A low-temperature co-fired ceramic material of zinc-boron-silicate system and its preparation method

Abstract

The present invention relates to the technical field of microwave dielectric materials, and provides a zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material and a preparation method thereof. The present invention mixes ZBS glass powder and a binder, and then sequentially performs aging, granulation and press molding, and then sintering the obtained blank at 700-850°C to obtain a zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material. The present invention can obtain a glass-ceramic with a pure Zn2SiO4 crystal phase and a dense structure by sintering at a low temperature; the raw materials used in the present invention are non-corrosive, not likely to cause harm to the human body, and are environmentally friendly. The results of the examples show that the dielectric constant of the ZBS glass-ceramic obtained by the present invention at 1MHz is adjustable in the range of 5.5-6.2, and the dielectric loss is (0.43-7.2)×10 ‑3 within the range.

Description

Technical Field

[0001] The present invention relates to the technical field of microwave dielectric materials, and in particular to a zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material and a preparation method thereof. Background Art

[0002] In recent years, the electronics industry has demanded that electronic components develop in a higher-frequency direction. Low-temperature co-fired ceramics (LTCC), with their excellent dielectric, mechanical, and low-temperature sintering properties, perfectly meet the requirements of integrated circuits for high signal transmission speeds and high performance. In the field of high-frequency microwave communications, the dielectric constant is inversely proportional to the signal transmission rate. Therefore, LTCC substrates require materials with a lower dielectric constant. The lower the dielectric constant, the higher the signal transmission rate.

[0003] Low-temperature co-firing technology has attracted increasing attention in the development of integration and miniaturization. However, the low-dielectric, low-loss glass-ceramic system that has been widely studied is the CaO-B2O3-SiO2 (CBS) glass-ceramic system, whose sintering temperature is generally 800°C to 900°C (CN112225547A, CN112299825A). However, there are fewer studies on the ZnO-B2O3-SiO2 (ZBS) glass-ceramic system with low-temperature co-firing potential. Currently, there are reports on the preparation of ZBS glass powder as a sintering aid. For example, Chinese patent CN104193324 A discloses a ZnO-MgO-TiO2-based LTCC material, which discloses a method for preparing ZBS glass powder. This technology prepares ZBS glass powder from a composition of 40% to 70% ZnO, 25% to 45% B2O3, and 5% to 15% SiO2 by molar percentage. The ZBS glass powder and the main crystalline phase are (Zn 1-x Mg x ) TiO3-yTiO2 powders are co-sintered to produce LTCC materials with a high dielectric constant (20-27) and a relatively high sintering temperature (850°C-900°C). In existing technical research, ZBS glass is often added to ceramic powders as a sintering aid to lower the sintering temperature. However, there has been little research on the low-temperature sintering of ZBS glass powder into glass-ceramics for use as LTCC materials.

[0004] As industrial production continues to increase its demand for high-frequency communication technology, existing LTCC materials are unable to meet application requirements. Therefore, the development of new material systems similar to CBS micro-glass systems is of great practical significance. Summary of the Invention

[0005] In view of this, the present invention provides a zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material and a preparation method thereof. The zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material provided by the present invention has excellent dielectric properties and a low sintering temperature.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] A method for preparing a zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material comprises the following steps:

[0008] The ZBS glass powder and the binder are mixed and then aged, granulated and pressed to obtain a green blank; the ZBS glass powder is prepared from ZnO, H3BO3 and SiO2 according to the following molar percentages: ZnO 53-70 mol%, B2O3 12-20 mol%, SiO2 15-30 mol%; the H3BO3 is calculated based on the molar number of B2O3;

[0009] The green blank is sintered to obtain the zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material; the sintering temperature is 700-850°C.

[0010] Preferably, the preparation method of the ZBS glass powder includes: mixing ZnO, H3BO3 and SiO2, heating and melting the mixture, quenching the resulting molten glass liquid in water to obtain a glass body; ball-milling the glass body, followed by screening and drying to obtain ZBS glass powder.

[0011] Preferably, the heating and melting temperature is 1350-1450°C, and the holding time is 2-4 hours;

[0012] The ball milling conditions include: the ball milling medium is deionized water, the grinding balls are zirconia balls, the ball milling speed is 300-450 rpm, and the ball milling time is 6-12 hours.

[0013] Preferably, the binder is a polyvinyl alcohol solution, the mass concentration of the polyvinyl alcohol solution is 3-5%; the polyvinyl alcohol solution and the ZBS The mass ratio of the glass powder is 1:(35-45).

[0014] Preferably, the compression molding pressure is 70-100 MPa.

[0015] Preferably, the heating rate to the sintering temperature is 5-10° C. / min; and the sintering holding time is 30-60 min.

[0016] The present invention also provides a zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material prepared by the preparation method described in the above scheme, wherein the zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material includes the following components in molar fractions: ZnO 53~70mol%, B2O312~20mol%, and SiO215~30mol%.

[0017] Preferably, the molar ratio of SiO2 to B2O3 is 1.4±0.05, and the molar ratio of ZnO to B2O3 is 3.2-4.8.

[0018] Preferably, the zinc-borosilicate glass-ceramics low-temperature co-fired ceramic material has a Zn2SiO4 crystal phase.

[0019] Preferably, the dielectric constant of the zinc borosilicate glass-ceramic low-temperature co-fired ceramic material at 1 MHz is 5.5-6.2, and the dielectric loss is (0.43-7.2)×10 -3

[0020] The present invention provides a method for preparing a zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material, comprising the following steps: mixing ZBS glass powder and a binder, followed by aging, granulation, and pressing to obtain a green body; the ZBS glass powder is prepared from ZnO, H₃BO₃, and SiO₂ in the following molar percentages: 53-70 mol% ZnO, 12-20 mol% B₂O₃, and 15-30 mol% SiO₂; the H₃BO₃ being calculated as the molar number of B₂O₃; and sintering the green body to obtain the zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material; the sintering temperature is 700-850°C. Sintering the green body at 700-850°C yields a glass-ceramic (hereinafter referred to as ZBS glass-ceramic) with a pure Zn₂SiO₄ crystalline phase and a dense structure. Furthermore, the ZnO, H₃BO₃, and SiO₂ used in the present invention are non-corrosive and unlikely to cause harm to the human body. Compared with other systems of microcrystalline glass, the ZBS microcrystalline glass of the present invention has a low sintering temperature, better dielectric properties, simple process, short production cycle, high output, and is environmentally friendly.

[0021] The results of the embodiment show that with the increase of Zn / B ratio, the Zn2SiO4 crystal phase precipitated in the ZBS glass-ceramics system gradually decreases, and the dielectric constant of the obtained ZBS glass-ceramics at 1MHz is adjustable in the range of 5.5 to 6.2, and the dielectric loss is in the range of (0.43 to 7.2)×10 -3 within the range. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 XRD patterns of the ZBS glass powders prepared in Examples 1 to 6;

[0023] Figure 2 DSC curves of the ZBS glass powders prepared in Examples 1 to 6;

[0024] Figure 3 XRD patterns of the ZBS glass-ceramics prepared in Examples 1 to 6;

[0025] Figure 4These are the dielectric property test results of the ZBS glass-ceramics prepared in Examples 1 to 6. DETAILED DESCRIPTION

[0026] The present invention provides a method for preparing a zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material, comprising the following steps:

[0027] The ZBS glass powder and the binder are mixed and then aged, granulated and pressed to obtain a green blank; the ZBS glass powder is prepared from ZnO, H3BO3 and SiO2 according to the following molar percentages: ZnO 53-70 mol%, B2O3 12-20 mol%, SiO2 15-30 mol%; the H3BO3 is calculated based on the molar number of B2O3;

[0028] The green blank is sintered to obtain the zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material; the sintering temperature is 700-850°C.

[0029] The present invention comprises mixing ZBS glass powder and a binder, followed by aging, granulation, and pressing to obtain a biscuit. The ZBS glass powder is prepared from ZnO, H3BO3, and SiO2 according to the following molar percentages: 53-70 mol% ZnO, 12-20 mol% B2O3, and preferably 15-30 mol% SiO2; the H3BO3 is calculated as the mole of B2O3. In the ZBS glass powder, the molar ratio of SiO2 to B2O3 is preferably 1.4±0.05, and the molar ratio of ZnO to B2O3 is preferably 3.2-4.8, more preferably 3.2, 3.4, 3.6, 3.8, 4.0, and 4.2. The present invention adjusts the content of each component by maintaining the SiO2 / B2O3 molar ratio constant and varying the ZnO / B2O3 molar ratio to obtain a ZBS glass capable of sintering a pure Zn2SiO4 crystal phase at a low temperature.

[0030] In the present invention, the preparation method of the ZBS glass powder includes: mixing ZnO, H3BO3, and SiO2, heating and melting the mixture, quenching the resulting molten glass in water to obtain a glass body; ball-milling the glass body, followed by screening and drying to obtain the ZBS glass powder. In the present invention, the purity of the ZnO, H3BO3, and SiO2 is preferably above 99%; the mixing is preferably performed in a three-dimensional mixer; the mixing time is preferably 1 hour; the heating and melting temperature is preferably 1350-1450°C, more preferably 1400°C, and the holding time for the heating and melting is preferably 2-4 hours, more preferably 2-3 hours; after obtaining the molten glass, the molten glass is preferably poured into deionized water for quenching.

[0031] After obtaining the glass body, the present invention ball-mills the glass body and then sequentially sieves and dries it to obtain ZBS glass powder. In the present invention, the ball milling conditions preferably include: the ball milling medium is deionized water, the grinding balls are zirconia balls, the ball milling speed is 300-450 rpm, preferably 350-400 rpm, and the ball milling time is 6-12 hours, preferably 8-10 hours; the mesh size of the sieve is preferably 500 mesh, and the drying temperature is preferably 80°C.

[0032] In the present invention, the binder is preferably a polyvinyl alcohol solution, the mass concentration of the polyvinyl alcohol solution is preferably 3-5%, more preferably 4%; the polyvinyl alcohol solution and the ZBS The mass ratio of the glass powder is preferably 1:(35-45), more preferably 1:40; the aging time is preferably 18-24 hours; after aging, the granules are preferably screened and then granulated; the present invention has no special requirements for the granulation, and conditions well known in the art can be used; the pressing pressure is preferably 70-100 MPa; therefore, the diameter of the blank is preferably 10 mm and the thickness is preferably 2 mm.

[0033] After obtaining the green blank, the present invention sintered the green blank to obtain the zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material; the sintering temperature is 700-850°C, preferably 700-750°C, and more preferably 700°C; the heating rate to the sintering temperature is preferably 5-10°C / min; the sintering holding time is preferably 30-60min; after sintering is completed, it can be cooled with the furnace.

[0034] The present invention also provides a zinc-borosilicate glass-ceramic low-temperature co-fired ceramic (LTCC) material (denoted as ZBS glass-ceramic) prepared by the preparation method described in the above scheme, comprising the following components in molar fractions: ZnO 53-70 mol%, B2O3 12-20 mol%, and SiO2 15-30 mol%.

[0035] In the present invention, the molar fraction of ZnO in the zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material is preferably 56-65 mol%, more preferably 58-61 mol%, the molar fraction of B2O3 is preferably 15-17.8 mol%, more preferably 15.5-17.16 mol%, and the molar fraction of SiO2 is preferably 15-30 mol%, preferably 21-25.5 mol%, more preferably 22-24.51 mol%.

[0036] In the present invention, the molar ratio of SiO2 and B2O3 in the zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material is preferably 1.4, and the molar ratio of ZnO and B2O3 is preferably 3.2-4.8, more preferably 3.2, 3.4, 3.6, 3.8, 4.0 and 4.2.

[0037] In the present invention, the zinc borosilicate glass-ceramics low-temperature co-fired ceramic material has a Zn2SiO4 crystal phase; the zinc borosilicate glass-ceramics low-temperature co-fired ceramic material has a dielectric constant of 5.5 to 6.2 and a dielectric loss of (0.43 to 7.2)×10 -3 .

[0038] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0039] Example 1

[0040] 56.85mol%ZnO-17.77mol%B2O3-25.38mol%SiO2 glass-ceramics

[0041] Step 1: Using ZnO, H₃BO₃, and SiO₂ as raw materials (all raw materials with a purity of ≥99%), weigh them according to the desired ratio of ZnO, B₂O₃, and SiO₂ in the target product and mix them in a three-dimensional mixer for one hour. After thorough mixing, heat the raw materials to 1400°C in a resistance furnace and hold for two hours to produce molten glass. This molten glass is then poured into deionized water and rapidly quenched to produce a vitreous body.

[0042] Step 2: Mill the glass in a planetary ball mill using deionized water as the grinding medium, zirconium oxide balls, at a speed of 450 rpm for 8 hours. The milled glass was then passed through a 500-mesh sieve and dried in an 80°C oven to obtain ZBS glass powder.

[0043] Step 3: Add a 4wt% polyvinyl alcohol solution (PVA:ZBS) to the ZBS glass powder (mass ratio of 1:40). The mixture is aged, sieved, and granulated to obtain a mixed powder of glass powder and PVA. The mixed powder is pressed at 100 MPa on a uniaxial tablet press to produce 10mm x 2mm Φ discs.

[0044] Step 4: Place the blank in a muffle furnace, heat it to 700°C at a heating rate of 5°C / min, keep it warm for 30 minutes, and then cool it in the furnace to obtain a microcrystalline glass with a composition of 56.85mol% ZnO-17.77mol% B2O3-25.38mol% SiO2.

[0045] Example 2

[0046] 58.33mol%ZnO-17.16mol%B2O3-24.51mol%SiO2 glass-ceramics

[0047] Step 1: Using ZnO, H₃BO₃, and SiO₂ as raw materials (all raw materials with a purity of ≥99%), weigh them according to the desired ratio of ZnO, B₂O₃, and SiO₂ in the target product and mix them in a three-dimensional mixer for one hour. After thorough mixing, heat the raw materials to 1400°C in a resistance furnace and hold for two hours to produce molten glass. This molten glass is then poured into deionized water and rapidly quenched to produce a vitreous body.

[0048] Step 2: Mill the glass in a planetary ball mill using deionized water as the grinding medium, zirconium oxide balls, at a speed of 450 rpm for 8 hours. The milled glass was then passed through a 500-mesh sieve and dried in an 80°C oven to obtain ZBS glass powder.

[0049] Step 3: Add a 4wt% polyvinyl alcohol solution (PVA:Glass powder mass ratio:1:40) to the glass powder. The mixture is aged, sieved, and granulated to obtain a mixed powder of glass powder and PVA solution. The mixed powder is pressed on a uniaxial tablet press at a pressure of 100 MPa to obtain 10mm x 2mm Φ discs.

[0050] Step 4: Place the blank in a muffle furnace, heat it to 700°C at a heating rate of 5°C / min, keep it warm for 30 minutes, and then cool it in the furnace. Then, you can get a microcrystalline glass with a composition of 58.33mol% ZnO-17.16mol% B2O3-24.51mol% SiO2 by cooling it in the furnace.

[0051] Example 3

[0052] 59.71mol%ZnO-16.59mol%B2O3-23.70mol%SiO2 glass-ceramics

[0053] Step 1: Using ZnO, H₃BO₃, and SiO₂ as raw materials (all raw materials with a purity of ≥99%), weigh them according to the desired ratio of ZnO, B₂O₃, and SiO₂ in the target product and mix them in a three-dimensional mixer for one hour. After thorough mixing, heat the raw materials to 1400°C in a resistance furnace and hold for two hours to produce molten glass. This molten glass is then poured into deionized water and rapidly quenched to produce a vitreous body.

[0054] Step 2: Mill the glass in a planetary ball mill using deionized water as the grinding medium, zirconium oxide balls, at a speed of 450 rpm for 8 hours. The milled glass was then passed through a 500-mesh sieve and dried in an 80°C oven to obtain ZBS glass powder.

[0055] Step 3: Add a 4wt% polyvinyl alcohol solution (PVA:glass powder mass ratio of 1:40) to the ZBS glass powder. The mixture is aged, sieved, and granulated to obtain a mixed powder of glass powder and PVA solution. The mixed powder is pressed at 100 MPa on a unidirectional tablet press to obtain 10mm x 2mm Φ discs.

[0056] Step 4: Place the blank in a muffle furnace, heat it to 700°C at a heating rate of 5°C / min, keep it warm for 30 minutes, and then cool it in the furnace to obtain a microcrystalline glass with a composition of 59.71mol% ZnO-16.59mol% B2O3-23.70mol% SiO2.

[0057] Example 4

[0058] 61.02mol%ZnO-16.06mol%B2O3-22.92mol%SiO2 glass-ceramics

[0059] Step 1: Using ZnO, H₃BO₃, and SiO₂ as raw materials (all raw materials with a purity of ≥99%), weigh them according to the desired ratio of ZnO, B₂O₃, and SiO₂ in the target product and mix them in a three-dimensional mixer for one hour. After thorough mixing, heat the raw materials to 1400°C in a resistance furnace and hold for two hours to produce molten glass. This molten glass is then poured into deionized water and rapidly quenched to produce a vitreous body.

[0060] Step 2: Mill the glass in a planetary ball mill using deionized water as the grinding medium, zirconium oxide balls, at a speed of 450 rpm for 8 hours. The milled glass was then passed through a 500-mesh sieve and dried in an 80°C oven to obtain ZBS glass powder.

[0061] Step 3: Add a 4wt% polyvinyl alcohol solution (PVA:glass powder mass ratio of 1:40) to the ZBS glass powder. The mixture is aged, sieved, and granulated to obtain a mixed powder of glass powder and PVA solution. The mixed powder is pressed at 100 MPa on a unidirectional tablet press to obtain 10mm x 2mm Φ discs.

[0062] Step 4: Place the blank in a muffle furnace, heat it to 700°C at a heating rate of 5°C / min, keep it warm for 30 minutes, and then cool it in the furnace to obtain a microcrystalline glass with a composition of 61.02mol% ZnO-16.06mol% B2O3-22.92mol% SiO2.

[0063] Example 5

[0064] 62.22mol%ZnO-15.56mol%B2O3-22.22mol%SiO2 glass-ceramics

[0065] Step 1: Using ZnO, H₃BO₃, and SiO₂ as raw materials (all raw materials with a purity of ≥99%), weigh them according to the desired ratio of ZnO, B₂O₃, and SiO₂ in the target product and mix them in a three-dimensional mixer for one hour. After thorough mixing, heat the raw materials to 1400°C in a resistance furnace and hold for two hours to produce molten glass. This molten glass is then poured into deionized water and rapidly quenched to produce a vitreous body.

[0066] Step 2: Mill the glass in a planetary ball mill using deionized water as the grinding medium, zirconium oxide balls, at a speed of 450 rpm for 8 hours. The milled glass was then passed through a 500-mesh sieve and dried in an 80°C oven to obtain ZBS glass powder.

[0067] Step 3: Add a 4wt% polyvinyl alcohol solution (PVA solution to ZBS glass powder mass ratio of 1:40) to the ZBS glass powder. The mixture is aged, sieved, and granulated to obtain a mixed powder of glass powder and polyvinyl alcohol (PVA) solution. This mixed powder is pressed at 100 MPa on a uniaxial tablet press to produce 10mm x 2mm Φ discs.

[0068] Step 4: Place the blank in a muffle furnace, heat it to 700°C at a heating rate of 5°C / min, keep it warm for 30 minutes, and then cool it in the furnace to obtain a microcrystalline glass with a composition of 62.22mol% ZnO-15.56mol% B2O3-22.22mol% SiO2.

[0069] Example 6

[0070] 63.36mol%ZnO-15.09mol%B2O3-21.55mol%SiO2 glass-ceramics

[0071] Step 1: Weigh ZnO, H₃BO₃, and SiO₂ (purity ≥ 99%) and mix them in a three-dimensional mixer for 1 hour. After thorough mixing, heat the mixture to 1400°C in a resistance furnace for 2 hours to produce molten glass. This molten glass is then poured into deionized water and rapidly quenched to produce a vitreous body.

[0072] Step 2: Mill the glass in a planetary ball mill using deionized water as the grinding medium, zirconium oxide balls, at a speed of 450 rpm for 8 hours. The milled glass was then passed through a 500-mesh sieve and dried in an 80°C oven to obtain ZBS glass powder.

[0073] Step 3: Add a 4wt% polyvinyl alcohol solution (PVA solution to glass powder mass ratio of 1:40) to the ZBS glass powder. The mixture is aged, sieved, and granulated to obtain a mixed powder of glass powder and polyvinyl alcohol (PVA) solution. This mixed powder is pressed at 100 MPa on a uniaxial tablet press to produce 10mm x 2mm Φ discs.

[0074] Step 4: Place the blank in a muffle furnace, heat it to 700°C at a heating rate of 5°C / min, keep it warm for 30 minutes, and then cool it in the furnace to obtain a microcrystalline glass with a composition of 63.36mol% ZnO-15.09mol% B2O3-21.55mol% SiO2.

[0075] Performance testing:

[0076] 1. The dielectric properties of the ZBS glass-ceramics prepared in Examples 1 to 6 were tested, and the results are shown in Table 1.

[0077] Table 1 Dielectric properties of ZBS glass-ceramics sintered at 700℃ / 30min (1MHz)

[0078]

[0079] According to the data in Table 1, it can be seen that the ZBS glass-ceramics prepared by the present invention has a relatively low dielectric constant, low dielectric loss, and excellent dielectric properties.

[0080] 2. Figure 1 The XRD patterns of the ZBS glass powders prepared in Examples 1 to 6 are as follows. Figure 1It can be seen that there is no obvious diffraction peak in the XRD pattern, only a bun peak appears at about 30°, and the sharpness of the bun peak gradually weakens with the increase of the ZnO / B2O3 molar ratio, indicating that all ZBS glass powders are completely amorphous and are in a non-crystalline state.

[0081] 3. Figure 2 The DSC curves of the ZBS glass powders prepared in Examples 1 to 6 are shown in FIG. Figure 2 It can be seen that at a heating rate of 5°C / min, most glass samples have obvious glass transition temperatures (T g ), crystallization starting temperature (T c ) and exothermic crystallization peak temperature (T p ). The exothermic crystallization peak temperature of the glass sample (T p ) is related to the formation of Zn2SiO4 crystal phase. At a heating rate of 5℃ / min, as the ZnO / B2O3 molar ratio increases from 3.2 to 4.2, T g The value increases from 641℃ to 651℃. The increase of ZnO / B2O3 molar ratio means the decrease of B2O3 content in glass, which indicates that reducing the content of low-melting-point B2O3 can significantly increase T g , therefore, T g With the increase of ZnO / B2O3 molar ratio, the p The peak intensity and sharpness of the ZnO / B2O3 decrease significantly with the increase of the ZnO / B2O3 molar ratio. Although the crystallization peak moves from 716.4℃ (for ZnO / B2O3=3.2) to 691.4℃ (for ZnO / B2O3=4.2), the crystallization peak protrusion gradually decreases with the increase of the ZnO / B2O3 molar ratio. Therefore, it is speculated that with the increase of the ZnO / B2O3 molar ratio, the SiO2 content decreases and the precipitation of Zn2SiO4 becomes more difficult.

[0082] 4. Figure 3 The XRD patterns of the ZBS glass-ceramics prepared in Examples 1 to 6 are shown in Table 1. Figure 3 It can be seen that after sintering at 700°C for 30 minutes, the obtained ZBS glass-ceramics precipitates pure Zn2SiO4 crystal phase, and the diffraction peak intensity of the Zn2SiO4 crystal phase weakens with the increase of the ZnO / B2O3 molar ratio. This is because the SiO2 content decreases with the increase of the ZnO / B2O3 molar ratio.

[0083] 5. Figure 4 The dielectric properties test results of the ZBS glass-ceramics prepared in Examples 1 to 6 are as follows. Figure 4It can be seen that with the increase of the ZnO / B2O3 molar ratio, the Zn2SiO4 crystal phase precipitated from the ZBS glass-ceramics gradually decreases, and the glass phase content increases, so that the dielectric constant and dielectric loss of the ZBS glass-ceramics both increase as the ZnO / B2O3 molar ratio increases.

[0084] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for preparing a zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material, characterized in that: The following steps are involved: The ZBS glass powder and the binder are mixed and then aged, granulated and pressed to obtain a green blank; The ZBS glass powder is prepared from ZnO, H3BO3 and SiO2 according to the following molar percentages: ZnO 53-70 mol%, B2O3 12-20 mol%, SiO2 15-30 mol%; the H3BO3 is calculated based on the molar number of B2O3; the molar ratio of ZnO to B2O3 in the ZBS glass powder is 3.2-4.8; Sintering the green body to obtain the zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material; the sintering temperature is 700-750° C.; The zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material has a Zn2SiO4 crystal phase.

2. The preparation method according to claim 1, characterized in that The preparation method of the ZBS glass powder comprises: mixing ZnO, H3BO3 and SiO2, heating and melting the mixture, quenching the obtained molten glass liquid in water to obtain a glass body; ball-milling the glass body, and then sieving and drying the mixture in sequence to obtain the ZBS glass powder.

3. The preparation method according to claim 2, characterized in that The heating and melting temperature is 1350-1450°C, and the holding time is 2-4 hours; The ball milling conditions include: the ball milling medium is deionized water, the grinding balls are zirconia balls, the ball milling speed is 300-450 rpm, and the ball milling time is 6-12 hours.

4. The preparation method according to claim 1, characterized in that The binder is a polyvinyl alcohol solution, the mass concentration of the polyvinyl alcohol solution is 3-5%; the mass ratio of the polyvinyl alcohol solution to the ZBS glass powder is 1:(35-45).

5. The preparation method according to claim 1, characterized in that The pressure of the compression molding is 70-100 MPa.

6. The preparation method according to claim 1, characterized in that The heating rate for heating to the sintering temperature is 5 to 10° C. / min; and the sintering holding time is 30 to 60 minutes.

7. The zinc-borosilicate glass-ceramics low-temperature co-fired ceramic material prepared by the preparation method according to any one of claims 1 to 6, characterized in that: The zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material includes the following components in molar fractions: ZnO 53-70 mol%, B2O3 12-20 mol%, SiO2 15-30 mol%; the molar ratio of ZnO to B2O3 is 3.2-4.8; the zinc-borosilicate glass-ceramic low-temperature co-fired ceramic material has a Zn2SiO4 crystal phase.

8. The zinc-borosilicate glass-ceramics low-temperature co-fired ceramic material according to claim 7, characterized in that: The molar ratio of SiO2 to B2O3 is 1.4±0.

05.

9. The zinc-borosilicate glass-ceramics low-temperature co-fired ceramic material according to claim 7, characterized in that: The dielectric constant of the zinc borosilicate glass-ceramic low-temperature co-fired ceramic material at 1 MHz is 5.5-6.2, and the dielectric loss is (0.43-7.2)×10 -3 .

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