CN116621565A - Ceramic composition, ceramic substrate, and preparation method and application of ceramic substrate - Google Patents

Ceramic composition, ceramic substrate, and preparation method and application of ceramic substrate Download PDF

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CN116621565A
CN116621565A CN202310391589.1A CN202310391589A CN116621565A CN 116621565 A CN116621565 A CN 116621565A CN 202310391589 A CN202310391589 A CN 202310391589A CN 116621565 A CN116621565 A CN 116621565A
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ceramic
ceramic substrate
composition
tio
oxide
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邱基华
陈烁烁
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Guangdong Advanced Ceramic Material Technology Co ltd
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Guangdong Advanced Ceramic Material Technology Co ltd
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Abstract

The invention discloses a ceramic composition, a ceramic substrate, and a preparation method and application thereof, and belongs to the field of ceramic materials. The ceramic composition provided by the invention comprises the following components in percentage by mass: 97-99% alumina, 0.5-2% Ba x Sr 1‑x TiO 3 0.3 to 0.7 percent of glass phase and 0.2 to 0.7 percent of rare earth oxide; wherein x=0.3 to 0.5; the glass phase comprises MgO, caO and SiO 2 . The ceramic composition provided by the invention has the advantages of high dielectric constant, low dielectric loss, high breakdown strength and high density after being prepared into a ceramic substrate, and is used for preparing a ceramic substrateElectronic devices, particularly high frequency electronic devices, have wide application.

Description

Ceramic composition, ceramic substrate, and preparation method and application of ceramic substrate
Technical Field
The invention belongs to the field of ceramic materials, and particularly relates to a ceramic composition, a ceramic substrate, a preparation method and application thereof.
Background
In recent years, with the rapid development of the 5G electronic communication market, electronic products are being developed toward high integration, and the requirements for materials for high-frequency and high-speed signals are increasing. When a high frequency signal passes through the dielectric layer,molecules in the medium will attempt to orient according to these electromagnetic signals, and although in reality the molecules in the medium are cross-linked and cannot actually orient, the change in frequency causes the molecules to move constantly, thus generating a large amount of heat, causing a loss of energy, also known as dielectric loss. The existence of dielectric loss can cause the temperature of the electronic device to rise, thereby reducing the service life and increasing the production cost, so that in the actual production process, the designed device not only has high dielectric constant epsilon r And breakdown strength E b While having a low dielectric loss tan delta.
Alumina ceramic substrates are widely used in high frequency circuit substrates due to their good thermal conductivity, mechanical strength and dielectric properties, but in practical application development in the high frequency electronics field, higher breakdown strength and lower dielectric loss are also required to meet practical requirements. Therefore, increasing the dielectric constant, breakdown strength, and reducing dielectric loss of alumina ceramic substrates are of great importance in high frequency substrate applications.
The main components of the aluminum oxide ceramic substrate at present comprise 90-99% of aluminum oxide, fluxing agents, dispersing agents, binders and the like with different contents, the dielectric constant and dielectric loss of the ceramic substrate mainly depend on the intrinsic dielectric properties of the aluminum oxide with main crystal phase, the dielectric constant of the aluminum oxide ceramic is usually between 9 and 10, the breakdown strength is about 18kV/mm, and the dielectric loss is less than 10 -4 . However, the improvement of the intrinsic performance of the material is very difficult, so that when only alumina powder is used as a single ceramic material in a substrate in actual production, the great improvement of the dielectric performance of the ceramic substrate is difficult to realize, thereby limiting the application of the ceramic substrate in a high-frequency circuit substrate.
Disclosure of Invention
In order to overcome the problems of the prior art, an object of the present invention is to provide a ceramic composition, and a ceramic substrate manufactured by using the ceramic composition has high dielectric constant, low dielectric loss, high breakdown strength and high density.
Another object of the present invention is to provide a ceramic substrate comprising the above ceramic composition.
The third object of the present invention is to provide a method for manufacturing the ceramic substrate.
A fourth object of the present invention is to provide an application of the ceramic composition or the ceramic substrate in an electronic device.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a ceramic composition comprising the following components in percentage by mass: 97-99% alumina, 0.5-2% Ba x Sr 1-x TiO 3 0.3 to 0.7 percent of glass phase and 0.2 to 0.7 percent of rare earth oxide; wherein x=0.3 to 0.5; the glass phase comprises MgO, caO and SiO 2
In the ceramic composition, alumina is used as a main component, and is used as a main crystal phase after being prepared into a ceramic substrate; barium strontium titanate (Ba) x Sr 1-x TiO 3 ) The dielectric property of the ceramic substrate is improved by the synergistic effect of aluminum oxide and barium strontium titanate as doping phases; the addition of the glass phase can reduce the sintering temperature of the ceramic; the addition of rare earth oxide promotes the growth of crystal grains and the improvement of density in the sintering process.
Barium strontium titanate (Ba) x Sr 1-x TiO 3 ) Is a complete solid solution of strontium titanate and barium titanate, has a typical perovskite structure, and simultaneously has BaTiO 3 High dielectric constant (about 1400 f at room temperature) and SrTiO 3 Low dielectric loss (about 0.012), high breakdown strength, etc., and therefore, will be Ba x Sr 1-x TiO 3 The addition to alumina ceramics is effective in improving the dielectric properties. In addition, during sintering Ba x Sr 1-x TiO 3 With alumina to form TiO 2 Due to Ti 4+ Radius (86 pm) to Al 3+ The radius (53 pm) of Ti is slightly larger 4+ Replacement of Al 3+ Resulting in deformation of the crystal lattice to generate defects which activate the crystal lattice and reduce the activation energy for sintering the alumina ceramic, thereby promoting sintering thereof.
Dielectric constant and breakdown strength of ceramic substrateWith Ba x Sr 1-x TiO 3 The increase of the addition amount shows a trend of increasing and then decreasing, and when the addition amount is low (less than 0.5%), the addition amount cannot effectively promote the compactness of the ceramic, so that the dielectric property of the ceramic cannot be improved; and when the addition amount exceeds 2%, ba x Sr 1-x TiO 3 The reaction with alumina occurs to generate more second phases, thereby causing the overall dielectric constant of the ceramic to be reduced; when Ba is x Sr 1-x TiO 3 When the amount of the additive is about 1.5%, not only densification of the ceramic can be promoted, but also a large amount of the second phase is not generated, so that the dielectric constant and the breakdown strength of the ceramic substrate can be effectively improved.
The glass phase can generate glass liquid phase in the sintering process, particles are generated by the liquid phase through the surface tension effect to bond and fill pores, migration of particles of a main crystal phase can be promoted, abnormal growth of alumina crystal grains is restrained, and therefore the sintering temperature is reduced; in addition, the glass liquid phase is positioned at the grain boundary to prevent migration of free charges, and the free charges are accumulated at the barrier to form macroscopic electric dipole moment, so that the dielectric constant and the breakdown strength of the ceramic are improved.
When the addition amount of the glass phase is small, a liquid phase cannot be effectively formed with the alumina ceramic, so that the porosity of the ceramic cannot be effectively reduced and the sintering temperature cannot be reduced; when the addition amount is large, ba x Sr 1-x TiO 3 And the content of rare earth oxide is reduced, the liquid phase formation process of the rare earth oxide and alumina ceramic cannot be effectively promoted, and thus the sintering temperature cannot be reduced.
The rare earth oxide can promote the filling of pores in the ceramic, reduce the porosity of the alumina ceramic, refine grains and effectively improve the densification degree and the breakdown strength; the rare earth oxide can also effectively promote the components such as glass to form a low-melting-point liquid phase, thereby effectively reducing the melting point of the ceramic substrate material; in addition, the rare earth oxide has a large ionic radius so that it cannot be solid-dissolved in alumina, and it can block migration of other ions (such as alkali metal oxide contained in alumina powder) at grain boundaries, thereby reducing dielectric loss of alumina ceramic.
When the addition amount of the rare earth oxide is too low, the components such as glass cannot be effectively promoted to form a low-melting-point liquid phase, so that the melting point of the ceramic substrate material cannot be effectively reduced; when the addition amount is too high, a large amount thereof exists on the grain boundary of the alumina ceramic, seriously hampering the migration rate of the grain boundary, and being unfavorable for the formation of a dense structure.
Preferably, in the ceramic composition, ba x Sr 1-x TiO 3 The method comprises the following steps: baTiO is mixed with 3 And SrTiO 3 Mixing, drying and discharging glue to obtain the Ba x Sr 1-x TiO 3
Preferably, the Ba x Sr 1-x TiO 3 In the preparation method of (2), the mixture is crushed; further preferably, the pulverizing means is selected from ball milling; still more preferably, the ball milling mode is selected from wet ball milling.
Preferably, the Ba x Sr 1-x TiO 3 In the preparation method, the ball milling time is 3-10 h; further preferably, the Ba x Sr 1-x TiO 3 In the preparation method, the ball milling time is 4-8 hours; still more preferably, the Ba x Sr 1-x TiO 3 In the preparation method, the ball milling time is 5-7 h.
Preferably, the Ba x Sr 1-x TiO 3 In the preparation method, the drying temperature is 70-140 ℃; further preferably, the Ba x Sr 1-x TiO 3 In the preparation method, the drying temperature is 80-130 ℃; still more preferably, the Ba x Sr 1-x TiO 3 In the preparation method, the drying temperature is 90-120 ℃.
Preferably, the Ba x Sr 1-x TiO 3 In the preparation method, the glue discharging temperature is 1100-1400 ℃; further preferably, the Ba x Sr 1-x TiO 3 In the preparation method, the glue discharging temperature is 1200-1350 ℃; still more preferably, the Ba x Sr 1-x TiO 3 In the preparation method of (2), the temperature of glue dischargingIs 1250-1300 ℃.
Preferably, the Ba x Sr 1-x TiO 3 In the preparation method, the glue discharging time is 3-6 hours; further preferably, the Ba x Sr 1-x TiO 3 In the preparation method, the glue discharging time is 3.5-5.5 h; still more preferably, the Ba x Sr 1-x TiO 3 In the preparation method, the glue discharging time is 4-5 h.
Preferably, in the ceramic composition, the rare earth oxide includes at least one of lanthanum oxide, neodymium oxide, dysprosium oxide, cerium oxide, yttrium oxide, or erbium oxide; further preferably, in the ceramic composition, the rare earth oxide includes at least one of lanthanum oxide, neodymium oxide, dysprosium oxide, cerium oxide, or yttrium oxide; still more preferably, in the ceramic composition, the rare earth oxide includes at least one of lanthanum oxide, neodymium oxide, dysprosium oxide, or cerium oxide.
Preferably, in the ceramic composition, the average particle size of the rare earth oxide is 0.5 to 2 μm; further preferably, in the ceramic composition, the average particle diameter of the rare earth oxide is 0.8 to 1.8 μm; still more preferably, in the ceramic composition, the average particle diameter of the rare earth oxide is 1 to 1.5 μm.
Preferably, the mass ratio of MgO to CaO in the glass phase is 1: (0.7-1.3); further preferably, the mass ratio of MgO to CaO in the glass phase is 1: (0.8-1.2); still more preferably, the mass ratio of MgO and CaO in the glass phase is 1: (0.85-1.15); more preferably, the mass ratio of MgO to CaO in the glass phase is 1: (0.9-1.1).
Preferably, mgO and SiO in the glass phase 2 The mass ratio of (2) is 1: (1.6-2.4); further preferably, mgO and SiO in the glass phase 2 The mass ratio of (2) is 1: (1.7-2.3); still more preferably, mgO and SiO in the glass phase 2 The mass ratio of (2) is 1: (1.8-2.2); more preferably, mgO and SiO in the glass phase 2 The mass ratio of (2) is 1: (1.9-2.1).
Preferably, mgO, caO and SiO in the glass phase 2 The mass ratio of (2) is 1: (0.7-1.3): (1.6-2.4); further preferably, mgO, caO and SiO in the glass phase 2 The mass ratio of (2) is 1: (0.8-1.2): (1.7-2.3); still more preferably, mgO, caO and SiO in the glass phase 2 The mass ratio of (2) is 1: (0.85-1.15): (1.8-2.2); more preferably, mgO, caO and SiO in the glass phase 2 The mass ratio of (2) is 1: (0.9-1.1): (1.9-2.1).
Preferably, in the ceramic composition, the mass percentage of the alumina is 97.1-98.5%; further preferably, in the ceramic composition, the mass percentage of the alumina is 97.2-98%; still more preferably, the ceramic composition has a mass percentage of alumina of 97.4 to 97.8%.
Preferably, in the ceramic composition, ba x Sr 1-x TiO 3 The mass percentage of (2) is 0.8-1.9%; further preferably, in the ceramic composition, ba x Sr 1-x TiO 3 The mass percentage of (2) is 1.0-1.8%; still more preferably, in the ceramic composition, ba x Sr 1-x TiO 3 The mass percentage of (2) is 1.2-1.7%.
Preferably, in the ceramic composition, the mass percentage of the glass phase is 0.35-0.65%; further preferably, the ceramic composition has a glass phase content of 0.4 to 0.6% by mass; still more preferably, the ceramic composition has a glass phase content of 0.45 to 0.55% by mass.
Preferably, in the ceramic composition, the mass percentage of the rare earth oxide is 0.25-0.65%; further preferably, in the ceramic composition, the mass percentage of the rare earth oxide is 0.3-0.6%; still more preferably, the mass percentage of rare earth oxide in the ceramic composition is 0.35 to 0.55%.
Preferably, the ceramic composition comprises the following components in percentage by mass: 97.1-98.5% alumina, 0.8-1.9% Ba x Sr 1-x TiO 3 0.35 to 0.65 percent of glass phase and 0.25 to 0.65 percent of rare earth oxide.
Further preferably, the ceramic composition comprises the following components in percentage by mass: 97.2-98% alumina, 1.0-1.8% Ba x Sr 1-x TiO 3 0.4 to 0.6 percent of glass phase and 0.3 to 0.6 percent of rare earth oxide.
Still more preferably, the ceramic composition comprises the following components in percentage by mass: 97.4 to 97.8 percent of alumina and 1.2 to 1.7 percent of Ba x Sr 1-x TiO 3 0.35 to 0.55 percent of glass phase and 0.35 to 0.55 percent of rare earth oxide.
A second aspect of the invention provides a ceramic substrate comprising the ceramic composition of the first aspect of the invention.
A third aspect of the present invention provides a method for preparing a ceramic substrate according to the second aspect of the present invention, comprising the steps of: alumina, ba x Sr 1-x TiO 3 、MgO、CaO、SiO 2 Mixing, casting and sintering the rare earth oxide, the dispersing agent and the binder to obtain the ceramic substrate.
Preferably, in the preparation method of the ceramic substrate, the dispersing agent comprises at least one of oleic acid, triolein, fish oil or phosphate; further preferably, in the preparation method of the ceramic substrate, the dispersant includes at least one of oleic acid, triolein or phosphate; still further preferably, in the method for preparing a ceramic substrate, the dispersant includes oleic acid, phosphate or a combination thereof.
Preferably, in the preparation method of the ceramic substrate, the dosage of the dispersing agent is 0.1-3% of the mass of the ceramic composition; further preferably, in the preparation method of the ceramic substrate, the amount of the dispersing agent is 0.3-2.5% of the mass of the ceramic composition; still more preferably, in the method for preparing a ceramic substrate, the dispersant is used in an amount of 0.5 to 2% by mass of the ceramic composition.
Preferably, in the preparation method of the ceramic substrate, the binder comprises at least one of polyvinyl butyral (PVB), acrylic resin, methylcellulose, ethylcellulose, nitrocellulose ester, polyurethane resin, or phenolic resin; further preferably, in the preparation method of the ceramic substrate, the binder includes at least one of polyvinyl butyral (PVB), acrylic resin, methylcellulose, ethylcellulose, or nitrocellulose ester; still further preferably, in the method for manufacturing a ceramic substrate, the binder includes at least one of polyvinyl butyral (PVB), acrylic resin, or methylcellulose.
Preferably, in the preparation method of the ceramic substrate, the using amount of the binder is 1-20% of the mass of the ceramic composition; further preferably, in the preparation method of the ceramic substrate, the amount of the binder is 3-15% of the mass of the ceramic composition; still more preferably, in the method for manufacturing a ceramic substrate, the binder is used in an amount of 5 to 10% by mass of the ceramic composition.
Preferably, in the method for preparing a ceramic substrate, the ceramic substrate is further crushed after being mixed; further preferably, the pulverizing means is selected from ball milling.
Preferably, in the preparation method of the ceramic substrate, the ball milling solvent is selected from organic solvents; further preferred, the organic solvent comprises toluene, isopropanol, or a combination thereof; still more preferably, the organic solvent includes a volume ratio of 1: toluene and isopropyl alcohol of (0.5-2); more preferably, the volume ratio of toluene to isopropanol is 1: (0.8-1.5).
Preferably, in the preparation method of the ceramic substrate, the ball milling medium is selected from alumina.
Preferably, in the preparation method of the ceramic substrate, the mass ratio of the ceramic composition to the ball milling medium is 1: (1-2); further preferably, in the preparation method of the ceramic substrate, the mass ratio of the ceramic composition to the ball milling medium is 1: (1.2-1.8); still further preferably, in the preparation method of the ceramic substrate, the mass ratio of the ceramic composition to the ball milling medium is 1: (1.4-1.6).
Preferably, in the preparation method of the ceramic substrate, the ball milling time is 10-30 hours; further preferably, in the preparation method of the ceramic substrate, the ball milling time is 12-25 hours; still more preferably, in the method for preparing a ceramic substrate, the ball milling time is 15 to 20 hours.
Preferably, in the preparation method of the ceramic substrate, deaeration is performed before casting; further preferably, the defoaming time is 5-10 hours; still more preferably, the defoaming time is 6 to 8 hours.
Preferably, in the method for preparing a ceramic substrate, the adhesive is discharged before sintering.
In the preparation method of the ceramic substrate, the adhesive can be discharged after the adhesive is discharged before sintering, so that the ceramic substrate with better performance is obtained.
Preferably, in the preparation method of the ceramic substrate, the glue discharging temperature is 250-400 ℃; further preferably, in the preparation method of the ceramic substrate, the glue discharging temperature is 280-380 ℃; still more preferably, in the method for manufacturing a ceramic substrate, the glue discharging temperature is 300-350 ℃.
Preferably, in the preparation method of the ceramic substrate, the glue discharging time is 20-36 hours; further preferably, in the preparation method of the ceramic substrate, the glue discharging time is 22-34 hours; still more preferably, in the method for manufacturing a ceramic substrate, the adhesive discharging time is 24 to 32 hours.
Preferably, in the preparation method of the ceramic substrate, the sintering temperature is 1400-1800 ℃; further preferably, in the preparation method of the ceramic substrate, the sintering temperature is 1500-1700 ℃; still more preferably, in the method for manufacturing a ceramic substrate, the sintering temperature is 1550 to 1650 ℃.
Preferably, in the preparation method of the ceramic substrate, the sintering time is 15-30 hours; further preferably, in the preparation method of the ceramic substrate, the sintering time is 18-28 hours; still more preferably, in the method for producing a ceramic substrate, the sintering time is 20 to 25 hours.
A fourth aspect of the invention provides the use of a ceramic composition according to the first aspect of the invention or a ceramic substrate according to the second aspect of the invention in an electronic device.
Preferably, the electronic device is a high-frequency electronic device; further preferably, the high-frequency electronic device is a high-frequency circuit substrate.
The beneficial effects of the invention are as follows: the invention provides a ceramic composition, which has the advantages of high dielectric constant, low dielectric loss, high breakdown strength and high density after being manufactured into a ceramic substrate. In the ceramic composition, alumina is used as a main component, and is used as a main crystal phase after being prepared into a ceramic substrate; barium strontium titanate (Ba) x Sr 1-x TiO 3 ) The dielectric property of the ceramic substrate is improved by the synergistic effect of aluminum oxide and barium strontium titanate as doping phases; the addition of the glass phase can reduce the sintering temperature of the ceramic; the addition of rare earth oxide promotes the growth of crystal grains and the improvement of density in the sintering process.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, since various modifications and adaptations may be made by those skilled in the art in light of the teachings herein. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a selection within the suitable ranges by the description herein and are not intended to be limited to the specific data described below. The starting materials, reagents or apparatus used in the following examples and comparative examples were obtained from conventional commercial sources or by known methods unless otherwise specified.
Example 1
The composition ratio of the ceramic composition in this example is as follows:
composition of the composition Alumina oxide Ba x Sr 1-x TiO 3 Glass phase Rare earth oxide
Mass percent 97% 2% 0.3% 0.7%
Wherein Ba is x Sr 1-x TiO 3 X=0.4 in (a); mgO in glass phase: caO: siO (SiO) 2 Mass ratio 1:1:2; the rare earth oxide is lanthanum oxide, and the average grain diameter of the rare earth oxide is 1-1.5 mu m.
The alumina ceramic substrate in this embodiment is prepared by the following preparation method, and specifically includes the following steps:
(1)Ba 0.4 Sr 0.6 TiO 3 preparation of powder
Pre-synthesized BaTiO 3 With SrTiO 3 Powder according to 2:3, carrying out wet ball milling for 5 hours by taking water as a medium, drying the mixed powder at 90 ℃, grinding and pressing the dried mixture into relatively loose blocks, and preserving the temperature in a glue discharging furnace at 1250 ℃ for 4 hours to synthesize Ba 0.4 Sr 0.6 TiO 3 And (3) grinding the powder body into fine powder for standby after cooling.
(2) Ball milling
Ba is added to 0.4 Sr 0.6 TiO 3 Alumina, mgO, caO, siO 2 Mixing lanthanum oxide, dispersant phosphate (the dosage is 0.5-2% of the mass of the ceramic composition) and binder PVB (the dosage is 5-10% of the mass of the ceramic composition), and then ball millingThe volume ratio of the solvent is 1:1, wherein the ball milling medium is alumina balls, and the mass ratio of the powder to the alumina balls is 1:1.5, ball milling for 18 hours to obtain mixed slurry.
(3) Casting process
Vacuum defoaming is carried out on the mixed slurry, and the defoaming time is 6 hours; and carrying out tape casting molding on the vacuum defoamed slurry to obtain a green body.
(4) Sintering
And standing the green body at room temperature for 3 days, then performing glue discharging and sintering in a glue discharging furnace, firstly discharging glue at 300 ℃ for 24 hours, discharging the binder in the green body, then heating to 1550 ℃ and maintaining for 20 hours for sintering to obtain the alumina ceramic substrate.
Example 2
This example differs from example 1 in the composition ratio of the ceramic composition. The composition ratio of the ceramic composition in this example is as follows:
composition of the composition Alumina oxide Ba x Sr 1-x TiO 3 Glass phase Rare earth oxide
Mass percent 97.2% 1.7% 0.7% 0.4%
Example 3
This example differs from example 1 in the composition ratio of the ceramic composition. The composition ratio of the ceramic composition in this example is as follows:
composition of the composition Alumina oxide Ba x Sr 1-x TiO 3 Glass phase Rare earth oxide
Mass percent 97.5% 1.5% 0.5% 0.5%
Example 4
This example differs from example 1 in the composition ratio of the ceramic composition. The composition ratio of the ceramic composition in this example is as follows:
composition of the composition Alumina oxide Ba x Sr 1-x TiO 3 Glass phase Rare earth oxide
Mass percent 98% 1% 0.4% 0.6%
Example 5
This example differs from example 1 in the composition ratio of the ceramic composition. The composition ratio of the ceramic composition in this example is as follows:
composition of the composition Alumina oxide Ba x Sr 1-x TiO 3 Glass phase Rare earth oxide
Mass percent 99% 0.5% 0.3% 0.2%
Example 6
This embodiment differs from embodiment 3 in that Ba x Sr 1-x TiO 3 X=0.3.
Ba of the present embodiment 0.3 Sr 0.7 TiO 3 The preparation method of (2) is as follows:
pre-synthesized BaTiO 3 With SrTiO 3 Powder according to 3: weighing 7 mol ratio, ball milling with water as medium for 6 hr, stoving at 100deg.C, grinding and pressing into loose block, and maintaining at 1250 deg.C for 4 hr in a glue discharging furnace to synthesize Ba 0.3 Sr 0.7 TiO 3 And (3) grinding the powder body into fine powder for standby after cooling.
Example 7
This embodiment differs from embodiment 3 in that Ba x Sr 1-x TiO 3 X=0.5.
Ba of the present embodiment 0.5 Sr 0.5 TiO 3 The preparation method of (2) is as follows:
pre-synthesized BaTiO 3 With SrTiO 3 Powder according to 1: weighing 1 molar ratio, ball milling for 6 hours by using water as a medium through a wet method, drying the mixed powder at 100 ℃, grinding and pressing the dried mixed powder into relatively loose blocks, and synthesizing Ba in a glue discharging furnace at 1250 ℃ for 4 hours 0.5 Sr 0.5 TiO 3 And (3) grinding the powder body into fine powder for standby after cooling.
Example 8
This example differs from example 3 in that MgO in the glass phase: caO: siO (SiO) 2 The mass ratio of (2) is 1:0.7:2.
example 9
This example differs from example 3 in the glass phaseMgO of (b): caO: siO (SiO) 2 The mass ratio of (2) is 1:1.3:2.
example 10
This example differs from example 3 in that MgO in the glass phase: caO: siO (SiO) 2 The mass ratio of (2) is 1:1:1.6.
example 11
This example differs from example 3 in that MgO in the glass phase: caO: siO (SiO) 2 The mass ratio of (2) is 1:0.7:2.4.
example 12
The present embodiment differs from embodiment 1 in that the rare earth oxide is Nd 2 O 3
Example 13
The present embodiment differs from embodiment 1 in that the rare earth oxide is Dy 2 O 3
Example 14
The present embodiment differs from embodiment 1 in that the rare earth oxide is CeO 2
Comparative example 1
This comparative example differs from example 1 in the composition ratio of the ceramic composition. The composition ratio of the ceramic composition in this comparative example is as follows:
composition of the composition Alumina oxide Ba x Sr 1-x TiO 3 Glass phase Rare earth oxide
Mass percent 95% 2.8% 0.9% 1.3%
Comparative example 2
This comparative example differs from example 1 in the composition ratio of the ceramic composition. The composition ratio of the ceramic composition in this comparative example is as follows:
composition of the composition Alumina oxide Ba x Sr 1-x TiO 3 Glass phase Rare earth oxide
Mass percent 99.5% 0.3% 0.1% 0.1%
Comparative example 3
This comparative example differs from example 1 in the composition ratio of the ceramic composition. The composition ratio of the ceramic composition in this comparative example is as follows:
composition of the composition Alumina oxide Ba x Sr 1-x TiO 3 Glass phase Rare earth oxide
Mass percent 98.3% 0.3% 0.7% 0.7%
Comparative example 4
This comparative example differs from example 1 in the composition ratio of the ceramic composition. The composition ratio of the ceramic composition in this comparative example is as follows:
composition of the composition Alumina oxide Ba x Sr 1-x TiO 3 Glass phase Rare earth oxide
Mass percent 97% 2.3% 0.3% 0.4%
Comparative example 5
This comparative example differs from example 1 in the composition ratio of the ceramic composition. The composition ratio of the ceramic composition in this comparative example is as follows:
composition of the composition Alumina oxide Ba x Sr 1-x TiO 3 Glass phase Rare earth oxide
Mass percent 97.5% 2% 0.1% 0.4%
Comparative example 6
This comparative example differs from example 1 in the composition ratio of the ceramic composition. The composition ratio of the ceramic composition in this comparative example is as follows:
composition of the composition Alumina oxide Ba x Sr 1-x TiO 3 Glass phase Rare earth oxide
Mass percent 97.5% 1% 0.9% 0.6%
Comparative example 7
This comparative example differs from example 1 in the composition ratio of the ceramic composition. The composition ratio of the ceramic composition in this comparative example is as follows:
composition of the composition Alumina oxide Ba x Sr 1-x TiO 3 Glass phase Rare earth oxide
Mass percent 97.5% 2% 0.5% 0%
Comparative example 8
This comparative example differs from example 1 in the composition ratio of the ceramic composition. The composition ratio of the ceramic composition in this comparative example is as follows:
composition of the composition Alumina oxide Ba x Sr 1-x TiO 3 Glass phase Rare earth oxide
Mass percent 98% 1.4% 0.5% 0.1%
Comparative example 9
This comparative example differs from example 1 in the composition ratio of the ceramic composition. The composition ratio of the ceramic composition in this comparative example is as follows:
composition of the composition Alumina oxide Ba x Sr 1-x TiO 3 Glass phase Rare earth oxide
Mass percent 97.5% 1.5% 0.5% 1%
Comparative example 10
This comparative example differs from example 3 in that Ba x Sr 1-x TiO 3 X=0.2.
Ba of this comparative example 0.2 Sr 0.8 TiO 3 The preparation method of (2) is as follows:
pre-synthesized BaTiO 3 With SrTiO 3 Powder according to 1: the weight was carried out in a molar ratio of 4,wet ball milling with water as medium for 6 hr, stoving at 100 deg.c, grinding the stoving mixture to form loose block, and maintaining at 1250 deg.c in a glue draining furnace for 4 hr to synthesize Ba 0.2 Sr 0.8 TiO 3 And (3) grinding the powder body into fine powder for standby after cooling.
Comparative example 11
This comparative example differs from example 3 in that Ba x Sr 1-x TiO 3 X=0.6 in (a).
Ba of this comparative example 0.6 Sr 0.4 TiO 3 The preparation method of (2) is as follows:
pre-synthesized BaTiO 3 With SrTiO 3 Powder according to 3: weighing 2 mol ratio, ball milling with water as medium for 6 hr, stoving at 100deg.C, grinding and pressing into loose block, and maintaining at 1250 deg.C for 4 hr in a glue discharging furnace to synthesize Ba 0.6 Sr 0.4 TiO 3 And (3) grinding the powder body into fine powder for standby after cooling.
Comparative example 12
This comparative example differs from example 3 in that MgO in the glass phase: caO: siO (SiO) 2 The mass ratio of (2) is 1:0.5:2.
comparative example 13
This comparative example differs from example 3 in that MgO in the glass phase: caO: siO (SiO) 2 The mass ratio of (2) is 1:1.5:2.
comparative example 14
This comparative example differs from example 3 in that MgO in the glass phase: caO: siO (SiO) 2 The mass ratio of (2) is 1:1:1.
comparative example 15
This comparative example differs from example 3 in that MgO in the glass phase: caO: siO (SiO) 2 The mass ratio of (2) is 1:1:3.
comparative example 16
This comparative example differs from example 1 in the composition ratio of the ceramic composition. The composition ratio of the ceramic composition in this comparative example is as follows:
composition of the composition Alumina oxide Ba x Sr 1-x TiO 3 Glass phase Rare earth oxide
Mass percent 99% 0% 0.3% 0.7%
Performance testing
The ceramic substrates prepared in examples 1 to 14 and comparative examples 1 to 16 were subjected to the test in table 1.
Table 1 ceramic substrate performance tests of examples 1 to 14 and comparative examples 1 to 16
The results of the ceramic substrate performance tests of examples 1 to 14 and comparative examples 1 to 16 are shown in Table 2.
Table 2 results of performance tests on ceramic substrates of examples 1 to 14 and comparative examples 1 to 16
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As can be seen from the above examples and comparative examples:
ba of examples 1-5 x Sr 1-x TiO 3 The addition amount gradually decreases, and the dielectric constant and breakdown strength of the ceramic substrate follow Ba x Sr 1-x TiO 3 The increase in the added amount showed a tendency of rising before decreasing, and it was further verified from specific performance data that when Ba was added x Sr 1-x TiO 3 The mass percentage of the ceramic substrate is 1.2 to 1.7 percent, and the performance of the whole ceramic substrate is most excellent.
As is clear from examples and comparative examples 1 to 4, when the addition amount is low (the addition amounts of comparative examples 2 and 3 are each 0.3%), the ceramic substrate is degraded in density, dielectric properties and breakdown strength. And when the addition amount exceeds 2% (the addition amount of comparative example 1 is 2.8%, the addition amount of comparative example 4 is 2.3%), since Ba x Sr 1-x TiO 3 More second phases react with alumina and the overall dielectric constant of the ceramic decreases.
As is clear from examples and comparative examples 5 to 6 and comparative examples 12 to 15, by selecting an appropriate addition amount and addition range of the glass phase, a ceramic substrate having a good dielectric property can be obtained, and when the addition amount is small (the addition amount of comparative example 5 is 0.1%), a liquid phase cannot be effectively formed with alumina ceramic, and thus the porosity of the ceramic cannot be effectively reduced, and the density is small. When the addition amount thereof was large (addition amount of comparative example 6 was 0.9%), ba x Sr 1-x TiO 3 And the content of rare earth oxide is reduced, the liquid phase formation process of the rare earth oxide and alumina ceramic cannot be effectively promoted, and thus the sintering temperature cannot be reduced, and the performance of the whole substrate is reduced.
As is clear from examples and comparative examples 7 to 9, when the addition amount of the rare earth oxide is too low or not added, the formation of a low melting point liquid phase by the equal components of glass cannot be effectively promoted, and thus the melting point of the ceramic substrate material cannot be effectively lowered; when the addition amount is too high, a large amount thereof exists on the grain boundary of the alumina ceramic, seriously hampering the migration rate of the grain boundary, and being unfavorable for the formation of a dense structure. The density of the ceramic substrate decreases.
From examples and comparative examples 10 to 11, when Ba x Sr 1-x TiO 3 The ratio of the Ba to the Sr is proper, so that the defects generated during sintering of the alumina ceramic substrate can be well overcome, and the ceramic substrate has better dielectric property, density and breakdown strength.
As is clear from examples and comparative example 16, ba was not added x Sr 1-x TiO 3 The ceramic substrate made of the ceramic material has high dielectric property, high breakdown strength and relatively low density.
After the ceramic composition provided by the invention is prepared into a ceramic substrate, the ceramic composition has the advantages of high dielectric constant, low dielectric loss, high breakdown strength and high density, and has wide application in electronic devices, especially high-frequency electronic devices.

Claims (10)

1. The ceramic composition is characterized by comprising the following components in percentage by mass: 97-99% alumina,
0.5~2%Ba x Sr 1-x TiO 3 0.3 to 0.7 percent of glass phase and 0.2 to 0.7 percent of rare earth oxide; wherein x=0.3 to 0.5; the glass phase comprises MgO, caO and SiO 2
2. The ceramic composition of claim 1, wherein the rare earth oxide comprises at least one of lanthanum oxide, neodymium oxide, dysprosium oxide, cerium oxide, yttrium oxide, or erbium oxide.
3. The ceramic composition according to claim 2, wherein the rare earth oxide has an average particle diameter of 0.5 to 2 μm.
4. A ceramic composition according to any one of claims 1 to 3, wherein the mass ratio of MgO and CaO in the vitreous phase is 1: (0.7-1.3);
and/or, mgO and SiO in the glass phase 2 The mass ratio of (2) is 1: (1.6-2.4).
5. A ceramic composition according to any one of claims 1 to 3, comprising the following components in mass percent:
97.1-98.5% alumina, 0.8-1.9% Ba x Sr 1-x TiO 3 0.35 to 0.65 percent of glass phase and 0.25 to 0.65 percent of rare earth oxide.
6. A ceramic substrate comprising the ceramic composition of any one of claims 1 to 5.
7. The method for preparing a ceramic substrate according to claim 6, comprising the steps of: alumina, ba x Sr 1- x TiO 3 、MgO、CaO、SiO 2 Mixing, casting and sintering the rare earth oxide, the dispersing agent and the binder to obtain the ceramic substrate.
8. The method of claim 7, wherein the dispersant comprises at least one of oleic acid, glycerol trioleate, fish oil, or phosphate;
and/or the binder comprises at least one of polyvinyl butyral, acrylic resin, methyl cellulose, ethyl cellulose, nitrocellulose ester, polyurethane resin, or phenolic resin.
9. The method according to claim 7, wherein the sintering temperature is 1400 to 1800 ℃.
10. Use of a ceramic composition or a ceramic substrate in an electronic device, characterized in that the ceramic composition is according to any one of claims 1 to 5 and the ceramic substrate is according to claim 6.
CN202310391589.1A 2023-04-13 2023-04-13 Ceramic composition, ceramic substrate, and preparation method and application of ceramic substrate Pending CN116621565A (en)

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