CN1872753A - Ceramic material of microcrystalline glass, and preparation method - Google Patents

Ceramic material of microcrystalline glass, and preparation method Download PDF

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Publication number
CN1872753A
CN1872753A CNA2005100210015A CN200510021001A CN1872753A CN 1872753 A CN1872753 A CN 1872753A CN A2005100210015 A CNA2005100210015 A CN A2005100210015A CN 200510021001 A CN200510021001 A CN 200510021001A CN 1872753 A CN1872753 A CN 1872753A
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solution
compound
ceramic material
glass
preparation
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周晓华
袁颖
张树人
钟朝位
杨成韬
李波
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University of Electronic Science and Technology of China
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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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Glass Compositions (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

This invention relates to a low-temperature co-sintering method for preparing microcrystalline glass ceramic of CaO-B2O3-SiO2 system. The microcrystalline glass ceramic is composed of: CaO 25-55 wt.%, B2O3 20-40 wt.%, SiO2 25-60 wt.%, ZnO 0.1-5 wt.%, P2O5 0.1-10 wt.%, and rare earth oxides 0.01-1.2 wt.%. the rare earth metals include Y, La, Sm, Gd, Dy, Ho and Yb. The microcrystalline glass ceramic has such advantages as high chemical uniformity, good uniformity of material purity, and good repeatability of properties.

Description

Ceramic material of microcrystalline glass and preparation method thereof
Technical field
The present invention relates to material science and technology, particularly a kind of low temperature co-fired CaO-B 2O 3-SiO 2The preparation technology of system devitrified glass ceramics.
Background technology
Along with miniaturization, slimming, the integrated and high frequency development of electronics, more and more stricter requirement has been proposed in aspects such as the low-k of miniaturization, densification, low resistanceization and the baseplate material of integrated circuit wiring, low-thermal-expansion rate, high heat conductance.The traditional ceramics substrate adopts Al usually 2O 3Mullite, materials such as AlN, but because its sintering temperature is at 1500～1900 ℃, if adopt sintering method simultaneously, conductor material can only be selected insoluble metal Mo and W etc., certainly will cause a series of insoluble problems like this: (1) burning altogether need carry out in reducing atmosphere, increased technology difficulty, sintering temperature is too high, need to adopt special sintering stove (2) because the resistivity of Mo and W itself is higher, and the cloth line resistance is big, the signal transmission causes distortion easily, loss increases, it is all bigger than normal that the wiring miniaturization is restricted the specific inductivity of (3) dielectric material, therefore can increase signal transmission delay time, particularly is not suitable for the ultra-high frequency circuit.In order to address the above problem, nineteen eighty-two has developed glass by Hughes Electronics and has mixed the low-temperature co-fired ceramic substrate (Low Temperature Co-fired Ceramic) that burns altogether with pottery.Because its firing temperature is about in the of 900 ℃, the conductor wiring material can adopt the low Au of resistivity, Ag, Cu, Ag-Pd etc., can realize the miniaturization wiring.And,, must reduce signal delay time, and signal transmission delay time is with the square root of dielectric material specific inductivity for adapting to the needs of high speed circuit
Figure A20051002100100041
Be directly proportional.For this reason, for baseplate material, must reduce the specific inductivity of dielectric material.Therefore, the low temperature co-fired low-k ceramic substrate material of exploitation has broad application prospects.
At present, low-temperature sintering low-k stupalith can be divided into three major types: devitrified glass system, glass add compound system, the amorphous glass system of ceramic stopping composition.In recent years, people add on Ceramic Composite system and the devitrified glass at glass and have carried out a large amount of work, have developed many sintering temperature and low low-k ceramic systems.Glass adds ceramic systems and generally constitutes glass reticulattion by boron and silicon, and the formation thing of these glass adds the reticulattion that the oxide-based element of reductive can be rebuild glass that is difficult to of unit price or two valency alkalescence.Many LTCC are based on and prepare on the borosilicate glass basis.
United States Patent (USP) (US Patent 5258335) has been invented the low temperature co-fired CaO-B of a kind of low-k by Ferro company 2O 3-SiO 2The system glass ceramic material, each is formed proportioning and is: CaO 35～55wt%, B 2O 30～55wt%, SiO 210～65wt%.This patented invention two class glass ceramic materials: (1) CaO-B 2O 3-SiO 2System (2) B 2O 3-SiO 2System adds at least a alkali metal (Na, K, Li) again.Adopt this glass ceramic material of traditional glass prepared, be about to CaO, B 2O 3, SiO 2The powder mixing and ball milling, drying, in alumina crucible in 1400～1500 ℃ of complete fusions and homogenizing.800～950 ℃ of sintering gained glass-ceramic DIELECTRIC CONSTANT=4.5～5.2 (1KHz), dielectric loss tg δ＜0.003 (1KHz).Insulation resistance IR＞10 under the 200V DC electric field 11Ω.
Chinese invention patent (application number 02124131.7), this patented invention a kind of glass ceramics for HF chip inductor, by CaO, B 2O 3, SiO 2, ZnO, P 2O 5Five kinds of one-tenth are grouped into, and the proportioning of each composition is: CaO 25～60wt%, B 2O 310～50wt%, SiO 210～60wt%, ZnO 1～10wt%, P 2O 51～5wt%.The preparation method of this ceramic material of microcrystalline glass adopts traditional glass technology, is about to CaO, B 2O 3, SiO 2, ZnO, P 2O 5The powder mixing and ball milling, drying, in alumina crucible in 1300～1400 ℃ of complete fusions and homogenizing.Melts in the crucible quenched obtains transparent glass cullet body into distilled water, obtains the glass powder that median size is 0.5～2.0 μ m, i.e. ceramic material of microcrystalline glass through wet ball grinding.By devitrified glass ceramics DIELECTRIC CONSTANT=4.9～5.5 (1MHz) of ceramic material of microcrystalline glass preparation, dielectric loss tg δ=0.001～0.0025 (1MHz), and sintering temperature lower (750～850 ℃) can burn altogether with silver electrode.
Summary of the invention
Technical problem to be solved by this invention is, a kind of preparation method of ceramic material of microcrystalline glass is provided, and prepared ceramic material of microcrystalline glass has excellent in chemical homogeneity and material purity homogeneity, and good performance repeatability.
The technical scheme that the present invention solve the technical problem employing is, a kind of ceramic material of microcrystalline glass is provided, and component comprises: CaO:25～55wt%, B 2O 3: 20～40wt%, SiO 2: 25～60wt%, ZnO:0.1～5wt%, P 2O 5: 0.1～10wt%, rare earth oxide: 0.01～1.2wt%.
The present invention also provides a kind of preparation method of ceramic material of microcrystalline glass, may further comprise the steps:
1) weighing Ca compound, boron compound, zn cpds, rare earth oxide are dissolved in concentrated nitric acid, obtain solution A, described calcium cpd is calcic and the compound that dissolves in nitric acid, described boron compound is boracic and the compound that dissolves in nitric acid, and described zn cpds is the compound that contains zinc and dissolve in nitric acid;
2) measuring tetraethoxy, stablizer, dehydrated alcohol mixes and is solution B;
3) to behind the solution A heating evaporation, with solution A and solution B uniform mixing, reaction forms colloidal sol;
4) baking step 3) colloidal sol that makes, obtain xerogel;
5) pre-burning xerogel forms vitreum;
6) vitreum is ground, form glass ceramic powder.
In the step 1), each compound component proportions is calculated as according to oxide compound: CaO:25～55wt%, B 2O 3: 20～40wt%, SiO 2: 25～60wt%, ZnO:0.1～5wt%, P 2O 5: 0.1～10wt%, rare earth oxide: 0.01～1.2wt%.
Step 2) in, according to volume ratio, tetraethoxy: the scope of stablizer is 5: 1～5: 2, tetraethoxy: ethanol scope 2: 1～1: 3, described stablizer are one or more in tetrahydrofuran (THF), methyl ethyl diketone or the ethylene glycol ethyl ether.Described calcium cpd is CaO, Ca (NO 3) 2, CaCO 3Or CaAc 2Described boron compound is B 2O 3Or H 3BO 3Described zn cpds is ZnO, Zn (NO 3) 2Or ZnAc 2Also want the weighing phosphorus compound to be dissolved in concentrated nitric acid in the step 1), described phosphorus compound is H 3PO 4Or NH 4H 2PO 4Further, described calcium cpd is CaCO 3, described boron compound is H 3BO 3, described phosphorus compound is H 3PO 4, described silicon compound is a tetraethoxy, and described zn cpds is ZnO, and described rare earth compound is a rare earth oxide, and each compound component proportions is calculated as according to oxide compound: CaO:25～55wt%, B 2O 3: 20～40wt%, SiO 2: 25～60wt%, ZnO:0.1～5wt%, P 2O 5: 0.1～10wt%, rare earth oxide: 0.01～1.2wt%.
Further, described step 3) is that to the solution A heating evaporation, the volume ratio of solution A and solution B is: solution A/solution B=1.0～2.5 o'clock, with solution A and solution B uniform mixing, reaction forms colloidal sol.Perhaps, described step 3) is: to the solution A heating evaporation, when the volume ratio of solution A and solution B was solution A/solution B=1.5, controlled temperature was between 65 ℃～95 ℃, the solution A that stirs is poured into make its thorough mixing reaction form colloidal sol in the solution B.Described step 4 is: colloidal sol is put into baking oven, adjust temperature at 50～130 ℃, form gel behind 5～10h, drying became xerogel after 2～5 days; Described step 5 is: at 300 ℃～650 ℃ following pre-burning xerogel of temperature, form vitreum; In the described step 6, use zirconium oxide balls, powder and deionized water ratio are 1: 1, and time 5～20h promptly obtains glass ceramic powder after the drying.
Also comprise step 7:, dry-pressing formed under the pressure of 10～30Mpa with the glass ceramic material powder that makes through granulation, and under 750～950 ℃ of temperature, be incubated 15～120 minutes, promptly obtain devitrified glass ceramics.
The invention has the beneficial effects as follows, adopt the devitrified glass ceramics of method preparation of the present invention, can realize the height homogenizing, chemical uniformity is good, the good uniformity of material purity, performance good reproducibility.
Synthesis temperature is low, and technology is simple, and control can reduce production costs and reduce the complicacy of preparation link easily effectively, is suitable for the scale operation manufacturing.This glass ceramic material can be at 750～900 ℃ of dense sinterings, and the microtexture of sintered compact is made up of a large amount of fine-grains, more glassy phase and a small amount of pore, is a kind of typical devitrified glass ceramics, as shown in Figure 1.Utilize the prepared devitrified glass ceramics of glass ceramic material of the present invention have low specific inductivity (ε＜5.5,1MHz) and dielectric loss (tg δ＜0.003,1MHz).
This ceramic material of microcrystalline glass is applicable to makes low temperature co-fired multilayer ceramic substrate (LTCC) and high-frequency multilayer chip inductor (MLCI) etc.
The invention will be further described below in conjunction with the drawings and specific embodiments.
Description of drawings
Fig. 1 is the scanning electron microscope Photomicrograph of devitrified glass ceramics of the present invention surface (5%HF corrodes 3min).
Embodiment
Embodiment 1
By weight percentage CaO (25～55wt%), B 2O 3(20～40wt%), ZnO:(0.1～5wt%), P 2O 5: (0.1～10wt%), Y 2O 3(0.01～0.5wt%) can convert and obtains CaCO 3, H 3BO 3, ZnO, H 3PO 4, Y 2O 3Consumption, accurately take by weighing CaCO according to the consumption that calculates gained 3, H 3BO 3, ZnO, H 3PO 4, Y 2O 3Be dissolved in the concentrated nitric acid, the heating evaporation solvent obtains reaction mixture A, the temperature (65 ℃～95 ℃) of control solution A.SiO by weight percentage 2(10～65wt%), accurately measure tetraethoxy, stablizer, dehydrated alcohol and mix in proportion (stablizer employing methyl ethyl diketone, tetraethoxy: ethanol scope 2: 1～1: 3; Tetraethoxy: the scope of stablizer is 5: 1～5: 2) must reaction mixture B.When A solution heating is concentrated to a certain degree (about B liquor capacity 1.5 times), A is poured among the B, constantly stirring is fully reacted it.Colloidal sol is put into baking oven, and adjusting temperature is 50～130 ℃, forms gel after 5～10 hours, and oven dry becomes xerogel after 2～5 days.Xerogel gets vitreum 300～650 ℃ of (being incubated 1 hour) pre-burnings.Pre-burned powder through wet ball grinding (ratio of glass and deionized water is 1: 1,20 hours time), is drying to obtain glass ceramic powder No.1 of the present invention.Through granulation (ratio of glass ceramic material powder and 5% polyvinyl alcohol is 80/20), dry-pressing formed under the pressure of 15Mpa.The dry-pressing sheet is earlier 600 ℃ of binder removals (being incubated 1 hour), is heated to 850 ℃ and be incubated 15 minutes then rapidly, promptly obtains well behaved devitrified glass ceramics No.1, and performance is as shown in table 1.
Embodiment 2
By weight percentage CaO (25～50wt%), B 2O 3(20～30wt%), and ZnO (1～5wt%), P 2O 5(1～10wt%), Y 2O 3(0.01～0.5wt%) conversion CaCO 3, H 3BO 3, ZnO, H 3PO 4, Y 2O 3Consumption, accurately take by weighing CaCO according to the consumption that calculates gained 3, H 3BO 3, ZnO, H 3PO 4, Y 2O 3Be dissolved in the concentrated nitric acid, the heating evaporation solvent obtains reaction mixture A, the temperature (65 ℃～95 ℃) of control solution A.SiO by weight percentage 2(25～50wt%), accurately measure tetraethoxy, methyl ethyl diketone, dehydrated alcohol and mix in proportion, reaction mixture B.When A solution heating is concentrated to a certain degree (about B liquor capacity 1.5 times), A is poured among the B, constantly stirring is fully reacted it.Colloidal sol is put into baking oven, and adjusting temperature is 50～130 ℃, gel behind 5～10h, and oven dry becomes xerogel after 2～5 days.Xerogel gets vitreum 300～650 ℃ of (being incubated 1 hour) pre-burnings.Pre-burned powder through wet ball grinding (ratio of glass and deionized water is 1: 1,20 hours time), is drying to obtain glass ceramic powder No.2 of the present invention.Through granulation (ratio of glass ceramic material powder and 5% polyvinyl alcohol is 80/20), dry-pressing formed under the pressure of 15Mpa.The dry-pressing sheet is earlier 600 ℃ of binder removals (being incubated 1 hour), is heated to 850 ℃ and be incubated 15 minutes then rapidly, promptly obtains well behaved devitrified glass ceramics No.2, and is as shown in table 1.
Embodiment 3
By weight percentage CaO (30～40wt%), B 2O 3(10～30wt%), and ZnO (1～5wt%), P 2O 5(5～10wt%), Sm 2O 3(0.01～0.5wt%) conversion CaCO 3, H 3BO 3, ZnO, H 3PO 4, Sm 2O 3Consumption, accurately take by weighing CaCO according to the consumption that calculates gained 3, H 3BO 3, ZnO, H 3PO 4, Sm 2O 3Be dissolved in the concentrated nitric acid, the heating evaporation solvent obtains reaction mixture A, the temperature (65 ℃～95 ℃) of control solution A.SiO by weight percentage 2(20～45wt%), accurately measure tetraethoxy, methyl ethyl diketone, dehydrated alcohol and mix in proportion, reaction mixture B.When A solution heating is concentrated to a certain degree (about B liquor capacity 1.5 times), A is poured among the B, constantly stirring is fully reacted it.Colloidal sol is put into baking oven, and adjusting temperature is 50～130 ℃, gel behind 5～10h, and oven dry becomes xerogel after 2～5 days.Xerogel gets vitreum 300～650 ℃ of (being incubated 1 hour) pre-burnings.Pre-burned powder through wet ball grinding (ratio of glass and deionized water is 1: 1,20 hours time), is drying to obtain glass ceramic powder No.3 of the present invention.Through granulation (ratio of glass ceramic material powder and 5% polyvinyl alcohol is 80/20), dry-pressing formed under the pressure of 15Mpa.The dry-pressing sheet is earlier 600 ℃ of binder removals (being incubated 1 hour), is heated to 850 ℃ and be incubated 15 minutes then rapidly, promptly obtains well behaved devitrified glass ceramics No.3, and is as shown in table 1.
Embodiment 4
By weight percentage CaO (30～40wt%), B 2O 3(20～25wt%), and ZnO (1～5wt%), P 2O 5(5～10wt%), Gd 2O 3(0.01～0.5wt%) conversion CaCO 3, H 3BO 3, ZnO, H 3PO 4, Gd 2O 3Consumption, accurately take by weighing CaCO according to the consumption that calculates gained 3, H 3BO 3, ZnO, H 3PO 4, Gd 2O 3Be dissolved in the concentrated nitric acid, the heating evaporation solvent obtains reaction mixture A, the temperature (65 ℃～95 ℃) of control solution A.SiO by weight percentage 2(30～45wt%), accurately measure tetraethoxy, methyl ethyl diketone, dehydrated alcohol and mix in proportion, reaction mixture B.When A solution heating is concentrated to a certain degree (about B liquor capacity 1.5 times), A is poured among the B, constantly stirring is fully reacted it.Colloidal sol is put into baking oven, and adjusting temperature is 50～130 ℃, gel behind 5～10h, and oven dry becomes xerogel after 2～5 days.Xerogel gets vitreum 300～650 ℃ of (being incubated 1 hour) pre-burnings.Pre-burned powder through wet ball grinding (ratio of glass and deionized water is 1: 1,20 hours time), is drying to obtain glass ceramic powder No.4 of the present invention.Through granulation (ratio of glass ceramic material powder and 5% polyvinyl alcohol is 80/20), dry-pressing formed under the pressure of 15Mpa.The dry-pressing sheet is earlier 600 ℃ of binder removals (being incubated 1 hour), is heated to 850 ℃ and be incubated 15 minutes then rapidly, promptly obtains well behaved devitrified glass ceramics No.4, and is as shown in table 1.
Embodiment 5
1, by weight percentage CaO (25～65wt%), B 2O 3(1～40wt%), and ZnO (1～10wt%), P 2O 5(2～15wt%), Gd 2O 3(0.05～0.5wt%) conversion CaCO 3, H 3BO 3, ZnO, H 3PO 4, Gd 2O 3Consumption, accurately take by weighing CaCO according to the consumption that calculates gained 3, H 3BO 3, ZnO, H 3PO 4, Gd 2O 3Be dissolved in the concentrated nitric acid, the heating evaporation solvent obtains reaction mixture A, the temperature (65 ℃～95 ℃) of control solution A.
2, SiO by weight percentage 2(10～65wt%), accurately measure tetraethoxy, stablizer methyl ethyl diketone, dehydrated alcohol and mix in proportion, reaction mixture B.
3, heating evaporation A solution when A solution heating is concentrated to a certain degree (about B liquor capacity 2 times), is poured A among the B into, constantly stirs it is fully reacted formation colloidal sol.
4, colloidal sol is put into baking oven, adjusting temperature is 50～130 ℃, forms gel behind 5～10h, and oven dry becomes xerogel after 2～5 days.
5, xerogel gets vitreum 300～650 ℃ of (being incubated 1 hour) pre-burnings.
6, powder that will be pre-burned is drying to obtain glass ceramic powder of the present invention through wet ball grinding (ratio of glass and deionized water is 1: 1,20 hours time).
7, granulation (ratio of glass ceramic material powder and 5% polyvinyl alcohol is 80/20), dry-pressing formed under the pressure of 15Mpa.The dry-pressing sheet is earlier 600 ℃ of binder removals (being incubated 1 hour), is heated to 850 ℃ and be incubated 15 minutes then rapidly, promptly obtains well behaved devitrified glass ceramics.
Embodiment 6
The difference of present embodiment and embodiment 5 is that in the step 2, stablizer adopts tetrahydrofuran (THF) and methyl ethyl diketone, also can adopt ethylene glycol ethyl ether; In the step 4, colloidal sol is without heating, and directly at room temperature ageing 5～24h forms gel, and then gel being placed on drying in oven becomes xerogel.
The performance of sintered sample in each example of table 1
Sample Shrinking percentage (%) Relative density (%) Specific inductivity (1MHz) Dielectric loss (* 10 -3， 1MHz) Thermal expansivity (* 10 -6/℃， 800℃) Insulation resistance (M Ω, 200V D.C.)
No.1 No.2 No.3 21.8 21.6 21.4 97.7 97.2 98.1 3.6 4.6 5.2 2.4 0.90 0.62 8.3 8.6 8.1 ＞10 5＞10 5＞10 5
No.4 21.3 98.5 5.6 0.60 7.9 ＞10 5

Claims (10)

1, ceramic material of microcrystalline glass, component comprises:
CaO:25～55wt%, B 2O 3: 20～40wt%, SiO 2: 25～60wt%, ZnO:0.1～5wt%, P 2O 5: 0.1～10wt%, the oxide compound of rare earth element: 0.01～1.2wt%, described rare earth element comprises: Y, La, Sm, Gd, Dy, Ho or Yb.
2, the preparation method of ceramic material of microcrystalline glass may further comprise the steps:
1) weighing Ca compound, boron compound, zn cpds, rare earth oxide are dissolved in concentrated nitric acid, obtain solution A, described calcium cpd is calcic and the compound that dissolves in nitric acid, described boron compound is boracic and the compound that dissolves in nitric acid, and described zn cpds is the compound that contains zinc and dissolve in nitric acid;
2) measuring tetraethoxy, stablizer, dehydrated alcohol mixes and is solution B;
3) to behind the solution A heating evaporation, with solution A and solution B uniform mixing, reaction forms colloidal sol;
4) baking step 3) colloidal sol that makes, obtain xerogel;
5) pre-burning xerogel forms vitreum;
6) vitreum is ground, form glass ceramic powder.
3, the preparation method of ceramic material of microcrystalline glass as claimed in claim 2, it is characterized in that, step 2) in, tetraethoxy: the scope of stablizer is 5: 1～5: 2, tetraethoxy: alcoholic acid scope 2: 1～1: 3, described stablizer are one or more in tetrahydrofuran (THF), methyl ethyl diketone or the ethylene glycol ethyl ether.
As the preparation method of claim 2 or 3 described ceramic material of microcrystalline glass, it is characterized in that 4, described calcium cpd is CaO, Ca (NO 3) 2, CaCO 3Or CaAc 2Described boron compound is B 2O 3Or H 3BO 3Described zn cpds is ZnO, Zn (NO 3) 2Or ZnAc 2
5, the preparation method of ceramic material of microcrystalline glass as claimed in claim 2 is characterized in that, also wants the weighing phosphorus compound to be dissolved in concentrated nitric acid in the step 1), and described phosphorus compound is H 3PO 4Or NH 4H 2PO 4
As the preparation method of claim 2 or 5 described ceramic material of microcrystalline glass, it is characterized in that 6, described calcium cpd is CaCO 3, described boron compound is H 3BO 3, described phosphorus compound is H 3PO 4, described silicon compound is a tetraethoxy, and described zn cpds is ZnO, and described rare earth compound is a rare earth oxide; Each compound component proportions is calculated as according to oxide compound: CaO:25～55wt%, B 2O 3: 20～40wt%, SiO 2: 25～60wt%, ZnO:0.1～5wt%, P 2O 5: 0.1～10wt%, rare earth oxide: 0.01～1.2wt%.
7, the preparation method of ceramic material of microcrystalline glass as claimed in claim 2 is characterized in that, described step 3 is, to the solution A heating evaporation, the volume ratio of solution A and solution B is: solution A/solution B=1.0～2.5 o'clock, with solution A and solution B uniform mixing, reaction forms colloidal sol.
8, the preparation method of ceramic material of microcrystalline glass as claimed in claim 6, it is characterized in that, described step 3 is: to the solution A heating evaporation, when the volume ratio of solution A and solution B is solution A/solution B=1.5, controlled temperature is between 65 ℃～95 ℃, the solution A that stirs is poured into make its thorough mixing reaction form colloidal sol in the solution B.
9, the preparation method of ceramic material of microcrystalline glass as claimed in claim 6 is characterized in that, described step 4 is: colloidal sol is put into baking oven, adjust temperature at 50～130 ℃, form gel behind 5～10h, drying became xerogel after 2～5 days; Described step 5 is: at 300 ℃～650 ℃ following pre-burning xerogel of temperature, form vitreum; In the described step 6, use zirconium oxide balls, powder and deionized water ratio are 1: 1, and time 5～20h promptly obtains glass ceramic powder after the drying.
10, the preparation method of ceramic material of microcrystalline glass as claimed in claim 6, it is characterized in that, also comprise step 7: use the glass ceramic material powder that makes through granulation, dry-pressing formed under the pressure of 10～30Mpa, and under 750～950 ℃ of temperature, be incubated 15～120 minutes, promptly obtain devitrified glass ceramics.
CNA2005100210015A 2005-05-31 2005-05-31 Ceramic material of microcrystalline glass, and preparation method Pending CN1872753A (en)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101033132B (en) * 2007-02-13 2010-10-13 电子科技大学 Middle-temperature sintering high temperature stabilization type ceramic capacitor dielectric material
CN101182120B (en) * 2007-12-07 2011-07-27 内蒙古科技大学 Method for manufacturing glass-ceramics
CN102173755A (en) * 2011-01-20 2011-09-07 深圳振华富电子有限公司 Low-temperature co-fired ceramic material, raw materials and preparation process thereof
CN103395994A (en) * 2013-07-29 2013-11-20 云南云天化股份有限公司 Low-temperature co-fired ceramic material and preparation method thereof
CN104876446A (en) * 2015-05-07 2015-09-02 秦皇岛爱迪特高技术陶瓷有限公司 Zirconium-reinforced immediate-processing microcrystalline glass and composition thereof, and preparation method and application thereof
CN105856079A (en) * 2016-05-11 2016-08-17 江苏耐锐特磨料磨具有限公司 Low-temperature sintered high-strength microcrystallite glass-ceramic grinding wheel and preparation method thereof
CN106904962A (en) * 2017-02-28 2017-06-30 华南理工大学 A kind of preparation method of bioactive oxidation zirconium dental porcelain
WO2018010633A1 (en) * 2016-07-12 2018-01-18 深圳顺络电子股份有限公司 Cbs-class ltcc material and manufacturing method thereof
US10160689B2 (en) 2016-07-12 2018-12-25 Shenzhen Sunlord Electronics Co., Ltd. CBS-based LTCC material and preparation method thereof
CN110228948A (en) * 2019-05-14 2019-09-13 重庆邮电大学 A kind of novel photoluminescent transparent glass ceramics and preparation method thereof
CN110342915A (en) * 2019-08-01 2019-10-18 电子科技大学 A kind of high thermal expansion calcium borosilicate base ceramic packaging material and preparation method thereof
CN113024122A (en) * 2021-03-10 2021-06-25 嘉兴佳利电子有限公司 SiO (silicon dioxide)2High-frequency low-dielectric low-temperature co-fired ceramic material and preparation method thereof
CN114671614A (en) * 2022-04-14 2022-06-28 电子科技大学 Low-dielectric low-calcium low-loss aluminum boron silicon-based microcrystalline glass material and preparation method thereof

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101033132B (en) * 2007-02-13 2010-10-13 电子科技大学 Middle-temperature sintering high temperature stabilization type ceramic capacitor dielectric material
CN101182120B (en) * 2007-12-07 2011-07-27 内蒙古科技大学 Method for manufacturing glass-ceramics
CN102173755A (en) * 2011-01-20 2011-09-07 深圳振华富电子有限公司 Low-temperature co-fired ceramic material, raw materials and preparation process thereof
CN102173755B (en) * 2011-01-20 2013-01-23 深圳振华富电子有限公司 Low-temperature co-fired ceramic material, raw materials and preparation process thereof
CN103395994A (en) * 2013-07-29 2013-11-20 云南云天化股份有限公司 Low-temperature co-fired ceramic material and preparation method thereof
CN103395994B (en) * 2013-07-29 2015-11-25 云南云天化股份有限公司 A kind of low-temperature co-burning ceramic material and preparation method thereof
CN104876446A (en) * 2015-05-07 2015-09-02 秦皇岛爱迪特高技术陶瓷有限公司 Zirconium-reinforced immediate-processing microcrystalline glass and composition thereof, and preparation method and application thereof
CN105856079A (en) * 2016-05-11 2016-08-17 江苏耐锐特磨料磨具有限公司 Low-temperature sintered high-strength microcrystallite glass-ceramic grinding wheel and preparation method thereof
US10160689B2 (en) 2016-07-12 2018-12-25 Shenzhen Sunlord Electronics Co., Ltd. CBS-based LTCC material and preparation method thereof
WO2018010633A1 (en) * 2016-07-12 2018-01-18 深圳顺络电子股份有限公司 Cbs-class ltcc material and manufacturing method thereof
CN106904962A (en) * 2017-02-28 2017-06-30 华南理工大学 A kind of preparation method of bioactive oxidation zirconium dental porcelain
CN110228948A (en) * 2019-05-14 2019-09-13 重庆邮电大学 A kind of novel photoluminescent transparent glass ceramics and preparation method thereof
CN110342915A (en) * 2019-08-01 2019-10-18 电子科技大学 A kind of high thermal expansion calcium borosilicate base ceramic packaging material and preparation method thereof
CN113024122A (en) * 2021-03-10 2021-06-25 嘉兴佳利电子有限公司 SiO (silicon dioxide)2High-frequency low-dielectric low-temperature co-fired ceramic material and preparation method thereof
CN114671614A (en) * 2022-04-14 2022-06-28 电子科技大学 Low-dielectric low-calcium low-loss aluminum boron silicon-based microcrystalline glass material and preparation method thereof
CN114671614B (en) * 2022-04-14 2022-11-18 电子科技大学 Low-dielectric low-loss calcium-boron-silicon-based microcrystalline glass material and preparation method thereof

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