CN110683769B - Reinforced calcium-boron-silicon glass-ceramic composite material and preparation method thereof - Google Patents

Reinforced calcium-boron-silicon glass-ceramic composite material and preparation method thereof Download PDF

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CN110683769B
CN110683769B CN201911023621.0A CN201911023621A CN110683769B CN 110683769 B CN110683769 B CN 110683769B CN 201911023621 A CN201911023621 A CN 201911023621A CN 110683769 B CN110683769 B CN 110683769B
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powder
glass
temperature
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ceramic
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CN110683769A (en
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缪锡根
缪波
何纪生
申亮
潘华路
吴长明
罗万
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Ganzhou Zhongao New Porcelain Technology Co ltd
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Ganzhou Zhongao New Porcelain Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/002—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of fibres, filaments, yarns, felts or woven material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/02—Pretreated ingredients
    • C03C1/026—Pelletisation or prereacting of powdered raw materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/02—Compositions for glass with special properties for coloured glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/02—Fibres; Filaments; Yarns; Felts; Woven material
    • C03C2214/03—Fibres; Filaments; Yarns; Felts; Woven material surface treated, e.g. coated
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/04—Particles; Flakes
    • C03C2214/05—Particles; Flakes surface treated, e.g. coated
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/20—Glass-ceramics matrix

Abstract

The invention discloses a preparation method of a reinforced calcium-boron-silicon glass-ceramic composite material. The composite material comprises a matrix consisting of glass powder, a sintering aid and a colorant, and an alumina reinforcing phase with the volume percentage of 5-35%. The glass powder comprises the following specific components in percentage by mass: CaO 35-50%, B2O310‑25％，SiO235‑50％，Al2O30.1‑1.5％，MgO 0.1‑1.5％，ZrO20.1-2.5%; mixing the glass powder with 0.5-3.5% of external adulterant by mass percent, wherein the composite sintering aid is as follows: xV2O5‑yTeO2‑z3Li2O·2B2O3The composite colorant is Cr2O3\Co2O3\CuO\MnO20-1.5% of any one or more of the above components in percentage by mass. The invention utilizes flaky, whisker-shaped or short-fiber-shaped alumina with good reinforcing and toughening effects, and simultaneously adopts a method of laminating the staged hot-pressing casting sheets to reinforce and toughen the calbyssoside microcrystalline glass with good high-frequency dielectric properties, thereby preparing the composite material plane or curved substrate with high strength and low loss.

Description

Reinforced calcium-boron-silicon glass-ceramic composite material and preparation method thereof
Technical Field
The invention relates to a microcrystalline glass composite material, belongs to the technical field of composite materials, and particularly relates to a reinforced calcium-boron-silicon microcrystalline glass composite material and a preparation method thereof.
Background
With the advent of wireless charging, the 5G era and the intelligent society, inorganic non-metallic materials (glass and ceramics) are becoming more and more popular because of their performance such as no signal interference problem and wear resistance. The cover plate material related to the rear cover of the 5G mobile phone is required to have good dielectric properties (such as low dielectric constant and low dielectric loss) under microwave or high-frequency conditions and excellent thermomechanical properties (such as high mechanical strength and good heat dissipation). Stabilized zirconia ceramic materials have been used for cell phone covers, primarily because of its jade-like texture and high strength, but its high dielectric constant and high hardness result in expensive processing costs. The mobile phone cover is made of hot bending glass material, and the mechanical strength and fracture toughness of the glass are lower although the processing cost of the glass is low.
Therefore, there is a need to develop a mobile phone housing material or a high frequency microwave transparent radome material having good microwave dielectric properties, high mechanical strength and high thermal stability. Undoubtedly, the microcrystalline glass is one of the materials that can be selected for the back plate of the mobile phone, and has the performance between that of ceramic and glass materials, the easy processability of glass, the high mechanical strength of ceramic, and the like.
The microcrystalline glass has many types, and the calcium borosilicate system microcrystalline glass attracts attention because of the characteristics of low dielectric constant, low loss, stable high-frequency performance, low-temperature sintering and the like, and can be widely applied to the fields of phased-array radar antennas, high-frequency 5G communication devices and the like. However, the borosilicate glass ceramics have a narrow process window, which is characterized in that the performance of the borosilicate glass ceramics is too sensitive to the components of the parent glass, and the requirements on the processing process and the surface activity of the glass powder are too strict, and the nature of the borosilicate glass ceramics is that the cooperativity requirements on the blank densification process and the crystallization process of the borosilicate parent glass powder are too high, and in addition, the mechanical properties, such as strength and thermal properties, such as thermal conductivity, of the borosilicate glass ceramics under the traditional sintering process are not ideal.
The preparation method of the calcium borosilicate glass powder has at least three methods, and each method has the advantages and disadvantages:
sol-gel method: although the components are not volatilized, the calcining temperature is low, and the crucible material is not volatilizedThe requirement on corrosion resistance is not high, but the cost of raw materials is high, the densification temperature of a sintered body is high, and the production period is long; solid-phase reaction method: similar to the sol-gel method, the requirements for raw materials such as granularity are relaxed, and the method is more suitable for batch production, but the procedures of calcining, ball milling and the like are more complicated, and the sintering temperature is too high; melting-water quenching: it has the problem that the constituent elements, especially B2O3The high-temperature volatilization, the erosion of the glass liquid to the crucible and the like, but the requirements on the granularity, the purity or the variety of the raw materials are relatively loose, and the method is also suitable for the mass production of hundreds of kilograms to tons.
In the prior art, the densification process and the crystallization process of a calcium-boron-silicon microcrystalline glass system are not strictly distinguished, namely, the advantages of structural regulation and control of densification and crystallization are not exerted, so that the sintering density is low, the crystallization degree is not high, and meanwhile, the reinforcing and toughening effects of an optimized addition phase are not realized, so that the mechanical strength of the material is difficult to exceed 200MPa, the requirements of high-strength high-frequency wave-transmitting performance cannot be met, and the material is difficult to be applied to the fields of military radomes or civil 5G mobile phone shells and the like.
Therefore, how to control the low-temperature sintering and crystallization processes of calcium borosilicate and optimize the microstructure (the types and relative contents of ceramic phase, glass phase and pores) of the sintered body so as to obtain the calcium borosilicate microcrystalline glass composite material with high mechanical strength and high dielectric property becomes a technical problem which needs to be solved urgently by those skilled in the art at present.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide a preparation method of a reinforced calcium-boron-silicon glass-ceramic composite material, wherein the components of a calcium-boron-silicon glass-ceramic system are designed to be simply regulated into CaO and B2O5、SiO2The ratio between the two is developed to adopt internal doping (namely, the dopant is in the glass body), further adopt external doping (or add filler), and finally develop towards the direction of constructing composite materials so as to improve the comprehensive properties of the materials.
The object of the present invention and the way to solve the technical problem are achieved by adopting the following technical solutions. According to the invention, the reinforced calcium-boron-silicon glass-ceramic composite material comprises a matrix construction mixture consisting of glass powder, a sintering aid and a colorant, and an alumina reinforcing phase;
the calcium borosilicate glass powder contains a composite internal doped oxide, and the glass powder comprises the following specific components in percentage by mass:
CaO 35-50％，B2O310-25％，SiO2 35-50％，Al2O3 0.1-1.5％，MgO 0.1-1.5％，ZrO20.1-2.5％；
based on the mass of the calcium borosilicate glass powder, 0.5 to 3.5 percent of foreign impurities, namely a composite sintering aid and a colorant, are added, wherein the composite sintering aid is as follows:
xV2O5-yTeO2-z3Li2O·2B2O3a composition;
relative to the glass powder, the mass percentage of x is 0.1-1.5%; y is 0.1% -1.5%; z is 0% -1%; and x + y + z is 0.3% -2%;
the composite colorant is Cr2O3\Co2O3\CuO\MnO2Any one or any combination of more than one, the mass percent of the colorant is 0-1.5%;
base materials based on the mixture (glass powder, sintering aid and colorant) are added with 5-35% of alumina composite powder material (reinforcing phase) by volume percentage; wherein, the volume percentage of the flaky alumina is 1-15%; the volume percentage of the granular alumina is 4-20%, the volume percentage of the short fiber-shaped or whisker-shaped alumina is 0-10%, and the strengthening and toughening action mechanisms of the alumina comprise crack deflection, fiber extraction and the like.
Further, in the composite sintering aid, V2O5Has a melting point of 690 ℃ and a particle size<1.5 mm; the TeO2Has a melting point of 733 ℃ and a particle size<1.5 mm; the 3Li2O·2B2O3Has a melting point of 773 ℃ and a particle size<1.5mm, which are all added or mixed in as micron or submicron sized particles.
In addition, the invention also provides a preparation method of the calcium-boron-silicon glass-ceramic composite material, which comprises the following steps:
1) preparing raw material powder:
a) preparing CBS glass powder by a melting-water quenching method;
b) preparation of 3Li2O·2B2O3Compound low-temperature ceramic powder: with Li2O and H3BO3The raw materials are as follows: 4, grinding the two raw materials fully and uniformly by dry ball milling, then placing the mixed powder in a corundum crucible in a loose manner (without compaction), putting the mixture into a furnace, slowly heating to 670 ℃, preserving heat for 6 hours at the temperature, then cooling the mixture along with the furnace, crushing the loose body after the solid phase reaction, and ball milling the loose body into fine powder;
c) preparation of hydrophobic dispersed (non-agglomerated) mixed powder: weighing CBS glass powder, a composite sintering aid and a coloring agent according to a formula proportion, wet-grinding, performing low-temperature vacuum drying or baking mixed powder at the temperature higher than 100 ℃, adding a solid dispersing agent, performing dry ball milling, and sieving to obtain hydrophobic dispersed mixed powder;
d) preparing a Coupling Agent (CA) modified reinforced alumina powder raw material (reinforcing phase): firstly, dispersing alumina powder into alcohol by an ultrasonic method, and simultaneously hydrolyzing CA by deionized water, wherein the addition amount of CA is 0.5-1.5% relative to the mass percentage of the powder; secondly, adding the hydrolyzed CA solution into the alcohol powder suspension, and continuously stirring for 4-6 hours; then, drying the mixed suspension by adopting a vacuum drying method; and finally, performing ball milling to scatter and screen the powder to obtain the reinforced powder treated by CA.
The selection requirement of the coupling agent is that the hydrophilic inorganic group and OH on the surface of the powder body-The groups are capable of forming a bond, while the lipophilic organic groups facing the organic solution should have good thermal decomposition or volatilization properties, both of which are required for the casting process.
2) Preparing a tape casting sheet of the composite powder material:
adding a hydrophobic powder material serving as a matrix and reinforcing powder treated by a coupling agent serving as a reinforcing phase into a mixed organic solvent in sequence according to a ratio, ultrasonically stirring for a period of time such as 1 hour, then adding a dispersing agent, ultrasonically stirring for a period of time, then sequentially adding a binder, a plasticizer and a defoaming agent under the condition of continuous ultrasonic stirring, uniformly dispersing for 4-6 hours, then performing vacuum defoaming treatment on the slurry to prepare qualified casting slurry, and finally completing casting and drying processes on a casting machine to obtain a casting belt with the thickness of 120-2000 mu m;
3) preparing a blank (plane or curved surface) of the composite powder and discharging glue:
superposing more than two layers of casting sheets together, laminating the superposed layers through a plane or curved surface mold (such as double-opening mold), and after the double-opening mold is removed, laminating and removing glue on the superposed layers of the casting sheets by utilizing a conformal porous ceramic splint such as a porous refractory plate or/and ceramic or glass fiber fabric cloth and the like;
4) and (3) densifying the degummed composite powder blank by utilizing a hot pressing process:
a conformal ceramic mold, such as an alumina or mullite or silicon carbide mold, is adopted, a boron nitride band or ceramic fiber cloth is used as a stress buffer layer or a breathable layer, a composite powder blank is stacked between two breathable layers (or at least one breathable layer is contacted with the blank), then two parts of a double-open mold are covered, then the temperature is raised in an air furnace, and when the temperature is raised to a certain temperature between the softening point of CBS glass and the lowest (or first) crystallization temperature, the temperature is preserved.
On the other hand, when the temperature reaches the softening temperature of the glass, the pressure load (10-40MPa) can be applied to the blank through the mold, under the action of pressure and relatively high temperature, the viscous flow of the CBS glass and the liquid phase sintering mechanism of the sintering aid can cause the rapid densification of the blank, and the densification is realized by ensuring the high strength of the composite substrate;
5) carrying out crystallization treatment on the composite substrate after hot-pressing densification:
the pressure load is removed at the later stage of the hot pressing process, the temperature is raised, and when the temperature is raised to a certain temperature between 850 ℃ and 950 ℃, the sintering is carried out for 15-60min at the temperature; in other words, the glass matrix densification under the hot-pressing condition is firstly realized in the front and back time periods in the same furnace, then the glass matrix crystallization under the pressureless heating condition is realized, crystal nuclei (nanometer size) grow into crystal grains (micrometer size), and finally the microcrystalline glass composite substrate (plane or curved surface, depending on the shape of a hot-pressing mold) is obtained;
6) finish machining of the microcrystalline glass composite substrate:
the microcrystalline glass composite substrate obtained in the step 5) needs to be precisely processed, including grinding and polishing, and the microcrystalline glass composite substrate is easier to process because the hardness and the dielectric constant of the substrate material are lower than those of the conventional stabilized zirconia substrate.
Further, in the step a), the preparation method of the CBS glass powder comprises the specific processes of batching, mixing, and melting, wherein the melting temperature is 1450-.
Furthermore, in the step b), in order to make the components more uniform and the solid phase reaction more complete, the ball milling powder is continuously calcined under the same conditions, and then ball milling is carried out again, and finally 3Li with the granularity (D50) less than 2 mu m is obtained2O·2B2O3The compound powder.
Further, in the step C), in order to disperse the baked mixed powder while reducing the water absorption during the subsequent process, a water-repellent dispersing powder such as paraffin or stearic acid (C)18H36O2) Or the lauric acid and the baking mixed powder are subjected to dry ball milling for 1 to 5 hours according to the mass percentage of 0.2 to 2.0 percent, a horizontal ball mill with a ceramic lining is used for ball milling, and finally the ball is filtered by a screen with the aperture of 300 mu m to obtain the hydrophobic dispersed mixed powder.
Further, in the step d), the coupling agent is a silane coupling agent (SCA: c10H20O5Si). The present invention preferably employs silane coupling agents such as KH-550, KH-560, KH-570, etc., but other coupling agents such as tetrabutyl titanate (C)16H36O4Ti), aluminate esters, and the like.
Further, in the step 2), the organic solvent is a mixed solution of alcohol and butanone, the dispersant is castor oil, glycerol and triolein, and the ultrasonic stirring time is 1 hour; the adhesive is polyvinyl butyral (PVB), the plasticizer is dibutyl phthalate, and the defoaming agent is tributyl phosphate.
Further, in the step 3), the glue discharging temperature is generally not higher than 550 ℃, if a PVB adhesive is adopted, the PVB can be discharged by slowly raising the temperature and keeping the temperature for 2 hours at the maximum temperature of 450 ℃, and the degummed composite substrate material blank is prepared.
Furthermore, in step 6), annealing and stress-relieving treatment may be performed on the processed substrate, or silver burning treatment may be performed after printing a circuit, or selective chemical plating or electroplating treatment may be performed, so as to embed some passive microwave devices, such as an antenna, etc., in the inner surface of the substrate; if the substrate material itself has no colorant, a colored coating or the like (such as an anti-fingerprint film) can be coated on one side of the substrate; other subsequent treatment processes, such as laser engraving, surface coating or application of anti-fingerprint films, etc., are not excluded.
By means of the technical scheme, the invention has the following advantages and beneficial technical effects:
1) flaky, whisker-shaped or short-fiber-shaped alumina with good reinforcing and toughening effects is used for reinforcing and toughening calcium-boron-silicon microcrystalline glass with good high-frequency dielectric properties to prepare a high-performance (strength is more than 250MPa) low-loss (<0.001) composite material substrate, and the method is a brand-new material design scheme;
2) the addition of the reinforcing and toughening phase brings challenges to the densification of the calcium-borosilicate-based composite material, and if the structure is not dense, the improvement of the material strength is not facilitated, so that the hot pressing process with good densification effect is adopted, and the report of preparing the calcium-borosilicate microcrystalline glass by the hot pressing process is not seen at present;
3) because the calcium borosilicate is microcrystalline glass and relates to the densification and crystallization or crystallization process of glass powder, the setting of the hot pressing process just considers the characteristic that the two processes of the microcrystalline glass need to be performed cooperatively, namely the invention respectively adopts low temperature and high pressure to realize the densification process, and then adopts the heat treatment condition of high temperature and normal pressure to realize the crystallization of a glass matrix in the composite material, thereby forming the microcrystalline glass composite material substrate with optimized structure;
4) the invention not only adopts the hot pressing process to realize densification, but also adopts a novel composite sintering aid to widen the densification process window of the calcium-boron-silicon glass-ceramic substrate without obviously reducing the dielectric property of the material, and the V-based material is based on2O5-TeO2-3Li2O·2B2O3The combined composite sintering aid is unique;
5) because the substrate (plane or curved plate) is thinner and is generally less than 5mm, the invention adopts the casting process to form the substrate blank, but the casting process has strict requirements on the dispersibility and the hydrophobicity of the powder material, so the invention carries out the special dehydration and hydrophobic treatment on the calcium borosilicate glass powder.
Drawings
FIG. 1 is a process flow diagram of a calcium-boron-silicon glass-ceramic composite substrate;
FIG. 2(a) is a mold assembly drawing of the hot pressing process of the calcium borosilicate glass-ceramic composite planar substrate; FIG. 2(b) is a drawing showing the assembly of the mold for the hot pressing process of the calcium-boron-silicon glass-ceramic composite 3D curved substrate;
FIG. 3 shows the result of DSC (differential scanning calorimetry) analysis of a calcium borosilicate glass frit;
fig. 4 is an SEM (scanning secondary electron microscope) microstructure photograph of a calborosilicate glass ceramic (sintered body after sintering of glass powder body).
1-hearth; 2-a plane ceramic mould upper mould; 21-air holes; 3-ceramic fiber cloth or ceramic powder layer; 4-laminating the tape-casting sheet into a non-adhesive green body; a 5-boron nitride liner or coating; 6-plane ceramic die lower die
1' -hearth; 2' -curved surface ceramic mould upper mould; 21' -air holes; 3' -ceramic fiber cloth; 4' -laminating the tape-casting sheet into a glue-free blank; 5' -boron nitride liners or coatings; 6' -curved surface ceramic die lower die
Detailed Description
The present invention will be described in more detail below with reference to specific preferred embodiments and drawings, but the present invention is not limited to the following embodiments.
The invention discloses a reinforced Calcium Borosilicate (CBS) glass ceramic composite material, which comprises a matrix mixture consisting of glass powder, a sintering aid and a colorant and an alumina reinforcing phase.
The calcium borosilicate glass powder contains a composite internal doped oxide, and the glass powder comprises the following specific components (by mass percent):
CaO 35-50％，B2O3 10-25％，SiO2 35-50％，Al2O3 0.1-1.5％，MgO 0.1-1.5％，ZrO20.1-2.5%, wherein the last three oxides are inner doped oxides; based on the mass of the calcium borosilicate glass powder, 0.5 to 3.5 percent of external doping impurities such as a composite sintering aid and a coloring agent are added, wherein the composite sintering aid is as follows:
x V2O5(melting point 690 ℃ C.) -yTeO2(melting point 733 ℃ C.) -z3Li2O·2B2O3(melting point 773 ℃) a composition (in mass percent relative to the glass frit, x is 0.1% to 1.5%, y is 0.1% to 1.5%, z is 0% to 1%, and x + y + z is 0.3% to 2%).
And the composite colorant is Cr2O3\Co2O3\CuO\MnO2Any one or any combination of more than one of the above, and the content of the colorant is 0-1.5% (mass percentage relative to the glass powder).
Based on the base material of the mixture (glass powder, sintering aid and colorant), 5-35% of alumina composite powder material is added, wherein, the flaky alumina accounts for 1-15%, the granular alumina accounts for 4-20%, the short fiber (or whisker) alumina accounts for 0-10%, and the strengthening and toughening action mechanisms of the alumina composite powder material comprise crack deflection, fiber extraction and the like.
Fig. 1 shows a process flow chart of the calcium-boron-silicon glass-ceramic composite substrate according to the present invention. As can be seen from fig. 1, the process flow is:
glass powder, sintering aid and coloring agent as base material are first mixed homogeneously and hydrophobic treated, and alumina powder as reinforcing phase is also surface treated with coupling agent for good dispersion in casting slurry. Then, casting sheets are prepared by a casting process and laminated to form a blank of the composite substrate material. Since the casting sheet contains a large amount of transitional organic matter (which plays a role in green body molding), green body binder removal is performed. And then, the hot-pressing equipment is utilized to carry out two processes of densification and crystallization of the substrate material by stages on the non-glue blank, and finally, the production of the high-strength low-loss planar or curved substrate is completed through the precision machining and surface modification processes.
The invention adopts the composite sintering aid, adds the flaky alumina/alumina fiber, uses hydrophobic treatment, adopts a low-temperature hot pressing method to realize the densification of the material, then crystallizes the material at a higher temperature of more than 850 ℃ and less than 900 ℃, and finally prepares the glass-ceramic composite material substrate (a plane plate or a curved plate) with high strength and good dielectric property. The application of the low-temperature co-fired antenna comprises the fields of a base station antenna housing, a wireless charging substrate, a microwave device substrate, a low-temperature co-fired circuit substrate, a phased array radar base, an airplane patch antenna and the like besides a 5G mobile phone back plate.
The invention applies the hot pressing process to the calcium borosilicate glass-based composite blank body, so that the glass substrate can be rapidly densified under the condition of no or no obvious crystallization, and the invention is beneficial to finally obtaining the microcrystalline glass composite material substrate with high strength and low loss, and the used hot pressing temperature (for example, the temperature is less than 815 ℃) is much lower than that of the traditional ceramic material, namely, the used hot pressing temperature is equivalent to the temperature used in the hot bending process of the traditional 3D glass mobile phone backboard, so the invention is easier to realize in process and equipment.
The calcium-boron-silicon glass-ceramic composite material substrate has advantages in structural design and performance regulation, for example, the substrate is easier to process than a yttria-stabilized zirconia ceramic substrate, and the dielectric property and mechanical strength of the substrate are higher than those of a 3D pure glass mobile phone backboard.
Because the reinforcing and toughening effects of the flaky, whisker-shaped or fibrous alumina are better than those of granular alumina, the performance of the calcium-boron-silicon glass-ceramic/alumina composite material is obviously superior to that of a reported calcium-boron-silicon glass-ceramic/alumina granular composite material prepared by a sintering method.
The invention carries out hydrophobic treatment and surface modification treatment of the coupling agent on the used powder raw material, so that all oxide components can be uniformly dispersed in a casting belt or a substrate, and the adoption of the composite sintering aid widens the densification temperature range, namely V2O5The melting point (690 ℃) of the glass is higher than the crystallization temperature (819 ℃), liquid phase sintering and glass viscous flow sintering mechanisms occur simultaneously, rapid densification of the composite material is facilitated, and the uniform and dense (or small-pore) microstructure is beneficial to improvement of comprehensive performance of the composite material.
In the hot-press densification of the present invention, the case of very small amounts of devitrification is not excluded, but mainly the nucleation is not excluded, because even a large number of nuclei (of nanometer size) do not have a significant adverse effect on the densification. On the contrary, the pre-nucleation of the glass is beneficial to the crystallization and grain growth process of the final glass, so the invention can carry out the normal pressure crystallization in the temperature range of the glass crystallization temperature (such as 820 ℃) and below 900 ℃ (the common temperature limit of low temperature co-firing, limited by the melting temperature of silver paste), and can prepare the microcrystalline glass composite material substrate (a plane plate or a curved plate, depending on the shape of the mould) with high mechanical strength and good dielectric property.
The invention adopts flaky, granular and fibrous alumina as a reinforcing agent, and has the advantages of high strength, oxidation resistance, good thermal conductivity, matching thermal expansion coefficient with calcium borosilicate glass ceramics, low dielectric constant, cheap raw materials and the like. Silicon nitride (Si)3N4) Whiskers or short fibers are also good choices, but they are expensive and have a low coefficient of thermal expansion.
Vanadium pentoxide (V)2O5) Has toxic effect, and can be replacedTo non-toxic vanadia compounds, e.g. Bi (VO)3)5、Cu(VO3)2、Zn(VO3)2And the like.
The calcium-boron-silicon glass powder used in the invention is preferably prepared by a melting-water quenching method, but other methods are not excluded, such as a solid-phase reaction method, a sol-gel method and the like.
The hot pressing process can be the traditional condition of heat conduction heating and unidirectional pressurization, and can also be a mode of direct current heating and unidirectional pressurization, such as adopting a discharge plasma sintering process or a hot isostatic pressing process with anisotropic pressurization, but the hot pressing process is simpler on traditional hot pressing process equipment, easier in process parameter regulation and lower in production cost.
If the strength requirement on the calcium-boron-silicon microcrystalline glass composite substrate is not high, for example, not higher than 200MPa, the hot pressing process can be replaced by the traditional normal-pressure sintering process, or only heating and no pressurizing are needed in the hot pressing process, or a special pressurizing device is not needed in the sintering process, and the purpose can be achieved only by using the self weight of the upper die with double die sinking.
As shown in fig. 2(a), a mold assembly diagram of the calborosilicate microcrystalline glass composite planar substrate in the hot pressing process is shown.
As shown in fig. 2(a), after being laminated and de-glued, the tape casting sheet is placed on a planar ceramic lower die 6 covered with a boron nitride liner or coated with an isolation coating 5, the upper surface of the laminated blank body can be covered with a breathable ceramic fiber cloth or a ceramic powder thin layer 3, then a planar ceramic upper die 2 containing a plurality of air vents 21 is covered, then the planar ceramic upper die and the planar ceramic upper die are sent into a furnace chamber 1 of hot-pressing equipment together, and then the compact microcrystalline glass composite planar substrate is prepared according to a preset heating and pressurizing process system.
As shown in fig. 2(b), a mold assembly diagram of the hot pressing process of the calcium-boron-silicon glass-ceramic composite 3D curved substrate is shown.
As can be seen in fig. 2(b), after lamination and binder removal, the cast sheet is placed on a curved ceramic lower die 6 ' covered with a boron nitride liner or coated with a barrier coating 5 ', and the upper surface of the green laminate may also be covered with a gas permeable ceramic fiber cloth 3 '. Then covering a curved ceramic upper die 2 'with a plurality of air holes, then sending the ceramic upper die and the curved ceramic upper die into a furnace chamber 1' of hot-pressing equipment, and then preparing the compact curved substrate of the glass-ceramic composite material according to a preset heating and pressurizing process schedule.
Example 1
A preparation method of the alumina reinforced calcium borosilicate glass-ceramic composite material plane plate comprises the following steps:
1. preparing raw material powder:
a) the CBS glass powder is prepared by a melting-water quenching method, which comprises the steps of weighing materials according to a formula, mixing the materials by a horizontal ball mill in a dry method for 3-5 hours, smelting by platinum, wherein the smelting temperature is 1450-1500 ℃, the heat preservation time or the glass liquid homogenization time is 0.5-2 hours, carrying out deionized water quenching on the glass liquid after the homogenization time is up, and then carrying out ball milling for 16-24 hours until the granularity median diameter (D50) of the glass powder is 0.5-2.3 mu m. FIG. 3 is the result of DSC (differential scanning calorimetry) analysis of the calborosilicate glass frit. The calcium borosilicate glass powder is prepared by a melting-water quenching-ball milling method, the median diameter D50 in the granularity of the glass powder is less than 2.5 mu m, the glass powder is amorphous, and the result of x-ray diffraction analysis proves that the calcium borosilicate glass powder is prepared by the melting-water quenching-ball milling method. The glass powder can generate structural change in the heating process, and the structural change is from rigidity to plasticity, glass softening and secondary crystallization, and the transition temperatures are marked in the figure. These transition temperatures are of great guidance in the selection of the densification and crystallization process parameters of the glass.
b) Preparation of 3Li2O·2B2O3Compound low-temperature ceramic powder: with analytically pure Li2O and H3BO3According to the following steps of 3: 4, grinding the two raw materials fully and uniformly by dry ball milling, then loosely placing the mixed powder into a corundum crucible, putting the corundum crucible into a furnace, slowly heating to 670 ℃, preserving heat for 6 hours at the temperature, then cooling along with the furnace, crushing the loose body after the solid phase reaction, and ball milling the loose body into powder; in order to make the components more uniform and make the solid phase reaction more complete, the ball-milled powder is continuously calcined once by the same method, and then the ball is re-sinteredGrinding once to obtain 3Li smaller than 2 μm2O·2B2O3A compound powder;
c) preparing hydrophobic dispersion mixed powder: weighing 500g of CBS glass powder, 10g of composite sintering aid and 2.5g of coloring agent according to the formula proportion, wet grinding, and baking the mixed powder slurry for 4-10 hours at the temperature higher than 100 ℃. In order to disperse the baked mixed powder and reduce the water absorption during the subsequent process, stearic acid (C) is a hydrophobic dispersion powder18H36O2) Dry ball milling is carried out on the mixture and the baked mixed powder for 4 to 10 hours according to the proportion of 0.5 percent (mass percentage), a horizontal ball mill with a ceramic lining is adopted for ball milling, and finally the mixture is sieved by a screen with the aperture of 300 mu m to obtain the hydrophobic dispersed mixed powder.
d) Preparing a Coupling Agent (CA) modified reinforced alumina powder raw material:
first, 250g of alumina powder was dispersed in alcohol by ultrasonic method while using deionized water to make silane coupling agent (SCA: C)10H20O5Si) hydrolysis, wherein the addition amount of the SCA relative to the powder is 1.5 percent (mass percentage); secondly, adding the hydrolyzed SCA solution into the alcohol powder suspension, and continuing stirring for 6 hours; then, drying the mixed suspension by adopting a vacuum drying method; and finally, performing ball milling and screening to obtain the reinforced powder treated by SCA.
2) Preparing a tape casting sheet of the composite powder material:
sequentially mixing a hydrophobic powder material and the reinforcing powder treated by the coupling agent according to the proportion of 66: 34 (equal to about 76:25 volume ratio) is added into a mixed organic solvent (such as mixed liquor of 70: 30 mass ratio of ethyl ketone), the solid content of the powder is controlled at about 65 wt%, ultrasonic stirring is carried out for a period of time such as 1 hour, then 2 g of castor oil, 2 g of glycerol and 1.5g of triolein are correspondingly added into each 100 g of solvent as composite dispersing agents, ultrasonic stirring is carried out for a period of time such as 1 hour, then 25 percent (mass percent) of adhesive polyvinyl butyral (PVB) solution is sequentially added under the condition of continuous ultrasonic stirring, the PVB content is 5 percent of the mass ratio relative to the dry weight of the mixed powder, 30 to 40 g of plasticizer dibutyl phthalate and 2.5 ml of defoamer tributyl phosphate are added into 500ml of casting slurry, vacuum defoaming treatment is carried out on the slurry after uniform dispersion is carried out for 4 to 6 hours, and finally, finishing the casting and drying processes on a casting machine to obtain a casting belt with the thickness of 120-2000 mu m.
3) Preparing a green body (plane) of the composite powder and discharging glue:
because the single-layer thickness of the casting sheet is not more than 2mm, more than two layers of casting sheets need to be overlapped together by a low-temperature press, the pressing temperature is 70 ℃, the pressure is less than 20MPa, and the pressure head is a smooth stainless steel plate. To ensure the shape during the subsequent binder removal process, the laminated cast sheet is laminated again with a conformal porous ceramic flat splint, such as a porous refractory plate or/and a ceramic or glass fiber fabric cloth, and binder removal is performed with a binder removal oven. The PVB is discharged by slowly heating up for example 1 ℃/min and keeping the temperature for 2 hours at the maximum temperature of 450 ℃, and the degummed composite substrate material blank is prepared. Because the flaky and/or fibrous aluminum oxide has a reinforcing effect on the glass powder body, the non-glue composite body has enough body strength, which provides convenience for the next hot-pressing process.
4) And (3) densifying the degummed composite powder blank by utilizing a hot pressing process:
the composite powder blank is placed between two layers of permeable layers (or at least one layer of permeable layer is contacted with the blank) by adopting a flat ceramic die (figure 2(a)) which is made of corundum-mullite or reaction-sintered silicon carbide material and utilizing a boron nitride strip (sheet) or ceramic fiber cloth and the like as a stress buffer layer or a permeable layer. Then placing between the upper and lower dies of the double-die, then opening the furnace in the air atmosphere and raising the temperature to 790 ℃ (for example 720 ℃ higher than the softening point of the CBS glass, but 815 ℃ lower than the minimum crystallization temperature of the CBS glass), and then keeping the temperature for 15-60 min.
On the other hand, when the pressurizing process is started in the heating process, for example, when the temperature reaches the softening temperature of the glass, the pressure load (10-40MPa) can be applied to the blank body through the pressure transmission of the die, and the pressure loading time is 15-30 min.
Under the action of pressure and relatively high temperature, the viscous flow of the CBS glass and the liquid phase sintering mechanism of the sintering aid work simultaneously, resulting in rapid densification of the green body. During this hot pressing, nucleation of the CBS glass matrix itself should also be initiated or completed, since it is generally believed that the glass nucleation temperature is 10-30 ℃ higher than the glass transition temperature (Tg), which provides a good prerequisite for crystallization at higher temperatures.
5) Carrying out crystallization treatment on the composite substrate after hot-pressing densification:
in order to obtain excellent dielectric property and mechanical strength, the pressure load is removed at the later stage of the hot pressing process, the temperature is raised to a certain temperature between 850-.
Compared with the process of using another normal pressure sintering furnace for crystallization treatment after the single hot pressing densification, the process of sequentially completing densification and crystallization in the same furnace saves more time, electric energy and cost.
6) Finish machining of the microcrystalline glass composite substrate:
the microcrystalline glass composite substrate in the step 5) needs to be subjected to precision processing including grinding, polishing and other working procedures to obtain a finished product. In order to measure the three-point bending strength of the composite substrate, samples were selected from the substrate, cut into 5 or more rectangular samples (36x8x5mm), and the strength values were measured on a universal material tester at 250-350 MPa. The properties of the glass-ceramic composite substrates are shown in table 1, which also compares the properties of the calcium-borosilicate glass-ceramic base materials.
As can be seen from the data in Table 1, the microcrystalline glass composite material with the addition of the reinforcing phase of alumina has significantly improved mechanical strength and dielectric loss, and particularly the three-point bending strength is improved by 2 to 3 times.
TABLE 1 comparison of properties of calborosilicate glass-ceramics and their composites
Figure GDA0003491639180000111
Example 2
A preparation method of the alumina-reinforced calcium-boron-silicon glass-ceramic composite material 3D curved plate comprises the following steps:
1. preparing raw material powder:
a) the CBS glass powder is prepared by a melting-water quenching method, and relates to weighing and proportioning according to a formula, wherein CaB is used2O4H substituted for 2/33BO3And a corresponding portion of CaCO3The method comprises the following steps of mixing materials for 5-10 hours by a horizontal ball mill with a corundum lining through a dry method, smelting by a corundum crucible, wherein the smelting temperature is 1400-1450 ℃, the heat preservation time or the homogenization time of glass liquid is 90-150min, after the homogenization time is up, allowing the glass liquid to flow into a space between a water-cooled stainless steel double roller coated with a ceramic coating with thermal shock resistance to carry out quenching and solidification, carrying out dry ball milling on glass fragments for 10-16 hours, and then carrying out stirring and grinding by horizontal closed zirconia until the particle size median diameter (D50) of the glass powder is 1.5-2.5 mu m.
Fig. 4 is an SEM (scanning secondary electron microscope) microstructure photograph of a sintered body after the calcium borosilicate glass powder is pressed into a compact and sintered. A small amount of pores can be seen in the picture, but the picture is basically compact, a small amount of glass phase inevitably exists in the microstructure, but the glass phase cannot be seen in the picture, and a precipitated phase (mainly CaSiO) in the microstructure3) Is also implicitly visible because CaSiO3The crystalline phase is generally flaky crystalline grains, so the appearance of lath-shaped fractures is realized. The compactness of the microstructure and the flaky shape of the crystal grains are beneficial to the dielectric property and the mechanical property of the microcrystalline glass.
b) Preparing hydrophobic dispersion mixed powder: 500g of CBS glass powder and 10g (6g V) of composite sintering aid are weighed according to the proportion of the formula2O5,4g TeO2) And 2.5g of a colorant (CuO 1g, Co)2O31.5g) of a binder, adding water to wet grind, and baking the mixed powder slurry at a temperature higher than 100 ℃ for 4 to 10 hours. To disperse the baked mixed powder and reduce water absorption during the subsequent processDispersing hydrophobic lauric acid (C) in water12H24O2) Dry ball milling is carried out on the mixture and the baked mixed powder for 1 to 4 hours according to the proportion of 1.0 percent (mass percentage), an omnibearing planetary ball mill made of zirconia is adopted for ball milling, and finally the mixture is sieved by a sieve with the aperture of 300 mu m to obtain the hydrophobic dispersed mixed powder.
c) Preparing a Coupling Agent (CA) modified reinforced alumina powder raw material:
first, 150g of flaky alumina powder (3 to 20 μm in diameter) was dispersed in alcohol by ultrasonic method while tetrabutyl titanate (C) was dissolved in deionized water16H36O4Ti; TCA) coupling agent is hydrolyzed, and the addition amount of TCA relative to the powder is 1.0 percent (mass percentage);
secondly, adding the hydrolyzed TCA solution into the alcohol powder suspension, and continuously stirring for 4 hours;
then, drying the mixed suspension by adopting a vacuum drying method; finally, ball milling is carried out for 0.5 to 1 hour at low speed by corundum balls and sieving is carried out, thus obtaining the reinforced flaky alumina powder treated by TCA and having no obvious change in shape and size.
2) Preparing a tape casting sheet of the composite powder material:
sequentially mixing a hydrophobic powder material and the reinforcing powder treated by the coupling agent according to the weight ratio of 79.6: adding 20.4 mass ratio (about 85:15 volume ratio) into mixed organic solvent (such as mixed solution of alcohol and butanone 50:50 mass ratio), controlling solid content of powder at about 60 wt%, and ultrasonically stirring for a period of time such as 1 hr. Then, correspondingly adding 2 g of castor oil, 2 g of glycerol and 1.5g of triolein as composite dispersants to 100 g of solvent, carrying out ultrasonic stirring for a period of time such as 1 hour, sequentially adding 25 percent (mass percentage) of binder polyvinyl butyral (PVB) solution under the condition of continuous ultrasonic stirring to enable the PVB content to reach 5 percent of mass ratio relative to the dry weight of the mixed powder, then adding 30-40 g of plasticizer dibutyl phthalate and 2.5 ml of defoamer tributyl phosphate to 500ml of casting slurry, uniformly dispersing for 4-6 hours, carrying out vacuum defoaming treatment on the slurry to prepare qualified casting slurry, and finally completing casting and drying processes on a casting machine to obtain a casting belt with the thickness of 150-2000 mu m.
3) Preparing a green body (curved surface) of the composite powder and discharging rubber:
because the single-layer thickness of the casting sheet is not more than 2mm, more than two layers of casting sheets need to be overlapped together by a low-temperature press, the pressing temperature is 70 ℃, the pressure is less than 20MPa, the curved surface pressure head or the pressing plate is a smooth stainless steel plate, and the surface of the curved surface pressure head or the pressing plate is provided with a lubricating release film so as to separate and laminate.
In order to ensure the shaping in the subsequent glue discharging process, the laminated casting sheet is clamped by flexible ceramic or glass fiber fabric cloth, and is placed in a conformal curved surface mold for glue discharging by using a glue discharging furnace. The PVB is discharged by slowly heating up for example 1 ℃/min and keeping the temperature for 2 hours at the maximum temperature of 450 ℃, and the degummed composite substrate material blank is prepared.
4) And (3) densifying the degummed composite powder blank by utilizing a hot pressing process:
a curved ceramic mold (figure 2(b)) is adopted, the composite powder blank is made of corundum mullite or zircon materials, boron nitride strips (sheets) or aluminum-silicon ceramic fiber cloth and the like are used as stress buffer layers or air-permeable layers, the composite powder blank is placed between two air-permeable layers (or at least one air-permeable layer is in contact with the blank), then the composite powder blank is placed between an upper mold and a lower mold of a double-open mold, then the furnace is opened and the temperature is raised in the air atmosphere, the temperature is raised to 790 ℃ (the temperature is higher than the softening point of CBS glass, such as 720 ℃, but lower than the minimum crystallization temperature of the CBS glass, such as 815 ℃), and then the temperature is maintained for 15-60 min.
On the other hand, when the pressurizing process is started in the heating process, for example, when the temperature reaches the softening temperature of the glass, the pressure load (10-40MPa) can be applied to the blank body through the pressure transmission of the die, and the pressure loading time is 15-30 min.
Under the action of pressure and relatively high temperature, the viscous flow of the CBS glass and the liquid phase sintering mechanism of the sintering aid work simultaneously, resulting in rapid densification of the green body. During this hot pressing, nucleation of the CBS glass matrix itself should also be initiated or completed, since it is generally believed that the glass nucleation temperature is 10-30 ℃ higher than the glass transition temperature (Tg), which provides a good prerequisite for crystallization at higher temperatures.
5) Carrying out crystallization treatment on the composite substrate after hot-pressing densification:
in order to obtain excellent dielectric property and mechanical strength, the pressure load is removed at the later stage of the hot pressing process, the temperature is raised to a certain temperature between 850-.
Compared with the process of performing the densification and the crystallization in the same furnace in sequence by using another normal-pressure sintering furnace after the densification is performed by hot pressing, the process of sequentially completing the densification and the crystallization in the same furnace saves more time, electric energy and cost.
It is to be added that also relatively inexpensive graphite moulds can be used if the hot-pressing equipment used is protected by a vacuum or atmosphere.
6) Finish machining of the microcrystalline glass composite substrate:
the microcrystalline glass composite substrate in the step 5) needs to be subjected to precision processing including grinding, polishing and other working procedures to obtain a finished product. In order to measure the three-point bending strength of the composite substrate, samples were selected from the substrate, cut into 5 or more rectangular samples (36x8x5mm), and the strength values were measured on a universal material tester at 250-350 MPa. The properties of the glass-ceramic composite substrates are shown in table 1, which also compares the properties of the calcium-borosilicate glass-ceramic base materials. From the data in table 1, it is clear that the mechanical strength and dielectric loss of the microcrystalline glass composite material with the addition of the reinforcing phase alumina are both significantly improved, and especially the three-point bending strength is doubled.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, so that any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.

Claims (8)

1. A preparation method of a reinforced calcium-boron-silicon glass-ceramic composite material is characterized by comprising the following steps: the matrix of the composite material is derived from calcium borosilicate glass powder, a composite sintering aid and a colorant mixture;
the glass powder comprises the following specific components in percentage by mass:
CaO 35-50％，B2O310-25％，SiO2 35-50％，Al2O3 0.1-1.5％，MgO 0.1-1.5％，ZrO20.1-2.5％；
based on the mass of the calcium borosilicate glass powder, 0.5 to 3.5 percent of external doping impurities are additionally added, and the external doping impurities comprise a composite sintering aid and a colorant, wherein the composite sintering aid is as follows:
x V2O5-yTeO2-z3Li2O·2B2O3a composition;
relative to the mass of the glass powder, the x is 0.1 to 1.5 percent; y is 0.1% -1.5%; z is 0% -1%; and x + y + z is 0.3% -2%;
the colorant is Cr2O3\Co2O3\CuO\MnO2Any one or a combination of more than one of; the mass percent of the colorant is 0-1.5% relative to the mass of the glass powder;
a matrix mixture consisting of the glass powder, the composite sintering aid and the colorant is added with 5 to 35 volume percent of reinforcing phase-alumina composite powder; wherein, the volume percentage of the flaky alumina is 1-15%; the volume percentage of the granular alumina is 4-20%, and the volume percentage of the short fiber-shaped or whisker-shaped alumina is 0-10%;
the preparation method of the calcium-boron-silicon glass-ceramic composite material comprises the following steps:
1) preparing raw material powder:
a) preparing calcium borosilicate CBS glass powder by a melting-water quenching method;
b) preparation of 3Li2O·2B2O3Compound low-temperature ceramic powder: using analytically pure Li2O and H3BO3According to the following steps of 3: 4, fully grinding the two raw materials by dry ball millingUniformly mixing, loosely placing the mixed powder into a corundum crucible, putting the corundum crucible into a furnace, slowly heating to 670 ℃, keeping the temperature for 6 hours, cooling along with the furnace, crushing loose blocks after the solid phase reaction, and ball-milling the loose blocks into fine powder;
c) preparing hydrophobic dispersion mixed powder: weighing CBS glass powder, a composite sintering aid and a coloring agent according to a formula proportion, wet-grinding, then carrying out low-temperature vacuum drying or baking wet-ground powder at the temperature higher than 100 ℃, carrying out dry ball milling on 0.2-2.0 mass percent of hydrophobic dispersant paraffin powder or stearic acid powder or lauric acid powder and baked mixed powder for 1-5 hours together in order to disperse the baked mixed powder and simultaneously reduce the water absorption in the subsequent process, wherein the ball mill is a horizontal ball mill lined with wear-resistant ceramics, and finally passing through a screen with the aperture of 300 mu m to obtain hydrophobic dispersed mixed powder;
d) preparing a coupling agent CA modified alumina powder raw material: firstly, dispersing alumina powder into alcohol by an ultrasonic method, and simultaneously hydrolyzing CA by deionized water, wherein the addition amount of CA is 0.5-1.5% relative to the mass percentage of the powder; secondly, adding the hydrolyzed CA solution into the alcohol powder suspension, and continuously stirring for 2-6 hours; then, drying the mixed suspension by adopting a vacuum drying method; finally, ball milling and screening are carried out to obtain the alumina powder raw material treated by CA;
2) preparing a tape casting sheet of the composite powder material:
sequentially adding a hydrophobic powder material serving as a matrix and an alumina powder material treated by a coupling agent serving as a reinforcing phase into a mixed organic solvent, ultrasonically stirring, adding a dispersing agent, ultrasonically stirring again, sequentially adding a binder, a plasticizer and a defoaming agent under the condition of continuous ultrasonic stirring, uniformly dispersing for 4-6 hours, performing vacuum defoaming treatment on the obtained slurry to prepare qualified casting slurry, and finally completing casting and drying processes on a casting machine to obtain a casting belt or a raw porcelain belt or a casting sheet with the thickness of 120-2000 mu m;
3) preparing a green body of the composite powder and discharging glue:
superposing more than two layers of casting sheets together, laminating the casting sheets together through a plane or curved surface mold, then removing double mold opening, and carrying out glue discharging on the casting sheet lamination under the pressure limited condition by utilizing a conformal porous ceramic clamping plate and/or glass fiber fabric cloth;
4) and (3) densifying the degummed composite powder blank by utilizing a hot pressing process:
the method comprises the following steps of (1) adopting a conformal ceramic mold of alumina, mullite or silicon carbide, using a boron nitride strip or ceramic fiber cloth as a stress buffer layer or a breathable layer, stacking a composite powder blank between two stress buffer layers or breathable layers, covering two parts of a double-opening conformal ceramic mold, heating in air in a furnace to raise the temperature to a certain temperature between the softening point and the lowest crystallization temperature of CBS glass, and then preserving the temperature; when the temperature reaches the softening temperature of the glass, a pressure load of 10-40MPa is applied to the blank through a mould, and under the action of the pressure and relatively high temperature, the viscous flow of the CBS glass and the liquid-phase sintering mechanism of the composite sintering aid cause the rapid densification of the composite powder blank;
5) carrying out crystallization treatment on the composite substrate after hot-pressing densification:
the pressure load is removed at the later stage of the hot pressing process, the furnace temperature is raised, and when the temperature is raised to a certain temperature between 850 ℃ and 950 ℃, the sintering is carried out for 15-60min at the temperature; the densification of the glass-based mixture blank under the hot-pressing condition is firstly realized in the same furnace in the front and back time periods, and then the crystallization of the CBS glass under the non-pressure heating condition is realized, so that the main crystal phase beta-CaSiO3Growing crystal grains to finally obtain a calcium-boron-silicon microcrystalline glass composite substrate;
6) finish machining of the microcrystalline glass composite substrate:
the microcrystalline glass composite substrate in the step 5) needs to be precisely processed, including grinding and polishing.
2. The method for preparing a calborosilicate glass-ceramic composite material according to claim 1, wherein: in the compound sintering aid, V2O5Has a melting point of 690 ℃ and a particle size<1.5 mm; the TeO2Has a melting point of 733 ℃ and a particle size<1.5 mm; the 3Li2O·2B2O3Has a melting point of773 deg.C, granularity<1.5mm。
3. The method for preparing a calborosilicate glass-ceramic composite material according to claim 1, wherein: in the step a), the preparation method of the CBS glass powder comprises the specific processes of material preparation, material mixing and smelting, wherein the smelting temperature is 1450-.
4. The method for preparing a calborosilicate glass-ceramic composite material according to claim 1, wherein: in the step b), in order to make the components more uniform and in order to make the reaction between the solid phases more thorough, the ball milling powder is continuously calcined once by the same method and ball milled once again, and finally the Li with the grain diameter less than 2 mu m 3 is obtained2O·2B2O3The compound powder.
5. The method for preparing a calborosilicate glass-ceramic composite material according to claim 1, wherein: in the step d), the coupling agent adopts a silane coupling agent SCA: c10H20O5Si。
6. The method for preparing a calborosilicate glass-ceramic composite material according to claim 1, wherein: in the step 2), the organic solvent is a mixed solution of alcohol and butanone, the dispersant is castor oil, glycerol and triolein, and the ultrasonic stirring time is 1 hour; the adhesive is polyvinyl butyral (PVB), the plasticizer is dibutyl phthalate, and the defoaming agent is tributyl phosphate.
7. The method for preparing a calborosilicate glass-ceramic composite material according to claim 1, wherein: in the step 3), the glue discharging temperature is not more than 550 ℃; the method specifically comprises the following steps: and (3) adopting PVB binder, slowly raising the temperature, keeping the temperature for 2 hours at the maximum temperature of 450 ℃, and then removing the PVB to prepare the degummed composite substrate material blank.
8. The method for preparing a calborosilicate glass-ceramic composite material according to claim 1, wherein: in the step 6), annealing and stress-relieving treatment are carried out on the processed substrate, or silver burning treatment or selective chemical plating or electroplating treatment is carried out after electronic slurry is printed, and a plurality of passive microwave device antennas are arranged in the inner surface of the substrate;
or other subsequent treatment processes of laser engraving, surface coating or coating of the anti-fingerprint film.
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