CN116639973A - High-toughness ceramic dielectric material and preparation method thereof - Google Patents
High-toughness ceramic dielectric material and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 44
- 239000003989 dielectric material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000000843 powder Substances 0.000 claims abstract description 34
- 239000011521 glass Substances 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 14
- 229910016569 AlF 3 Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000004108 freeze drying Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 29
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 26
- 235000010413 sodium alginate Nutrition 0.000 claims description 26
- 229940005550 sodium alginate Drugs 0.000 claims description 26
- 239000000661 sodium alginate Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 14
- 239000004615 ingredient Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000007710 freezing Methods 0.000 claims description 12
- 230000008014 freezing Effects 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000005245 sintering Methods 0.000 abstract description 7
- 238000005303 weighing Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 229910010293 ceramic material Inorganic materials 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 238000000859 sublimation Methods 0.000 description 4
- 230000008022 sublimation Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 2
- 238000010344 co-firing Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/475—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on bismuth titanates
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3258—Tungsten oxides, tungstates, or oxide-forming salts thereof
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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Abstract
The invention discloses a high-toughness ceramic dielectric material which comprises the following raw materials in percentage by mass: 10-30% of glass powder and Bi 4 Ti 2.92 W 0.07 Ta 0.01 O 12 70-90%. The glass powder comprises the following raw materials in percentage by mass: mgO 5-40%, siO 2 5‑30％、CeO 2 5‑30％、Al 2 O 3 5-30% and AlF 3 5-30%. The invention adopts the method of adding glass powder and freeze drying, not only reduces the sintering temperature, but also forms a porous lamellar structure, and the ceramic dielectric material has high toughness, high dielectric constant, low dielectric loss and high temperature stability.
Description
Technical Field
The invention relates to a high-toughness ceramic dielectric material and a preparation method thereof, belonging to the technical field of ceramic dielectric materials.
Background
The low-temperature co-fired ceramic technology is first introduced by the United states in the middle of the 80 s of the last century, integrates passive devices and packaging, and is a multilayer ceramic manufacturing technology. The low temperature co-firing ceramic technology adopts thick film material technology, and the main means of the technology is to sinter and mold the electronic element once by using a pre-designed structure.
The low-temperature co-firing ceramic technology is a technology in which low-temperature sintering ceramic powder is manufactured into a green ceramic tape with accurate and compact thickness, a required circuit pattern is manufactured on the green ceramic tape by utilizing processes such as laser drilling, micropore grouting, precise conductor paste printing and the like, a plurality of passive elements (such as a transformer (T), a resistor (R), an inductor (L) and a capacitor (C)) are embedded in the green ceramic tape, then the ceramic tape is laminated together, and sintered at the temperature of below 900 ℃ to manufacture a passive integrated component of a three-dimensional circuit network, or a three-dimensional circuit substrate with built-in passive elements can be manufactured, and an IC (integrated circuit) and an active device can be attached to the surface of the three-dimensional circuit substrate to manufacture a passive/active integrated functional module, so that miniaturization, light weight, high performance and multifunctional design of electronic components and packaging modules are realized.
Low temperature co-productionThe technology of firing ceramic materials has become an important foundation for the technological development of high-density packaging, electronic component integration, miniaturization, light weight, high reliability and the like. At present, most of researches on low-temperature cofired ceramic materials are concentrated on ceramic materials with different dielectric constants, and more BaO-Ln is reported 2 O 3 -TiO 2 (Ln is rare earth element), baTi 4 O 9 、Al 2 O 3 Etc., and the research on the mechanical properties of ceramic materials is relatively lagging, and it is difficult to meet the development requirements of modern electronic information technology, such as whether the chemical mechanical polishing and packaging processes can withstand the process of high mechanical force.
Therefore, research and development of ceramic materials which can be co-fired with electrode materials such as silver and copper at low temperature and have excellent properties such as high toughness, high dielectric and low loss are of great significance in promoting the development of modern electronic information technology in terms of serialization of materials and reduction of the size of electronic components.
Disclosure of Invention
In order to solve the defects in the prior art, the invention discloses a high-toughness ceramic dielectric material and a preparation method thereof, wherein the ceramic dielectric material has high toughness, high dielectric constant, low dielectric loss and high temperature stability.
The invention is realized by the following technical scheme:
the high-toughness ceramic dielectric material comprises the following raw materials in percentage by mass: 10-30% of glass powder and Bi 4 Ti 2.92 W 0.07 Ta 0.01 O 12 70-90％。
The glass powder comprises the following raw materials in percentage by mass: mgO 5-40%, siO 2 5-30％、CeO 2 5-30％、Al 2 O 3 5-30% and AlF 3 5-30％。
The preparation method of the high-toughness ceramic dielectric material comprises the following steps in sequence:
1) Bi as a raw material 2 O 3 、WO 3 、Ta 2 O 5 And TiO 2 According to the general formula Bi 4 Ti 2.92 W 0.07 Ta 0.01 O 12 Is weighed into a mixture according to the stoichiometric ratio, ball-milled and then passed through 120-250 holes/cm 2 Sample separation sieve, heating to 1000-1100 ℃, and preserving heat for 2-4 hours to obtain a frit A;
2) MgO 5-40 wt% and SiO 5 wt% 2 5-30％、CeO 2 5-30％、Al 2 O 3 5-30% and AlF 3 5-30% of molten water is cooled, ground and screened to obtain glass powder B;
3) Mixing 10-30% of glass powder B and 70-90% of frit A according to the mass percentage to obtain a mixture C;
4) Preparing sodium alginate solution by 2% of sodium alginate and 98% of deionized water according to the mass percentage;
5) Adding 70-80% of sodium alginate solution and 2-5% of ammonium citrate into the ingredient C, ball-milling, vacuum defoaming and directional freeze-drying;
6) After the drying is finished, the green body is slowly heated to 830-860 ℃ in the air atmosphere, then is insulated for 1 hour, and is cooled to obtain the ceramic medium.
The ball milling time in the step 1) is 4-6 hours, and the ball milling medium is zirconia balls with the diameter of 1 mm.
The temperature rising rate in the step 1) is 7-9 ℃/min.
The freezing temperature in the step 5) is-10 ℃, 30 ℃ below zero and 50 ℃ below zero, and the directional freezing time is 5-8 hours.
The drying time in the step 5) is 20-23 hours.
The heating process in the step 6) is divided into two stages: the first stage, heating from room temperature to 400-500 ℃ at a heating rate of 2-5 ℃/min; and in the second stage, heating from 400-500 ℃ to 830-860 ℃ at a heating rate of 5-8 ℃/min.
Compared with the prior art, the invention has the following beneficial effects: bi of the invention 4 Ti 2.92 W 0.07 Ta 0.01 O 12 The series dielectric ceramic has moderate sintering temperature, generally about 1100 ℃, typical lamellar structure and high dielectric constant. In addition, the ceramic material also has adjustable capacity temperature coefficient and lower loss, and is a dielectric ceramic with good performancePorcelain material. The invention selects Bi 4 Ti 2.92 W 0.07 Ta 0.01 O 12 In the system, the glass powder is added and a freeze drying method is adopted, so that the sintering temperature is reduced, a porous lamellar structure is formed, and the fracture energy is absorbed, so that the purposes of high toughness and excellent performance are achieved.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a graph showing the results of the temperature coefficient TCC test for the ceramic dielectric materials prepared in example 1, example 2, example 3 and example 4. As can be seen from the figure: as the temperature increases, the temperature coefficient overall shows a slow rising trend, but the temperature coefficient is within +/-15%, so that higher temperature stability is achieved.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to these embodiments, and all changes and equivalents that do not depart from the spirit of the invention are intended to be included in the scope of the invention.
Example 1
The high-toughness ceramic dielectric material comprises the following raw materials in percentage by mass: 10% of glass powder and Bi 4 Ti 2.92 W 0.07 Ta 0.01 O 12 90%, wherein the glass powder comprises the following raw materials in percentage by mass: mgO 5%, siO 2 30％、CeO 2 30％、Al 2 O 3 30% and AlF 3 5％。
The preparation process is as follows:
1) Bi as a raw material 2 O 3 、WO 3 、Ta 2 O 5 And TiO 2 According to the general formula Bi 4 Ti 2.92 W 0.07 Ta 0.01 O 12 Proportioning, ball milling for 4 hours on a ball mill with the rotating speed of 400r/min, drying in a common oven with the speed of 3.3kw at the temperature of 100 ℃, and passing through 120 holes/cm 2 The sample separation sieve is heated to 1000 ℃ at the speed of 7 ℃/min, and the temperature is kept at 1000 ℃ for 2 hours, so as to obtain the frit A.
2) Weighing 5g of MgO and SiO 2 30g、CeO 2 30g、Al 2 O 3 30g and AlF 3 5g, mixing, melting, water cooling, grinding and sieving to obtain glass powder B.
3) And (3) proportioning, namely weighing the frit A and the glass powder B according to the mass ratio of 90% of the frit A to 10% of the glass powder B, and uniformly mixing to obtain a proportioning C.
4) And weighing sodium alginate and deionized water according to the mass ratio of 2% of sodium alginate to 98% of deionized water to prepare sodium alginate solution.
5) Weighing sodium alginate solution and ammonium citrate according to the mass ratio of the sodium alginate solution with the ingredient C of 70% and the ammonium citrate with the ingredient C of 2%, adding the ingredient C, ball-milling for 10 hours on a ball mill with the rotating speed of 400r/min, and placing the slurry for 30 minutes under the vacuum condition to remove bubbles in vacuum. Injecting the slurry after bubble removal into a self-made mould, and putting the mould into a dryer to control the freezing temperature to be minus 10 ℃, minus 30 ℃ and minus 50 ℃ respectively, and directionally freezing for 5 hours. The mold was removed and rapidly demolded, and placed in a freeze dryer for sublimation for 20 hours.
6) After the drying is finished, heating the green body to 400 ℃ at a heating rate of 2 ℃/min in air atmosphere, heating to 830 ℃ at a heating rate of 5 ℃/min, sintering, preserving heat for 1 hour, and cooling to obtain the ceramic medium.
The ceramic dielectric media prepared in this example were tested for dielectric properties at a frequency of 1MHz and the results are shown in table 1 and fig. 1.
TABLE 1
Example 2
The high-toughness ceramic dielectric material comprises the following raw materials in percentage by mass: 15% of glass powder and Bi 4 Ti 2.92 W 0.07 Ta 0.01 O 12 85%, wherein the glass powder comprises the following raw materials in percentage by mass: mgO 40%, siO 2 5％、CeO 2 5％、Al 2 O 3 20% and AlF 3 30％。
The preparation process is as follows:
1) Bi as a raw material 2 O 3 、WO 3 、Ta 2 O 5 And TiO 2 According to the general formula Bi 4 Ti 2.92 W 0.07 Ta 0.01 O 12 Proportioning, ball milling for 5 hours on a ball mill with the rotating speed of 400r/min, drying in a common oven with the speed of 3.3kw at the temperature of 100 ℃, and passing through 200 holes/cm 2 The sample sieve was warmed to 1050℃at a rate of 7℃per minute and incubated at 1050℃for 3 hours to give frit A.
2) Weighing 40g of MgO and SiO 2 5g、CeO 2 5g、Al 2 O 3 20g and AlF 3 30g, mixing, melting, water cooling, grinding and sieving to obtain glass powder B.
3) And (3) proportioning, namely weighing the frit A and the glass powder B according to the mass ratio of 85% of the frit A to 15% of the glass powder B, and uniformly mixing to obtain a proportioning C.
4) And weighing sodium alginate and deionized water according to the mass ratio of 2% of sodium alginate to 98% of deionized water to prepare sodium alginate solution.
5) Weighing sodium alginate solution and ammonium citrate according to the mass ratio of the sodium alginate solution with the ingredient C of 75% and the ammonium citrate with the ingredient C of 3%, adding the ingredient C, ball-milling for 10 hours on a ball mill with the rotating speed of 400r/min, placing the slurry for 30 minutes under the vacuum condition, and performing vacuum defoaming. Injecting the slurry after bubble removal into a self-made mould, and putting the mould into a dryer to control the freezing temperature to be minus 10 ℃, minus 30 ℃ and minus 50 ℃ respectively, and directionally freezing for 6 hours. The mold was removed and rapidly demolded, and placed in a freeze dryer for sublimation for 21 hours.
6) After the drying is finished, heating the green body to 450 ℃ at a heating rate of 3 ℃/min in air atmosphere, heating to 840 ℃ at a heating rate of 6 ℃/min, sintering, preserving heat for 1 hour, and cooling to obtain the ceramic medium.
The ceramic dielectric media prepared in this example were tested for dielectric properties at a frequency of 1MHz and the results are shown in table 2 and fig. 1.
TABLE 2
Example 3
The high-toughness ceramic dielectric material comprises the following raw materials in percentage by mass: 20% of glass powder and Bi 4 Ti 2.92 W 0.07 Ta 0.01 O 12 80% of glass powder, wherein the glass powder comprises the following raw materials in percentage by mass: mgO 30%, siO 2 20％、CeO 2 20％、Al 2 O 3 5% and AlF 3 25％。
The preparation process is as follows:
1) Bi as a raw material 2 O 3 、WO 3 、Ta 2 O 5 And TiO 2 According to the general formula Bi 4 Ti 2.92 W 0.07 Ta 0.01 O 12 Proportioning, ball milling for 6 hours on a ball mill with the rotating speed of 400r/min, drying in a common oven with the speed of 3.3kw at the temperature of 100 ℃, and passing through 250 holes/cm 2 Sample separation sieves are heated to 1080 ℃ at the speed of 8 ℃/min, and the temperature is kept at 1080 ℃ for 4 hours, so as to obtain the frit A.
2) Weighing 30g of MgO and SiO 2 20g、CeO 2 20g、Al 2 O 3 5g and AlF 3 25g, mixing, melting, water cooling, grinding and sieving to obtain glass powder B.
3) And (3) proportioning, namely weighing the frit A and the glass powder B according to the mass ratio of 80% of the frit A to 20% of the glass powder B, and uniformly mixing to obtain a proportioning C.
4) And weighing sodium alginate and deionized water according to the mass ratio of 2% of sodium alginate to 98% of deionized water to prepare sodium alginate solution.
5) Weighing sodium alginate solution and ammonium citrate according to the mass ratio of the sodium alginate solution with 78% of the ingredients C and the ammonium citrate with 4%, adding the ingredients C, ball-milling for 10 hours on a ball mill with the rotating speed of 400r/min, and placing the slurry for 30 minutes under the vacuum condition to remove bubbles in vacuum. Injecting the slurry after bubble removal into a self-made mould, and putting the mould into a dryer to control the freezing temperature to be minus 10 ℃, minus 30 ℃ and minus 50 ℃ respectively, and directionally freezing for 7 hours. The mold was removed and rapidly demolded and placed in a freeze dryer for sublimation for 22 hours.
6) After the drying is finished, heating the green body to 480 ℃ at a heating rate of 4 ℃/min in air atmosphere, heating to 850 ℃ at a heating rate of 7 ℃/min, sintering, preserving heat for 1 hour, and cooling to obtain the ceramic medium.
The ceramic dielectric media prepared in this example were tested for dielectric properties at a frequency of 1MHz and the results are shown in table 3 and fig. 1.
TABLE 3 Table 3
Example 4
The high-toughness ceramic dielectric material comprises the following raw materials in percentage by mass: 30% of glass powder and Bi 4 Ti 2.92 W 0.07 Ta 0.01 O 12 70%, wherein the glass powder comprises the following raw materials in percentage by mass: mgO 20%, siO 2 20％、CeO 2 20％、Al 2 O 3 20% and AlF 3 20％。
The preparation process is as follows:
1) Bi as a raw material 2 O 3 、WO 3 、Ta 2 O 5 And TiO 2 According to the general formula Bi 4 Ti 2.92 W 0.07 Ta 0.01 0 12 Proportioning, ball milling for 4.5 hours on a ball mill with the rotating speed of 400r/min, drying in a common oven with the speed of 3.3kw at the temperature of 100 ℃, and passing through 250 holes/cm 2 The sample sieve is heated to 1100 ℃ at a speed of 9 ℃/min, and is kept at 1100 ℃ for 2.5 hours, so as to obtain the frit A.
2) Weighing 20g of MgO and SiO 2 20g、CeO 2 20g、Al 2 O 3 20g and AlF 3 20g, mixing, melting, water cooling, grinding and sieving to obtain glass powder B.
3) And (3) proportioning, namely weighing the frit A and the glass powder B according to the mass ratio of 70% of the frit A to 30% of the glass powder B, and uniformly mixing to obtain a proportioning C.
4) And weighing sodium alginate and deionized water according to the mass ratio of 2% of sodium alginate to 98% of deionized water to prepare sodium alginate solution.
5) Weighing sodium alginate solution and ammonium citrate according to the mass ratio of the sodium alginate solution with the ingredient C of 80% and the ammonium citrate with the ingredient C of 5%, adding the ingredient C, ball-milling for 10 hours on a ball mill with the rotating speed of 400r/min, and placing the slurry for 30 minutes under the vacuum condition to remove bubbles in vacuum. Injecting the slurry after bubble removal into a self-made mould, and putting the mould into a dryer to control the freezing temperature to be minus 10 ℃, minus 30 ℃ and minus 50 ℃ respectively, and directionally freezing for 8 hours. The mold was removed and rapidly demolded, and placed in a freeze dryer for sublimation for 23 hours.
6) After the drying is finished, heating the green body to 500 ℃ at a heating rate of 5 ℃/min in air atmosphere, heating to 860 ℃ at a heating rate of 8 ℃/min, sintering, preserving heat for 1 hour, and cooling to obtain the ceramic medium.
The ceramic dielectric media prepared in this example were tested for dielectric properties at a frequency of 1MHz and the results are shown in table 4 and fig. 1.
TABLE 4 Table 4
The dielectric properties of examples 1-4 were tested using the following test methods and test equipment:
a. testing of dielectric constant ε and loss tan delta
The capacitance C and the dielectric loss tan δ (test frequency was 1 MHz) of the capacitor were measured using a HEWLETT PACKARD 4278A capacitance tester, and the dielectric constant epsilon was calculated by the following formula:
wherein: capacitance of the C-sample, unit pF; d-thickness of the sample piece, unit cm; d-diameter of sintered sample piece, unit cm.
b. Test of temperature coefficient TCC (-55 ℃ -180 ℃)
The capacitance temperature coefficient (test frequency is 1 MHz) of the capacitor is obtained by measuring the change condition of the capacitance of a sample along with the temperature by using a 6425 type WAYKERR bridge, a GZ-ESPEC MC-710F high-low temperature box and an HM27002 type capacitor C-T/V characteristic special tester, and the calculation formula is as follows:
wherein: the reference temperature is 25 ℃, C 0 For a capacity of 25℃C 1 At a temperature t 1 Is a function of the capacity of the battery.
c. Fracture toughness testing
The test pieces were cut and polished to a length of 25mm, a width of 2.5mm and a height of 5mm, respectively. And preparing a transverse incision with the depth of 2.5mm and the width of 0.5mm at the midpoint of the test piece by using a MY-106 type dental polishing hand piece, then placing the test piece on an AGS-10KN type universal material testing machine, wherein the span is 15mm, and loading the test piece until the test piece breaks by adopting a three-point bending mode and at a loading rate of 0.05 mm/min. And the fracture toughness of the test specimen was calculated by the following formula:
wherein: k (K) IC Is fracture toughness (MPa.m) 1/2 ) The method comprises the steps of carrying out a first treatment on the surface of the S, B, w, a respectively represent the loading span, thickness, width and size parameters of the middle crack of the test sample; p is the central load of middle loading; f (a/w) is the shape correction coefficient of the different test pieces. The calculation formula for the present sample f (a/w) is:
the foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
The present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The high-toughness ceramic dielectric material is characterized by comprising the following raw materials in percentage by mass: 10-30% of glass powder and Bi 4 Ti 2.92 W 0.07 Ta 0.01 O 12 70-90％。
2. The high-toughness ceramic dielectric material according to claim 1, wherein the glass powder comprises the following raw materials in percentage by mass: mgO 5-40%, siO 2 5-30％、CeO 2 5-30％、Al 2 O 3 5-30% and AlF 3 5-30％。
3. The preparation method of the high-toughness ceramic dielectric material is characterized by comprising the following steps in sequence:
1) Bi as a raw material 2 O 3 、WO 3 、Ta 2 O 5 And TiO 2 According to the general formula Bi 4 Ti 2.92 W 0.07 Ta 0.01 O 12 Is weighed into a mixture according to the stoichiometric ratio, ball-milled and then passed through 120-250 holes/cm 2 Sample separation sieve, heating to 1000-1100 ℃, and preserving heat for 2-4 hours to obtain a frit A;
2) MgO 5-40 wt% and SiO 5 wt% 2 5-30％、CeO 2 5-30％、Al 2 O 3 5-30% and AlF 3 5-30% of molten water is cooled, ground and screened to obtain glass powder B;
3) Mixing 10-30% of glass powder B and 70-90% of frit A according to the mass percentage to obtain a mixture C;
4) Preparing sodium alginate solution by 2% of sodium alginate and 98% of deionized water according to the mass percentage;
5) Adding 70-80% of sodium alginate solution and 2-5% of ammonium citrate into the ingredient C, ball-milling, vacuum defoaming and directional freeze-drying;
6) After the drying is finished, the green body is slowly heated to 830-860 ℃ in the air atmosphere, then is insulated for 1 hour, and is cooled to obtain the ceramic medium.
4. The method for preparing a high-toughness ceramic dielectric material according to claim 3, wherein the ball milling time in the step 1) is 4-6 hours, and the ball milling medium is zirconia balls with a diameter of 1 mm.
5. The method for preparing a high-toughness ceramic dielectric material according to claim 3, wherein the heating rate in the step 1) is 7-9 ℃/min.
6. A method for preparing a high toughness ceramic dielectric material according to claim 3, wherein the freezing temperature in said step 5) is-10 ℃, -30 ℃, -50 ℃, and the directional freezing time is 5-8 hours.
7. A method for producing a high-toughness ceramic dielectric material according to claim 3, wherein the drying time in said step 5) is 20 to 23 hours.
8. A method for preparing a high-toughness ceramic dielectric material according to claim 3, wherein the heating process in the step 6) is divided into two stages: the first stage, heating from room temperature to 400-500 ℃ at a heating rate of 2-5 ℃/min; and in the second stage, heating from 400-500 ℃ to 830-860 ℃ at a heating rate of 5-8 ℃/min.
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| CN110156457A (en) * | 2019-04-28 | 2019-08-23 | 太原师范学院 | A kind of low-temperature co-fired ceramic medium material and preparation method thereof |
| CN110171967A (en) * | 2019-06-05 | 2019-08-27 | 太原师范学院 | A kind of low-temperature co-fired ceramic medium material and preparation method thereof |
| CN114538916A (en) * | 2022-03-03 | 2022-05-27 | 太原理工大学 | Low-temperature co-fired ceramic dielectric material and preparation method thereof |
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| CN1237546A (en) * | 1998-03-03 | 1999-12-08 | 株式会社小原 | Glass-ceramic substrate for magnetic information recording medium |
| WO2018040749A1 (en) * | 2016-08-30 | 2018-03-08 | 深圳顺络电子股份有限公司 | Low temperature co-fired ceramic material and preparation method therefor |
| CN110156457A (en) * | 2019-04-28 | 2019-08-23 | 太原师范学院 | A kind of low-temperature co-fired ceramic medium material and preparation method thereof |
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