CN105859272B - Method for preparing nanometer negative expansion ceramic LiAlSiO4 by low temperature sintering - Google Patents
Method for preparing nanometer negative expansion ceramic LiAlSiO4 by low temperature sintering Download PDFInfo
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Abstract
The present invention provides a kind of low-temperature sintering preparation nanometer negative expansion ceramics LiAlSiO4Method, first using sol-gel method prepare LiAlSiO4Precursor powder, mixes ethyl orthosilicate in proportion, ethyl alcohol, deionized water, and hydrochloric acid produces silica solution and magnetic agitation；Then aluminium isopropoxide is mixed in proportion, and deionized water and hydrochloric acid are produced alumina sol and stirred；Lithium nitrate solution is made in lithium nitrate dissolution in deionized water；Lithium nitrate solution is slowly added into silica solution stirring, then mixed liquor is added in alumina sol, stirs to get LiAlSiO4Colloidal sol, after dry, grinding, sintering obtains LiAlSiO under high temperature4Presoma.Then negative expansion ceramics LiAlSiO is prepared using SPS method4, by LiAlSiO4Presoma is encased in graphite jig, is sintered in SPS equipment, and a nanometer negative expansion ceramics LiAlSiO is finally obtained4.The LiAlSiO of this method preparation4Negative expansion material has many advantages, such as that at low cost, sample preparation speed is fast, nano-scale particle, density is big, negative thermal expansion is excellent, is suitble to large-scale production.
Description
Technical field
The invention belongs to functional material preparation technical field, in particular to a kind of low-temperature sintering preparation nanometer negative expansion ceramics
LiAlSiO4Method.
Background technique
It is well known that most materials expand as the temperature rises, that is, show the thermal expansion coefficient being positive.It is different
Material is varied with temperature with different expansion rates, is expanded with heat and contract with cold and often be will lead to device with expansion coefficient mismatch generation thermal shock
Fatigue, performance decline, provisional or eventual failure are even broken, and are had serious consequences.In order to solve the problems, it needs
The special material with negative expansion or zero thermal expansion is prepared, so-called performance refers in a certain temperature range, with the liter of temperature
The volume of height, material is shunk.Negative expansion material can be used for the coefficient of expansion of controlled material, has very high research and answers
With value, such as: it can be compound by being carried out with general positive thermal expansion material, form the compound of thermal expansion coefficient controllable precise
Material, this composite material can reduce the internal stress of high-temperature material to greatest extent, increase the heat shock resistance intensity of material, thorough
Bottom solves the problems, such as expansion coefficient mismatch, improves the stability (stability especially under extreme conditions) of device, can answer extensively
For in the device under the precision instruments such as space material, engine components, integrated circuit board and optical device and extreme condition.
In the past twenty years, following a few classes: the AM of cubic structure can be divided into about the research of negative expansion material2O8(A
=Zr, Hf, M=Mo, W), the A of orthohormbic structure2M3O12(A=transition metal；M=W, Mo), the eucryptite LiAlSiO of six sides4
(β-eucryptite), the NaZr of hexagonal structure2P3O12Family, the AMO of perovskite structure3(A=Ba, Sr, Pb；M=Ti, Zr),
The Mn of anti-perovskite structure3AN (A represents transition metal) and cyanide Zn (CN)2Equal material systems.Especially beta-eucryptite
LiAlSiO4Skeleton structure with high quartz, Al partly replace Si, form (Si, A1) O2Structural framing.In low temperature item
Under part, lithium ion is occupied in the tetrahedral coordination center by four oxygen atom ligands, structure in an orderly manner by six oxygen atom shapes
At the octahedral center of coordination be vacancy.At high temperature, lithium ion mobility is to octahedral site, so that octahedral vacancy is swollen
Swollen, a, b axis increase, and c-axis shortens, therefore beta-eucryptite LiAlSiO4Show good negative thermal expansion.
And tradition preparation LiAlSiO4Method be mainly direct sintering, direct sintering is by mixture straight forming
After be put into sintering furnace and be sintered to 1300 DEG C, prepare LiAlSiO4Ceramics form negative expansion ceramic material.Direct sintering technique
It is fairly simple, but since mixture cannot be full and uniform, the stronger ceramic material of negative thermal expansion is hardly resulted in, and due to length
The high temperature sintering of time causes crystal growth particle larger, and stomata is more, forms a large amount of micro-crack, and the density of sample is lower,
Therefore urgently develop it is a kind of it is at low cost, sample preparation speed is fast, is suitble to large-scale production, nano-scale particle, density bearing greatly swollen
Swollen ceramics LiAlSiO4Preparation method.
The present invention provides a kind of low-temperature sinterings to prepare nanometer negative expansion ceramics LiAlSiO4Method, utilize collosol and gel
Method combination SPS sintering method prepares nanometer negative expansion ceramics LiAlSiO4Sample, sol-gal process are passed through under liquid-phase condition
Hydrolysis and condensation reaction, form the colloidal sol of stable transparent, then aged formation gel, and gel can be received by dry, sintering
A kind of method of the powder body material of meter ruler cun, this method can obtain at a lower temperature component uniformly, particle size distribution
Nano-powder relatively narrow, with high purity.And SPS is " discharge plasma sintering ", is a kind of new skill risen in recent years in Material Field
Art.Pass through localized hyperthermia caused by the spark discharge at comprehensively control DC pulse energization initial stage, discharge impact when SPS is sintered
Pressure, surface cleaning effect, Joule heating and electric field diffusion and other effects, the sintering velocity being exceedingly fast, and obtain high-densit
It is the sintering that is rapidly heated from the spontaneous heat effect in powder inside when the Even Sintering body SPS sintering of degree, significantly inhibits crystal grain and grow up
Effect, the thermal efficiency is high compared with conventional sintering method, when SPS is sintered, point of discharge dispersion, homogeneous heating, therefore is easy to get height
The pressure sintered body of quality.Simultaneously at present using sol-gal process combination SPS sintering method preparation nanometer negative expansion ceramics
LiAlSiO4The data of sample is rarely reported.
Summary of the invention
The present invention proposes a kind of low-temperature sintering preparation nanometer negative expansion ceramics LiAlSiO4Method, solve the prior art
In prolonged high temperature sintering cause crystal growth particle larger, stomata is more, form a large amount of micro-crack, the density of sample compared with
It is low, while the poor problem of negative thermal expansion of material.
The technical scheme of the present invention is realized as follows: a kind of low-temperature sintering prepares nanometer negative expansion ceramics LiAlSiO4
Method, the steps include:
(1) LiAlSiO is prepared using sol-gel method4Precursor powder:
A, by ethyl orthosilicate, ethyl alcohol, deionized water, hydrochloric acid magnetic agitation 1-5 hours, ethyl orthosilicate, ethyl alcohol, go from
The ratio between amount of sub- water, hydrochloric acid substance is 1:40:40:0.3, produces silica solution；
B, by aluminium isopropoxide, deionized water and hydrochloric acid 50-95 DEG C stirring 3-9 hours, aluminium isopropoxide, deionized water and salt
The ratio between amount of acid substance is 1:100:0.2, produces alumina sol；
C, lithium nitrate dissolution is made lithium nitrate solution in deionized water, the amount of the substance of lithium nitrate and deionized water it
Than for 1:50；
D, step C) prepare lithium nitrate solution be slowly added into step A) preparation silica solution in, stir 1-5 hours,
Then mixed liquor is added to step B) in the alumina sol of preparation, stirring obtains LiAlSiO in 4-7 hours4Colloidal sol；
LiAlSiO4Colloidal sol obtains white gels in 50-100 DEG C of dry 6-24h, small in 600 DEG C of pre-burning 1-3 after white gels grinding
When, obtain LiAlSiO4Presoma；
(2) negative expansion ceramics LiAlSiO is prepared using plasma discharging method (SPS)4, will be obtained in step 1)
LiAlSiO4Precursor powder is packed into graphite jig, and sintering is prepared into a nanometer negative expansion pottery in plasma discharging (SPS) equipment
Porcelain LiAlSiO4。
The beneficial effects of the present invention are: it is swollen to realize that low-temperature sintering preparation nanometer is born using sol-gel method combination SPS method
Swollen ceramics LiAlSiO4, nanometer negative expansion LiAlSiO that this method can realize that low temperature, quickly preparation density is high, have excellent performance4Pottery
Ceramic material.The LiAlSiO of this method preparation4Negative expansion material has fast at low cost, sample preparation speed, nano-scale particle, close
The advantages that degree is big, negative thermal expansion is excellent is suitble to large-scale production.
Detailed description of the invention
Fig. 1 is the nanometer negative expansion LiAlSiO of embodiment 1-5 preparation4The X-ray diffraction analysis result of ceramic material.
Fig. 2 is the nanometer negative expansion LiAlSiO that embodiment 3 is prepared4The scanning electron microscopic picture of ceramic material.
Fig. 3 is the nanometer negative expansion LiAlSiO of embodiment 1-5 preparation4The negative thermal expansion result of ceramic material.
Specific embodiment
Embodiment 1
A kind of low-temperature sintering preparation nanometer negative expansion ceramics LiAlSiO4Method, the steps include:
(1) LiAlSiO is prepared using sol-gel method4Precursor powder.Using ethyl orthosilicate (TEOS, Si
(OC2H5)4), aluminium isopropoxide (AIP, C9H21AlO3) and lithium nitrate (LiNO3) it is raw material.First by the ratio between the amount of substance 1:40:
40:0.3 mixing ethyl orthosilicate, ethyl alcohol, deionized water produce silica solution in hydrochloric acid magnetic agitation 2 hours；Then according to substance
The ratio between amount 1:100:0.2 mixing aluminium isopropoxide, deionized water and hydrochloric acid produce alumina sol, it is small in 85 DEG C of oil bath stirrings 3
When.Lithium nitrate solution (the ratio between amount of substance of the two 1:50) is made in lithium nitrate dissolution in deionized water.Lithium nitrate solution
It is slowly added into silica solution, stirs 1 hour, then mixed liquor is added in alumina sol, stirring obtains for 4 hours
LiAlSiO4Colloidal sol.Colloidal sol obtains white gels after 70 DEG C of dry 6h, after white gels grinding, 600 DEG C pre-burning 2 hours,
Obtain LiAlSiO4Presoma.
(2) negative expansion ceramics LiAlSiO is prepared using SPS method4, by LiAlSiO4Precursor powder is packed into graphite jig,
It is sintered in plasma discharging (SPS) equipment.Wherein sintering parameter are as follows: selection pressure is 50MPa, and heating rate is 100 DEG C/min,
Sintering temperature is 700 DEG C, soaking time 5min, is prepared into a nanometer negative expansion ceramics LiAlSiO4。
Fig. 1 is the X-ray diffraction of sample prepared by example 1 as a result, result is not found the diffraction of other impurity phases
Peak suggests the formation of pure LiAlSiO4.And its bulk density is measured by Archimedes's drainage, the sample of example preparation
Relative density be 94%.Should be the result shows that sample to be finer and close, interior void is less.
Fig. 3 is change curve of the relative length of ceramics prepared by embodiment 1 with temperature, the length of the ceramics sample
Reduce as the temperature increases, shows that prepared material is negative expansion ceramic material.
Embodiment 2
A kind of low-temperature sintering preparation nanometer negative expansion ceramics LiAlSiO4Method, the steps include:
(1) LiAlSiO is prepared using sol-gel method4Precursor powder.Using ethyl orthosilicate (TEOS, Si
(OC2H5)4), aluminium isopropoxide (AIP, C9H21AlO3) and lithium nitrate (LiNO3) it is raw material.First by the ratio between the amount of substance 1:40:
40:0.3 mixing ethyl orthosilicate, ethyl alcohol, deionized water, hydrochloric acid produce silica solution in magnetic agitation 2 hours；Then according to substance
The ratio between amount 1:100:0.2 mixing aluminium isopropoxide, deionized water and hydrochloric acid produce alumina sol, it is small in 85 DEG C of oil bath stirrings 3
When.Lithium nitrate solution (the ratio between amount of substance of the two 1:50) is made in lithium nitrate dissolution in deionized water.Lithium nitrate solution
It is slowly added into silica solution, stirs 1 hour, mixed liquor is then added to alumina sol, stirring obtains LiAlSiO in 4 hours4
Colloidal sol.Colloidal sol obtains white gels in 70 DEG C of dryings afterwards for 24 hours.White gels grinding after, 600 DEG C pre-burning 2 hours, obtain
LiAlSiO4Presoma.
(2) negative expansion ceramics LiAlSiO is prepared using SPS method4, by LiAlSiO4Precursor powder is packed into graphite jig,
It is sintered in plasma discharging (SPS) equipment.Wherein sintering parameter are as follows: selection pressure is 50MPa, and heating rate is 100 DEG C/min,
Sintering temperature is 800 DEG C, soaking time 5min, is prepared into a nanometer negative expansion ceramics LiAlSiO4。
Fig. 1 is the X-ray diffraction of sample prepared by example 2 as a result, foring pure LiAlSiO as the result is shown4.And pass through
Archimedes's drainage measures its bulk density, and the relative density of the sample of example preparation is 92%.Sample is with higher
Relative density shows that sample is finer and close, and interior void is less.
Fig. 3 is change curve of the relative length of ceramics prepared by embodiment 2 with temperature, the length of the ceramics sample
Reduce as the temperature increases, shows that prepared material is negative expansion ceramic material.
Embodiment 3
A kind of low-temperature sintering preparation nanometer negative expansion ceramics LiAlSiO4Method, the steps include:
(1) LiAlSiO is prepared using sol-gel method4Precursor powder.Using ethyl orthosilicate (TEOS, Si
(OC2H5)4), aluminium isopropoxide (AIP, C9H21AlO3) and lithium nitrate (LiNO3) it is raw material.First by the ratio between the amount of substance 1:40:
40:0.3 mixing ethyl orthosilicate, deionized water, produces silica solution in hydrochloric acid magnetic agitation 2 hours at ethyl alcohol；Then according to substance
The ratio between amount 1:100:0.2 mixing aluminium isopropoxide, deionized water and hydrochloric acid produce alumina sol, it is small in 85 DEG C of oil bath stirrings 3
When.Lithium nitrate solution (the ratio between amount of substance of the two 1:50) is made in lithium nitrate dissolution in deionized water.Lithium nitrate solution
It is slowly added into silica solution, stirs 1 hour, mixed liquor is then added to alumina sol, stirring obtains LiAlSiO in 4 hours4
Colloidal sol.White gels are obtained after colloidal sol is 15 hours dry at 70 DEG C.White gels grinding after, 600 DEG C pre-burning 2 hours, obtain
LiAlSiO4Presoma.
(2) negative expansion ceramics LiAlSiO is prepared using SPS method4, by LiAlSiO4Precursor powder is packed into graphite jig,
It is sintered in plasma discharging (SPS) equipment.Wherein sintering parameter are as follows: selection pressure is 50MPa, and heating rate is 100 DEG C/min,
Sintering temperature is 900 DEG C, soaking time 5min, is prepared into a nanometer negative expansion ceramics LiAlSiO4。
Fig. 1 is the X-ray diffraction of sample prepared by example 3 as a result, foring pure LiAlSiO as the result is shown4。
Fig. 2 is the Cross Section Morphology of sample prepared by example 3 and the scanning electron microscope (SEM) photograph of surface topography, is as can be seen from the figure made
The even particle size of standby sample, average grain is in 720nm or so, the far smaller than particle of the sample of conventional high-temperature sintering preparation
Size, while the cavity of the sample of this method preparation is less, can significantly improve the density of ceramics sample, has finer and close
Property, and its bulk density is measured by Archimedes's drainage, the relative density of the sample of example preparation is 93%.Fig. 3 is
The relative length of ceramics prepared by embodiment 3 with temperature change curve, the length of the ceramics sample with temperature increasing
Add and reduce, shows that prepared material is negative expansion ceramic material.
Embodiment 4
A kind of low-temperature sintering preparation nanometer negative expansion ceramics LiAlSiO4Method, the steps include:
(1) LiAlSiO is prepared using sol-gel method4Precursor powder.Using ethyl orthosilicate (TEOS, Si
(OC2H5)4), aluminium isopropoxide (AIP, C9H21AlO3) and lithium nitrate (LiNO3) it is raw material.First by the ratio between the amount of substance 1:40:
40:0.3 mixing ethyl orthosilicate, deionized water, produces silica solution in hydrochloric acid magnetic agitation 2 hours at ethyl alcohol；Then according to substance
The ratio between amount 1:100:0.2 mixing aluminium isopropoxide, deionized water and hydrochloric acid produce alumina sol, it is small in 85 DEG C of oil bath stirrings 3
When.Lithium nitrate solution (the ratio between amount of substance of the two 1:50) is made in lithium nitrate dissolution in deionized water.Lithium nitrate solution
It is slowly added into silica solution, stirs 1 hour, mixed liquor is then added to alumina sol, stirring obtains LiAlSiO in 4 hours4
Colloidal sol.Colloidal sol obtains white gels after 70 DEG C of dry 18h.White gels grinding after, 600 DEG C pre-burning 2 hours, obtain
LiAlSiO4Precursor powder.
(2) negative expansion ceramics LiAlSiO is prepared using SPS method4, by LiAlSiO4Precursor powder is packed into graphite jig,
It is sintered in plasma discharging (SPS) equipment.Wherein sintering parameter are as follows: selection pressure is 50MPa, and heating rate is 100 DEG C/min,
Sintering temperature is 1000 DEG C, soaking time 5min, is prepared into a nanometer negative expansion ceramics LiAlSiO4。
Fig. 1 is the X-ray diffraction of sample prepared by example 4 as a result, foring pure LiAlSiO as the result is shown4.And pass through
Archimedes's drainage measures its bulk density, and the relative density of the sample of example preparation is 91%.Fig. 3 is 4 institute of embodiment
With the change curve of temperature, the length of the ceramics sample reduces the relative length of the ceramics of preparation as the temperature increases,
Show that prepared material is negative expansion ceramic material.
Embodiment 5
A kind of low-temperature sintering preparation nanometer negative expansion ceramics LiAlSiO4Method, the steps include:
(1) LiAlSiO is prepared using sol-gel method4Precursor powder.Using ethyl orthosilicate (TEOS, Si
(OC2H5)4), aluminium isopropoxide (AIP, C9H21AlO3) and lithium nitrate (LiNO3) it is raw material.First by the ratio between the amount of substance 1:40:
40:0.3 mixing ethyl orthosilicate, deionized water, produces silica solution in hydrochloric acid magnetic agitation 2 hours at ethyl alcohol；Then according to substance
The ratio between amount 1:100:0.2 mixing aluminium isopropoxide, deionized water and hydrochloric acid produce alumina sol, it is small in 85 DEG C of oil bath stirrings 3
When.Lithium nitrate solution (the ratio between amount of substance of the two 1:50) is made in lithium nitrate dissolution in deionized water.Lithium nitrate solution
It is slowly added into silica solution, stirs 1 hour, mixed liquor is then added to alumina sol, stirring obtains LiAlSiO in 4 hours4
Colloidal sol.Colloidal sol obtains white gels after 70 DEG C of dry 20h.White gels grinding after, 600 DEG C pre-burning 2 hours, obtain
LiAlSiO4Precursor powder.
(2) negative expansion ceramics LiAlSiO is prepared using SPS method4, by LiAlSiO4Precursor powder is packed into graphite jig,
It is sintered in plasma discharging (SPS) equipment.Wherein sintering parameter are as follows: selection pressure is 50MPa, and heating rate is 100 DEG C/min,
Sintering temperature is 1100 DEG C, soaking time 5min, is prepared into a nanometer negative expansion ceramics LiAlSiO4。
Fig. 1 is the X-ray diffraction of sample prepared by example 5 as a result, foring pure LiAlSiO as the result is shown4.And pass through
Archimedes's drainage measures its bulk density, and the relative density of the sample of example preparation is 91%.Fig. 3 is 5 institute of embodiment
With the change curve of temperature, the length of the ceramics sample reduces the relative length of the ceramics of preparation as the temperature increases,
Show that prepared material is negative expansion ceramic material.
Embodiment 6
A kind of low-temperature sintering preparation nanometer negative expansion ceramics LiAlSiO4Method, the steps include:
(1) LiAlSiO is prepared using sol-gel method4Precursor powder.Using ethyl orthosilicate (TEOS, Si
(OC2H5)4), aluminium isopropoxide (AIP, C9H21AlO3) and lithium nitrate (LiNO3) it is raw material.First by the ratio between the amount of substance 1:40:
40:0.3 mixing ethyl orthosilicate, deionized water, produces silica solution in hydrochloric acid magnetic agitation 5 hours at ethyl alcohol；Then according to substance
The ratio between amount 1:100:0.2 mixing aluminium isopropoxide, deionized water and hydrochloric acid produce alumina sol, stirred 3 hours at 95 DEG C.Nitre
Lithium nitrate solution (the ratio between amount of substance of the two 1:50) is made in sour lithium dissolution in deionized water.Lithium nitrate solution is slowly added
Enter to silica solution, stirs 5 hours, mixed liquor is then added to alumina sol, stirring obtains LiAlSiO in 7 hours4Colloidal sol.
White gels are obtained after colloidal sol is 12 hours dry at 100 DEG C.White gels grinding after, 600 DEG C pre-burning 3 hours, obtain forerunner
Body.
(2) negative expansion ceramics LiAlSiO is prepared using SPS method4, by LiAlSiO4Precursor powder is packed into graphite jig,
It is sintered in plasma discharging (SPS) equipment.Wherein sintering parameter are as follows: selection pressure be 100MPa, heating rate be 120 DEG C/
Min, sintering temperature are 1200 DEG C, soaking time 3min, are prepared into a nanometer negative expansion ceramics LiAlSiO4。
Embodiment 7
A kind of low-temperature sintering preparation nanometer negative expansion ceramics LiAlSiO4Method, the steps include:
(1) using the LiAlSiO of sol-gel method method preparation4Precursor powder.Using ethyl orthosilicate (TEOS,
Si(OC2H5)4), aluminium isopropoxide (AIP, C9H21AlO3) and lithium nitrate (LiNO3) it is raw material.First by the ratio between the amount of substance 1:40:
40:0.3 ethyl orthosilicate, deionized water, produces silica solution in hydrochloric acid magnetic agitation 1 hour at ethyl alcohol；Then according to the amount of substance it
Alumina sol is produced than 1:100:0.2 mixing aluminium isopropoxide, deionized water and hydrochloric acid, is stirred 9 hours at 50 DEG C.Lithium nitrate is molten
Lithium nitrate solution (the ratio between amount of substance of the two 1:50) is made in solution in deionized water.Lithium nitrate solution is slowly added into silicon
Colloidal sol stirs 1 hour, mixed liquor is then added to alumina sol, and stirring obtains LiAlSiO in 4 hours4Colloidal sol.Colloidal sol exists
50 DEG C obtain white gels after drying 24 hours.After gel abrasive, 600 DEG C pre-burning 1 hour, obtain LiAlSiO4Precursor
End.
(2) negative expansion ceramics LiAlSiO is prepared using SPS method4, by LiAlSiO4Precursor powder is packed into graphite jig,
It is sintered in plasma discharging (SPS) equipment.Wherein sintering parameter are as follows: selection pressure is 10MPa, and heating rate is 90 DEG C/min,
Sintering temperature is 600 DEG C, soaking time 25min, is prepared into a nanometer negative expansion ceramics LiAlSiO4。
Embodiment 8
A kind of low-temperature sintering preparation nanometer negative expansion ceramics LiAlSiO4Method, the steps include:
(1) using the LiAlSiO of sol-gel method method preparation4Precursor powder.Using ethyl orthosilicate (TEOS,
Si(OC2H5)4), aluminium isopropoxide (AIP, C9H21AlO3) and lithium nitrate (LiNO3) it is raw material.First by the ratio between the amount of substance 1:40:
40:0.3 ethyl orthosilicate, deionized water, produces silica solution in hydrochloric acid magnetic agitation 1 hour at ethyl alcohol；Then according to the amount of substance it
Alumina sol is produced than 1:100:0.2 mixing aluminium isopropoxide, deionized water and hydrochloric acid, is stirred 6 hours at 50 DEG C.Lithium nitrate is molten
Lithium nitrate solution (the ratio between amount of substance of the two 1:50) is made in solution in deionized water.Lithium nitrate solution is slowly added into silicon
Colloidal sol stirs 4 hours, mixed liquor is then added to alumina sol, and stirring obtains LiAlSiO in 6 hours4Colloidal sol.Colloidal sol exists
50 DEG C obtain white gels after drying 16 hours.After gel abrasive, 600 DEG C pre-burning 1 hour, obtain LiAlSiO4Precursor
End.
(2) negative expansion ceramics LiAlSiO is prepared using SPS method4, by LiAlSiO4Precursor powder is packed into graphite jig,
It is sintered in plasma discharging (SPS) equipment.Wherein sintering parameter are as follows: selection pressure is 10MPa, and heating rate is 90 DEG C/min,
Sintering temperature is 600 DEG C, soaking time 25min, is prepared into a nanometer negative expansion ceramics LiAlSiO4。
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all spirit in invention
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (1)
1. a kind of low-temperature sintering prepares nanometer negative expansion ceramics LiAlSiO4Method, which is characterized in that the steps include:
(1) LiAlSiO is prepared using sol-gel method4Precursor powder:
A, by ethyl orthosilicate, ethyl alcohol, deionized water, hydrochloric acid magnetic agitation 1-5 hours, ethyl orthosilicate, ethyl alcohol, deionization
The ratio between amount of water, hydrochloric acid substance is 1:40:40:0.3, produces silica solution；
B, by aluminium isopropoxide, deionized water and hydrochloric acid 50-95 DEG C stirring 3-9 hours, aluminium isopropoxide, deionized water and hydrochloride
The ratio between amount of matter is 1:100:0.2, produces alumina sol；
C, lithium nitrate solution is made in lithium nitrate dissolution in deionized water, the ratio between lithium nitrate and the amount of substance of deionized water are
1:50；
D, step C) prepare lithium nitrate solution be slowly added into step A) preparation silica solution in, stir 1-5 hours, then
Mixed liquor is added to step B) in the alumina sol of preparation, stirring obtains LiAlSiO in 4-7 hours4Colloidal sol；LiAlSiO4It is molten
Glue obtains white gels in 50-100 DEG C of dry 6-24h, after white gels grinding, 600 DEG C pre-burning 1-3 hours, obtain
LiAlSiO4Presoma；
(2) negative expansion ceramics LiAlSiO is prepared using plasma discharging method4, by LiAlSiO obtained in step 1)4Precursor
End is packed into graphite jig, and sintering is prepared into a nanometer negative expansion ceramics LiAlSiO in plasma discharging equipment4；Sintering parameter is:
Pressure limit is 10-100 MPa, and heating rate is 90 ~ 120 DEG C/min, and sintering temperature is 600-1200 DEG C, soaking time 3-
25 min。
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| CN107093735B (en) * | 2017-06-06 | 2020-01-17 | 北京工业大学 | A Li21Si5/C composite material, preparation and application |
| CN108302942A (en) * | 2018-01-08 | 2018-07-20 | 朱性宇 | Electrode material of lithium battery prepares the preparation method with saggar, the protective layer of the saggar and saggar |
| CN110510670B (en) * | 2019-09-25 | 2022-02-22 | 河南工程学院 | One-dimensional composite material with high dielectric constant and low expansion coefficient and preparation method thereof |
| CN111559747B (en) * | 2020-05-20 | 2022-01-11 | 中国科学院重庆绿色智能技术研究院 | Preparation method of high-purity lithium feldspar |
| CN112250078B (en) * | 2020-10-29 | 2023-01-31 | 淄博辰东新材料有限公司 | Ultralow-expansion-coefficient eucryptite and preparation method thereof |
| CN120208656B (en) * | 2025-05-28 | 2025-09-02 | 赣州研创电子科技有限公司 | A method for preparing ultrafine particles of low-dielectric ceramic material for 6G |
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