CN115557784A - MZTA ceramic material and preparation method and application thereof - Google Patents

MZTA ceramic material and preparation method and application thereof Download PDF

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CN115557784A
CN115557784A CN202210857689.4A CN202210857689A CN115557784A CN 115557784 A CN115557784 A CN 115557784A CN 202210857689 A CN202210857689 A CN 202210857689A CN 115557784 A CN115557784 A CN 115557784A
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mzta
powder
basmt
temperature
flaky
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CN115557784B (en
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谢天翼
林慧兴
王怀志
任海深
赵相毓
姜少虎
彭海益
顾忠元
张奕
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to an MZTA ceramic material and a preparation method and application thereof. The chemical general formula of the MZTA ceramic material is Mg 1‑ x Zn x (Ti 1‑y Aly)O 3 Wherein x is more than 0 and less than or equal to 0.3, and y is more than 0 and less than or equal to 0.2.

Description

MZTA ceramic material and preparation method and application thereof
Technical Field
The invention relates to an MZTA ceramic material and a preparation method and application thereof, in particular to a low-temperature co-fired material and a preparation method and application thereof, and especially relates to a low-temperature co-fired material with medium dielectric constant, low dielectric loss and high heat conductivity and a preparation method and application thereof, belonging to the field of low-temperature co-fired materials.
Background
The low temperature co-fired ceramic (LTCC) technology is that low temperature sintered ceramic powder is made into a green ceramic tape with accurate thickness and compactness as a circuit substrate material, required circuit patterns are made on the green ceramic tape by utilizing the processes of laser drilling, micropore grouting, printing of precise conductor slurry and the like, a plurality of passive elements are embedded in the green ceramic tape, then the green ceramic tape and the green ceramic tape are laminated together and sintered at 900 ℃ to make a passive integrated component of a three-dimensional circuit network, and also can be made into a three-dimensional circuit substrate with the passive elements inside, and an IC and an active device can be pasted on the surface of the three-dimensional circuit substrate to make a passive/active integrated functional module.
In recent years, LTCC materials have been widely used in the fields of aerospace, military, wireless communication, electronic devices, wireless communication, automotive electronics, chemical and biomedical science, environmental energy and the like, and with the rapid development of military electronic machines, communication electronic products and consumer electronic products in the short, small, light and thin directions, microwave multi-chip module (MMCM) technology has been widely used due to its technical characteristics of light weight, small volume, low cost and high reliability. The multilayer chip component is an effective way for realizing the technology, and from the aspects of economy and environmental protection, the chip type of the microwave component requires that a microwave dielectric material can be co-fired with electrodes of base-price metal Cu or Ag with lower melting point and high conductivity, so that the microwave dielectric ceramic material can be co-fired with Cu or Ag at low temperature, and therefore people develop a novel low-temperature co-fired ceramic technology which is widely applied to the communication fields of aerospace, 5G base stations, automobile radars and the like and is used as a basic, common and key material in the communication fields. In spite of the current research situation of low-temperature co-fired ceramic materials at home and abroad in recent years, LTCC material systems can be divided into three categories: (1) microcrystalline glass based low temperature co-fired ceramic; (2) microwave dielectric ceramic-based low-temperature co-fired ceramic; and (3) novel low-temperature sintering temperature microwave dielectric ceramic.
In most of the research on LTCC, the dielectric constant of the microcrystalline glass-based low-temperature co-fired ceramic is below 10, and the microcrystalline glass-based low-temperature co-fired ceramic can only be used as a substrate sealing material and has low strength, so that the microcrystalline glass-based low-temperature co-fired ceramic cannot meet more and more application occasions requiring high dielectric constant LTCC materials.
Disclosure of Invention
Aiming at the defects of low dielectric constant, low strength and the like of the LTCC, the MZTA ceramic material, the medium, low-loss and high-thermal-conductivity LTCC material prepared by tape casting and isostatic pressing and the preparation method thereof are provided. A dielectric constant of 15-25 and a dielectric loss of less than 5 x 10 -4 (10 GHz), low cost and easy mass production of Mg 1-x Zn x (Ti 1-y Al y )O 3 A base LTCC material, a preparation method thereof and a capacitor prepared by the composite material.
In a first aspect, the invention provides an MZTA ceramic material, wherein the chemical formula of the MZTA ceramic material is Mg 1-x Zn x (Ti 1-y Aly)O 3 Wherein x is more than 0 and less than or equal to 0.3, and y is more than 0 and less than or equal to 0.2.
Preferably, x is more than or equal to 0.2 and less than or equal to 0.3; y is more than or equal to 0.1 and less than or equal to 0.2.
Preferably, the MZTA ceramic material has a dielectric constant of 20-25 and a dielectric loss of less than 2 x 10 -4 (10 GHz) and a thermal conductivity of 1-3W/(mK).
In a second aspect, the invention provides a preparation method of an MZTA ceramic material, which is based on the chemical general formula Mg of MZTA ceramic powder 1-x Zn x (Ti 1-y Aly)O 3 Weighing MgO powder, znO powder and Al 2 O 3 Powder, tiO 2 Mixing the powders, and calcining to obtain the MZTA ceramic material; the calcining temperature is 1150-1250 ℃, and the time is more than or equal to 3 hours.
In a third aspect, the invention provides MZTA ceramic powder prepared from the MZTA ceramic material; preferably, the particle size D of the MZTA ceramic powder 50 Is 0.1 to 5 μm, preferably 0.5 to 2 μm, and most preferably 1 μm.
In a fourth aspect, the invention provides an MZTA/BASMT/flaky BN low-temperature co-fired material, which is obtained by compounding BASMT glass powder, the MZTA ceramic powder and flaky BN powder.
Preferably, the BASMT glass powder has a chemical general formula of aB 2 O 3 -bAl 2 O 3 -cSiO 2 -dMgO-eTiO 2 Wherein a = 20-30 moL%, b = 0-10 moL%, c = 30-40 moL%, d = 20-30 moL%, e = 0-10 moL%, a + b + c + d + e =100moL%.
Preferably, the sum of the total mass of the BASMT glass powder, the MZTA ceramic powder and the flaky BN powder is 100wt%, the content of the MZTA ceramic powder is 50-70 wt%, the content of the BASMT glass powder is 30-40 wt%, and the content of the flaky BN powder is 0-10 wt%.
Preferably, the particle size D of the BASMT glass powder 50 0.5 to 2 μm, preferably 1 μm; the thickness of the flaky BN powder is 1-5 mu m, and the diameter of the flaky BN powder is 10-20 mu m.
Preferably, B is weighed according to the stoichiometric ratio of BASMT glass powder 2 O 3 Powder, al 2 O 3 Powder, siO 2 Powder, mgO powder, tiO 2 Mixing the powder balls, melting, and pouring in water to form BASMT glass; crushing or ball milling to obtain BASMT glass powder; the melting temperature is 1400-1500 ℃, and the heat preservation time is more than or equal to 2 hours.
Preferably, the MZTA/BASMT/sheet BN low-temperature co-fired material has the dielectric constant of 15-20 and the dielectric loss lower than 8 x 10 -4 (10 GHz), and the thermal conductivity is 2-8W/(mK) (preferably 5-8W/(mK)).
In a fifth aspect, the invention provides a preparation method of an MZTA/BASMT/flaky BN low-temperature co-fired material, which comprises the following steps:
(1) Modifying the flaky BN by using a modifier solution containing at least one modifier selected from polysilazane, acrylate, vinyl siloxane and methacrylic acid to obtain modified flaky BN;
(2) Mixing the modified BN flake, MZTA ceramic powder, BASMT glass powder, a binder and a solvent, and then carrying out tape casting and drying to obtain an MZTA/BASMT/flake BN membrane band;
(3) And (3) laminating a plurality of MZTA/BASMT/flaky BN membrane belts, and then performing hot isostatic pressing forming and sintering to obtain the MZTA/BASMT/flaky BN low-temperature co-fired material.
Preferably, in the step (1), the concentration of the modifier solution is 5wt%; the total amount of the modifier is 0-5 wt% of the flaky BN.
Preferably, in the step (2), the binder is at least one selected from PVB, ethyl cellulose and PVA; the addition amount of the binder is 5-10 wt% of the total mass of the BASMT glass powder, the MZTA ceramic powder and the flaky BN powder; the solvent is selected from at least one of alcohol, toluene, acetone and xylene.
Preferably, in the step (2), the casting temperature is 50-70 ℃, and the height of the scraper is 200-500 μm; the thickness of the obtained MZTA/BASMT/flaky BN membrane strip is 70-170 μm.
Preferably, in the step (3), the hot isostatic pressing temperature is 50-85 ℃, and the pressure is 30-70 MPa; the sintering temperature is 800-1000 ℃, and the sintering time is 1-4 hours.
In a sixth aspect, the invention provides a capacitor, which is characterized by being prepared from the MZTA/BASMT/flaky BN low-temperature co-fired material.
Has the advantages that:
in the invention, the MZTA ceramic material is a microwave dielectric ceramic material, the dielectric constant of the MZTA ceramic material is 15 to 20, and the dielectric loss of the MZTA ceramic material is lower than 8 multiplied by 10 -4 (10 GHz). The method is widely applied to the modern communication industries such as satellite communication, mobile communication and the like.
In the invention, the bonding force of BN and the glass matrix is improved by surface modification of h-BN, so that the dielectric loss of the composite material is reduced, and the heat conductivity coefficient is improved. In addition, the orientation of BN is directionally enhanced by a casting isostatic pressing mode, so that the heat conducting performance of the composite material is improved.
The LTCC material has the dielectric constant of 15-20 and the dielectric loss of less than 8 multiplied by 10 -4 (10 GHz), and is compounded with flaky BN to obtain the low temperature co-fired ceramic (LTCC) material with medium dielectric constant, low dielectric loss and high heat conductivity, low cost and easy mass production 1-x Zn x (Ti 1-y Al y )O 3 A base LTCC material. The method is widely applied to the modern communication industries such as satellite communication, mobile communication and the like.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
Disclosed herein are a microwave dielectric ceramic and a glass, wherein the microwave dielectric ceramic contains four main elements of Mg, zn, ti, al and O, and the glass contains five main elements of B, al, si, mg, ti and O.
In the invention, the chemical general formula of the microwave dielectric ceramic is Mg 1-x Zn x (Ti 1-y Al y )O 3 (abbreviated as MZTA), wherein x is more than 0 and less than or equal to 0.3, and y is more than 0 and less than or equal to 0.2. The chemical general formula of the glass for compounding is B 2 O 3 -Al 2 O 3 -SiO 2 -MgO-TiO 2 (BASMT) and flake BN. In an alternative embodiment, glass B 2 O 3 -Al 2 O 3 -SiO 2 -MgO-TiO 2 (BASMT) has a composition of B 2 O 3 ：20～30mol％、Al 2 O 3 ：0～10mol％、SiO 2 :30 to 40mol%, mgO:20 to 30mol%, znO:0 to 10mol percent, and the sum of the mol percent of the five compositions is 100 percent.
The microwave dielectric ceramic has both medium dielectric constant and low dielectric loss, for example, the dielectric constant can be 20-30, and the dielectric loss can be 2 x 10 -4 ～5×10 -4 . The disclosed glass has both a medium dielectric constant and a low dielectric loss, e.g., the dielectric constant can be 8-10 and the dielectric loss can be 8 x 10 -4 ～10×10 -4 。
Disclosed herein is an MZTA/BASMT/sheet BN low-temperature co-fired material, comprising: mg (magnesium) 1-x Zn x (Ti 1-y Al y )O 3 Powder (abbreviated as MZTA powder) 0 therein<x<0.3，0<y<0.2, and B 2 O 3 -Al 2 O 3 -SiO 2 -MgO-TiO 2 Powder (BASMT powder), B 2 O 3 ：20～30mol％、Al 2 O 3 ：0～10mol％、SiO 2 ：30～40mol％、MgO：20～30mol％、ZnO：0～10mol%. Preferably, the low-temperature co-fired material consists of MZTA powder/BASMT powder/flaky BN powder/binder.
In the invention, the MZTA/BASMT/flaky BN is compounded, because the BASMT glass has higher dielectric constant and lower dielectric loss and has lower glass transition point, the BASMT glass is easy to sinter and compact when being added into ceramic, and after being compounded with the MZTA ceramic and flaky BN, the sample has high compactness, so that the composite material has adjustable dielectric constant and lower dielectric loss.
In the composite dielectric material, MZTA ceramic can be used as a matrix, and BASMT glass and flaky BN can be used as fillers. In one embodiment, the composite dielectric material is formed as a capacitive material.
In the composite dielectric material, the mass of the MZTA ceramic powder can be 50 percent of the total mass of the MZTA ceramic/BASMT glass/flaky BN composite. The mass of the flaky BN can be 0-20% of the total mass of the MZTA ceramic/BASMT glass/flaky BN composite. At this mass fraction, a composite material having lower dielectric loss and higher thermal conductivity, e.g., dielectric loss of less than 8 x 10, can be made -4 (10 GHz), the thermal conductivity can reach 5W/(m.K) at most. More preferably, the mass of the MZTA ceramic is 50% of the total mass of the MZTA ceramic/BASMT glass/flaky BN, and the mass of the flaky BN is 5-10% of the total mass of the MZTA ceramic/BASMT glass/flaky BN.
In a preferred embodiment, the microwave dielectric ceramic in the composite dielectric material is granular, the grain diameter of the microwave dielectric ceramic is 1-5 μm, the surface energy of the adopted micron-level powder is low, agglomeration is not easy to occur, and pores among the granules are reduced. The dielectric loss can be reduced, and the thermal conductivity can be improved.
Next, the preparation methods of the above microwave dielectric ceramic and composite dielectric material are explained as examples.
First, MZTA powder is synthesized. MgO, znO and Al in MZTA microwave dielectric material 2 O、TiO 2 Weighing according to the proportion (stoichiometric ratio) and mixing uniformly. Wherein MgO can be 4MgCO 3 ·Mg(OH) 2 ·8H 2 And (4) converting the O. In one example, deionized water is used as a ball milling medium, and the deionized water is uniformly mixed on a planetary ball mill and dried. Material preparation: ball: the water is 1:1:1. ball milled powderThe particle size of the material can be 1-5 μm. And calcining the uniformly mixed raw materials to synthesize the MZTA powder. The calcination temperature may be 1100 to 1350 deg.C, preferably 1200 to 1300 deg.C. The incubation time is preferably 4h.
B is to be 2 O 3- Al 2 O 3 -SiO 2 -MgO-TiO 2 (BASMT) glass B 2 O 3 、Al 2 O 3 、SiO 2 、MgO、TiO 2 Weighing according to the proportion (stoichiometric ratio) and mixing uniformly. Wherein B is 2 O 3 Available of H 3 BO 3 And (6) converting. And performing secondary ball milling for 10 hours after melting to obtain the glass powder. The melting temperature may be 1400 to 1500 deg.C, preferably 1450 deg.C. The holding time is preferably 4h.
The low-temperature co-fired material can be prepared by mixing and granulating MZTA ceramic powder, BASMT glass and flaky BN. Further, casting, lamination, and isostatic pressing were performed to obtain a multilayer capacitor.
The grain diameter of MZTA ceramic powder may be 1-5 micron. The microwave dielectric ceramic powder and the glass powder can be obtained by ball milling the microwave dielectric ceramic prepared by the method.
And modifying the flaky BN and MZTA ceramics by using a coupling agent to obtain modified flaky BN and MZTA ceramic powder. Through modification, the hydrophilicity of the surface of the inorganic material can be changed, the bonding force between the flaky BN and MZTA ceramic powder and BASMT glass is increased, and the aims of reducing interface pores, reducing loss and improving the heat conductivity coefficient are fulfilled. For example, 1wt% of coupling agent modified BN and ceramic mixed with BASMT glass has dielectric constant of about 19 and dielectric loss lower than 5X 10 -4 And the thermal conductivity coefficient is about 5.2W/(m.K), which is improved by more than 100 percent compared with a pure MZTA/BASMT low-temperature co-fired system.
The coupling agent used for modification is polysilazane, which can form an interface layer of a glass-philic layer on the surface of the ceramic, so that the porosity of the composite material is further reduced while the bonding force of two phases is enhanced. The amount of the coupling agent may be 0 to 1.5% (mass fraction) of the flaky BN powder, preferably 1 to 1.5%.
In one example, the modified flaky BN powder is obtained by placing flaky BN powder into 10% polysilazane solution, the total amount of polysilazane is 0-1.5 wt% of ceramic, magnetically stirring for 5 hours, performing suction filtration, and drying at 120 ℃.
And uniformly mixing the modified flaky BN powder with MZTA ceramic powder and BASMT glass. The sheet-like BN and MZTA ceramic/BASMT glass were mixed in a ratio of 5:35:60, mixing, placing in a three-dimensional mixer, adding a solvent (such as alcohol) and a binder after uniformly mixing, placing the slurry in a casting machine, and casting at the temperature of 50-70 ℃ to obtain the casting film belt. And (3) performing laminated hot-press molding (the hot-press temperature is 50-85 ℃, the hot-press pressure is 30-70 MPa) and low-temperature sintering on the casting film belt to finally obtain the high-thermal-conductivity low-temperature co-fired material.
In the invention, the prepared high-thermal-conductivity low-temperature co-fired material has high and adjustable dielectric constant (15-20), and the dielectric loss is lower than 8 multiplied by 10 -4 . The high-thermal-conductivity low-temperature co-fired material has good processing performance on the premise of retaining excellent dielectric performance, and can meet the requirements of new-generation communication materials.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing description are intended to be included within the scope of the invention. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below. In the following examples, the dielectric constant and dielectric loss of the prepared substrate ceramic material were measured by the stripline method with the aid of an Agilent E8363APNA network analyzer.
Example 1
(1) Mixing MgO, znO and TiO 2 、Al 2 O 3 According to Mg 0.95 Zn 0.05 (Ti 0.95 Al 0.05 )O 3 Mixing according to the stoichiometric ratio, adding deionized water as a ball milling medium, performing ball milling for 10 hours, drying at 150 ℃, and calcining the powder for 4 hours at 1100 ℃;
(2) Adding deionized water into the calcined powder as a ball milling medium, performing secondary ball milling for 10 hours, and sieving to obtain D 50 1-5 μm of Mg 0.95 Zn 0.05 (Ti 0.95 Al 0.05 )O 3 Powder;
(3) Placing the powder into a 10% polysilazane solution, wherein the total amount of polysilazane is 1wt% of the ceramic, magnetically stirring for 5 hours, performing suction filtration, and drying at 120 ℃;
(4) B is to be 2 O 3 -Al 2 O 3 -SiO 2 -MgO-TiO 2 (BASMT-1)，B 2 O 3 、Al 2 O 3 、SiO 2 、MgO、TiO 2 According to the weight ratio of 25:5:30:30:10, melting, and performing secondary ball milling for 10 hours to obtain the glass powder. The melting temperature may be 1400 to 1500 deg.C, preferably 1450 deg.C. The holding time is preferably 4h. Adding de-alcohol as ball milling medium, ball milling for 10 hr, and drying at 150 deg.C to obtain D 50 Is BASMT-1 glass powder of 1-5 μm;
(5) Mixing flaky BN, BASMT glass powder and MZTA ceramic powder in a ratio of 5:35:60, mixing, placing in a three-dimensional mixer, uniformly mixing, adding alcohol and a binder, continuously mixing, placing the obtained slurry in a casting machine, and carrying out casting at the temperature of 60 ℃ to obtain a casting film belt;
(6) And (3) carrying out laminated hot-press molding on the casting film belt (the hot-press temperature is 75 ℃, the hot-press pressure is 70 MPa), and sintering at 850 ℃ for 2 hours to finally obtain the high-thermal-conductivity low-temperature co-fired material. The process parameters are listed in table 3, and the performance test results of the finally obtained capacitor material are shown in table 4.
Example 2
In this example 2, the preparation process of the high-thermal conductivity low-temperature co-fired material refers to example 1, and the difference is only that: in the step (1), mgO, znO and TiO are added 2 、Al 2 O 3 According to Mg 0.9 Zn 0.1 (Ti 0.95 Al 0.05 )O 3 Mixing the raw materials according to the stoichiometric ratio, adding deionized water as a ball milling medium, performing ball milling for 10 hours, drying the ball milling product at 150 ℃, and calcining the powder for 4 hours at 1100 ℃.
Example 3
In this example 3, the preparation process of the high-thermal conductivity low-temperature co-fired material refers to example 1, and the difference is only that: in the step (1), mgO, znO and TiO are added 2 、Al 2 O 3 According to Mg 0.85 Zn 0.15 (Ti 0.95 Al 0.05 )O 3 Mixing the raw materials according to the stoichiometric ratio, adding deionized water as a ball milling medium, performing ball milling for 10 hours, drying the ball milling product at 150 ℃, and calcining the powder for 4 hours at 1100 ℃.
Example 4
In this example 4, the preparation process of the high thermal conductivity low temperature co-fired material is as in example 1, except that: in the step (1), mgO, znO and TiO are added 2 、Al 2 O 3 According to Mg 0.8 Zn 0.2 (Ti 0.95 Al 0.05 )O 3 Mixing the raw materials according to the stoichiometric ratio, adding deionized water as a ball milling medium, performing ball milling for 10 hours, drying the ball milling product at 150 ℃, and calcining the powder for 4 hours at 1100 ℃.
Example 5
In this example 5, the preparation process of the high thermal conductivity low temperature co-fired material is as in example 1, except that: in the step (1), mgO, znO and TiO are added 2 、Al 2 O 3 According to Mg 0.75 Zn 0.25 (Ti 0.95 Al 0.05 )O 3 Mixing the raw materials according to the stoichiometric ratio, adding deionized water as a ball milling medium, carrying out ball milling for 10 hours, drying the mixture at 150 ℃, and calcining the powder for 4 hours at 1100 ℃.
Example 6
In this example 6, the preparation process of the high thermal conductivity low temperature co-fired material is as in example 1, except that: in the step (1), mgO, znO and TiO are added 2 、Al 2 O 3 According to Mg 0.7 Zn 0.3 (Ti 0.95 Al 0.05 )O 3 Mixing the raw materials according to the stoichiometric ratio, adding deionized water as a ball milling medium, performing ball milling for 10 hours, drying the ball milling product at 150 ℃, and calcining the powder for 4 hours at 1100 ℃.
Example 7
Example 7 the preparation process of the high thermal conductivity low temperature co-fired material is as in example 6 with the difference thatIn the following steps: in the step (1), mgO, znO and TiO are added 2 、Al 2 O 3 According to Mg 0.7 Zn 0.3 (Ti 0.9 Al 0.1 )O 3 Mixing the raw materials according to the stoichiometric ratio, adding deionized water as a ball milling medium, carrying out ball milling for 10 hours, drying the mixture at 150 ℃, and calcining the powder for 4 hours at 1100 ℃.
Example 8
In this example 8, the preparation process of the high thermal conductivity low temperature co-fired material is as follows, with reference to example 6, except that: in the step (1), mgO, znO and TiO are added 2 、Al 2 O 3 According to Mg 0.7 Zn 0.3 (Ti 0.85 Al 0.15 )O 3 Mixing the raw materials according to the stoichiometric ratio, adding deionized water as a ball milling medium, performing ball milling for 10 hours, drying the ball milling product at 150 ℃, and calcining the powder for 4 hours at 1100 ℃.
Example 9
In this example 9, the preparation process of the high thermal conductivity low temperature co-fired material is as follows, with reference to example 6, except that: in the step (1), mgO, znO and TiO are added 2 、Al 2 O 3 According to Mg 0.7 Zn 0.3 (Ti 0.8 Al 0.2 )O 3 Mixing the raw materials according to the stoichiometric ratio, adding deionized water as a ball milling medium, performing ball milling for 10 hours, drying the ball milling product at 150 ℃, and calcining the powder for 4 hours at 1100 ℃.
Example 10
In this example 10, the preparation process of the high thermal conductivity low temperature co-fired material is as follows, with reference to example 9, except that: in the step (5), the flaky BN, MZTA ceramic powder and BASMT glass powder are mixed in a proportion of 2.5:37.5:60, mixing, placing in a three-dimensional mixer, uniformly mixing, adding alcohol and a binder, continuously mixing, placing the obtained slurry in a casting machine, and carrying out casting at the temperature of 60 ℃ to obtain the casting film belt.
Example 11
In this example 11, the preparation process of the high thermal conductivity low temperature co-fired material is as follows, with reference to example 9, except that: in the step (5), the flaky BN, MZTA ceramic powder and BASMT glass powder are mixed in a proportion of 7.5:32.5:60, mixing, placing in a three-dimensional mixer, uniformly mixing, adding alcohol and a binder, continuously mixing, placing the obtained slurry in a casting machine, and casting at the temperature of 60 ℃ to obtain the casting film band.
Example 12
In this example 12, the preparation process of the high thermal conductivity low temperature co-fired material is as follows, with reference to example 9, except that: in the step (5), the flaky BN, MZTA ceramic powder and BASMT glass powder are mixed in a proportion of 10:30:60, mixing, placing in a three-dimensional mixer, uniformly mixing, adding alcohol and a binder, continuously mixing, placing the obtained slurry in a casting machine, and carrying out casting at the temperature of 60 ℃ to obtain the casting film belt.
Example 13
In this example 13, the preparation process of the high thermal conductivity low temperature co-fired material is as follows, with reference to example 9, except that: in the step (4), B 2 O 3 -Al 2 O 3 -SiO 2 -MgO-TiO 2 (BASMT-2)，B 2 O 3 、Al 2 O 3 、SiO 2 、MgO、TiO 2 According to the proportion of 20:5:35:30:10, melting, and performing secondary ball milling for 10 hours to obtain the glass powder.
Example 14
In this example 14, the preparation process of the high thermal conductivity low temperature co-fired material is as follows with reference to example 9, except that: in step (4), B is added 2 O 3 -Al 2 O 3 -SiO 2 -MgO-TiO 2 (BASMT-3)，B 2 O 3 、Al 2 O 3 、SiO 2 、MgO、TiO 2 According to the weight ratio of 30:5:30:25:10, melting, and performing secondary ball milling for 10 hours to obtain the glass powder.
Example 15
In this example 15, the preparation process of the high thermal conductivity low temperature co-fired material is as follows, with reference to example 9, except that: in the step (4), B 2 O 3 -Al 2 O 3 -SiO 2 -MgO-TiO 2 (BASMT-4)，B 2 O 3 、Al 2 O 3 、SiO 2 、MgO、TiO 2 According to the following steps of 25:5:40:20:10, melting, and performing secondary ball milling for 10 hours to obtain the glass powder.
Example 16
In this example 16, the preparation process of the high thermal conductivity low temperature co-fired material is as follows, with reference to example 9, except that: in the step (5), the flaky BN, BASMT glass powder and MZTA ceramic powder are mixed in a ratio of 5:35:60, mixing, placing in a three-dimensional mixer, uniformly mixing, adding alcohol and a binder, continuously mixing, placing the obtained slurry in a casting machine, and casting at the temperature of 60 ℃ to obtain a casting film belt; the used flake BN does not undergo polysilazane modification treatment.
Example 17
In this example 17, the preparation process of the high-thermal conductivity low-temperature co-fired material is as described in example 9, except that: in the step (5), the flaky BN, BASMT glass powder and MZTA ceramic powder are mixed in a ratio of 5:45:50, placing the mixture in a three-dimensional mixer, uniformly mixing, adding alcohol and a binder, continuously mixing, placing the obtained slurry in a casting machine, and carrying out casting at the temperature of 60 ℃ to obtain the casting film belt.
Example 18
In this example 18, the preparation process of the high thermal conductivity low temperature co-fired material is as follows with reference to example 9, except that: in the step (5), the flaky BN, BASMT glass powder and MZTA ceramic powder are mixed in a proportion of 0:30:70, mixing, placing in a three-dimensional mixer, uniformly mixing, adding alcohol and a binder, continuously mixing, placing the obtained slurry in a casting machine, and casting at the temperature of 60 ℃ to obtain a casting film band.
Comparative example 1
The preparation process of the high-thermal-conductivity low-temperature co-fired material in comparative example 1 refers to example 9, and the difference is only that: in the step (1), mgO, znO and TiO are added 2 、Al 2 O 3 According to Mg 0.7 Zn 0.3 TiO 3 Mixing the raw materials according to the stoichiometric ratio, adding deionized water as a ball milling medium, performing ball milling for 10 hours, drying the ball milling product at 150 ℃, and calcining the powder for 4 hours at 1100 ℃.
Comparative example 2
The preparation process of the high-thermal-conductivity low-temperature co-fired material in the comparative example 2 refers to the example 9, and the difference is only that: in the step (1), mgO, znO and TiO are added 2 、Al 2 O 3 According to Mg (Ti) 0.8 Al 0.2 )O 3 Mixing at a stoichiometric ratio of (A), adding deionizationUsing water as ball milling medium, ball milling for 10 hours, drying at 150 ℃, and calcining the powder material for 4 hours at 1100 ℃.
Comparative example 3
The preparation process of the high-thermal conductivity low-temperature co-fired material in the comparative example 3 is as follows, referring to example 9, and the difference is that: in the step (5), the flaky BN, BASMT glass powder and MZTA ceramic powder are mixed in a ratio of 5:55:40, uniformly mixing the mixture in a three-dimensional mixer, adding alcohol and a binder, continuously mixing, placing the obtained slurry in a casting machine, and carrying out casting at the temperature of 60 ℃ to obtain the casting film belt.
Comparative example 4
The preparation process of the high-thermal conductivity low-temperature co-fired material in the comparative example 4 is as follows, referring to example 9, and the difference is that: in the step (5), the flaky BN, BASMT glass powder and MZTA ceramic powder are mixed in a ratio of 5:15:80, placing the mixture in a three-dimensional mixer, uniformly mixing, adding alcohol and a binder, continuously mixing, placing the obtained slurry in a casting machine, and carrying out casting at the temperature of 60 ℃ to obtain the casting film belt.
Comparative example 5
The preparation process of the high-thermal-conductivity low-temperature co-fired material in the comparative example 5 refers to the example 9, and the difference is only that: in the step (5), the flaky BN, BASMT glass powder and MZTA ceramic powder are mixed in a proportion of 12.5:27.5:60, mixing, placing in a three-dimensional mixer, uniformly mixing, adding alcohol and a binder, continuously mixing, placing the obtained slurry in a casting machine, and casting at the temperature of 60 ℃ to obtain the casting film belt.
Table 1 shows the composition and performance parameters of the prepared MZTA ceramic materials:
Figure BDA0003756179850000091
Figure BDA0003756179850000101
table 2 shows the composition and performance parameters of the prepared BASMT glasses:
Figure BDA0003756179850000102
table 3 shows the material compositions of the LTCC materials prepared in examples 1-15:
Figure BDA0003756179850000103
Figure BDA0003756179850000111
table 4 shows the performance parameters of the LTCC materials prepared in examples 1-15:
Figure BDA0003756179850000112
Figure BDA0003756179850000121
as can be seen from Table 4, with the increase of Zn, the dielectric constant of the sample increases, the loss slowly increases, the thermal conductivity is basically unchanged, the ionic polarizability of Zn is higher than that of Mg, and the dielectric constant of the sample increases under the same density condition; along with the increase of Al, the dielectric constant of the sample is reduced, the loss is slowly reduced, the thermal conductivity is basically unchanged, the ionic polarizability of Ti is higher than that of Al, and the dielectric constant of the sample is reduced under the same density condition. When the content of the flaky BN is increased, the dielectric constant is continuously reduced, the loss is increased, the thermal conductivity is continuously increased, the thermal conductivity of the BN is higher and is more than 100W/(m.K) and is far higher than the dielectric constant of a system, so the overall thermal conductivity is increased, and when the flaky BN is too much, the loss is increased due to too many three-phase interfaces, but the thermal conductivity of the system is also increased due to the arrangement of the flaky BN. Thus example 9 achieved the best overall performance.

Claims (15)

1. An MZTA ceramic material, characterized in that, the chemical formula of the MZTA ceramic material is Mg 1-x Zn x (Ti 1-y Aly)O 3 Wherein x is more than 0 and less than or equal to 0.3, and y is more than 0 and less than or equal to 0.2.
2. The MZTA ceramic material of claim 1, wherein 0.2. Ltoreq. X.ltoreq.0.3; y is more than or equal to 0.1 and less than or equal to 0.2.
3. The MZTA ceramic material of claim 1 or claim 2, wherein said MZTA ceramic material has a dielectric constant of from 20 to 25 and a dielectric loss of less than 2 x 10 -4 (10 GHz) and a thermal conductivity of 1 to 3W/(mK).
4. A method for preparing MZTA ceramic materials of any of claims 1 to 3, wherein the chemical formula of the MZTA ceramic powder is Mg 1-x Zn x (Ti 1-y Aly)O 3 Weighing MgO powder, znO powder and Al 2 O 3 Powder, tiO 2 Mixing the powders, and calcining to obtain the MZTA ceramic material; the calcining temperature is 1150-1250 ℃, and the time is more than or equal to 3 hours.
5. An MZTA ceramic powder prepared from the MZTA ceramic material of any one of claims 1 to 3; preferably, the particle diameter D of the MZTA ceramic powder 50 0.5 to 2 μm.
6. An MZTA/BASMT/flaky BN low-temperature co-fired material, which is characterized by comprising BASMT glass powder, the MZTA ceramic powder and flaky BN powder of claim 5 which are compounded to obtain the MZTA/BASMT/flaky BN low-temperature co-fired material; the chemical general formula of the BASMT glass powder is aB 2 O 3 -bAl 2 O 3 -cSiO 2 -dMgO-eTiO 2 Wherein a = 20-30 moL%, b = 0-10 moL%, c = 30-40 moL%, d = 20-30 moL%, e = 0-10 moL%, a + b + c + d + e =100moL%.
7. The MZTA/BASMT/flaky BN low-temperature co-fired material of claim 6, wherein the total mass of the BASMT glass powder, the MZTA ceramic powder and the flaky BN powder is 100wt%, the content of the MZTA ceramic powder is 50 to 70wt%, the content of the BASMT glass powder is 30 to 40wt%, and the content of the flaky BN powder is 0 to 20wt%.
8. The MZTA/BASMT/flaky BN low-temperature co-fired material of claim 6, wherein the particle size D of the BASMT glass powder is 50 0.5-2 μm; the thickness of the flaky BN powder is 1-5 mu m, and the diameter of the flaky BN powder is 10-20 mu m.
9. The preparation method according to claim 6, wherein B is weighed according to the stoichiometric ratio of BASMT glass powder 2 O 3 Powder, al 2 O 3 Powder, siO 2 Powder, mgO powder, tiO 2 Mixing the powder balls, melting, and pouring in water to form BASMT glass; crushing or ball milling to obtain BASMT glass powder; the melting temperature is 1400-1500 ℃, and the heat preservation time is more than or equal to 2 hours.
10. The MZTA/BASMT/sheet BN low-temperature co-fired material of any one of claims 6 to 9, wherein said MZTA/BASMT/sheet BN low-temperature co-fired material has a dielectric constant of 15 to 20 and a dielectric loss of less than 8 x 10 -4 (10 GHz) and a thermal conductivity of 2-8W/(mK).
11. A method for preparing MZTA/BASMT/sheet BN low-temperature co-fired material according to any one of claims 6 to 10, comprising:
(1) Modifying the flaky BN by using a modifier solution containing at least one modifier selected from polysilazane, acrylate, vinyl siloxane and methacrylic acid to obtain modified flaky BN;
(2) Mixing the modified BN flake, MZTA ceramic powder, BASMT glass powder, a binder and a solvent, and then carrying out tape casting and drying to obtain an MZTA/BASMT/flake BN membrane band;
(3) And (3) laminating a plurality of MZTA/BASMT/flaky BN membrane belts, and then performing hot isostatic pressing forming and sintering to obtain the MZTA/BASMT/flaky BN low-temperature co-fired material.
12. The method according to claim 11, wherein in the step (1), the concentration of the modifier solution is 5wt%; the total amount of the modifier is 0-5 wt% of the flaky BN.
13. The production method according to claim 11, wherein in the step (2), the temperature of the tape casting is 50 to 70 ℃, and the height of the doctor blade is 200 to 500 μm; the thickness of the obtained MZTA/BASMT/sheet-shaped BN membrane strip is 70-170 μm.
14. The production method according to any one of claims 11 to 13, wherein in step (3), the hot isostatic pressing is performed at a temperature of 50 to 85 ℃ and a pressure of 30 to 70MPa; the sintering temperature is 800-1000 ℃, and the sintering time is 1-4 hours.
15. A capacitor prepared from the MZTA/BASMT/sheet BN low temperature co-fired material of any one of claims 6 to 10.
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