Nb2O5 0-2 parts, wherein the molar ratio of MgF2 to CaF2 in MgF2 / CaF2 is 2:1, Pr6O 11 Pr6O in SrO 11 The molar ratio of SrO is 1:1.

[0009] Another aspect of the present invention further provides a method for preparing the glass packaging material for the high temperature resistant armored cable, comprising:

[0010] Step 1: After the raw materials are uniformly mixed according to the molar percentage composition, they are placed in a platinum crucible to melt the glass raw materials;

[0011] Step 2: Pour out the molten glass liquid, and sequentially perform water quenching, drying, ball milling, and sieving to obtain alkali-free and low-boron Ba-La-Al-Zn-B system glass powder;

[0012] Step 3: Microcrystallize the alkali-free and low-boron Ba-La-Al-Zn-B system glass powder, cool the sample along with the furnace, and obtain the alkali-free and low-boron Ba-La-Al-Zn-B system microcrystalline glass material.

[0013] Preferably, the conditions for melting the glass raw materials in step 1 are: heating to 280-390°C at a heating rate of 2°C / min and keeping warm for 0.5-2.5 hours; continuing to heat to 1400-1650°C at a heating rate of 2-5°C / min and keeping warm for 1-2 hours.

[0014] Preferably, the conditions for microcrystallization treatment of the alkali-free low-boron Ba-La-Al-Zn-B system glass powder in step 3 are: heating the glass powder to 320-480°C at a rate of 5-10°C / min and keeping it warm for 2-2.5 hours.

[0015] In addition, the present invention also provides the material as a packaging material for high-temperature resistant armored cables, which is used for packaging high-temperature armored cables.

[0016] The glass packaging material for high-temperature resistant armored cables provided by the present invention and the preparation method thereof solve the technical problem that the high-temperature resistance performance of the high-temperature cable end packaging material currently used in the fields of aviation engines and nuclear power cannot meet the working condition requirements; after the material provided by the present invention is packaged with the high-temperature armored cable, the armored cable can work normally under harsh working conditions such as high temperature, vibration, humidity and heat, and at the same time, within the allowable temperature range, it can maintain high air tightness, the dielectric constant of the microcrystalline glass material at the sealing part is extremely low within the entire temperature range, and the interference with the signal transmission of the cable is very small, and the packaging glass material has a high and broad application prospect in the field of armored cables.

[0017] It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the present disclosure. DETAILED DESCRIPTION

[0018] The present invention is further explained below in conjunction with specific implementation schemes, but it is not intended to limit the protection scope of the present invention.

[0019] In order to solve the problem that the high temperature tolerance of armored cables cannot meet the application requirements under harsh working conditions, the present invention provides a packaging glass material that can achieve good wetting and packaging with high temperature armored cables under high temperature environment conditions;

[0020] Specifically, the glass packaging material for high temperature resistant armored cable provided by the present invention comprises, by mole percentage, 15-25 parts of BaO, 10-20 parts of ZnO, 5-15 parts of Al2O3, 10-20 parts of La2O3, 3-10 parts of B2O3, 0.5-4 parts of MgF2 / CaF2, and 10-20 parts of Pr6O3. 11 / SrO 0.05-0.70 parts, wherein the molar ratio of MgF2 to CaF2 in MgF2 / CaF2 is 2:1, Pr6O 11 Pr6O in SrO 11 The molar ratio of SrO is 1:1.

[0021] Preferably, it may also include: BaO 15-25 parts, ZnO 10-20 parts, Al2O3 5-15 parts, La2O3 10-20 parts, B2O3 3-10 parts, MgF2 / CaF2 0.5-4 parts, Pr6O 11 / SrO0.05-0.70 parts, CuO 0-1.5 parts, BeO0-1.5 parts, V2O5 0-1 parts, Y2O3 0-2 parts, Yb2O3 0-1.5 parts, CeO2 0-2 parts, Gd2O3 0-2 parts, Nb2O5 0-2 parts, wherein the molar ratio of MgF2 to CaF2 in MgF2 / CaF2 is 2:1, Pr6O 11 Pr6O in SrO 11The molar ratio of SrO is 1:1.

[0022] In the present invention, B2O3 is a glass network former, ZnO is a glass network regulating oxide, Al2O3 is an intermediate oxide, and MgF2 / CaF2 is a mixed nucleating agent, which is a necessary oxide in order to enable the solid solution to be smoothly precipitated from the glass in a microcrystalline state during the heat treatment process. High-valent oxides such as La2O3 and Nb2O5 mainly play a role in accumulation and can effectively improve the high temperature resistance in subsequent glass material applications. V2O5, CuO and CeO2, Gd2O3, Y2O3, Yb2O3, Pr6O 11 / SrO rare earth and alkaline earth are synergistically introduced as regulators of glass properties. Their synergistic addition to glass components can significantly improve the high temperature resistance and electrical properties of the glass.

[0023] The present invention adopts double fluoride as a crystal nucleating agent and adopts a method of synergistically introducing rare earth oxides and alkaline earth oxides to prepare an alkali-free low-boron Ba-La-Al-Zn-B system microcrystalline glass material. As a packaging material for high-temperature resistant armored cables, after being packaged with the high-temperature armored cable, the armored cable can work normally under harsh working conditions such as high temperature, vibration, humidity and heat, and at the same time, it can maintain a high air tightness within the allowable temperature range.

[0024] In addition, this embodiment also provides a method for preparing a glass packaging material for a high temperature resistant armored cable, comprising:

[0025] The above components are prepared by high temperature melting-annealing method, and alkali-free low-boron Ba-La-Al-Zn-B system glass powder is obtained through the steps of mixing, heat preservation, heating, melting, water quenching, ball milling, drying and annealing. Then, the above glass powder is heated and heat-insulated, and the glass powder is microcrystallized to obtain alkali-free low-boron Ba-La-Al-Zn-B system micro-ceramic glass powder.

[0026] Specifically, they include:

[0027] Step 1: After the raw materials are uniformly mixed according to the molar percentage composition, they are placed in a platinum crucible to melt the glass raw materials;

[0028] Step 2: Pour out the molten glass liquid, and sequentially perform water quenching, drying, ball milling, and sieving to obtain alkali-free and low-boron Ba-La-Al-Zn-B system glass powder;

[0029] Step 3: Microcrystallize the alkali-free and low-boron Ba-La-Al-Zn-B system glass powder, cool the sample along with the furnace, and obtain the alkali-free and low-boron Ba-La-Al-Zn-B system microcrystalline glass material.

[0030] Preferably, the conditions for melting the glass raw materials in step 1 are: heating to 280-390°C at a heating rate of 2°C / min and keeping warm for 0.5-2.5 hours; continuing to heat to 1400-1650°C at a heating rate of 2-5°C / min and keeping warm for 1-2 hours.

[0031] Preferably, the conditions for microcrystallization treatment of the alkali-free low-boron Ba-La-Al-Zn-B system glass powder in step 3 are: heating the glass powder to 320-480°C at a rate of 5-10°C / min and keeping it warm for 2-2.5 hours.

[0032] Finally, the present invention also provides an application of a glass packaging material for a high temperature resistant armored cable, wherein the glass powder and the high temperature armored cable are filled into a jacket with excellent mechanical and physical properties by a filling method for packaging.

[0033] After the glass packaging material for high-temperature resistant armored cables provided by the present invention is packaged with the high-temperature armored cable, the armored cable can work normally under harsh working conditions such as high temperature, vibration, humidity and heat, and can maintain high air tightness within the allowable temperature range. At the same time, the dielectric constant of the microcrystalline glass material at the sealing point is extremely low within the entire temperature range, and the interference with the signal transmission of the cable is very small. The packaging glass material has a broad application prospect in the field of armored cables.

[0034] The present invention is further explained below in conjunction with specific embodiments, but is not intended to limit the protection scope of the present invention.

[0035] Embodiment 1:

[0036] Glass packaging material for high temperature resistant armored cable: alkali-free low-boron Ba-La-Al-Zn-B system microcrystalline glass powder material, based on molar composition, including: BaO 25 parts, ZnO 15 parts, Al2O3 15 parts, La2O3 10 parts, B2O3 10 parts, MgF2 / CaF2 2 parts, Pr6O 11 / SrO 0.5 parts, Gd2O3 0.05 parts.

[0037] The method for preparing the above-mentioned alkali-free low-boron Ba-La-Al-Zn-B system microcrystalline glass powder material comprises the following steps:

[0038] The above components are weighed and mixed evenly according to the molar composition ratio, and agate balls are used as grinding media during the grinding process.

[0039] Put the mixed raw materials into a platinum crucible, heat them up to 360℃ at a rate of 2℃ / min and keep them warm for 1.5 hours; continue to heat them up to 1550℃ at a rate of 2-5℃ / min, cover the crucible to prevent the volatilization of boric acid, keep them warm for 1.5 hours, and melt the glass raw materials. Pour out the molten glass liquid, quench it with water, dry it, ball mill it, and sieve it through 80 mesh to obtain alkali-free and low-boron Ba-La-Al-Zn-B system glass powder. Heat the above glass powder to 360℃ at a rate of 5℃ / min and keep it warm for 2 hours, perform microcrystallization on the glass powder, and cool the sample with the furnace to obtain alkali-free and low-boron Ba-La-Al-Zn-B system microcrystalline glass material.

[0040] The prepared alkali-free low-boron Ba-La-Al-Zn-B system microcrystalline glass powder was sprayed with 0.1% PVA binder, passed through an 80-mesh sieve, aged for 12 h, and dry-pressed into round rod samples with a diameter of 5 mm and a length of 40 mm at 15 MPa. The linear expansion coefficient was tested and its linear expansion coefficient was 95×10 -7 / ℃(25~300℃); dry pressed into a glass blank with a diameter of 13mm and a thickness of 2mm by the same process, and a two-stage sintering method was adopted, first pre-sintered at 350℃ for 20min, then vitrified at 1100℃ for 30min, cooled naturally to room temperature, and polished by a polishing machine. The polished test sample was then cleaned with alcohol on the polished surface and dried to test its electrical properties. At room temperature 1KHZ, the dielectric constant was 6.9, and at 750℃, the dielectric constant was 6.5; the water resistance stability was tested to be level I; the acid resistance chemical stability was H1; after being packaged with a high-temperature armored cable at 1100℃, it was tested to withstand a pressure of 38Mpa, 2000V, 15min under AC, without breakdown; at room temperature, the vacuum leakage rate was 1.1×10 - 9 Pa﹒ 3 / sec; at room temperature, the insulation resistance between the outer shell and the core of the armored cable is ≥10 3 MΩ, the insulation resistance between the cores of the cable is ≥50MΩ; at 750℃, the insulation resistance between the cable sheath and the core is ≥5MΩ; the insulation resistance between the cores of the cable is ≥5MΩ.

[0041] Example 2

[0042] Glass packaging material for high temperature resistant armored cable: alkali-free low-boron Ba-La-Al-Zn-B system microcrystalline glass powder material, based on molar composition, including: BaO22 parts, ZnO 13 parts, Al2O3 15 parts, La2O3 17 parts, B2O3 8 parts, MgF2 / CaF2 4 parts, Pr6O 11 / SrO 0.7 parts, BeO 0.1 parts, V2O5 0.05 parts.

[0043] The method for preparing the above-mentioned alkali-free low-boron Ba-La-Al-Zn-B system microcrystalline glass powder material comprises the following steps:

[0044] The above components are weighed and mixed evenly according to the molar composition ratio, and agate balls are used as grinding media during the grinding process.

[0045] Put the mixed raw materials into a platinum crucible, heat them up to 380℃ at a rate of 2℃ / min and keep them warm for 1.5 hours; continue to heat them up to 1650℃ at a rate of 3℃ / min, cover the crucible to prevent the volatilization of boric acid, keep them warm for 2.0 hours, and melt the glass raw materials. Pour out the molten glass liquid, quench it with water, dry it, ball mill it, and sieve it through 80 mesh to obtain alkali-free and low-boron Ba-La-Al-Zn-B system glass powder. Heat the above glass powder to 420℃ at a rate of 5℃ / min and keep it warm for 2 hours, perform microcrystallization on the glass powder, and cool the sample with the furnace to obtain alkali-free and low-boron Ba-La-Al-Zn-B system microcrystalline glass material.

[0046] The prepared alkali-free low-boron Ba-La-Al-Zn-B system microcrystalline glass powder was sprayed with 0.1% PVA binder, passed through an 80-mesh sieve, aged for 12 h, and dry-pressed into round rod samples with a diameter of 5 mm and a length of 40 mm at 15 MPa. The linear expansion coefficient was tested and its linear expansion coefficient was 95×10 -7 / ℃(25~300℃); dry pressed into a glass blank with a diameter of 13mm and a thickness of 2mm by the same process, and a two-stage sintering method was adopted, first pre-sintered at 350℃ for 20min, then vitrified at 1100℃ for 30min, cooled naturally to room temperature, and polished by a polishing machine. The polished test sample was then cleaned with alcohol on the polished surface and dried to test its electrical properties. At room temperature 1KHZ, the dielectric constant was 7.6, and at 750℃, the dielectric constant was 7.2; the water resistance stability was tested to be level I; the acid resistance chemical stability was H1; after being packaged with a high-temperature armored cable at 1100℃, it was tested to withstand a pressure of 40Mpa, AC, 2000V, 15min, without breakdown; at room temperature, the vacuum leakage rate was 0.9×10 - 9 Pa﹒ 3 / sec; at room temperature, the insulation resistance between the outer shell and the core of the armored cable is 2×10 3 The insulation resistance between the core and the core of the cable is 55MΩ; at 750℃, the insulation resistance between the cable sheath and the core is 6MΩ; the insulation resistance between the core and the core of the cable is 5.5MΩ.

[0047] Those skilled in the art will readily appreciate other embodiments of the present invention after considering the specification and practicing the invention disclosed herein. This application is intended to cover any variations, uses or adaptations of the present invention that follow the general principles of the present invention and include common knowledge or customary techniques in the art that are not disclosed by the present invention. The specification and examples are to be considered exemplary only, and the true scope and spirit of the present invention are indicated by the following claims.

[0048] It should be understood that the present invention is not limited to what has been described above and that various modifications and changes may be made without departing from its scope. The scope of the present invention is limited only by the appended claims.

Claims

1. Glass packaging material for high temperature resistant armored cable, characterized in that: In terms of molar composition, it includes: BaO 15-25 parts, ZnO 10-20 parts, Al2O3 5-15 parts, La2O3 10-20 parts, B2O3 3-10 parts, MgF2 / CaF2 0.5-4 parts, Pr6O 11 / SrO 0.05-0.70 parts, wherein the molar ratio of MgF2 to CaF2 in MgF2 / CaF2 is 2:1, Pr6O 11 Pr6O in SrO 11 The molar ratio of SrO is 1:

1.

2. The glass packaging material for high temperature resistant armored cable according to claim 1, characterized in that: The composition includes, by mole, 15-25 parts of BaO, 10-20 parts of ZnO, 5-15 parts of Al2O3, 10-20 parts of La2O3, 3-10 parts of B2O3, 0.5-4 parts of MgF2 / CaF2, and 10-20 parts of Pr6O3. 11 / SrO0.05-0.70 parts, CuO 0-1.5 parts, BeO 0-1.5 parts, V2O5 0-1 parts, Y2O3 0-2 parts, Yb2O3 0-1.5 parts, CeO2 0-2 parts, Gd2O3 0-2 parts, Nb2O5 0-2 parts, wherein the molar ratio of MgF2 to CaF2 in MgF2 / CaF2 is 2:1, Pr6O 11 Pr6O in SrO 11 The molar ratio of SrO is 1:

1.

3. The method for preparing the glass packaging material for high temperature resistant armored cable according to any one of claims 1-2, characterized in that: include: Step 1: After the raw materials are uniformly mixed according to the molar percentage composition, they are placed in a platinum crucible to melt the glass raw materials; Step 2: Pour out the molten glass liquid, and sequentially perform water quenching, drying, ball milling, and sieving to obtain alkali-free and low-boron Ba-La-Al-Zn-B system glass powder; Step 3: Microcrystallize the alkali-free and low-boron Ba-La-Al-Zn-B system glass powder, cool the sample along with the furnace, and obtain the alkali-free and low-boron Ba-La-Al-Zn-B system microcrystalline glass material.

4. The method for preparing the glass packaging material for high temperature resistant armored cable according to claim 3, characterized in that: The conditions for melting the glass raw materials in step 1 are: heating to 280-390° C. at a heating rate of 2° C. / min and keeping warm for 0.5-2.5 hours; heating to 1400-1650° C. at a heating rate of 2-5° C. / min and keeping warm for 1-2 hours.

5. The method for preparing the glass packaging material for high temperature resistant armored cable according to claim 3, characterized in that: The conditions for microcrystallization treatment of the alkali-free low-boron Ba-La-Al-Zn-B system glass powder in step 3 are: heating the glass powder to 320-480°C at a rate of 5-10°C / min and keeping it warm for 2-2.5 hours.

6. Application of the glass packaging material for high temperature resistant armored cables according to any one of claims 1-2, characterized in that: The material is used as a packaging material for high temperature resistant armored cables and is used for packaging with high temperature armored cables.