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

Abstract

The invention discloses a low-temperature sintered microwave ceramic material and a preparation method thereof, and belongs to the technical field of materials. The low-temperature sintered microwave ceramic material comprises a main material-BaO-ZnO-TiO2, a first additive-BaCu(B2O5), a second additive-composite oxide and a third additive-MnO2. The preparation method comprises the following steps: taking BaCO3, ZnO and TiO2 as raw materials for synthesizing the main material-BaO-ZnO-TiO2, taking BaCO3, CuO and B2O3 as raw materials for synthesizing the first additive, taking BaCO3, ZnO, TiO2, SiO2 and B2O3 as raw materials for synthesizing the second additive, adding the first to third additives into the main material, performing ball-milling, drying, sieving, pelletizing, forming and rubber removing, and sintering in air at the temperature of 850-940 DEG C. The low-temperature sintered microwave ceramic material has the characteristics of high Q value, near-zero and serialized frequency temperature coefficient, moderate dielectric constant and good process stability through detection.

Description

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

Technical field

The invention belongs to field of material technology, relate to microwave ceramic material and preparation method thereof, especially a kind of low sintering microwave ceramic material and preparation method thereof.

Background technology

The fast development of microelectronic device and integrated device proposes high request to electronics miniaturization, lightweight, single active part is integrated cannot meet production application, passive device miniaturization must become a kind of trend, but the Metal cavity of traditional large volume used makes the integrated of microstrip circuit become difficulty.Microwave Multichip Module (MMCM) module is widely used because having lightweight, that volume is little, cost is low and reliability is high technical characterstic, and the effective way realizing this technology is development multilayer chip element.LTCC (Low Temperature Co-fired ceramic, LTCC) technology is because it has the advantages such as higher integration density, preferably high frequency characteristics, has become and has realized the integrated a kind of major way of Current electronic components and parts.What LTCC technology adopted is Miltilayer wiring structure, passive device integration and the passive and active device hybrid integrated technology of the assembling of a kind of 3 D stereo, the integrated of passive element (resistance, electric capacity, inductance, wave filter) and transmission line can be realized, again can surface mount IC element, for the reliability aspect realizing the miniaturization of device, the modularization of multi-functional and improve signal plays important role.The interconnecting conductor that LTCC technology uses is all generally the silver metal with excellent conductive characteristic, and its fusing point is lower is about 961 DEG C, this just require to be used in stupalith in LTCC technology must below 950 DEG C densified sintering product.In addition, the low-temperature co-burning ceramic material of Current commercialization application mostly belongs to glass-ceramic (glass-ceramic) system, its specific inductivity is less than normal, dielectric loss is bigger than normal, be mainly used in medium substrate material, as A6 (the ε r=5.7 of Ferro company of the U.S., tg δ=0.0012), 951 (ε r=7.85 of Dupont company, tg δ=0.0063), and the low temperature co-fired medium ceramic material of commercialization with the microwave dielectric property excellence of middle high-k is also deficienter.

BaO-TiO ₂series microwave dielectric ceramic develops the earliest and one of microwave dielectric material applied, as far back as 1975 with BaTi ₄o ₉the dielectric resonator that main crystal phase material makes just has been applied in actual microwave device, afterwards along with the research of microwave dielectric ceramic materials is paid attention in the world and extensively carries out, the more excellent novel material system of increasing microwave dielectric property is found and applies, and this relatively ancient ceramic systems is left in the basket gradually.But consider the factors such as cost and technology controlling and process in recent years, particularly find the BaO-ZnO-TiO of excellent combination property since 2000 ₂new system, in view of the microwave-medium ceramics system containing BaO, TiO2, ZnO tri-kinds of oxide compounds is simple, the prices of raw and semifnished materials are very cheap, and can apply at whole microwave frequency band, BaO-TiO ₂and BaO-ZnO-TiO ₂base microwave dielectric ceramics reenters the investigation and application visual field of people, and this is comprising the low-temperature sintering research of this system.

To BaO-TiO ₂and BaO-ZnO-TiO ₂the low-temperature sintering research of base microwave dielectric ceramics starts from about 2000, generally speaking, and BaO-TiO ₂the sintering temperature of system pottery at about 1300 DEG C, BaO-ZnO-TiO ₂the sintering temperature of system pottery is also more than 1200 DEG C, and its low-temperature sintering mainly adopts the approach of annex solution phase sintering auxiliary agent to realize.As " Japanese Applied Physics journal " (Japanese Journal of Applied Physics) article " 3ZnO-2B of 2002 ₂o ₃doping Ba ₂ti ₉o ₂₀the low-temperature sintering of pottery and microwave dielectric property " (Low temperature sintering and microwave dielectric properties ofBa ₂ti ₉o ₂₀ceramics with3ZnO-2B ₂o ₃addition) ZnO-B is reported in ₂o ₃glass can reduce Ba ₂ti ₉o ₂₀the sintering temperature to 940 DEG C of pottery, but the dephasign that the generation that can react between them is new, havoc microwave dielectric property, 1wt%ZnO-B ₂o ₃the Ba of glass-doped ₂ti ₉o ₂₀base microwave dielectric ceramics obtains microwave dielectric property under 940 DEG C/2h: ε r=27.3, Q × f=8300GHz, τ f=+2.5ppm/ DEG C." European ceramic journal " (Journal of Electroceramics) article " B of 2006 ₂o ₃with CuO to BaTi ₄o ₉the impact of ceramic sintering temperature and microwave dielectric property " report 2.0mol%B in (Effect of B2O3and CuO onthe sintering temperature and microwave dielectric properties of the BaTi4O9ceramics) ₂o ₃with the BaTi of 5.0mol%CuO doping ₄o ₉pottery, at 900 DEG C of sintering 2h, can obtain microwave dielectric property: ε r=36.3, Q × f=30500GHz, τ f=+28.1ppm/ DEG C.People furtherd investigate and found B afterwards ₂o ₃composite mixed why can the obtaining of-CuO is fallen burning effect preferably and keeps good microwave dielectric property, because a kind of fusing point low (850 DEG C) can be generated and microwave dielectric property excellence (ε r=7.4, Q × f=50000GHz, τ f=-32ppm/ DEG C) new compound phase BaCu (B ₂o ₅)." Japanese Applied Physics journal " (Japanese Journal of Applied Physics) article " BaCu (B of 2006 ₂o ₅) doping agent is to BaTi ₄o ₉the sintering temperature of pottery and the impact of microwave dielectric property " (Effect of BaCu (B2O5) additive on the sinteringtemperature and microwave dielectric properties of BaTi ₄o ₉ceramics) 12.0mol%BaCu (B is reported in ₂o ₅) the BaTi4O9 pottery that adulterates just can densified sintering product at 875 DEG C, the microwave dielectric property obtained is: ε r=32, and Q × f=10800GHz, τ f=+32ppm/ DEG C, XRD material phase analysis shows a considerable amount of Ba ₄ti ₁₃o ₃₀generate mutually.Can find, for low melting point oxide doping, most researchers all concentrates on selects B ₂o ₃, CuO, BaCu (B ₂o ₅) three kinds of oxide compound, wherein composite mixed B ₂o ₃-CuO or the BaCu (B that adulterates separately ₂o ₅) all demonstrate BaO-TiO ₂and BaO-ZnO-TiO ₂base microwave dielectric ceramics has unique liquid phase sintering effect, effectively can reduce sintering temperature, above-mentioned low fever's microwave-medium ceramics has excellent comprehensive microwave dielectric property or few, be mainly manifested in Q × f value not high enough, mostly at below 20000GHz, or temperature coefficient of resonance frequency τ f value is higher cannot meet practical application request.

The low-temperature sintered microwave dielectric ceramic material of current use is all in its high-k of strain after, low-loss and near-zero resonance frequency temperature coefficient feature, from material dielectric constant seriation and reduction electronic devices and components size aspect, currently need to develop that a kind of material cost is low, good process repeatability meets low loss characteristic simultaneously, and the low temperature co-fired stupalith with middle high-k can be realized with silver electrode material, to meet the application demand of micro-wave communication industry.

Summary of the invention

The object of the invention is the defect not easily returned to zero to overcome the poor and frequency-temperature coefficient of intermediary's low-temperature sintering microwave medium spillage of material characteristic in the past, by BaO-ZnO-TiO ₂first, second, third additive is introduced as properties-correcting agent in major ingredient, while remarkable reduction sintering temperature, reduce the loss degradation factors brought due to sintering agent, prepare have low-loss, nearly zero seriation frequency-temperature coefficient, with low cost and there is good process stability be applicable to low sintering microwave ceramic material.

For realizing object of the present invention, the technical solution used in the present invention is:

A kind of 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 aA+bB+cC, and wherein A represents alkalimetal oxide (preferred BaO), and B represents transition metal oxide (preferred ZnO, TiO ₂or ZnO and TiO ₂mixture), C represents nonmetal oxide (preferred B ₂o ₃, SiO ₂or B ₂o ₃and SiO ₂mixture); 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.

A preparation method for low temperature sintering microwave ceramic material, as shown in Figure 1, 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.

Low temperature sintering microwave ceramic material provided by the invention, has the Q value that lower loss is namely higher after testing, and nearly zero and the frequency-temperature coefficient of seriation, moderate specific inductivity and good technology stability.

Involved in the present invention to low-temperature sintered microwave dielectric ceramic material preparation method compared with traditional production technology, production process is substantially identical, principal feature is that of obtaining major ingredient crystalline phase symbiotic co-existence, compact structure and the good microwave-medium ceramics with sintering temperature and low and the higher quality factor of technology stability.

With XRD diffraction approach, material phase analysis is carried out as shown in Figure 2 to the low temperature sintering microwave ceramic sample after burning till, can confirm that obtained ceramic principal crystalline phase is BaTi ₄o ₉and BaZn ₂ti ₄o ₁₁, principal phase is not subject to the impact of sintering agent doping.Observe as shown in Figure 3 with scanning electron microscope sem to ceramic surface, can find out ceramic surface crystal grain comparatively even compact, the pottery burnt till after cooling does not occur that sintering agent introduces the large-area glass phase and crystal grain misgrowth brought.

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

1, not containing volatility or the heavy metals such as Pb, Cd, Bi in formula of the present invention, is a kind of environment friendly microwave dielectric ceramic;

2, the BaCu (B of the first additive ₂o ₅) and Second addition composite oxides can at the same temperature pre-burning synthesis, compare and adopt the low-temperature sintering microwave medium route of synthesis of multiple doping agent modification to have certain process advantage;

3, the high-performance at about 900 DEG C low-temperature sintering ceramics is achieved: higher Q × f value (16000 ~ 30000), the frequency-temperature coefficient (-6 ~ 14) of Medium dielectric constant (21 ~ 36) and seriation nearly zero;

4, starting material are sufficient at home, cheap, and technology stability is good, and the cost degradation making high performance low temperature burn till microwave ceramics becomes possibility.

Accompanying drawing explanation

Fig. 1 is schematic flow sheet of the present invention.

Fig. 2 is the XRD diffraction analysis figure of low temperature sintering microwave ceramic material prepared by the present invention.

Fig. 3 is the SEM scanning electron microscope (SEM) photograph of low temperature sintering microwave ceramic material prepared by the present invention.

Embodiment

Below in conjunction with embodiment, the present invention is conducted further description.

A preparation method for low temperature sintering microwave ceramic material, as shown in Figure 1, 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.

Embodiment 1:BaO-ZnO-TiO ₂the change of major ingredient proportioning is compared.

According to BaO-ZnO-TiO ₂major ingredient is fixed as 100g, the first additive B aCu (B ₂o ₅) being fixed as 13g, Second addition composite oxides are fixed as 0.1g, the 3rd additive MnO ₂be fixed as the weighing of 0.3g proportioning.In the process, be mainly at BaO-ZnO-TiO ₂baO-ZnO-TiO is changed in the synthesis of major ingredient ₂major ingredient proportioning.Wet-milling, material after oven dry adds polyvinyl alcohol water solution and carries out granulation, type is made at 25Mpa pressure, obtaining diameter is 15mm, and thickness is the cylinder green compact of 8mm, is then placed in air and sinters, slightly change according to the different sintering condition of major ingredient proportioning, temperature rise rate is 3 DEG C/min, and furnace cooling can obtain Temperature Firing Microwave Dielectric Ceramics, and ceramic main formula changing conditions, sintering process and dielectric properties parameter are in table 1.

Embodiment 2: the first additive B aCu (B ₂o ₅) doping change compare.

According to BaO:ZnO:TiO ₂=1:0.2:4 synthesizes BaO-ZnO-TiO ₂major ingredient, presses BaO-ZnO-TiO by ceramic formula ₂major ingredient is fixed as 100g, the first additive B aCu (B ₂o ₅) being respectively 3g, 5g, 7g, 9g, 11g, 13g, Second addition composite oxides are fixed as 0.3g, the 3rd additive MnO ₂be fixed as the weighing of 0.3g proportioning.Wet-milling, material after oven dry adds polyvinyl alcohol water solution and carries out granulation, type is made at 25Mpa pressure, obtaining diameter is 15mm, and thickness is the cylinder green compact of 8mm, is then placed in air and sinters, slightly change according to the different sintering condition of major ingredient proportioning, temperature rise rate is 3 DEG C/min, and furnace cooling can obtain Temperature Firing Microwave Dielectric Ceramics, and ceramic main formula changing conditions, sintering process and dielectric properties parameter are in table 2.

Embodiment 3: the change of Second addition doping is compared.

According to BaO:ZnO:TiO ₂=1:0.3:4 synthesizes major ingredient, and ceramic formula is pressed BaO-ZnO-TiO ₂major ingredient is fixed as 100g, the first additive B aCu (B ₂o ₅) being fixed as 11g, Second addition composite oxides are respectively 0.1g, 0.3g, 0.5g, 0.7g, 0.9g, the 3rd additive MnO ₂be fixed as the weighing of 0.7g proportioning.Wet-milling, material after oven dry adds polyvinyl alcohol water solution and carries out granulation, type is made at 25Mpa pressure, obtaining diameter is 15mm, thickness is the cylinder green compact of 8mm, is then placed in air and sinters, and temperature rise rate is 3 DEG C/min, furnace cooling can obtain Temperature Firing Microwave Dielectric Ceramics, and ceramic main formula changing conditions, sintering process and dielectric properties parameter are in table 3.

Embodiment 4: the three additive MnO ₂doping change is compared.

According to BaO:ZnO:TiO ₂=1:0.4:4 synthesizes major ingredient, and ceramic formula is pressed BaO-ZnO-TiO ₂major ingredient is fixed as 100g, the first additive B aCu (B ₂o ₅) being fixed as 11g, Second addition composite oxides are fixed as 0.5g, the 3rd additive MnO ₂be respectively the weighing of 0.1g, 0.5g, 0.9g, 1.3g, 1.7g proportioning.Wet-milling, material after oven dry adds polyvinyl alcohol water solution and carries out granulation, type is made at 25Mpa pressure, obtaining diameter is 15mm, thickness is the cylinder green compact of 8mm, is then placed in air and sinters, and temperature rise rate is 3 DEG C/min, furnace cooling can obtain Temperature Firing Microwave Dielectric Ceramics, and ceramic main formula changing conditions, sintering process and dielectric properties parameter are in table 4.

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.