A high-breaking fuse ceramic composite material and preparation method thereof

Abstract

The present invention relates to the field of fuses, and in particular to a high-breaking fuse ceramic composite material and a preparation method thereof, which comprises the following components by weight: 100-120 parts of aluminum oxide, 1-3 parts of magnesium oxide, 5-10 parts of silicon dioxide, 1-5 parts of zirconium oxide, ABO 3 5-10 parts of coated carbon nanotubes and 1-2 parts of sintering aid; wherein A is a rare earth element; B is a metal element. The ceramic composite material prepared by the present invention has good mechanical properties and excellent thermal shock resistance, which can meet the use requirements of high-breaking fuses.

Description

Technical Field

[0001] The invention relates to the field of fuses, in particular to a high-breaking fuse ceramic composite material and a preparation method thereof. Background Art

[0002] With the emergence of high-density, high-speed and high-reliability main structure microelectronic products, as a protective element for electronic equipment, traditional fuses have been unable to meet market demand due to their own defects such as large size, easy to break, and inability to achieve automated installation. This has prompted circuit protection components to develop in the direction of chip miniaturization, high safety reliability, and high precision, so the emergence of ceramic fuses has become an inevitable trend.

[0003] Alumina ceramics have extremely high hardness and rigidity, can provide good insulation properties, and have a dense structure, which is not easily corroded by corrosive media such as acids and alkalis. They are often used to produce ceramic fuses. However, they have low toughness, poor thermal shock resistance, and cannot withstand rapid temperature changes, which limits their application in fuses. Summary of the invention

[0004] Purpose of the invention: In view of the above technical problems, the present invention proposes a high-breakage fuse ceramic composite material and a preparation method thereof.

[0005] The technical solutions adopted are as follows:

[0006] A high-breaking fuse ceramic composite material, characterized in that it comprises the following components in parts by weight:

[0007] 100-120 parts of aluminum oxide, 1-3 parts of magnesium oxide, 5-10 parts of silicon dioxide, 1-5 parts of zirconium oxide, 5-10 parts of ABO3-coated carbon nanotubes, and 1-2 parts of sintering aid;

[0008] Wherein, A is a rare earth element;

[0009] B is a metal element.

[0010] Furthermore, A is any one or more of La, Ce, Yb, and Sm.

[0011] Furthermore, B is any one or more of Ti, Fe, Zr and Al.

[0012] Furthermore, the preparation method of the ABO3 coated carbon nanotubes is as follows:

[0013] The surfactant is dissolved in water to prepare a solution, and then the carbon nanotubes are added, and ultrasonic vibration is performed to obtain a suspension. Then, water-soluble A salt, water-soluble B salt and a precipitant are added to the suspension. After reacting for 1-10 hours, the precipitate is collected by centrifugation, washed and dried, and the temperature is raised to 800-1000°C and calcined for 1-5 hours.

[0014] Furthermore, the surfactant is any one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium octyl sulfonate, and potassium octyl sulfonate.

[0015] Furthermore, the precipitant is any one or more of ammonia water, sodium hydroxide, and potassium hydroxide.

[0016] Furthermore, the sintering aid includes magnesium fluoride, copper oxide and titanium dioxide.

[0017] Furthermore, the weight ratio of magnesium fluoride, copper oxide and titanium dioxide is 1-5:1-5:1-5.

[0018] The present invention also provides a method for preparing a high-breaking fuse ceramic composite material:

[0019] Alumina, magnesium oxide, silicon dioxide, zirconium oxide, ABO3 coated carbon nanotubes and sintering aids are mixed and ball-milled, then dried, a binder is added to granulate and then pressed into shape, the obtained green body is heated to 1450-1550°C, sintered for 2-4 hours and then cooled to room temperature in the furnace.

[0020] Furthermore, it is characterized in that the heating rate is 1-20°C / min.

[0021] Beneficial effects of the present invention:

[0022] The present invention provides a high-breaking fuse ceramic composite material, which uses alumina as a matrix. Alumina, magnesium oxide and silicon dioxide can generate cordierite with a low thermal expansion coefficient when sintered at high temperature, thereby reducing the thermal expansion coefficient of the ceramic composite material as a whole. The smaller the thermal expansion coefficient, the smaller the volume change caused by temperature change, the smaller the corresponding temperature stress, and the better the thermal shock resistance.

[0023] The introduction of ABO3 can promote the transformation of quartz, spinel and mullite with high thermal expansion coefficients remaining during sintering to cordierite, further improving the thermal shock resistance. The reason may be that ABO3 increases the diffusion coefficients of Si, Al and Mg ions, making it easier for them to transform to cordierite. It may also be that the solid solution of rare earth element A is conducive to the dissolution of quartz, spinel and mullite lattices at high temperatures and their transformation to cordierite.

[0024] The pull-out, bridging and crack deflection of carbon nanotubes hinder the expansion of cracks in the ceramic matrix and improve the fracture toughness of ceramic composites. At the same time, the addition of carbon nanotubes has played a role in hindering grain growth to a certain extent, which also plays a certain role in improving the mechanical properties of ceramic composites. At the same time, the high thermal conductivity of carbon nanotubes and the combined effect of bridging, pull-out and other toughening mechanisms generated by the addition dissipate the expansion energy of thermal shock cracks, greatly enhance the crack expansion resistance, effectively prevent the expansion and merging of thermal shock cracks, and make the ceramic composites show good thermal shock resistance.

[0025] However, due to the fact that carbon nanotubes are very easy to agglomerate, the inventors used ABO3 to coat them, which improved the dispersion of carbon nanotubes during mixing and gave full play to their strengthening and thermal shock resistance effects.

[0026] The sintering aid composed of magnesium fluoride, copper oxide and titanium dioxide can reduce the sintering activation energy of alumina ceramics, lower the sintering temperature, and form a molten phase to fill the pores between grains, promote the sintering densification of ceramics, and thus improve the mechanical strength of ceramic composite materials;

[0027] The ceramic composite material prepared by the present invention has good mechanical properties and excellent thermal shock resistance and can meet the use requirements of high-breaking fuses. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is a SEM image of crack growth of the ceramic composite material prepared in Example 1;

[0029] Figure 2 The SEM image of crack growth of the ceramic composite material prepared in Comparative Example 1;

[0030] It can be seen that the LaAlO3-coated carbon nanotubes bridge the two ends of the crack, preventing the crack from extending and improving the fracture toughness. DETAILED DESCRIPTION

[0031] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or the conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments is not specified, they are all conventional products that can be purchased commercially. The techniques not mentioned in the present invention are all referenced to the prior art. Unless otherwise specified, the following examples and comparative examples are parallel experiments, using the same processing steps and parameters.

[0032] Embodiment 1:

[0033] A high-breaking fuse ceramic composite material, comprising the following components in parts by weight:

[0034] 115 parts of aluminum oxide, 2 parts of magnesium oxide, 6 parts of silicon dioxide, 3 parts of zirconium oxide, 8 parts of LaAlO3-coated carbon nanotubes, 1 part of magnesium fluoride, 0.5 parts of copper oxide, and 0.5 parts of titanium dioxide;

[0035] The preparation method of LaAlO3 coated carbon nanotubes is as follows:

[0036] Dissolve 0.5 g of sodium dodecyl sulfate in 100 ml of water to prepare a solution, then add 1 g of carbon nanotubes, and ultrasonically oscillate for 30 minutes to obtain a suspension. Add 4.26 g of aluminum nitrate and 6.5 g of lanthanum nitrate to the suspension, stir for 10 minutes, and then slowly add ammonia water until the pH of the solution reaches 9. After stirring at room temperature for 2 hours, collect the precipitate by centrifugation, wash with water and dry, and then heat to 900°C and calcine for 3 hours.

[0037] Preparation method of the above-mentioned high breaking fuse ceramic composite material:

[0038] Alumina, magnesium oxide, silicon dioxide, zirconium oxide, LaAlO3-coated carbon nanotubes, magnesium fluoride, copper oxide and titanium dioxide are mixed and added into a planetary ball mill. The mixture is milled with ethanol as the milling medium for 5 hours and then dried. 10% polyvinyl alcohol is added as a binder for granulation. The mixture is pressed under a pressure of 100 MPa. The obtained green body is transferred to a tubular furnace, heated to 1550°C at a rate of 10°C / min, sintered for 2 hours, and then cooled to room temperature with the furnace.

[0039] Embodiment 2:

[0040] A high-breaking fuse ceramic composite material, comprising the following components in parts by weight:

[0041] 120 parts of aluminum oxide, 3 parts of magnesium oxide, 10 parts of silicon dioxide, 5 parts of zirconium oxide, 10 parts of LaAlO3-coated carbon nanotubes, 1 part of magnesium fluoride, 0.5 parts of copper oxide, and 0.5 parts of titanium dioxide;

[0042] Wherein, the preparation method of LaAlO3 coated carbon nanotubes is the same as that of Example 1;

[0043] Preparation method of the above-mentioned high breaking fuse ceramic composite material:

[0044] Alumina, magnesium oxide, silicon dioxide, zirconium oxide, LaAlO3-coated carbon nanotubes, magnesium fluoride, copper oxide and titanium dioxide are mixed and added into a planetary ball mill. The mixture is milled with ethanol as the milling medium for 5 hours and then dried. 10% polyvinyl alcohol is added as a binder for granulation. The mixture is pressed under a pressure of 100 MPa. The obtained green body is transferred to a tubular furnace, heated to 1550°C at a rate of 10°C / min, sintered for 2 hours, and then cooled to room temperature with the furnace.

[0045] Embodiment 3:

[0046] A high-breaking fuse ceramic composite material, comprising the following components in parts by weight:

[0047] 100 parts of aluminum oxide, 1.5 parts of magnesium oxide, 5 parts of silicon dioxide, 1 part of zirconium oxide, 5 parts of LaAlO3-coated carbon nanotubes, 1 part of magnesium fluoride, 0.5 parts of copper oxide, and 0.5 parts of titanium dioxide;

[0048] Wherein, the preparation method of LaAlO3 coated carbon nanotubes is the same as that of Example 1;

[0049] Preparation method of the above-mentioned high breaking fuse ceramic composite material:

[0050] Alumina, magnesium oxide, silicon dioxide, zirconium oxide, LaAlO3-coated carbon nanotubes, magnesium fluoride, copper oxide and titanium dioxide are mixed and added into a planetary ball mill. The mixture is milled with ethanol as the milling medium for 5 hours and then dried. 10% polyvinyl alcohol is added as a binder for granulation. The mixture is pressed under a pressure of 100 MPa. The obtained green body is transferred to a tubular furnace, heated to 1550°C at a rate of 10°C / min, sintered for 2 hours, and then cooled to room temperature with the furnace.

[0051] Comparative Example 1:

[0052] It is basically the same as Example 1, except that LaAlO3-coated carbon nanotubes are not added.

[0053] Comparative Example 2:

[0054] It is basically the same as Example 1, except that LaAlO3 and carbon nanotubes are used instead of LaAlO3 to coat the carbon nanotubes, that is, LaAlO3 and carbon nanotubes are added separately.

[0055] Comparative Example 3:

[0056] The method is basically the same as Example 1, except that carbon nanotubes are used instead of LaAlO3 to coat the carbon nanotubes.

[0057] Comparative Example 4:

[0058] It is basically the same as Example 1, except that only LaAlO3 is added.

[0059] Comparative Example 5:

[0060] The method is basically the same as Example 1, except that magnesium fluoride is not added.

[0061] Comparative Example 6:

[0062] The method is substantially the same as Example 1, except that copper oxide is not added.

[0063] Comparative Example 7:

[0064] The method is basically the same as Example 1, except that titanium dioxide is not added.

[0065] Performance Testing:

[0066] The ceramic composite materials prepared in Examples 1-3 of the present invention and Comparative Examples 1-7 were used as samples for performance testing;

[0067] ① The three-point bending method was used to test the bending strength of the sample, and the sample size was 3mm×4mm×36mm;

[0068] ② According to GB / T 23806-2009 "Fracture toughness test method for fine ceramics - single edge pre-cracked beam (SEPB) method", test the fracture toughness value of the sample;

[0069] ③ Heat the resistance furnace from room temperature to 800℃, then put the sample in and keep it warm for 20 minutes. After the sample is evenly heated, take it out and place it in 20℃ water for rapid cooling. Then carefully observe whether cracks appear on the surface of the sample. If cracks appear, terminate the experiment. If no cracks appear, repeat the above operation and record the number of thermal shock cycles that each sample can withstand. The more thermal shock cycles, the better the thermal shock resistance.

[0070] The test results are shown in Table 1 below:

[0071] Table 1:

[0072]

[0073] It can be seen from Table 1 above that the ceramic composite material prepared by the present invention has good mechanical properties and excellent thermal shock resistance and can meet the use requirements of high-breaking fuses.

[0074] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A high breaking fuse ceramic composite material, characterized in that: The composition is calculated by weight: 100-120 parts of aluminum oxide, 1-3 parts of magnesium oxide, 5-10 parts of silicon dioxide, 1-5 parts of zirconium oxide, 5-10 parts of LaAlO3 coated carbon nanotubes, and 1-2 parts of sintering aid; The preparation method of the LaAlO3 coated carbon nanotubes is as follows: The surfactant is dissolved in water to prepare a solution, and then the carbon nanotubes are added, and ultrasonic vibration is performed to obtain a suspension, and then water-soluble La salt, water-soluble Al salt and a precipitant are added to the suspension, and after reacting for 1-10 hours, the precipitate is collected by centrifugation, washed and dried, and the temperature is raised to 800-1000°C and calcined for 1-5 hours; The sintering aid comprises magnesium fluoride, copper oxide and titanium dioxide; The weight ratio of magnesium fluoride, copper oxide and titanium dioxide is 1-5:1-5:1-5; The preparation method of the above-mentioned high breaking fuse ceramic composite material is as follows: Alumina, magnesia, silica, zirconia, LaAlO3 coated carbon nanotubes and sintering aids are mixed and ball-milled and then dried. A binder is added to granulate and then pressed into shape. The resulting green body is heated to 1450-1550°C, sintered for 2-4 hours, and then cooled to room temperature in the furnace.

2. The high breaking fuse ceramic composite material according to claim 1, characterized in that: The surfactant is any one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium octyl sulfonate, and potassium octyl sulfonate.

3. The high breaking fuse ceramic composite material according to claim 1, characterized in that: The precipitant is any one or more of ammonia water, sodium hydroxide and potassium hydroxide.

4. The high breaking power fuse ceramic composite material according to claim 1, characterized in that: The heating rate is 1-20℃ / min.

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