阅读说明：本技术 低温烧结玻璃陶瓷粉及其制备方法和应用 (Low-temperature sintered glass ceramic powder and preparation method and application thereof ) 是由 李程峰 余明先 向明 王伟江 戴高环 刘建国 于 2021-09-17 设计创作，主要内容包括：本发明提供一种低温烧结玻璃陶瓷粉,由第一粉体和第二粉体复合而成,其中,按质量份数计,所述第一粉体为3-10份,所述第二粉体为1份。备所述第一粉体的原料包括1-50质量份的B-(2)O-(3)、35-65质量份的CaO和10-65质量份的SiO-(2)。制备所述第二粉体的原料包括1-50质量份的H-(3)BO-(3)、35-65质量份的CaO和10-65质量份的C-(8)H-(20)Si。还提供一种低温烧结玻璃陶瓷粉的制备方法,包括对所述第一粉体的原料进行混合、熔炼、淬冷、烘干、研磨和热处理。对所述第二粉体的原料进行溶解及喷雾造粒。还提供一种低温烧结玻璃陶瓷粉在低温共烧陶瓷基板中的应用。本发明的低温烧结玻璃陶瓷粉及其制备方法和应用,有效降低了介质材料的高频损耗、介电常数及热膨胀系数,使介质材料具有更优的综合性能。(The invention provides low-temperature sintered glass ceramic powder which is formed by compounding 3-10 parts by weight of first powder and 1 part by weight of second powder. The raw material for preparing the first powder comprises 1-50 parts by mass of B 2 O 3 35-65 parts by mass of CaO and 10-65 parts by mass of SiO 2 . The raw material for preparing the second powder comprises 1-50 parts by mass of H 3 BO 3 35-65 parts by mass of CaO and 10-65 parts by mass of C 8 H 20 And (3) Si. Also provides a preparation method of the low-temperature sintered glass ceramic powder, which comprises the steps of mixing, smelting, quenching, drying, grinding and heat treatment of the raw materials of the first powder. And dissolving and spray granulating the raw material of the second powder. Also provides the application of the low-temperature sintered glass ceramic powder in a low-temperature co-fired ceramic substrate. The low-temperature sintered glass ceramic powder and the preparation method and the application thereof effectively reduce the high-frequency loss, the dielectric constant and the thermal expansion coefficient of the dielectric material, so that the dielectric material has better comprehensive performance.)

1. The low-temperature sintered glass ceramic powder is characterized by being compounded from 3-10 parts by mass of first powder and 1 part by mass of second powder;

the raw material for preparing the first powder comprises 1-50 parts by mass of B₂O₃35-65 parts by mass of CaO and 10-65 parts by mass of SiO₂；

The raw material for preparing the second powder comprises 1-50 parts by mass of H₃BO₃35-65 parts by mass of CaO and 10-65 parts by mass of C₈H₂₀Si。

2. The low-temperature-sintered glass ceramic powder according to claim 1, characterized in that: the grain diameter of the first powder is 1-10 mu m, and/or the grain diameter of the second powder is 10-200 nm.

3. The low-temperature-sintered glass ceramic powder according to claim 1, characterized in that: the first powder needs to be subjected to heat treatment before being compounded with the second powder, the heat treatment temperature is 700-900 ℃, and the heating time of the heat treatment is 30-120 min.

4. The method for producing a low-temperature-sintered glass ceramic powder according to any one of claims 1 to 3, comprising the steps of:

preparing first powder: respectively weighing 1-50 parts by mass of B₂O₃35-65 parts by mass of CaO and 10-65 parts by mass of SiO₂Mixing, smelting to obtain a melt, and quenching, drying, grinding and thermally treating the melt to obtain first powder;

preparing second powder: respectively weighing 1-50 parts by mass of H₃BO₃35 to 65 parts by mass of CaO and10-65 parts by mass of C₈H₂₀Si, dissolving the mixture in water, and performing spray granulation to obtain second powder;

mixing: mixing the first powder and the second powder according to the weight ratio of 3-10: 1 to obtain the low-temperature sintered glass ceramic powder.

5. The method for preparing low-temperature sintered glass-ceramic powder according to claim 4, characterized in that: the smelting temperature range is 1200-1500 ℃, and the smelting time is 20-40 min.

6. The method for preparing low-temperature sintered glass-ceramic powder according to claim 4, characterized in that: the temperature range of the heat treatment is 700-900 ℃, and the heating time of the heat treatment is 30-120 min.

7. The method for preparing low-temperature sintered glass-ceramic powder according to claim 4, characterized in that: the temperature range of the spray granulation is 900-1100 ℃.

8. The method for preparing low-temperature sintered glass-ceramic powder according to claim 4, characterized in that: the grain diameter of the first powder is 1-10 μm.

9. The method for preparing low-temperature sintered glass-ceramic powder according to claim 4, characterized in that: the grain diameter of the second powder is 10-200 nm.

10. An application of low-temperature sintered glass ceramic powder in a low-temperature co-fired ceramic substrate is characterized in that the low-temperature sintered glass ceramic powder is prepared by the preparation method of the low-temperature sintered glass ceramic powder according to any one of claims 4 to 9.

Technical Field

The invention belongs to the technical field of functional ceramics, and particularly relates to low-temperature sintered glass ceramic powder and a preparation method and application thereof.

Background

With the rapid development of electronic communication technology, the number of electronic components in each unit volume is rapidly increased, and the demand for high-frequency and low-dielectric constant low-temperature co-fired ceramic substrates is increasing day by day, so that the dielectric material for preparing the ceramic substrate is required to have the performances of low dielectric constant, low high-frequency loss, thermal expansion coefficient similar to that of a chip, high thermal conductivity and the like.

At present, the low-temperature co-fired ceramic substrate often has the problems of high-frequency loss, large change of dielectric constant along with frequency, warping when being co-fired with metal slurry, low thermal conductivity and the like. The high frequency loss is mainly related to the excessive amorphous glass phase in the dielectric material, and the ionic conductance in the glass phase is the main source of the dielectric loss at high frequency. In the ceramic/glass system material, because the glass material is amorphous glass, the glass material still mainly exists in an amorphous structure after sintering, and thus the dielectric loss of the dielectric material under high frequency is greatly improved. In the glass ceramic body material, although a part of the crystallized glass forms a crystal structure in the sintering process due to the surface crystallization process, a larger part of the crystallized glass still exists in an amorphous structure, and the high-frequency loss performance of the dielectric material is also influenced.

Disclosure of Invention

The invention aims to overcome the defects in the prior art, and provides low-temperature sintered glass ceramic powder, a preparation method and application thereof, so as to solve the problems of high-frequency loss and large change of dielectric constant with frequency of a low-temperature sintered dielectric material.

In order to achieve the purpose, the invention adopts the technical scheme that:

the low-temperature sintered glass ceramic powder is formed by compounding 3-10 parts by weight of first powder and 1 part by weight of second powder;

the raw material for preparing the first powder comprises 1-50 parts by mass of B₂O₃35-65 parts by mass of CaO and 10-65 parts by mass of SiO₂；

The raw material for preparing the second powder comprises 1-50 parts by mass of H₃BO₃35-65 parts by mass of CaO and 10-65 parts by mass of C₈H₂₀Si。

The further improvement of the technical scheme is as follows:

the grain diameter of the first powder is 1-10 mu m, and/or the grain diameter of the second powder is 10-200 nm.

The first powder needs to be subjected to heat treatment before being compounded with the second powder, the heat treatment temperature is 700-900 ℃, and the heating time of the heat treatment is 30-120 min.

The invention also provides a preparation method of the low-temperature sintered glass ceramic powder, which comprises the following steps:

preparing first powder: respectively weighing 1-50 parts by mass of B₂O₃35-65 parts by mass of CaO and 10-65 parts by mass of SiO₂Mixing, smelting to obtain a melt, and quenching, drying, grinding and thermally treating the melt to obtain first powder;

preparing second powder: respectively weighing 1-50 parts by mass of H₃BO₃35-65 parts by mass of CaO and 10-65 parts by mass of C₈H₂₀Si, dissolving the mixture in water, and performing spray granulation to obtain second powder;

mixing: mixing the first powder and the second powder according to the weight ratio of 3-10: 1 to obtain the low-temperature sintered glass ceramic powder.

Further, the smelting temperature range is 1200-1500 ℃, and the smelting time is 20-40 min.

Further, the temperature range of the heat treatment is 700-900 ℃, and the heating time of the heat treatment is 30-120 min.

Further, the temperature range of the spray granulation is 900-1100 ℃.

Further, the particle size of the first powder is 1-10 μm.

The grain diameter of the second powder is 10-200 nm.

The invention also provides application of the low-temperature sintered glass ceramic powder in a low-temperature co-fired ceramic substrate, and the low-temperature sintered glass ceramic powder is prepared by the preparation method of the low-temperature sintered glass ceramic powder.

According to the technical scheme of the invention, the low-temperature sintered glass ceramic powder is CaO-B₂O₃-SiO₂According to the system, the raw materials for preparing the first powder and the second powder are reasonably selected, so that the amorphous glass phase in the dielectric material formed by low-temperature co-firing is controlled within a reasonable range, and is not too much or too little, and the problem of large high-frequency loss of the dielectric material can be effectively reduced. According to the preparation method of the low-temperature sintered glass ceramic powder, the first powder is subjected to crystallization heat treatment, so that on one hand, the content of an amorphous glass structure in the low-temperature co-fired dielectric material is reduced, the crystallinity of the low-temperature sintered glass ceramic powder is improved, and meanwhile, the densification temperature of the first powder is not changed, so that the dielectric constant and the thermal expansion coefficient of the dielectric material are reduced, and the problem of poor matching between the dielectric material and a metal conductor when the densification temperature is too high during co-firing is solved.

Drawings

FIG. 1 is a schematic flow chart of a method for preparing low-temperature sintered glass-ceramic powder according to an embodiment of the present invention.

Fig. 2 is a result of crystallinity measurement of the test sample 1 prepared in example 1 of the present invention.

Detailed Description

To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

Example (b): the embodiment provides a low-temperature sintered glass ceramic powder, which is formed by compounding a first powder and a second powder, wherein the first powder is 3-10 parts by mass, and the second powder is 1 part by mass.

The raw material for preparing the first powder comprises 1-50 parts by mass of B₂O₃(boron oxide), 35-65 parts by mass of CaO (calcium oxide) and 10-65 parts by mass of SiO₂(silicon oxide). The grain diameter of the first powder is 1-10 μm.

The raw material for preparing the second powder comprises 1-50 parts by mass of H₃BO₃(boric acid), 35-65 parts by mass of CaO (calcium oxide) and 10-65 parts by mass of C₈H₂₀Si (tetraethylsilane). The grain diameter of the second powder is 10-200 nm.

In a specific embodiment, the raw material of the first powder may include 10 parts by mass of B₂O₃45 parts by mass of CaO and 45 parts by mass of SiO₂Or comprises 5 parts by mass of B₂O₃47.5 parts by mass of CaO and 47.5 parts by mass of SiO₂Or comprises 10 parts by mass of B₂O₃50 parts by mass of CaO and 40 parts by mass of SiO₂。

In a specific embodiment, the raw material of the second powder may include 20 parts by mass of H₃BO₃40 parts by mass of CaO and 40 parts by mass of C₈H₂₀Si, or including 25 parts by mass of H₃BO₃37.5 parts by mass of CaO and 37.5 parts by mass of C₈H₂₀Si, or including 20 parts by mass of H₃BO₃50 parts by mass of CaO and 30 parts by mass of C₈H₂₀Si。

As shown in fig. 1, this embodiment further provides a method for preparing a low-temperature sintered glass ceramic powder, including the following steps:

s1, preparing first powder: respectively weighing 1-50 parts by mass of B₂O₃35-65 parts by mass of CaO and 10-65 parts by mass of SiO₂After being fully mixed, the mixture is placed in a corundum crucible or a platinum crucible for smelting, the smelting temperature range is 1200-1500 ℃, the smelting time is 20-40min, a melt is obtained, and the melt is poured into water for quenching. And drying the quenched melt, and carrying out ball milling and crushing to a particle size range of 1-10 mu m. And then placing the powder in a muffle furnace for heat treatment, wherein the heating temperature range of the heat treatment is 700-900 ℃, and the heating time of the heat treatment is 30-120min, so as to obtain the first powder.

S2, preparing second powder: respectively weighing 1-50 parts by mass of H₃BO₃35-65 parts by mass of CaO and 10-65 parts by mass of C₈H₂₀And Si, which is fully mixed, dissolved in water according to the concentration of 5-10 wt%, and subjected to spray atomization by a spray tower and smelting to obtain the second powder, wherein the temperature range of the spray atomization is 900-1100 ℃. The particle size range of the second powder is 10-200 nm.

S3, mixing: mixing the first powder and the second powder according to the weight ratio of 3-10: 1 to obtain the low-temperature sintered glass ceramic powder. In a specific embodiment, the mass ratio of the first powder to the second powder may be 4: 1. 5: 1. 8: 1 or 9: 1, etc.

Example 1: the preparation method of the low-temperature sintered glass ceramic powder of the embodiment comprises the following specific steps:

s1, preparing first powder: respectively weighing 10 parts by mass of B₂O₃45 parts by mass of CaO and 45 parts by mass of SiO₂After being fully mixed, the mixture is put into a corundum crucible or a platinum crucible for smelting, the smelting temperature is 1400 ℃, and the smelting time is 30minTo obtain a melt, and pouring the melt into water for quenching. After the quenched melt was dried, the particle size after ball milling was 5 μm. And then placing the powder in a muffle furnace for heat treatment, wherein the heating temperature of the heat treatment is 850 ℃, and the heating time of the heat treatment is 1h, so as to obtain the first powder.

S2, preparing second powder: respectively weighing 20 parts by mass of H₃BO₃40 parts by mass of CaO and 40 parts by mass of C₈H₂₀And Si, which is fully mixed, dissolved in water according to the concentration of 8 wt%, and subjected to spray atomization by a spray tower and smelting to obtain the second powder, wherein the temperature of the spray atomization is 1000 ℃. The particle size of the second powder is 15 nm.

S3, mixing: mixing the first powder and the second powder according to the ratio of 5: 1, and standing for a period of time to obtain the composite low-temperature sintered glass ceramic powder.

In order to verify the performance of the low-temperature sintered glass ceramic powder prepared in this embodiment, the low-temperature sintered glass ceramic powder may be subjected to tape casting, and then the temperature is maintained at 850 ℃ for 10min to prepare a test sample 1 for performance testing.

Example 2: the preparation method of the low-temperature sintered glass ceramic powder of the present embodiment is basically the same as the steps of embodiment 1, and is not repeated here, except that:

s1, preparing first powder: respectively weighing 5 parts by mass of B₂O₃47.5 parts by mass of CaO and 47.5 parts by mass of SiO₂. After being fully mixed, the mixture is put into a corundum crucible or a platinum crucible for smelting, the smelting temperature range is 1500 ℃, and the particle size after ball milling and crushing is 3-4 mu m. The heating temperature of the heat treatment was 800 ℃.

S2, preparing second powder: respectively weighing 25 parts by mass of H₃BO₃37.5 parts by mass of CaO and 37.5 parts by mass of C₈H₂₀Si, after thoroughly mixed, was dissolved in water at a concentration of 10 wt%.

S3, mixing: mixing the first powder and the second powder according to the ratio of 8: 1, and mixing the components in a mass ratio of 1.

In order to verify the performance of the low-temperature sintered glass ceramic powder prepared in this embodiment, the low-temperature sintered glass ceramic powder may be subjected to tape casting, and then the temperature is maintained at 850 ℃ for 10min to prepare a test sample 2 for performance testing.

Example 3: the preparation method of the low-temperature sintered glass ceramic powder of the present embodiment is basically the same as the steps of embodiment 1, and is not repeated here, except that:

s1, preparing first powder: respectively weighing 10 parts by mass of B₂O₃50 parts by mass of CaO and 40 parts by mass of SiO₂. The particle size after ball milling and crushing is 5-8 μm. The heating temperature of the heat treatment was 780 ℃ and the heating time of the heat treatment was 1.5 h.

S2, preparing second powder: respectively weighing 20 parts by mass of H₃BO₃50 parts by mass of CaO and 30 parts by mass of C₈H₂₀Si, mixed well, dissolved in water at a concentration of 6 wt%. The particle size of the second powder is 50 nm.

S3, mixing: mixing the first powder and the second powder according to a ratio of 4: 1, and mixing the components in a mass ratio of 1.

In order to verify the performance of the low-temperature sintered glass ceramic powder prepared in this embodiment, the low-temperature sintered glass ceramic powder may be subjected to tape casting, and then the temperature is maintained at 850 ℃ for 10min to prepare a test sample 3 for performance testing.

Comparative example 1: the comparative example provides a preparation method of a low-temperature co-fired dielectric material, which comprises the following steps:

s1, preparing first powder: respectively weighing 10 parts by mass of B₂O₃45 parts by mass of CaO and 45 parts by mass of SiO₂. And after fully mixing, putting the mixture into a muffle furnace for smelting at 1400 ℃ for 30min to obtain a melt, and pouring the melt into water for quenching. And drying the quenched melt, and performing ball milling crushing to obtain the first powder with the particle size of 3-5 microns.

S2, preparing second powder: respectively weighing 30 parts by massB of (A)₂O₃40 parts by mass of CaO and 40 parts by mass of C₈H₂₀And Si, fully mixing, putting into a muffle furnace for smelting at 1300 ℃ for 30min to obtain a melt, and pouring the melt into water for quenching. And drying the quenched melt, and performing ball milling crushing to obtain the second powder with the particle size of 3-5 microns.

S3, mixing: mixing the first powder and the second powder according to the ratio of 1: 1, and mixing the components in a mass ratio of 1.

In order to verify the performance of the low-temperature sintered glass ceramic powder prepared in this embodiment, the low-temperature sintered glass ceramic powder may be subjected to tape casting, and then the temperature is maintained at 850 ℃ for 10min to prepare a test sample 4 for performance testing.

Comparative example 2: the comparative example provides a preparation method of a low-temperature co-fired dielectric material, which comprises the following steps:

s1, preparing first powder: respectively weighing 10 parts by mass of B₂O₃45 parts by mass of CaO and 45 parts by mass of SiO₂. And after fully mixing, putting the mixture into a muffle furnace for smelting at 1400 ℃ for 30min to obtain a melt, and pouring the melt into water for quenching. And drying the quenched melt, and performing ball milling crushing to obtain the first powder with the particle size of 3-5 microns.

S2, preparing second powder: putting quartz sand into a muffle furnace for smelting at 1600 ℃ for 30min to obtain a melt, and pouring the melt into water for quenching. And drying the quenched melt, and performing ball milling crushing to obtain the second powder with the particle size of 3-5 microns.

S3, mixing: mixing the first powder and the second powder according to the ratio of 1: 1, and mixing the components in a mass ratio of 1.

In order to verify the performance of the low-temperature sintered glass ceramic powder prepared in this embodiment, the low-temperature sintered glass ceramic powder may be subjected to tape casting, and then the temperature is maintained at 850 ℃ for 10min to prepare a test sample 5 for performance testing.

The five test samples were tested and the test results are shown in table 1.

TABLE 1

As can be seen from the data in the above table, the low temperature sintered glass ceramic powders prepared by the embodiments 1 to 3 of the present invention have lower dielectric constant, lower dielectric loss, lower thermal expansion coefficient and higher crystallinity, and the combination properties are better than those of the two comparative examples.

According to the preparation method of the low-temperature sintered glass ceramic powder, firstly, the first powder is subjected to crystallization heat treatment, so that the content of an amorphous glass structure in the low-temperature co-fired dielectric material is reduced, and the densification temperature of the first powder is not changed. And the second nano-powder is used as a key material for reducing the densification temperature of the dielectric material. The crystallinity of the mixture of the first powder and the second powder after sintering reaches more than 90 percent, thereby not only solving the problem of large high-frequency loss, but also solving the problem of poor co-firing matching caused by overhigh densification temperature.

The invention also provides application of the low-temperature sintered glass ceramic powder in a low-temperature co-fired ceramic substrate, wherein the low-temperature sintered glass ceramic powder is prepared by the preparation method of any one of embodiments 1 to 3.

The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, but should be considered as the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above examples only express preferred embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.