CN103420670B - Low-temperature sintered microwave ceramic material and preparation method thereof - Google Patents

Abstract

A low-temperature sintered microwave ceramic material and a preparation method thereof belong to the field of material technology. It includes BaO-ZnO-TiO ₂ main material, first additive BaCu (B ₂ O ₅ ), second additive composite oxide and third additive MnO ₂ . Firstly, BaO-ZnO-TiO ₂ main material was synthesized from BaCO ₃ , ZnO and TiO ₂ , then the first additive was synthesized from BaCO ₃ , CuO and B ₂ O ₃ , and then BaCO ₃ , ZnO, TiO ₂ , SiO ₂ and B ₂ O ₃ as raw materials to synthesize the second additive, and then add the first, second, and third additives to the main material, and after ball milling, drying, sieving, granulation, molding and debinding, it will be heated in the air at 850 Firing at ~940°C. The low-temperature sintered microwave ceramic material provided by the invention has high Q value, nearly zero and serialized frequency temperature coefficient, moderate dielectric constant and good process stability after testing.

Description

A kind of low-temperature sintered microwave ceramic material and preparation method thereof

technical field

The invention belongs to the technical field of materials, and relates to a microwave ceramic material and a preparation method thereof, in particular to a low-temperature sintered microwave ceramic material and a preparation method thereof.

Background technique

The rapid development of microelectronic devices and integrated devices has put forward high requirements for the miniaturization and light weight of electronic equipment. The integration of a single active device can no longer meet the production application. It has become a trend that passive devices must be miniaturized. However, the traditional large volume The metal resonant cavity makes the integration of microstrip circuits difficult. Microwave multi-chip module (MMCM) modules are widely used because of their technical characteristics of light weight, small size, low cost and high reliability. An effective way to realize this technology is to develop multi-layer chip components. Low temperature co-fired ceramic (Low Temperature Co-fired ceramic, LTCC) technology has become a main way to realize the integration of current electronic components because of its advantages such as high integration density and good high-frequency characteristics. LTCC technology uses a multi-layer wiring structure, which is a three-dimensional assembly of passive device integration and passive active device hybrid integration technology, which can realize the integration of passive components (resistors, capacitors, inductors, filters) and transmission lines , and can be surface mounted IC components, which play an important role in realizing the miniaturization of devices, modularization of multiple functions and improving the reliability of signals. The interconnecting conductors used in LTCC technology are generally silver metals with excellent electrical conductivity, and their melting point is relatively low at about 961°C, which requires that the ceramic materials used in LTCC technology must be sintered densely below 950°C. In addition, most of the low-temperature co-fired ceramic materials currently commercially used belong to the glass-ceramic (glass-ceramic) system, which has a relatively small dielectric constant and a relatively large dielectric loss, and is mainly used in dielectric substrate materials, such as the A6 (εr=5.7, tgδ=0.0012), Dupont’s 951 (εr=7.85, tgδ=0.0063), and commercial low-temperature co-fired dielectric ceramic materials with medium and high dielectric constants and excellent microwave dielectric properties are still relatively scarce.

BaO-TiO ₂ series microwave dielectric ceramics are one of the earliest developed and applied microwave dielectric materials. As early as 1975, dielectric resonators made of BaTi ₄ O ₉ main crystal phase materials were applied to actual microwave components. With the research on microwave dielectric ceramic materials being valued and widely carried out around the world, more and more new material systems with better microwave dielectric properties have been discovered and applied, making this relatively ancient ceramic system gradually neglected. However, considering many factors such as cost and process control in recent years, especially since 2000, a new BaO-ZnO-TiO ₂ system with excellent comprehensive performance has been discovered. In view of the simple microwave dielectric ceramic system containing BaO, TiO2, and ZnO , The price of raw materials is very cheap, and can be applied in the whole microwave frequency band. BaO-TiO ₂ and BaO-ZnO-TiO ₂ based microwave dielectric ceramics have re-entered people's research and application vision, including the low-temperature sintering research of this system.

The low-temperature sintering research on BaO-TiO ₂ and BaO-ZnO-TiO ₂ based microwave dielectric ceramics began around 2000. Generally speaking, the sintering temperature of BaO-TiO ₂ system ceramics is about 1300 °C, and BaO-ZnO-TiO ₂ The sintering temperature of the system ceramics is also above 1200°C, and its low-temperature sintering is mainly achieved by adding liquid-phase sintering aids. For example, the article "Low temperature sintering and microwave dielectric properties of 3ZnO-2B ₂ O ₃ doped Ba ₂ Ti ₉ O ₂₀ ceramics" (Japanese Journal of Applied Physics) in 2002 properties ofBa ₂ Ti ₉ O ₂₀ ceramics with3ZnO-2B ₂ O ₃ addition) reported that ZnO-B ₂ O ₃ glass can reduce the sintering temperature of Ba ₂ Ti ₉ O ₂₀ ceramics to 940℃, but there will be a reaction between them to form The new impurity phase seriously damages the microwave dielectric properties. 1wt% ZnO-B ₂ O ₃ glass doped Ba ₂ Ti ₉ O ₂₀ based microwave dielectric ceramics obtained microwave dielectric properties at 940℃/2h: εr=27.3, Q×f=8300GHz, τf=+2.5ppm/℃. " _Effect of _{B2O3and CuO} on the sintering _temperature and microwave dielectric properties of the BaTi4O9ceramics) reported that 2.0mol% B ₂ O ₃ and 5.0mol% CuO doped BaTi ₄ O ₉ ceramics were sintered at 900°C for 2 hours, and the microwave dielectric properties can be obtained: εr=36.3, Q×f=30500GHz, τf =+28.1ppm/°C. Later, people conducted in-depth research and found that the reason why B ₂ O ₃ -CuO compound doping can achieve better heat reduction effect and maintain good microwave dielectric properties is because it will generate a low melting point (850 ℃) and excellent microwave dielectric properties. (εr=7.4, Q×f=50000GHz, τf=-32ppm/℃) new compound phase BaCu(B ₂ O ₅ ). "The Effect of BaCu(B ₂ O ₅ ) dopant on the sintering temperature and microwave dielectric properties of BaTi ₄ O ₉ ceramics" (Japanese Journal of Applied Physics) in 2006 (Effect of BaCu( B2O5)additive on the sinteringtemperature and microwave dielectric properties of BaTi ₄ O ₉ ceramics) reported that BaTi4O9 ceramics doped with 12.0mol% BaCu(B ₂ O ₅ ) can be sintered and dense at 875°C, and the obtained microwave dielectric properties are : εr=32, Q×f=10800GHz, τf=+32ppm/℃, XRD phase analysis shows that a considerable amount of Ba ₄ Ti ₁₃ O ₃₀ phase is formed. It can be found that for the doping of low-melting point oxides, most researchers focus on the selection of B ₂ O ₃ , CuO, and BaCu (B ₂ O ₅ ) oxides, among which B ₂ O ₃ -CuO or single Doping BaCu(B ₂ O ₅ ) shows that it has a unique liquid phase sintering effect on BaO-TiO ₂ and BaO-ZnO-TiO ₂ based microwave dielectric ceramics, which can effectively reduce the sintering temperature, but the above-mentioned low-fired microwave dielectric ceramics have excellent There are still not many comprehensive microwave dielectric properties, mainly because the Q×f value is not high enough, mostly below 20000 GHz, or the resonant frequency temperature coefficient τf value is too high to meet the actual application requirements.

The currently used low-temperature sintered microwave dielectric ceramic materials are trying their best to pursue the characteristics of high dielectric constant, low loss and near-zero resonance frequency temperature coefficient. From the perspective of serialization of material dielectric constant and reduction of electronic component size, current needs Develop a ceramic material with medium and high dielectric constant that has low raw material cost, good process repeatability and low loss characteristics, and can be co-fired with silver electrode materials at low temperature to meet the application needs of the microwave communication industry.

Contents of the invention

The purpose of the present invention is to overcome the defects of poor loss characteristics and difficult zero adjustment of the frequency temperature coefficient of the previous intermediary low-temperature sintered microwave dielectric materials, by introducing the first, second and _third additives into the main material of BaO-ZnO-TiO As a modifier, it not only reduces the sintering temperature significantly, but also reduces the loss deterioration factors caused by the sintering aid, and prepares a low-loss, near-zero series frequency temperature coefficient, low cost and good process stability. Low temperature sintered microwave ceramic material.

For realizing the purpose of the present invention, the technical scheme that the present invention adopts is:

A low-temperature sintered microwave ceramic material, comprising BaO-ZnO-TiO ₂ main material, the first additive, the second additive and the third additive, wherein:

The molar ratio of BaO:ZnO: _TiO2 in the main material of BaO-ZnO- _TiO2 is 1:(0.1～ _0.7 ) _: 4 _, and the main crystal phases are _BaTi4O9 and _BaZn2Ti4O11 ;

The first additive is a BaCu(B ₂ O ₅ ) compound, and its mass percentage content is 1wt%-15wt% of the main ingredient of BaO-ZnO- _TiO2 ;

The second additive is a composite oxide aA+bB+cC, wherein A represents an alkali metal oxide (preferably BaO), B represents a transition metal oxide (preferably ZnO, TiO ₂ or a mixture of ZnO and TiO ₂ ), and C represents a metalloid Oxide (preferably B ₂ O ₃ , SiO ₂ or a mixture of B ₂ O ₃ and SiO ₂ ); a, b, c are coefficients, a+b+c=1, and 0.05≤a≤0.15, 0.35≤b≤ 0.45, 0.45≤c≤0.55; the mass percentage content of the second additive is 0.1wt%～1.0wt% of the main ingredient of BaO-ZnO- _TiO2 ;

The third additive is MnO ₂ , and its mass percentage content is 0.1wt%˜2.0wt% of the main ingredient of BaO—ZnO—TiO ₂ .

A preparation method of a low-temperature sintered microwave ceramic material, as shown in Figure 1, comprises the following steps:

Step 1: BaO-ZnO- _TiO2 main material synthesis. Include the following steps:

Step 1-1: Using BaCO ₃ , ZnO and TiO ₂ as raw materials, prepare materials according to the molar ratio of BaO:ZnO:TiO ₂ =1:(0.1～0.7):4, and ball mill the prepared materials with deionized water as the ball milling medium , dried at 100°C after ball milling and passed through a 40-mesh sieve;

Step 1-2: pre-calcine the mixture treated in step 1-1 at a temperature of 1000°C to 1100°C for 3 to 5 hours to obtain BaO whose main crystal phases are BaTi ₄ O ₉ and BaZn ₂ Ti ₄ O ₁₁ -ZnO-TiO ₂ main material.

Step 2: First additive synthesis. Include the following steps:

Step 2-: 1: Using BaCO ₃ , CuO and B ₂ O ₃ as raw materials, prepare the materials according to the molar ratio of Ba:Cu:B=1:1:2, and use ethanol as the ball milling medium for ball milling, and at 75 Dry at ℃ and pass through a 40-mesh sieve;

Step 2-2: pre-calcining the mixture treated in step 2-1 at a temperature of 600°C-800°C for 1-2 hours to obtain the first additive BaCu(B ₂ O ₅ ) powder.

Step 3: Second additive synthesis. Include the following steps:

Step 3-1: Using BaCO ₃ , ZnO, TiO ₂ , SiO ₂ and B ₂ O ₃ as raw materials, according to BaO:(ZnO+TiO ₂ ):(SiO ₂ +B ₂ O ₃ )=(0.05～0.15): The mass ratio of (0.35～0.45):(0.45～0.55) is used for material preparation, and the material is prepared by ball milling with deionized water as the ball milling medium, and dried at 100°C and passed through a 40-mesh sieve;

Step 3-2: pre-calcining the ball mill material treated in step 3-1 at a temperature of 600° C. to 800° C. for 1 to 2 hours to obtain the second additive composite oxide powder.

Step 4: Add the first additive, the second additive and the third additive to the main material of BaO-ZnO-TiO ₂ to obtain the mixed system D. Taking the synthesized BaO-ZnO-TiO of step ₁ as a benchmark, add the first additive synthesized in step 2, the second additive synthesized in step 3 and the third additive MnO ₂ ; wherein: the addition amount of the first additive is equivalent to 1wt%-15wt% of the main material of BaO-ZnO- _TiO2 , the addition amount of the second additive is equivalent to 0.1wt%-1.0wt% of the main material of BaO-ZnO- _TiO2 , and the addition amount of the third additive is equivalent to BaO- 0.1wt% to 2.0wt% of the main material of ZnO- _TiO2 .

Step 5: The mixed system D obtained in Step 4 is mixed and ball milled with deionized water as the ball milling medium.

Step 6: Drying, sieving, granulating, molding and debinding the ball mill material obtained in Step 5 in sequence to obtain a green body.

Step 7: sintering the green body processed in step 6 in air at a temperature of 850-940° C. for 60-120 minutes, and cooling naturally to obtain a low-temperature sintered microwave ceramic material.

The low-temperature sintered microwave ceramic material provided by the invention has, through testing, relatively low loss, that is, a high Q value, near-zero and serialized frequency temperature coefficient, moderate dielectric constant and good process stability.

Compared with the traditional production technology, the preparation method of the low-temperature sintered microwave dielectric ceramic material involved in the present invention has basically the same production process. Microwave dielectric ceramics with higher sintering temperature and higher quality factor.

The phase analysis of the fired low-temperature sintered microwave ceramic sample was carried out by XRD diffraction method, as shown in Figure 2, it can be confirmed that the main crystal phases of the obtained ceramics are BaTi ₄ O ₉ and BaZn ₂ Ti ₄ O ₁₁ , and the main phase has no Affected by sintering aid doping. Observation of the ceramic surface with a scanning electron microscope (SEM) is shown in Figure 3. It can be seen that the grains on the ceramic surface are relatively uniform and compact, and the fired ceramics after cooling down do not have large-area glass phases and abnormal growth of grains caused by the introduction of firing aids. .

Compared with the prior art, the present invention has the following characteristics:

1. The formula of the present invention does not contain Pb, Cd, Bi and other volatile or heavy metals, and is an environmentally friendly microwave dielectric ceramic;

2. The BaCu(B ₂ O ₅ ) of the first additive and the composite oxide of the second additive can be pre-fired at the same temperature, which has certain advantages compared with the low-temperature sintering microwave dielectric synthesis route modified by various dopants. process advantages;

3. Realize the high performance of ceramics fired at a low temperature of about 900°C: high Q×f value (16000~30000), medium dielectric constant (21~36) and serialized near-zero frequency temperature coefficient (-6~ 14);

4. The raw materials are abundant in China, the price is low, and the process stability is good, which makes it possible to reduce the cost of high-performance low-temperature fired microwave ceramics.

Description of drawings

Fig. 1 is a schematic flow chart of the present invention.

Fig. 2 is an XRD diffraction analysis diagram of the low-temperature sintered microwave ceramic material prepared in the present invention.

Fig. 3 is a SEM scanning electron microscope image of the low-temperature sintered microwave ceramic material prepared in the present invention.

Detailed ways

The present invention will be further described below in combination with specific embodiments.

A preparation method of a low-temperature sintered microwave ceramic material, as shown in Figure 1, comprises the following steps:

Step 1: BaO-ZnO- _TiO2 main material synthesis. Include the following steps:

Step 1-1: Using BaCO ₃ , ZnO and TiO ₂ as raw materials, prepare materials according to the molar ratio of BaO:ZnO:TiO ₂ =1:(0.1～0.7):4, and ball mill the prepared materials with deionized water as the ball milling medium , dried at 100°C after ball milling and passed through a 40-mesh sieve;

Step 1-2: pre-calcine the mixture treated in step 1-1 at a temperature of 1000°C to 1100°C for 3 to 5 hours to obtain BaO whose main crystal phases are BaTi ₄ O ₉ and BaZn ₂ Ti ₄ O ₁₁ -ZnO-TiO ₂ main material.

Step 2: First additive synthesis. Include the following steps:

Step 2-: 1: Using BaCO ₃ , CuO and B ₂ O ₃ as raw materials, prepare the materials according to the molar ratio of Ba:Cu:B=1:1:2, and use ethanol as the ball milling medium for ball milling, and at 75 Dry at ℃ and pass through a 40-mesh sieve;

Step 2-2: pre-calcining the mixture treated in step 2-1 at a temperature of 600°C-800°C for 1-2 hours to obtain the first additive BaCu(B ₂ O ₅ ) powder.

Step 3: Second additive synthesis. Include the following steps:

Step 3-1: Using BaCO ₃ , ZnO, TiO ₂ , SiO ₂ and B ₂ O ₃ as raw materials, according to BaO:(ZnO+TiO ₂ ):(SiO ₂ +B ₂ O ₃ )=(0.05～0.15): The mass ratio of (0.35～0.45):(0.45～0.55) is used for material preparation, and the material is prepared by ball milling with deionized water as the ball milling medium, and dried at 100°C and passed through a 40-mesh sieve;

Step 3-2: pre-calcining the ball mill material treated in step 3-1 at a temperature of 600° C. to 800° C. for 1 to 2 hours to obtain the second additive composite oxide powder.

Step 4: Add the first additive, the second additive and the third additive to the main material of BaO-ZnO-TiO ₂ to obtain the mixed system D. Taking the synthesized BaO-ZnO-TiO of step ₁ as a benchmark, add the first additive synthesized in step 2, the second additive synthesized in step 3 and the third additive MnO ₂ ; wherein: the addition amount of the first additive is equivalent to 1wt%-15wt% of the main material of BaO-ZnO- _TiO2 , the addition amount of the second additive is equivalent to 0.1wt%-1.0wt% of the main material of BaO-ZnO- _TiO2 , and the addition amount of the third additive is equivalent to BaO- 0.1wt% to 2.0wt% of the main material of ZnO- _TiO2 .

Step 5: The mixed system D obtained in Step 4 is mixed and ball milled with deionized water as the ball milling medium.

Step 6: Drying, sieving, granulating, molding and debinding the ball mill material obtained in Step 5 in sequence to obtain a green body.

Step 7: sintering the green body processed in step 6 in air at a temperature of 850-940° C. for 60-120 minutes, and cooling naturally to obtain a low-temperature sintered microwave ceramic material.

Embodiment 1: BaO-ZnO-TiO ₂ Comparison of changes in the ratio of main ingredients.

According to the main material of BaO-ZnO- _TiO2 is fixed at 100g, the first additive BaCu( _B2O5 ) is fixed at _13g , the second additive composite oxide is fixed at 0.1g, and the third additive _MnO2 is fixed at 0.3g. material. In this process, it is mainly to change the proportion of BaO-ZnO-TiO ₂ main material in the synthesis of BaO-ZnO-TiO ₂ main material. Wet milling, adding polyvinyl alcohol aqueous solution to the dried material for granulation, pressing under 25Mpa pressure to obtain a cylindrical green body with a diameter of 15mm and a thickness of 8mm, and then sintering in the air, depending on the ratio of main materials The sintering conditions are slightly changed, the heating rate is 3°C/min, and the low-temperature sintered microwave dielectric ceramics can be prepared with the furnace cooling. The main formula changes, sintering process and dielectric performance parameters of the ceramics are shown in Table 1.

Example 2: Comparison of the doping amount of the first additive BaCu (B ₂ O ₅ ).

According to BaO:ZnO:TiO ₂ =1:0.2:4, the main material of BaO-ZnO-TiO ₂ was synthesized, and the ceramic formula was fixed at 100g according to the main material of BaO-ZnO-TiO ₂ , the first additive BaCu(B ₂ O ₅ ) 3g, 5g, 7g, 9g, 11g, 13g respectively, the second additive composite oxide is fixed at 0.3g, and the third additive _MnO2 is fixed at 0.3g. Wet milling, adding polyvinyl alcohol aqueous solution to the dried material for granulation, pressing under 25Mpa pressure to obtain a cylindrical green body with a diameter of 15mm and a thickness of 8mm, and then sintering in the air, depending on the ratio of main materials The sintering conditions are slightly changed, the heating rate is 3°C/min, and the low-temperature sintered microwave dielectric ceramics can be prepared with the furnace cooling. The main formula changes, sintering process and dielectric performance parameters of the ceramics are shown in Table 2.

Embodiment 3: Comparison of the doping amount of the second additive.

Synthesize the main material according to BaO:ZnO:TiO ₂ =1:0.3:4, fix the ceramic formula to 100g according to the main material of BaO-ZnO-TiO ₂ , fix the first additive BaCu(B ₂ O ₅ ) to 11g, and the second Additive composite oxides are 0.1g, 0.3g, 0.5g, 0.7g, 0.9g respectively, and the third additive MnO ₂ is fixed at 0.7g and weighed. After wet grinding and drying, add polyvinyl alcohol aqueous solution for granulation, and press molding under 25Mpa pressure to obtain a cylindrical green body with a diameter of 15mm and a thickness of 8mm, which is then sintered in air at a heating rate of 3°C/ min, and the low-temperature sintered microwave dielectric ceramics can be prepared with the furnace cooling.

Example 4: Comparison of the doping amount of the third additive MnO ₂ .

Synthesize the main material according to BaO:ZnO:TiO ₂ =1:0.4:4, fix the ceramic formula to 100g according to the main material of BaO-ZnO-TiO ₂ , fix the first additive BaCu(B ₂ O ₅ ) to 11g, and the second The additive composite oxide is fixed at 0.5g, and the third additive _MnO2 is 0.1g, 0.5g, 0.9g, 1.3g, and 1.7g, respectively. After wet grinding and drying, add polyvinyl alcohol aqueous solution for granulation, and press molding under 25Mpa pressure to obtain a cylindrical green body with a diameter of 15mm and a thickness of 8mm, which is then sintered in air at a heating rate of 3°C/ min, and the low-temperature sintered microwave dielectric ceramics can be prepared with cooling in the furnace. Table 4 shows the main formula changes, sintering process and dielectric performance parameters of the ceramics.

Table 1

Table 2

table 3

Table 4

Claims (1)

1. a preparation method for low temperature sintering microwave ceramic material, comprises the following steps:

Step 1:BaO-ZnO-TiO ₂major ingredient synthesizes; Comprise the following steps:

Step 1-1: with BaCO ₃, ZnO and TiO ₂for raw material, according to BaO:ZnO:TiO ₂=1:(0.1 ~ 0.7): the mol ratio of 4 is got the raw materials ready, and will get the raw materials ready with deionized water is that ball-milling medium carries out ball milling, dries and cross 40 mesh sieves after ball milling at 100 DEG C;

Step 1-2: by the pre-burning 3 ~ 5 hours under 1000 DEG C ~ 1100 DEG C temperature condition of the compound after step 1-1 process, obtaining principal crystalline phase is BaTi ₄o ₉and BaZn ₂ti ₄o ₁₁baO-ZnO-TiO ₂major ingredient;

Step 2: the first additive synthesis; Comprise the following steps:

Step 2-1: with BaCO ₃, CuO and B ₂o ₃for raw material, get the raw materials ready by the mol ratio of Ba:Cu:B=1:1:2, will get the raw materials ready with ethanol is that ball-milling medium carries out ball milling, and dries at 75 DEG C and cross 40 mesh sieves;

Step 2-2: by the pre-burning 1 ~ 2 hour under 600 DEG C ~ 800 DEG C temperature condition of the compound after step 2-1 process, obtain the first additive B aCu (B ₂o ₅) powder;

Step 3: Second addition synthesizes; Comprise the following steps:

Step 3-1: with BaCO ₃, ZnO, TiO ₂, SiO ₂and B ₂o ₃for raw material, according to BaO:(ZnO+TiO ₂): (SiO ₂+ B ₂o ₃)=(0.05 ~ 0.15): (0.35 ~ 0.45): the mass ratio of (0.45 ~ 0.55) is got the raw materials ready, will get the raw materials ready with deionized water is that ball-milling medium carries out ball milling, and dries at 100 DEG C and cross 40 mesh sieves;

Step 3-2: by the ball milling material after step 3-1 process, under 600 DEG C ~ 800 DEG C temperature condition, pre-burning 1 ~ 2 hour, obtains Second addition composite oxide power;

Step 4: at BaO-ZnO-TiO ₂add the first additive, Second addition and the 3rd additive in major ingredient, obtain mixed system D; With the BaO-ZnO-TiO synthesized by step 1 ₂major ingredient is benchmark, the Second addition that the first additive of the 2-in-1 one-tenth of interpolation step, step 3 are synthesized and the 3rd additive MnO ₂; Wherein: the addition of the first additive is equivalent to BaO-ZnO-TiO ₂1wt% ~ the 15wt% of major ingredient, the addition of Second addition is equivalent to BaO-ZnO-TiO ₂0.1wt% ~ the 1.0wt% of major ingredient, the addition of the 3rd additive is equivalent to BaO-ZnO-TiO ₂0.1wt% ~ the 2.0wt% of major ingredient;

Step 5: by step 4 gained mixed system D is that ball-milling medium carries out mixing and ball milling with deionized water;

Step 6: step 5 gained ball milling material is carried out drying successively, sieves, granulation, shaping and binder removal process, obtain green billet;

Step 7: the green billet after processing through step 6 is sintered 60 ~ 120 minutes in atmosphere under 850 ~ 940 DEG C of temperature condition, namely obtains low temperature sintering microwave ceramic material after naturally cooling;

Described low temperature sintering microwave ceramic material, comprises BaO-ZnO-TiO ₂major ingredient, the first additive, Second addition and the 3rd additive, wherein:

Described BaO-ZnO-TiO ₂baO:ZnO:TiO in major ingredient ₂mol ratio is 1:(0.1 ~ 0.7): 4, principal crystalline phase is BaTi ₄o ₉and BaZn ₂ti ₄o ₁₁;

Described first additive is BaCu (B ₂o ₅) compound, its mass percentage content is BaO-ZnO-TiO ₂1wt% ~ the 15wt% of major ingredient;

Described Second addition is composite oxides aBaO+b (ZnO+TiO ₂)+c (SiO ₂+ B ₂o) ₃, wherein a, b, c are coefficients, a+b+c=1, and 0.05≤a≤0.15,0.35≤b≤0.45,0.45≤c≤0.55; The mass percentage content of Second addition is BaO-ZnO-TiO ₂0.1wt% ~ the 1.0wt% of major ingredient;

Described 3rd additive is MnO ₂, mass percentage content is BaO-ZnO-TiO ₂0.1wt% ~ the 2.0wt% of major ingredient.