CN106477895B - A kind of sandy kaoline base cordierite glass-ceramic material and its low temperature preparation method - Google Patents

A kind of sandy kaoline base cordierite glass-ceramic material and its low temperature preparation method Download PDF

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CN106477895B
CN106477895B CN201610962973.2A CN201610962973A CN106477895B CN 106477895 B CN106477895 B CN 106477895B CN 201610962973 A CN201610962973 A CN 201610962973A CN 106477895 B CN106477895 B CN 106477895B
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glass
sandy kaoline
kaoline
sandy
ceramic material
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CN106477895A (en
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李珍
宋丽
黄焱球
沈毅
李飞
李光辉
蒋世军
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China University of Geosciences
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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
    • C03C10/0036—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 containing SiO2, Al2O3 and a divalent metal oxide as main constituents
    • C03C10/0045—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 containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • 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

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  • Crystallography & Structural Chemistry (AREA)
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Abstract

A kind of sandy kaoline base cordierite glass-ceramic is made of the raw material of following mass percent: sandy kaoline 25-50%, aluminum oxide 20-26%, Si oxide 7-28%, magnesium oxide 10-15%, auxiliary agent 5-7%.The invention also includes the preparation methods of sandy kaoline base cordierite glass-ceramic material.The devitrified glass of the present invention only includes single object phase, is α-cordierite phase, belongs to magnesium al-si system, good physical performance；The preparation method process flow of the present invention is simple, and raw material sources are abundant, does not generate tailing, energy saving, protection environment without removing sand and purifying using sial element in natural sandy kaoline as the element source of cordierite glass-ceramic；The impurity component in sandy kaoline serves as auxiliary agent simultaneously, can reduce sintering temperature, advantageously reduces hole, promotes the generation of α-cordierite phase, pushes low temperature co-fired realization, be of great significance to industrialized production.

Description

A kind of sandy kaoline base cordierite glass-ceramic material and its low temperature preparation method
Technical field
The present invention relates to low-temperature co-fired ceramic substrate material, especially a kind of sandy kaoline base cordierite glass-ceramic material Material and its low temperature preparation method.
Background technique
Low-temperature co-fired ceramics (LTCC) technology is that will have the ceramics of low temperature co-fired knot ability as substrate, is assembled on it Various parts and low-resistivity conducting wire are sintered the technology that microelectronic product is made at 1000 DEG C or less.LTCC Technology (LTCC) it is the mainstream technology for preparing multilayer electronic device at present, is the mainstay of passive integration technology.LTCC technology is to base Plate material mainly has following requirement: (1) sintering temperature is lower than 950 DEG C, so as to the low-resistivities, low melting point such as Cu, Ag, Au Plain conductor realize cofiring；(2) dielectric constant is low, and dielectric loss is low.Time delay and dielectric constant of the signal on substrate Square root it is directly proportional, that is to say, that dielectric constant is smaller, signal transmission it is faster.Dielectric loss can cause energy dissipation, and And this portion of energy can largely be changed into thermal energy, can reduce service life and its stability of device work in this way.(3) thermal expansion system Several and used semiconductor material (Si:3.5~4.5 × 10-6K-1Or GaAs:5.7 × 10-6K-1) matching, to reduce use The thermal stress of baseplate material and the semiconductor chip for being bonded in its surface in the process.(5) high mechanical strength.Substrate is for device Have the function of supporting and protect, the indispensable performance of good mechanical strength.(6) chemical stability will be got well.Good chemical stabilization Property can prevent it from reacting with other elements and environment composition, expand the use scope of product.At present extensively research and The LTCC material of commercialization achieves huge success mainly based on devitrified glass system in practical applications.
Cordierite glass-ceramic, since it is with low-k, low-dielectric loss, high-termal conductivity, low thermal coefficient of expansion (close to Si or GaAs), the excellent characteristics such as mechanical strength height, it is considered to be the ideal baseplate material of LTCC Technology.But Using chemically pure reagent as raw material, according to theoretical stoichiometric ratio, in the case where being not added with any sintering aid or Nucleating Agent, violet The sintering temperature of green stone devitrified glass is high, and sintering range is narrow, its sintering densification is caused to be deteriorated, and voids content is high；And in low temperature Under the conditions of easily form μ-cordierite phase, μ-cordierite dielectric properties and hot expansibility inequality, can deteriorate devitrified glass entirety Dielectric properties and hot expansibility, so that product is dfficult to apply to LTCC technology.Therefore, function admirable α-is prepared under low temperature Cordierite glass-ceramic is the target studied at present.In recent years, people attempted to prepare violet blueness with natural minerals are primary raw material Stone devitrified glass, such as potassium feldspar, perlite etc., but use sandy kaoline mine that α-violet is prepared for raw material direct sintering The method of green stone devitrified glass is rarely reported.
Kaolin has many excellent performances, is widely used in papermaking, ceramics, refractory material, chemical industry, medicine, stone The departments such as oil, building materials and national defence, occupy an important position in national economy and national defense construction.China's kaolin resource is abundant, point Cloth is extensive, but wherein high grade kaolinite resource is gradually reducing, and some places even the phenomenon that resource exhaustion occur, in it is low Kaolin is on the high side, totally shows the status of " good is few, and more is bad ".Sandy kaoline therein: soil property is loose, plastic Property weaker, chiltern mass fraction > 50%, impurity content is high.By traditional kaolin using method must carry out removing for raw ore Husky and purification, can thus generate a large amount of tailing, substantially reduce the utilization rate of sandy kaoline, meanwhile, energy consumption is increased, it is dirty Environment is contaminated.
Summary of the invention
The technical problem to be solved by the present invention is to, overcome above-mentioned difficulties of the existing technology, provide it is a kind of will be direct Smashed sandy kaoline prepares glass precursor as primary raw material, after energy is prepared in glass presoma low-temperature sintering Meet the α-cordierite microcrystal glass material and its low temperature preparation method of ltcc substrate material requirements.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of sandy kaoline base cordierite glass-ceramic material of the present invention, by the raw material system of following mass percent At: sandy kaoline 25-50%, aluminum oxide 20-26%, Si oxide 7-28%, magnesium oxide 10-15%, auxiliary agent 5- 7%.
Further, the aluminum oxide is Al2O3, Si oxide SiO2, magnesium oxide MgO, described MgO, Al2O3With SiO2It is to analyze pure, MgO, Al in raw material2O3And SiO2Molar ratio be 2-2.5:2:5.
Further, the auxiliary agent includes fluxing agent and Nucleating Agent, and the fluxing agent is B2O3, the Nucleating Agent is P2O5。
Further, the B2O3By H3BO3It provides, the P2O5By NH4H2PO4It provides.
A kind of low temperature preparation method of sandy kaoline base cordierite glass-ceramic material of the present invention, including following step It is rapid:
(1) sandy kaoline, aluminum oxide, Si oxide, magnesium oxide and auxiliary agent are taken according to above-mentioned mass percent, it will Sandy kaoline is ground into the powder less than 100 mesh, and aluminum oxide, Si oxide and magnesium oxide is then added, makes in raw material The molar ratio of magnesium oxide, aluminum oxide and Si oxide is 2-2.5:2:5, adds auxiliary agent, is sufficiently mixed, before glass is made Body raw material；
(2) by glass precursor raw material melt water quenching made from step (1), wet-milling is dry, and glass powder is made；
(3) by glass powder compression moulding made from step (2), green body is made；
(4) green body made from step (3) is first warming up to 600 DEG C, keeps the temperature 0.5h, then be warming up to 850-925 DEG C, keep the temperature 6- 10h, cooled to room temperature；
Obtain cordierite glass-ceramic material.
Further, in the step (1), sandy kaoline is first crushed, then by planetary ball mill wet-milling to 100 mesh with Under, drying obtains sandy kaoline powder.
Further, in the step (2), glass precursor raw material is placed in high temperature furnace, and 4-6h is kept the temperature at 1550 DEG C and is filled Divide melting, water quenching obtains vitreum, and vitreum is ground to mean particle size by planetary ball mill wet ball grinding 6-8h It is dry for 1-3um, obtain glass powder.
Further, in the step (3), glass powder and binder ground and mixed is uniform, it is protected under 15-25MPa pressure 3-5min is held, compression moulding obtains green body.
Further, the binder is the poly-vinyl alcohol solution that mass fraction is 5%, and the glass powder and polyvinyl alcohol are molten The ratio of liquid is 1g:0.06-0.2mL.
Further, in the step (4), the green body at the uniform velocity heats up in low temperature oven, and heating rate is 5-10 DEG C/min.
Compared with prior art, the invention has the following advantages: the devitrified glass of the present invention only includes single object phase, For α-cordierite phase, belong to magnesium al-si system, consistency is high, High anti bending strength (120Mpa or more), dielectric constant it is small (6.5 with Under), dielectric loss is small (0.015 or less), and thermal stability is good, low (1.11-3.97 × 10 of thermal expansion coefficient-6/K(20-600 DEG C)), as the temperature rises, the coefficient of expansion is increased；Thermal expansion coefficient is small under low temperature, and deformation is small, under higher temperature with The matched coefficients of thermal expansion of semiconductor Si.Crystallized glass article function admirable meets low-temperature co-fired ceramics (LTCC) baseplate material Requirement, can be applied to Electronic Packaging field, have good Commercial Prospect.The preparation method process flow letter of the present invention Single, raw material sources are abundant, efficiently utilize element of the sial element as cordierite glass-ceramic in natural sandy kaoline Source is directly raw material using sandy kaoline, without removing sand and purify, does not generate tailing, energy saving.Chiltern kaolinite simultaneously The impurity components such as alkali metal oxide included in soil can serve as auxiliary agent, reduce sintering temperature, advantageously reduce hole, promote Into the generation of α-cordierite phase, the utilization rate and added value of sandy kaoline are greatly improved, answering for sandy kaoline has been widened The temperature of devitrified glass preparation is reduced under the premise of guaranteeing devitrified glass object phase and performance with field, reduces energy consumption, to work The production of industry metaplasia is of great significance.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
Embodiment 1
The chemical composition (mass percent) of sandy kaoline:
SiO2- 70-76%, Al2O3- 14-20%, K2O -3-5%, Na2O -0-0.2%, CaO -0-0.1%, MgO -0-0.1%, Fe2O3- 0.5-1%, MnO -0-0.02%, P2O5- 0-0.02%, TiO2- 0.3-0.5%；
The sandy kaoline for meeting said components requirement is first crushed, then using planetary mills wet-milling to 100 mesh hereinafter, later Drying obtains sandy kaoline powder.Sandy kaoline powder 30g is taken, analytically pure MgO, Al are added in sandy kaoline powder2O3With SiO2, make MgO, Al in raw material2O3And SiO2Molar ratio be 2.5:2:5, add NH4H2PO4And H3BO3, so that P2O5+B2O3 Mass percent be 5~6%, be sufficiently mixed, prepare glass precursor raw material；
Glass precursor raw material is poured into corundum crucible, corundum crucible is placed in high temperature furnace, is kept the temperature at 1550 DEG C 4h is sufficiently melted, and without cooling, is directly taken out under the high temperature conditions, and water quenching in water is poured into, and obtains vitreum, and vitreum passes through Planetary ball mill wet ball grinding 6h, being ground to mean particle size is 1-3um, dry, obtains glass powder；
The poly-vinyl alcohol solution ground and mixed for being 5% by glass powder and mass fraction is uniform, and glass powder is molten with polyvinyl alcohol The ratio of liquid is 1g:0.08mL, and 5min is kept under 15MPa pressure, and green body is made in compression moulding；
Green body is put into low temperature oven, is first at the uniform velocity warming up to 600 DEG C, keeps the temperature 0.5h, then be at the uniform velocity warming up to 925 DEG C, is kept the temperature 6h, heating rate are 5 DEG C/min, cooled to room temperature；
Obtain cordierite glass-ceramic material.
The devitrified glass of the present invention only includes single object phase, is α-cordierite phase, belongs to magnesium al-si system, and consistency is high, High anti bending strength, dielectric constant is small, and dielectric loss is small, and thermal stability is good, and thermal expansion coefficient is low, thermally expands system with the raising of temperature Number increased, thermal expansion coefficient is small under low temperature, and deformation is small, under higher temperature with the matched coefficients of thermal expansion of semiconductor Si. Crystallized glass article function admirable meets the requirement of low-temperature co-fired ceramics (LTCC) baseplate material, 1000 DEG C of the field LTCC with It is down cryogenic conditions, can be applied to Electronic Packaging field, there is good Commercial Prospect.The preparation method technique of the present invention Process is simple, and raw material sources are abundant, efficiently utilizes in natural sandy kaoline sial element as cordierite glass-ceramic Element source, be directly raw material using sandy kaoline, without removing sand and purify, do not generate tailing, it is energy saving.Sand simultaneously The impurity components such as alkali metal oxide included in matter kaolin can serve as auxiliary agent, reduce sintering temperature, advantageously reduce Hole promotes the generation of α-cordierite phase, greatly improves the utilization rate and added value of sandy kaoline, widened chiltern kaolinite The application field of soil reduces the temperature of devitrified glass preparation under the premise of guaranteeing devitrified glass object phase and performance, reduces energy Consumption, is of great significance to industrialized production.
The performance parameter of one cordierite glass-ceramic material of table
Embodiment 2
The chemical composition (mass percent) of sandy kaoline:
SiO2- 70-76%, Al2O3- 14-20%, K2O -3-5%, Na2O -0-0.2%, CaO -0-0.1%, MgO -0-0.1%, Fe2O3- 0.5-1%, MnO -0-0.02%, P2O5- 0-0.02%, TiO2- 0.3-0.5%；
The sandy kaoline for meeting said components requirement is first crushed, then using planetary mills wet-milling to 100 mesh hereinafter, later Drying obtains sandy kaoline powder.Sandy kaoline powder 40g is taken, analytically pure MgO, Al are added in sandy kaoline powder2O3With SiO2, make MgO, Al in raw material2O3And SiO2Molar ratio be 2.3:2:5, add NH4H2PO4And H3BO3, so that P2O5+B2O3 Mass percent be 5-6%, be sufficiently mixed, prepare glass precursor material；
Glass precursor raw material is poured into corundum crucible, corundum crucible is placed in high temperature furnace, is kept the temperature at 1550 DEG C 5h is sufficiently melted, and without cooling, is directly taken out under the high temperature conditions, and water quenching in water is poured into, and obtains vitreum, and vitreum passes through Planetary ball mill wet ball grinding 7h, being ground to mean particle size is 1-3um, dry, obtains glass powder；
The poly-vinyl alcohol solution ground and mixed for being 5% by glass powder and mass fraction is uniform, and glass powder is molten with polyvinyl alcohol The ratio of liquid is 1g:0.1mL, and 4min is kept under 20MPa pressure, and green body is made in compression moulding；
Green body is put into low temperature oven, is first warming up to 600 DEG C, keeps the temperature 0.5h, then be warming up to 900 DEG C, keeps the temperature 8h, heating speed Rate is 8 DEG C/min, cooled to room temperature；
Obtain cordierite glass-ceramic material.
The devitrified glass of the present invention only includes single object phase, is α-cordierite phase, belongs to magnesium al-si system, and consistency is high, High anti bending strength, dielectric constant is small, and dielectric loss is small, and thermal stability is good, and thermal expansion coefficient is low, thermally expands system with the raising of temperature Number increased, thermal expansion coefficient is small under low temperature, and deformation is small, under higher temperature with the matched coefficients of thermal expansion of semiconductor Si. Crystallized glass article function admirable meets the requirement of low-temperature co-fired ceramics (LTCC) baseplate material, can be applied to Electronic Packaging Field has good Commercial Prospect.The preparation method process flow of the present invention is simple, and raw material sources are abundant, effective land productivity The sial element in natural sandy kaoline has been used directly to be using sandy kaoline as the element source of cordierite glass-ceramic Raw material does not generate tailing without removing sand and purify, energy saving.Alkali metal oxide included in sandy kaoline simultaneously Equal impurity components can serve as auxiliary agent, reduce sintering temperature, advantageously reduce hole, promote the generation of α-cordierite phase, greatly The utilization rate and added value for improving sandy kaoline, have widened the application field of sandy kaoline, are guaranteeing devitrified glass object Mutually and under the premise of performance, the temperature of devitrified glass preparation is reduced, reduces energy consumption, is of great significance to industrialized production.
The performance parameter of two cordierite glass-ceramic material of table
Embodiment 3
The chemical composition (mass percent) of sandy kaoline:
SiO2- 70-76%, Al2O3- 14-20%, K2O -3-5%, Na2O -0-0.2%, CaO -0-0.1%, MgO -0-0.1%, Fe2O3- 0.5-1%, MnO -0-0.02%, P2O5- 0-0.02%, TiO2- 0.3-0.5%；
The sandy kaoline for meeting said components requirement is first crushed, then using planetary mills wet-milling to 100 mesh hereinafter, later Drying obtains sandy kaoline powder.Sandy kaoline powder 50g is taken, analytically pure MgO, Al are added in sandy kaoline powder2O3With SiO2, make MgO, Al in raw material2O3And SiO2Molar ratio be 2.1:2:5, add NH4H2PO4And H3BO3, so that P2O5+B2O3 Mass percent be 5-6%, be sufficiently mixed, prepare glass precursor material；
Glass precursor material is poured into corundum crucible, corundum crucible is placed in high temperature furnace, is kept the temperature at 1550 DEG C 6h is sufficiently melted, and without cooling, is directly taken out under the high temperature conditions, and water quenching in water is poured into, and obtains vitreum, and vitreum passes through Planetary ball mill wet ball grinding 8h, being ground to mean particle size is 1-3um, dry, obtains glass powder；
The poly-vinyl alcohol solution ground and mixed for being 5% by glass powder and mass fraction is uniform, and glass powder is molten with polyvinyl alcohol The ratio of liquid is 1g:0.12mL, and 3min is kept under 25MPa pressure, and green body is made in compression moulding；
Green body is put into low temperature oven, is first warming up to 600 DEG C, keeps the temperature 0.5h, then be warming up to 875 DEG C, keeps the temperature 10h, heating Rate is 10 DEG C/min, cooled to room temperature；
Obtain cordierite glass-ceramic material.
The devitrified glass of the present invention only includes single object phase, is α-cordierite phase, belongs to magnesium al-si system, and consistency is high, High anti bending strength, dielectric constant is small, and dielectric loss is small, and thermal stability is good, and thermal expansion coefficient is low, thermally expands system with the raising of temperature Number increased, thermal expansion coefficient is small under low temperature, and deformation is small, under higher temperature with the matched coefficients of thermal expansion of semiconductor Si. Crystallized glass article function admirable meets the requirement of low-temperature co-fired ceramics (LTCC) baseplate material, can be applied to Electronic Packaging Field has good Commercial Prospect.The preparation method process flow of the present invention is simple, and raw material sources are abundant, effective land productivity The sial element in natural sandy kaoline has been used directly to be using sandy kaoline as the element source of cordierite glass-ceramic Raw material does not generate tailing without removing sand and purify, energy saving.Alkali metal oxide included in sandy kaoline simultaneously Equal impurity components can serve as auxiliary agent, reduce sintering temperature, advantageously reduce hole, promote the generation of α-cordierite phase, greatly The utilization rate and added value for improving sandy kaoline, have widened the application field of sandy kaoline, are guaranteeing devitrified glass object Mutually and under the premise of performance, the temperature of devitrified glass preparation is reduced, reduces energy consumption, is of great significance to industrialized production.
The performance parameter of three cordierite glass-ceramic material of table
Embodiment 4
The chemical composition (mass percent) of sandy kaoline:
SiO2- 56-60%, Al2O3- 20-28%, K2O -3-5%, Na2O -0-0.2%, CaO -0.1-0.2%, MgO -0.1-0.2%, Fe2O3- 1-1.5, MnO -0-0.02%, P2O5- 0.02-0.03%, TiO2- 0.3-0.4%；
The sandy kaoline for meeting said components requirement is first crushed, then using planetary mills wet-milling to 100 mesh hereinafter, later Drying obtains sandy kaoline powder.Sandy kaoline powder 30g is taken, analytically pure MgO, Al are added in sandy kaoline powder2O3With SiO2, make MgO, Al in raw material2O3And SiO2Molar ratio be 2:2:5, add NH4H2PO4And H3BO3, so that P2O5+B2O3's Mass percent is 6-7%, is sufficiently mixed, and glass precursor raw material is prepared；
Glass precursor raw material is poured into corundum crucible, corundum crucible is placed in high temperature furnace, is kept the temperature at 1550 DEG C 5h is sufficiently melted, and without cooling, is directly taken out under the high temperature conditions, and water quenching in water is poured into, and obtains vitreum, and vitreum passes through Planetary ball mill wet ball grinding 6h, being ground to mean particle size is 1-3um, dry, obtains glass powder；
The poly-vinyl alcohol solution ground and mixed for being 5% by glass powder and mass fraction is uniform, and glass powder is molten with polyvinyl alcohol The ratio of liquid is 1g:0.15mL, and 4min is kept under 20MPa pressure, and green body is made in compression moulding；
Green body is put into low temperature oven, is first warming up to 600 DEG C, keeps the temperature 0.5h, then be warming up to 925 DEG C, keeps the temperature 6h, heating speed Rate is 8 DEG C/min, cooled to room temperature；
Obtain cordierite glass-ceramic material.
The devitrified glass of the present invention only includes single object phase, is α-cordierite phase, belongs to magnesium al-si system, and consistency is high, High anti bending strength, dielectric constant is small, and dielectric loss is small, and thermal stability is good, and thermal expansion coefficient is low, thermally expands system with the raising of temperature Number increased, thermal expansion coefficient is small under low temperature, and deformation is small, under higher temperature with the matched coefficients of thermal expansion of semiconductor Si. Crystallized glass article function admirable meets the requirement of low-temperature co-fired ceramics (LTCC) baseplate material, can be applied to Electronic Packaging Field has good Commercial Prospect.The preparation method process flow of the present invention is simple, and raw material sources are abundant, effective land productivity The sial element in natural sandy kaoline has been used directly to be using sandy kaoline as the element source of cordierite glass-ceramic Raw material does not generate tailing without removing sand and purify, energy saving.Alkali metal oxide included in sandy kaoline simultaneously Equal impurity components can serve as auxiliary agent, reduce sintering temperature, advantageously reduce hole, promote the generation of α-cordierite phase, greatly The utilization rate and added value for improving sandy kaoline, have widened the application field of sandy kaoline, are guaranteeing devitrified glass object Mutually and under the premise of performance, the temperature of devitrified glass preparation is reduced, reduces energy consumption, is of great significance to industrialized production.
The performance parameter of four cordierite glass-ceramic material of table
Embodiment 5
The chemical composition (mass percent) of sandy kaoline:
SiO2- 56-60%, Al2O3- 20-28%, K2O -3-5%, Na2O -0-0.2%, CaO -0.1-0.2%, MgO -0.1-0.2%, Fe2O3- 1-1.5, MnO -0-0.02%, P2O5- 0.02-0.03%, TiO2- 0.3-0.4%；
The sandy kaoline for meeting said components requirement is first crushed, then using planetary mills wet-milling to 100 mesh hereinafter, later Drying obtains sandy kaoline powder.Sandy kaoline powder 40g is taken, analytically pure MgO, Al are added in sandy kaoline powder2O3With SiO2, make MgO, Al in raw material2O3And SiO2Molar ratio be 2.2:2:5, add NH4H2PO4And H3BO3, so that P2O5+B2O3 Mass percent be 6-7%, be sufficiently mixed, prepare glass precursor raw material；
Glass precursor raw material is poured into corundum crucible, corundum crucible is placed in high temperature furnace, is kept the temperature at 1520 DEG C 6h is sufficiently melted, and without cooling, is directly taken out under the high temperature conditions, and water quenching in water is poured into, and obtains vitreum, and vitreum passes through Planetary ball mill wet ball grinding 8h, being ground to mean particle size is 1-3um, dry, obtains glass powder；
The poly-vinyl alcohol solution ground and mixed for being 5% by glass powder and mass fraction is uniform, and glass powder is molten with polyvinyl alcohol The ratio of liquid is 1g:0.2mL, and 4min is kept under 25MPa pressure, and green body is made in compression moulding；
Green body is put into low temperature oven, is first warming up to 600 DEG C, keeps the temperature 0.5h, then be warming up to 900 DEG C, keeps the temperature 8h, heating speed Rate is 10 DEG C/min, cooled to room temperature；
Obtain cordierite glass-ceramic material.
The devitrified glass of the present invention only includes single object phase, is α-cordierite phase, belongs to magnesium al-si system, and consistency is high, High anti bending strength, dielectric constant is small, and dielectric loss is small, and thermal stability is good, and thermal expansion coefficient is low, thermally expands system with the raising of temperature Number increased, thermal expansion coefficient is small under low temperature, and deformation is small, under higher temperature with the matched coefficients of thermal expansion of semiconductor Si. Crystallized glass article function admirable meets the requirement of low-temperature co-fired ceramics (LTCC) baseplate material, can be applied to Electronic Packaging Field has good Commercial Prospect.The preparation method process flow of the present invention is simple, and raw material sources are abundant, effective land productivity The sial element in natural sandy kaoline has been used directly to be using sandy kaoline as the element source of cordierite glass-ceramic Raw material does not generate tailing without removing sand and purify, energy saving.Alkali metal oxide included in sandy kaoline simultaneously Equal impurity components can serve as auxiliary agent, reduce sintering temperature, advantageously reduce hole, promote the generation of α-cordierite phase, greatly The utilization rate and added value for improving sandy kaoline, have widened the application field of sandy kaoline, are guaranteeing devitrified glass object Mutually and under the premise of performance, the temperature of devitrified glass preparation is reduced, reduces energy consumption, is of great significance to industrialized production.
The performance parameter of five cordierite glass-ceramic material of table
Bound, section value and the technique of each raw material usage amount of each raw material and the present invention cited by the present invention Bound, the section value of parameter (such as temperature, pressure, time) are able to achieve the present invention, embodiment numerous to list herein.
Above embodiments are merely to illustrate the preferred embodiment of the present invention, but the present invention is not limited to above-mentioned embodiment party Formula, the field those of ordinary skill within the scope of knowledge, that is done within the spirit and principles in the present invention is any Modification, equivalent substitute and improvement etc. should all be covered within the claimed technical proposal scope of the present invention.

Claims (8)

1. a kind of sandy kaoline base cordierite glass-ceramic material, which is characterized in that by the raw material system of following mass percent At: sandy kaoline 25-50%, aluminum oxide 20-26%, Si oxide 7-28%, magnesium oxide 10-15%, auxiliary agent 5- 7%；The chemical composition of sandy kaoline is SiO2, Al2O3, K2O, Na2O, CaO, MgO, Fe2O3, MnO, P2O5, TiO2；It is described to help Agent includes fluxing agent and Nucleating Agent, and the fluxing agent is B2O3, the Nucleating Agent is P2O5；
The low temperature preparation method of the sandy kaoline base cordierite glass-ceramic material, comprising the following steps:
(1) sandy kaoline, aluminum oxide, Si oxide, magnesium oxide and auxiliary agent are taken according to above-mentioned mass percent, by chiltern Kaolin is ground into the powder less than 100 mesh, and aluminum oxide, Si oxide and magnesium oxide is then added, and makes magnesia in raw material The molar ratio of compound, aluminum oxide and Si oxide is 2-2.5:2:5, adds auxiliary agent, is sufficiently mixed, and glass presoma is made Raw material；
(2) by glass precursor raw material melt water quenching made from step (1), wet-milling is dry, and glass powder is made；
(3) by glass powder compression moulding made from step (2), green body is made；
(4) green body made from step (3) is first warming up to 600 DEG C, keeps the temperature 0.5h, then be warming up to 850-925 DEG C, keep the temperature 6-10h, Cooled to room temperature；
Obtain cordierite glass-ceramic material.
2. sandy kaoline base cordierite glass-ceramic material according to claim 1, which is characterized in that the alumina Object is Al2O3, Si oxide SiO2, magnesium oxide MgO, described MgO, Al2O3And SiO2It is that analysis is pure, MgO in raw material, Al2O3And SiO2Molar ratio be 2-2.5:2:5.
3. sandy kaoline base cordierite glass-ceramic material according to claim 1, which is characterized in that the B2O3By H3BO3It provides, the P2O5By NH4H2PO4It provides.
4. sandy kaoline base cordierite glass-ceramic material according to claim 1, which is characterized in that the step (1) in, sandy kaoline is first crushed, then by planetary ball mill wet-milling to 100 mesh hereinafter, drying, obtains sandy kaoline powder Body.
5. sandy kaoline base cordierite glass-ceramic material according to claim 1, which is characterized in that the step (2) in, glass precursor raw material is placed in high temperature furnace, and 4-6h is kept the temperature at 1500-1550 DEG C and is sufficiently melted, water quenching obtains glass Glass body, for vitreum by planetary ball mill wet ball grinding 6-8h, being ground to mean particle size is 1-3um, dry, obtains glass Powder.
6. sandy kaoline base cordierite glass-ceramic material according to claim 1, which is characterized in that the step (3) in, glass powder and binder ground and mixed is uniform, 3-5min is kept under 15-25MPa pressure, compression moulding obtains base Body.
7. sandy kaoline base cordierite glass-ceramic material according to claim 6, which is characterized in that the binder The ratio of the poly-vinyl alcohol solution for being 5% for mass fraction, the glass powder and poly-vinyl alcohol solution is 1g:0.06-0.2mL.
8. sandy kaoline base cordierite glass-ceramic material according to claim 1, which is characterized in that the step (4) in, the green body at the uniform velocity heats up in low temperature oven, and heating rate is 5-10 DEG C/min.
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