CN115557784B - 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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CN115557784B
CN115557784B CN202210857689.4A CN202210857689A CN115557784B CN 115557784 B CN115557784 B CN 115557784B CN 202210857689 A CN202210857689 A CN 202210857689A CN 115557784 B CN115557784 B CN 115557784B
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powder
mzta
bamt
flaky
ceramic
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CN115557784A (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, a preparation method and application thereof. The M isThe ZTA ceramic material has the chemical general formula of 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 cofiring material and a preparation method and application thereof, and particularly relates to a low-temperature cofiring material with medium dielectric constant, low dielectric loss and high heat conduction and a preparation method and application thereof, belonging to the field of low-temperature cofiring materials.
Background
The low temperature co-firing ceramic technology (LTCC) is to make low temperature sintered ceramic powder into ceramic belt with precise and compact thickness as circuit substrate material, to make required circuit pattern on the ceramic belt by laser drilling, micro-hole grouting, precise conductor paste printing and other processes, to embed multiple passive elements therein, to laminate them together, to sinter at 900 deg.C to make into passive integrated component of three-dimensional circuit network, or to make into three-dimensional circuit substrate with built-in passive elements, on the surface of which IC and active devices can be mounted to make into passive/active integrated functional module.
In recent years, LTCC materials have been widely used in the fields of aerospace, military, wireless communication, electronic equipment, wireless communication, automotive electronics, chemical and biological medical treatment, environmental energy, etc., and along with the rapid development of military electronic complete machines, communication electronic products and consumer electronic products are rapidly developed in the directions of short, small, light and thin, and microwave multi-chip module (MMCM) technology is widely used due to the technical characteristics of light weight, small volume, low cost and high reliability. The multilayer chip element is an effective way for realizing the technology, and from the aspects of economy and environmental protection, the chip type microwave element needs to be co-fired with an electrode of base metal Cu or Ag with low melting point and high conductivity, so that the microwave dielectric ceramic material needs to be co-fired with Cu or Ag at low temperature, and the novel low-temperature co-fired ceramic technology is developed for the purpose, and is widely applied to the communication fields of aerospace, 5G base stations, automobile radars and the like and used as a basic, common and critical material in the microwave dielectric material. In recent years, the research status of low-temperature co-fired ceramic materials at home and abroad can be divided into three categories: (1) glass-ceramic-based low-temperature cofiring ceramics; (2) microwave dielectric ceramic-based low-temperature cofiring ceramic; (3) novel low-temperature sintering temperature microwave dielectric ceramics.
In most of the research of LTCC, the dielectric constant of the glass-ceramic-based low-temperature co-fired ceramic is below 10, and the glass-ceramic-based low-temperature co-fired ceramic can only be applied as a substrate sealing material, has lower strength, and cannot meet 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-heat-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 5×10 -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 from the composite material.
In a first aspect, the present invention provides an MZTA ceramic material having the chemical formula 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 dielectric constant of the MZTA ceramic material is 20-25, and the dielectric loss is lower than 2 multiplied by 10 -4 The thermal conductivity is 1 to 3W/(mK) (10 GHz).
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 powder, and calcining to obtain the MZTA ceramic material; the calcining temperature is 1150-1250 ℃ and the calcining time is more than or equal to 3 hours.
In a third aspect, the invention provides MZTA ceramic powder, which is prepared from the MZTA ceramic material; preferably, the particle diameter D of the MZTA ceramic powder 50 0.1 to 5. Mu.m, preferably 0.5 to 2. Mu.m, most preferably 1. Mu.m.
In a fourth aspect, the invention provides an MZTA/BAMT/flaky BN low-temperature cofiring material, which is obtained by compounding BAMT glass powder, the MZTA ceramic powder and flaky BN powder.
Preferably, the chemical general formula of the BAMT glass powder is aB 2 O 3 -bAl 2 O 3 -cSiO 2 -dMgO-eTiO 2 Wherein a=20 to 30moL%, b=0 to 10moL%, c=30 to 40moL%, d=20 to 30moL%, e=0 to 10moL%, a+b+c+d+e=100 mol%.
Preferably, the total mass sum of the BAMT 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 BAMT glass powder is 30-40 wt%, and the content of the flaky BN powder is 0-10 wt%.
Preferably, the particle diameter D of the BAMT glass powder 50 0.5 to 2. Mu.m, preferably 1. Mu.m; the thickness of the flaky BN powder is 1-5 mu m, and the diameter is 10-20 mu m.
Preferably, B is weighed according to the stoichiometric ratio of the BAMT glass powder 2 O 3 Powder, al 2 O 3 Powder, siO 2 Powder, mgO powder, tiO 2 Mixing the powder balls, and meltingPouring in water to form BAMT glass; then crushing or ball milling to obtain BAMT glass powder; the melting temperature is 1400-1500 ℃, and the heat preservation time is more than or equal to 2 hours.
Preferably, the dielectric constant of the MZT/BAMT/flaky BN low-temperature cofiring material is 15-20, and the dielectric loss is lower than 8 multiplied by 10 -4 (10 GHz), the thermal conductivity is 2 to 8W/(mK) (preferably 5 to 8W/(mK)).
In a fifth aspect, the invention provides a preparation method of an MZTA/BAMT/flaky BN low-temperature cofiring material, comprising the following steps:
(1) Modifying the flaky BN by using a modifier solution containing at least one modifier of polysilazane, acrylic ester, vinyl siloxane and methacrylic acid to obtain modified flaky BN;
(2) Mixing modified BN sheet, MZT ceramic powder, BAMT glass powder, a binder and a solvent, and performing tape casting molding and drying to obtain an MZT/BAMT/sheet BN film tape;
(3) Laminating a plurality of MZT/BAMT/sheet BN membrane bands, and performing hot isostatic pressing and sintering to obtain the MZT/BAMT/sheet BN low-temperature cofiring material.
Preferably, in 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, ethylcellulose and PVA; the addition amount of the binder is 5-10wt% of the total mass of the BAMT glass powder, the MZTA ceramic powder and the flaky BN powder; the solvent is at least one selected from the group consisting of alcohol, toluene, acetone and xylene.
Preferably, in the step (2), the temperature of the casting molding is 50-70 ℃, and the height of the scraper is 200-500 μm; the thickness of the obtained MZT/BAMT/sheet BN membrane strip is 70-170 mu m.
Preferably, in the step (3), the temperature of the hot isostatic pressing 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 in that the capacitor is prepared from the MZTA/BAMT/flaky BN low-temperature cofiring material.
The beneficial effects are that:
in the invention, the MZTA ceramic material is a microwave dielectric ceramic material, the dielectric constant is 15-20, and the dielectric loss 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 binding force of the BN and the glass matrix is improved by surface modification of the 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 tape casting isostatic pressing mode, so that the heat conducting property of the composite material is improved.
The LTCC material of the invention has the dielectric constant of 15-20 and the dielectric loss of less than 8 multiplied by 10 -4 (10 GHz) and sheet BN to obtain the LTCC material with medium dielectric constant, low dielectric loss and high heat conduction, 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 invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof.
Disclosed herein are a microwave dielectric ceramic and a glass, wherein the microwave dielectric ceramic contains Mg, zn, ti, al and O as four main elements, and the glass contains B, al, si, mg, ti and O as five main elements.
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 formula of the glass used for compounding is B 2 O 3 -Al 2 O 3 -SiO 2 -MgO-TiO 2 (BASMT) and flaky BN. In an alternative embodiment, glass B 2 O 3 -Al 2 O 3 -SiO 2 -MgO-TiO 2 (BASMT) composition B 2 O 3 ：20～30mol％、Al 2 O 3 ：0～10mol％、SiO 2 : 30-40 mol percent of MgO: 20-30 mol percent of ZnO:0 to 10mol percent, and the sum of the five components is 100 percent.
The microwave dielectric ceramic of the present disclosure has both an intermediate dielectric constant and a low dielectric loss, for example, the dielectric constant may be 20 to 30 and the dielectric loss may be 2×10 -4 ～5×10 -4 . The glass of the present disclosure has both an intermediate dielectric constant and a low dielectric loss, for example, the dielectric constant may be 8 to 10 and the dielectric loss may be 8×10 -4 ～10×10 -4 。
Disclosed herein is an MZTA/BASMT/platy BN low temperature cofiring material comprising: mg of 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, 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 : 30-40 mol percent of MgO: 20-30 mol percent of ZnO:0 to 10mol percent. Preferably, the low temperature cofiring material consists of MZTA powder/BASMT powder/platy BN powder/binder.
In the invention, MZT/BAMT/sheet BN is compounded, and the BAMT glass has higher dielectric constant and lower dielectric loss, has lower glass transition point, is easy to sinter and compact when being added into ceramics, and has high sample compactness after being compounded with MZTA ceramics and sheet BN, 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 BAMT glass and platy 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% of the total mass of the MZTA ceramic/BAMT glass/flaky BN composite. The mass of the flaky BN can be 0-20% of the total mass of the MZT ceramic/BAMT glass/flaky BN composite. At this mass fraction, the composite material can be made to have lower dielectric loss and higher thermal conductivityFor example, dielectric losses lower than 8X 10 -4 (10 GHz), the thermal conductivity is up to 5W/(mK). More preferably, the mass of the MZTA ceramic is 50% of the total mass of the MZTA ceramic/BAMT glass/platelet BN, and the mass of the platelet BN is 5-10% of the total mass of the MZTA ceramic/BAMT glass/platelet BN.
In a preferred embodiment, the microwave dielectric ceramic in the composite dielectric material is granular, the grain diameter is 1-5 mu m, the surface energy of the powder adopting micron level is low, agglomeration is not easy to occur, and air holes among grains are reduced. Can reduce dielectric loss and improve thermal conductivity.
Next, the method of preparing the above microwave dielectric ceramic and composite dielectric material is described as an example.
MZTA powder was first synthesized. MgO, znO, 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 O conversion. In one example, deionized water is used as a ball milling medium, and the mixture is uniformly mixed and dried on a planetary ball mill. And (3) material: ball: the water is 1:1:1. the particle size of the powder after ball milling can be 1-5 mu m. Calcining the uniformly mixed raw materials to synthesize MZTA powder. The calcination temperature may be 1100 to 1350 ℃, preferably 1200 to 1300 ℃. The incubation time is preferably 4 hours.
Will B 2 O 3- Al 2 O 3 -SiO 2 -MgO-TiO 2 B in (BASMT) glass 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 Usable H 3 BO 3 And (5) converting. And (5) performing secondary ball milling for 10 hours after melting to obtain glass powder. The melting temperature may be 1400-1500 ℃, preferably 1450 ℃. The incubation time is preferably 4 hours.
The low-temperature cofiring material can be prepared by mixing and granulating MZTA ceramic powder, BAMT glass and flaky BN. Further casting, lamination, and isostatic pressing, a multilayer capacitor can be obtained.
The particle size of the MZTA ceramic powder (or microwave dielectric ceramic powder) can be 1-5 μm. 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 ceramic 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 junction and the force between the flaky BN and MZT ceramic powder and the BAMT glass are increased, the interface pores are reduced, and the purposes of reducing loss and improving the heat conductivity coefficient are achieved. For example, 1wt% coupling agent modified BN and ceramic are mixed with BAMT glass, a dielectric constant of about 19, a dielectric loss of less than 5X 10 -4 And the heat conductivity coefficient is about 5.2W/(m.K), which is improved by more than 100% compared with a pure MZTA/BAMT low-temperature cofiring system.
The coupling agent used for modification is polysilazane, and the polysilazane can form an interface layer of a glass-philic layer on the surface of the ceramic, so that the bonding force of two phases is enhanced, and the porosity of the composite material is further reduced. The coupling agent may be used in an amount of 0 to 1.5% by mass, preferably 1 to 1.5% by mass, of the flake BN powder.
In one example, the flaky BN powder is placed in a polysilazane solution with the concentration of 10%, the total amount of polysilazane is 0-1.5 wt% of the ceramic, the mixture is magnetically stirred for 5 hours, and the mixture is filtered by suction and dried at 120 ℃ to obtain the modified flaky BN powder.
Mixing the modified flaky BN powder with MZTA ceramic powder and BASTT glass uniformly. Sheet BN and MZTA ceramic/BAMT glass were mixed at a ratio of 5:35:60, placing the mixture into a three-dimensional mixer, adding a solvent (such as alcohol) and a binder after uniformly mixing, placing the slurry into a casting machine, and casting at 50-70 ℃ to obtain the casting film belt. And (3) carrying out lamination hot-press forming (the hot-press temperature is 50-85 ℃ and the hot-press pressure is 30-70 MPa) and low-temperature sintering on the casting film belt to finally obtain the high-heat-conductivity low-temperature cofiring material.
In the invention, the prepared high-heat-conductivity low-temperature cofiring material has high dielectric constant and adjustable dielectric loss (15-20) which is lower than 8 multiplied by 10 -4 . The high-heat-conductivity low-temperature cofiring 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 further illustrated by the following 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 upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. 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 suitable selection from the description herein and are not intended to be limited to the specific values described below. In the following examples, dielectric constants and dielectric losses of the prepared substrate ceramic materials were measured by a stripline method with the aid of an Agilent E8363 pana network analyzer.
Example 1
(1) Will MgO, znO, tiO 2 、Al 2 O 3 According to Mg 0.95 Zn 0.05 (Ti 0.95 Al 0.05 )O 3 Adding deionized water as a ball milling medium, ball milling for 10 hours, drying at 150 ℃, and calcining the powder at 1100 ℃ for 4 hours;
(2) Adding deionized water as a ball milling medium into the calcined powder, performing secondary ball milling for 10 hours, and sieving to obtain D 50 Mg of 1-5 μm 0.95 Zn 0.05 (Ti 0.95 Al 0.05 )O 3 Powder;
(3) Placing the powder into polysilazane solution with the concentration of 10%, wherein the total amount of polysilazane is 1wt% of the ceramic, magnetically stirring for 5 hours, and drying at 120 ℃ after suction filtration;
(4) Will B 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 The following steps are 25:5:30:30:10, and performing secondary ball milling for 10 hours after melting to obtain glass powder. The melting temperature may be 1400-1500 ℃, preferably 1450 ℃. The incubation time is preferably 4 hours. Adding alcohol as ball milling medium, ball milling for 10 hr, and stoving at 150 deg.c to obtain D 50 BASMT-1 glass powder of 1-5 μm;
(5) Sheet BN, BASMT glass frit and MZTA ceramic powder at 5:35:60, mixing, placing the mixture in a three-dimensional mixer, adding alcohol and binder for continuous mixing, placing the obtained slurry in a casting machine, and casting at 60 ℃ to obtain a casting film belt;
(6) And (3) carrying out lamination hot-press forming (the hot-press temperature is 75 ℃ and the hot-press pressure is 70 MPa) on the casting film belt, and then sintering for 2 hours at 850 ℃ to finally obtain the high-heat-conductivity low-temperature cofiring material. The process parameters are shown in Table 3, and the final capacitive materials are shown in Table 4 as the performance test results.
Example 2
The preparation process of the high thermal conductivity low temperature cofiring material in this example 2 is different from that of example 1 only in that: in step (1), mgO, znO, tiO 2 、Al 2 O 3 According to Mg 0.9 Zn 0.1 (Ti 0.95 Al 0.05 )O 3 Adding deionized water as ball milling medium, ball milling for 10 hours, drying at 150 ℃, and calcining the powder at 1100 ℃ for 4 hours.
Example 3
The preparation process of the high thermal conductivity low temperature cofiring material in this example 3 is different from that of example 1 only in that: in step (1), mgO, znO, tiO 2 、Al 2 O 3 According to Mg 0.85 Zn 0.15 (Ti 0.95 Al 0.05 )O 3 Adding deionized water as ball milling medium, ball milling for 10 hours, drying at 150 ℃, and calcining the powder at 1100 ℃ for 4 hours.
Example 4
The preparation process of the high thermal conductivity low temperature cofiring material in this example 4 is different from that of example 1 only in that: in step (1), mgO, znO, tiO 2 、Al 2 O 3 According to Mg 0.8 Zn 0.2 (Ti 0.95 Al 0.05 )O 3 Adding deionized water as ball milling medium, ball milling for 10 hours, drying at 150 ℃, and calcining the powder at 1100 ℃ for 4 hours.
Example 5
The preparation process of the high thermal conductivity low temperature cofiring material in this example 5 is different from that of example 1 only in that: in step (1), mgO, znO, tiO 2 、Al 2 O 3 According to Mg 0.75 Zn 0.25 (Ti 0.95 Al 0.05 )O 3 Adding deionized water as ball milling medium, ball milling for 10 hours, drying at 150 ℃, and calcining the powder at 1100 ℃ for 4 hours.
Example 6
The preparation process of the high thermal conductivity low temperature cofiring material in this example 6 is different from that of example 1 only in that: in step (1), mgO, znO, tiO 2 、Al 2 O 3 According to Mg 0.7 Zn 0.3 (Ti 0.95 Al 0.05 )O 3 Adding deionized water as ball milling medium, ball milling for 10 hours, drying at 150 ℃, and calcining the powder at 1100 ℃ for 4 hours.
Example 7
The preparation process of the high thermal conductivity low temperature cofiring material in this example 7 is different from that of example 6 only in that: in step (1), mgO, znO, tiO 2 、Al 2 O 3 According to Mg 0.7 Zn 0.3 (Ti 0.9 Al 0.1 )O 3 Adding deionized water as ball milling medium, ball milling for 10 hours, drying at 150 ℃, and calcining the powder at 1100 ℃ for 4 hours.
Example 8
The preparation process of the high thermal conductivity low temperature cofiring material in this example 8 is different from that of example 6 only in that: in step (1), mgO, znO, tiO 2 、Al 2 O 3 According to Mg 0.7 Zn 0.3 (Ti 0.85 Al 0.15 )O 3 Adding deionized water as ball milling medium, ball milling for 10 hours, drying at 150 ℃, and calcining the powder at 1100 ℃ for 4 hours.
Example 9
Preparation process of high-thermal-conductivity low-temperature cofiring material in embodiment 9Referring to example 6, the only difference is that: in step (1), mgO, znO, tiO 2 、Al 2 O 3 According to Mg 0.7 Zn 0.3 (Ti 0.8 Al 0.2 )O 3 Adding deionized water as ball milling medium, ball milling for 10 hours, drying at 150 ℃, and calcining the powder at 1100 ℃ for 4 hours.
Example 10
The preparation process of the high thermal conductivity low temperature cofiring material in this example 10 is different from that of example 9 only in that: in the step (5), flaky BN, MZTA ceramic powder and BAMT glass powder are mixed according to the ratio of 2.5:37.5:60, placing the mixture into a three-dimensional mixer, adding alcohol and binder for continuous mixing after the mixture is uniformly mixed, placing the obtained slurry into a casting machine, and casting at the temperature of 60 ℃ to obtain the casting film belt.
Example 11
The preparation process of the high thermal conductivity low temperature cofiring material in this example 11 is different from that of example 9 only in that: in the step (5), flaky BN, MZTA ceramic powder and BAMT glass powder are mixed according to the ratio of 7.5:32.5:60, placing the mixture into a three-dimensional mixer, adding alcohol and binder for continuous mixing after the mixture is uniformly mixed, placing the obtained slurry into a casting machine, and casting at the temperature of 60 ℃ to obtain the casting film belt.
Example 12
The preparation process of the high thermal conductivity low temperature cofiring material in this example 12 is different from that of example 9 only in that: in the step (5), flaky BN, MZTA ceramic powder and BAMT glass powder are mixed according to the proportion of 10:30:60, placing the mixture into a three-dimensional mixer, adding alcohol and binder for continuous mixing after the mixture is uniformly mixed, placing the obtained slurry into a casting machine, and casting at the temperature of 60 ℃ to obtain the casting film belt.
Example 13
The preparation process of the high thermal conductivity low temperature cofiring material in this example 13 is different from that of example 9 only in that: in the step (4), B is 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 The weight ratio is 20:5:35:30:10, and performing secondary ball milling for 10 hours after melting to obtain glass powder.
Example 14
The preparation process of the high thermal conductivity low temperature cofiring material in this example 14 is different from that of example 9 only in that: in the step (4), B is 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 The preparation method comprises the following steps of: 5:30:25:10, and performing secondary ball milling for 10 hours after melting to obtain glass powder.
Example 15
The preparation process of the high thermal conductivity low temperature cofiring material in this example 15 is different from that of example 9 only in that: in the step (4), B is 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 The following steps are 25:5:40:20:10, and performing secondary ball milling for 10 hours after melting to obtain glass powder.
Example 16
The preparation process of the high thermal conductivity low temperature cofiring material in this example 16 is different from that of example 9 only in that: in the step (5), flaky BN, BAMT glass powder and MZT ceramic powder are mixed according to the proportion of 5:35:60, placing the mixture into a three-dimensional mixer, adding alcohol and binder for continuous mixing after the mixture is uniformly mixed, placing the obtained slurry into a casting machine, and casting at 60 ℃ to obtain a casting film belt; the used platelet-shaped BN was not subjected to polysilazane modification.
Example 17
The preparation process of the high thermal conductivity low temperature cofiring material in this example 17 is different from that of example 9 only in that: in the step (5), flaky BN, BAMT glass powder and MZT ceramic powder are mixed according to the proportion of 5:45:50, mixing, placing the mixture in a three-dimensional mixer, adding alcohol and binder for continuous mixing, placing the obtained slurry into a casting machine, and casting at 60 ℃ to obtain the casting film belt.
Example 18
The preparation process of the high thermal conductivity low temperature cofiring material in this example 18 is different from that of example 9 only in that: in the step (5), flaky BN, BAMT glass powder and MZT ceramic powder are mixed according to the ratio of 0:30:70, placing the mixture into a three-dimensional mixer, adding alcohol and binder for continuous mixing after the mixture is uniformly mixed, placing the obtained slurry into a casting machine, and casting at 60 ℃ to obtain the casting film belt.
Comparative example 1
The preparation process of the high thermal conductivity low temperature cofiring material in this comparative example 1 is different from that of example 9 only in that: in step (1), mgO, znO, tiO 2 、Al 2 O 3 According to Mg 0.7 Zn 0.3 TiO 3 Adding deionized water as ball milling medium, ball milling for 10 hours, drying at 150 ℃, and calcining the powder at 1100 ℃ for 4 hours.
Comparative example 2
The preparation process of the high thermal conductivity low temperature cofiring material in this comparative example 2 is different from that of example 9 only in that: in step (1), mgO, znO, tiO 2 、Al 2 O 3 According to Mg (Ti) 0.8 Al 0.2 )O 3 Adding deionized water as ball milling medium, ball milling for 10 hours, drying at 150 ℃, and calcining the powder at 1100 ℃ for 4 hours.
Comparative example 3
The preparation process of the high thermal conductivity low temperature cofiring material in this comparative example 3 is different from that of example 9 only in that: in the step (5), flaky BN, BAMT glass powder and MZT ceramic powder are mixed according to the proportion of 5:55:40, mixing, placing the mixture in a three-dimensional mixer, adding alcohol and binder for continuous mixing, placing the obtained slurry into a casting machine, and casting at 60 ℃ to obtain the casting film belt.
Comparative example 4
The preparation process of the high thermal conductivity low temperature cofiring material in this comparative example 4 is different from that of example 9 only in that: in the step (5), flaky BN, BAMT glass powder and MZT ceramic powder are mixed according to the proportion of 5:15:80, placing the mixture into a three-dimensional mixer, adding alcohol and binder for continuous mixing after the mixture is uniformly mixed, placing the obtained slurry into a casting machine, and 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 cofiring material in this comparative example 5 is different from that of example 9 only in that: in the step (5), flaky BN, BAMT glass powder and MZT ceramic powder are mixed according to the ratio of 12.5:27.5:60, placing the mixture into a three-dimensional mixer, adding alcohol and binder for continuous mixing after the mixture is uniformly mixed, placing the obtained slurry into a casting machine, and casting at 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 BASMT glass prepared:
Figure BDA0003756179850000102
table 3 shows the material compositions of the low temperature cofiring materials prepared in examples 1-15:
Figure BDA0003756179850000103
Figure BDA0003756179850000111
table 4 shows the performance parameters of the low temperature cofiring materials prepared in examples 1-15:
Figure BDA0003756179850000112
Figure BDA0003756179850000121
as can be seen from table 4, as Zn increases, the dielectric constant of the sample increases, while the loss increases slowly, the thermal conductivity is substantially 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; with the increase of Al, the dielectric constant of the sample is reduced, the loss is reduced slowly, the thermal conductivity is basically unchanged, the ion polarization rate of Ti is higher than that of Al, and the dielectric constant of the sample is reduced under the same compactness 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 BN is higher than 100W/(m.K) and is far higher than the dielectric constant of the system, so that the overall thermal conductivity is increased, and when the flaky BN is too much, the loss is increased due to too much three-phase interfaces, but the arrangement of the flaky BN also increases the thermal conductivity of the system. Thus example 9 achieves the best overall performance.

Claims (11)

1. The MZTA/BAMT/flaky BN low-temperature cofiring material is characterized by comprising BAMT glass powder, MZTA ceramic powder and flaky BN powder which are compounded;
the chemical general formula of the BAMT glass powder is aB 2 O 3 -bAl 2 O 3 -cSiO 2 -dMgO-eTiO 2 Wherein a=20 to 30mol%, b=0 to 10mol%, c=30 to 40mol%, d=20 to 30mol%, e=0 to 10mol%, a+b+c+d+e=100 mol%;
the chemical general formula of the MZTA ceramic powder is Mg 1-x Zn x (Ti 1-y Al y )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;
the total mass sum of the BAMT 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 BAMT glass powder is 30-40 wt%, and the content of the flaky BN powder is below 20 wt%.
2. The MZTA/BASMT/flaky BN low temperature cofiring material according to claim 1, wherein x is 0.2-0.3; y is more than or equal to 0.1 and less than or equal to 0.2.
3. The MZTA/BASMT/platelet BN low temperature cofiring material according to claim 1, wherein the MZTA ceramic powder has a particle diameter D 50 0.5-2 μm.
4. The MZTA/BASMT/sheet BN low temperature cofiring material of claim 1, wherein the BASMT glass powder has a particle size D 50 0.5-2 mu m; the thickness of the flaky BN powder is 1-5 mu m, and the diameter is 10-20 mu m.
5. The MZTA/BAMT/flaky BN low-temperature cofiring material according to claim 1, wherein the B is weighed according to the stoichiometric ratio of BAMT glass powder 2 O 3 Powder, al 2 O 3 Powder, siO 2 Powder, mgO powder, tiO 2 Mixing the powder, melting and pouring the mixture into water to form BAMT glass; then crushing or ball milling to obtain BAMT glass powder; the melting temperature is 1400-1500 ℃, and the heat preservation time is more than or equal to 2 hours.
6. The MZTA/BASMT/sheet BN low temperature cofiring material according to any one of claims 1 to 5, wherein the MZTA/BASMT/sheet BN low temperature cofiring material has a dielectric constant of 15 to 20, a dielectric loss of less than 8 x 10 -4 The thermal conductivity is 2 to 8W/(mK).
7. A method for preparing the MZTA/BASMT/platelet BN low temperature cofired material as claimed in any one of claims 1 to 6, comprising:
(1) Modifying the flaky BN by using a modifier solution containing at least one modifier of polysilazane, acrylic ester, vinyl siloxane and methacrylic acid to obtain modified flaky BN;
(2) Mixing modified BN sheet, MZT ceramic powder, BAMT glass powder, a binder and a solvent, and performing tape casting molding and drying to obtain an MZT/BAMT/sheet BN film tape;
(3) Laminating a plurality of MZT/BAMT/sheet BN membrane bands, and performing hot isostatic pressing and sintering to obtain the MZT/BAMT/sheet BN low-temperature cofiring material.
8. The method of claim 7, wherein in step (1), the concentration of the modifier solution is 5wt%; the total amount of the modifier is 0-5 wt% of the flaky BN.
9. The method according to claim 7, wherein in the step (2), the temperature of the casting is 50 to 70 ℃ and the height of the doctor blade is 200 to 500 μm; the thickness of the obtained MZT/BAMT/sheet BN membrane strip is 70-170 mu m.
10. The method according to any one of claims 7-9, wherein in step (3), the hot isostatic pressing is performed at a temperature of 50-85 ℃ and a pressure of 30-70 MPa; the sintering temperature is 800-1000 ℃ and the sintering time is 1-4 hours.
11. A capacitor prepared from the MZTA/BASMT/platelet BN low temperature cofired material of any one of claims 1-6.
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