CN104876447A - Preparation method of Li-Al-Si porous microcrystalline glass - Google Patents
Preparation method of Li-Al-Si porous microcrystalline glass Download PDFInfo
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- CN104876447A CN104876447A CN201510246539.XA CN201510246539A CN104876447A CN 104876447 A CN104876447 A CN 104876447A CN 201510246539 A CN201510246539 A CN 201510246539A CN 104876447 A CN104876447 A CN 104876447A
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- devitrified glass
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Abstract
The invention discloses a preparation method of Li-Al-Si porous microcrystalline glass. The method is characterized in that by quickly heating to glass transition temperature and performing short-time thermal insulation in an original oxide and carbonate introduction mode, CO2 gas generated by reaction is uniformly distributed in the molten glass to obtain the porous microcrystalline glass comprising three seed structures, including lithium aluminosilicate (LiAlSi3O8), lithium disilicate (Li2Si2O5) and lithium metasilicate (Li2SiO3); and a secondary heat treatment mode is utilized to regulate the variety of the crystals inside the glass and enhance the crystal content, thereby preparing the porous microcrystalline glass product capable of satisfying the operating requirements, wherein the pore size is adjustable within the range.
Description
Technical field
The present invention relates to a kind of preparation method that can be used for the Li-Al-Si system porous devitrified glass of the occasions such as strainer, catalytic carrier and gas sensor.
Background technology
Porous material has the advantages such as density is little, quality is light, specific surface area is large, damping capacity is good because of it relative to conventional compact material, has good Physical and mechanical properties.Can be widely used in separation, filtration, gas distribution, noise reduction, shock-absorbing, packaging, many occasions such as heat insulation, be a kind of functional structure material with huge applications potentiality.Porous devitrified glass is gang important in porous material.Find devitrified glass so far from Corning company of U.S. Stookey, devitrified glass develops into polymorphic, compound functional materials, wherein Li gradually
2o-Al
2o
3-SiO
2microcrystalline glass in series is as the important kind of a class in devitrified glass system, and because of the rate of expansion that it is ultralow, good high temperature resistant and shock-resistance, obtains significant progress.At present, the Corning company of the U.S., the Schott company of Germany, the Nippon company of Japan, has all produced corresponding crystallized glass article for this system devitrified glass.
More about the preparation method of porous devitrified glass at present, but be substantially all obtain vesicular structure with glass block bulk treatment or first ball milling after glass material preparation is become powder, add foaming component sinter molding again, as document [Journal of Material Science, 2009,20:351-358], document [Journalof Brazil Chemical Society, 2004,15 (4): 464-467] etc.But these methods in the preparation, all needing raw material powder high temperature transformation is vitreum, then through excessive erosion or to add foaming agent foam shaping, complicated process of preparation, and crystalline structure is comparatively single in shaping product skeleton, relates to Li-Al-Si system porous microlitic structure and almost rarely have research to occur.And the present invention with native oxide or oxycompound carbonate for raw material, when reactant just enters molten state, utilize the CO that carbonate decomposition goes out
2the effect of gas and smelt surface tension, one-step moulding directly forms vesicular structure, and preparation technology is simple and shaping speed is fast.In addition, the present invention while porous, shaped, produce a large amount of crystal in hole wall structure body, utilizes second heat treatment mode, the composition of further adjustment porous devitrified glass crystal inside, can prepare the Li-Al-Si system porous devitrified glass goods meeting more service requirementss.
Summary of the invention
The object of this invention is to provide a kind of preparation method of new Li-Al-Si system porous devitrified glass, native oxide and its carbonate is adopted to introduce form, utilize reaction sintering to release gas and go out Li-Al-Si system even porous Structure of Glass Ceramic at next step shaping direct sintering of system molten state, and utilize second heat treatment mode, the composition of further adjustment porous devitrified glass crystal inside, prepares the porous devitrified glass goods meeting service requirements.
For reaching above object, the present invention takes following technical scheme to be achieved:
A preparation method for Li-Al-Si system porous devitrified glass, is characterized in that, comprise the steps:
(1) by mass percentage, by the LiO of 10-25%
2, the SiO of 68-80%
2, the Al of 8%-16%
2o
3, the %ZrO of 0.5-1
2, the K of 1-3%
2the CaO of O, 0.5-1%
2, the Na of 0.5-1%
2o carries out weighing and mixing, wherein LiO
2, K
2o, CaO
2, Na
2o all introduces with the form of carbonate;
(2) compound is loaded in crucible, be rapidly heated to 850-970 DEG C in air furnace, furnace cooling, form porous devitrified glass body;
(3) porous devitrified glass body is carried out two levels of thermal process, first stage thermal treatment temp is 400-500 DEG C, insulation 15-25 hour; Subordinate phase thermal treatment temp is 750-900 DEG C, insulation 20-30 hour.
In aforesaid method, the described mixing of step (1) adopts ball milling, and ball-milling medium is dehydrated alcohol, and the ratio of ball, material, medium is 2:1:1.
The type of feed of step (2) described compound in crucible is pine dress.Describedly be rapidly heated, temperature rise rate is 20-50 DEG C/min.The described two levels of thermal process of step (3), temperature rise rate is 2-5 DEG C/min.
Compared to existing technology, advantage of the present invention is:
1, adopt native oxide and carbonate to introduce form, be rapidly heated to glass transition temperature and carry out the technique of short period of time insulation, making the CO that reaction produces
2gas uniform is distributed in melten glass body, and then forms porous devitrified glass body, and its technique is simple, and sintering velocity is very fast, the uniform pore diameter after shaping.Utilize second heat treatment mode, the kind of adjustment inside glass crystal, improves crystalline content, prepares the porous devitrified glass goods meeting service requirements.
2, Li-Al-Si system of the present invention porous devitrified glass comprises lithium aluminosilicate (LiAlSi
3o
8), lithium bisilicate (Li
2si
2o
5), two kinds of crystal phase structures, have ultra-low thermal expansion, Heat stability is good, feature that intensity is high, the product finally obtained after second heat treatment, has good chemical stability and mechanical property.
Accompanying drawing explanation
Fig. 1 is back scattering (BSE) photo of the internal grain of the embodiment of the present invention 8 porous devitrified glass matrix of samples.Wherein, A figure is the microscopic appearance after powder one-step moulding; B figure is the microscopic appearance after formed body thermal treatment.
Fig. 2 is the XRD figure spectrum of the embodiment of the present invention 8 porous devitrified glass different steps.
Fig. 3 is the apparent form photo of embodiment of the present invention 8-8 porous devitrified glass.
Embodiment
Below in conjunction with specific embodiment the present invention done and further elaborate.
(1) by table 1 formula batching, wherein LiO
2, K
2o, CaO
2, Na
2the introducing form of O is respectively Na
2cO
3, K
2cO
3, Ca
2cO
3, Na
2cO
3, feedstock grade is experiment level analytical pure, and adopt ball milling method to mix, ball-milling medium is dehydrated alcohol, and the ratio of ball, material, medium is 2:1:1.
(2) be filled in crucible by loose for compound, with table 2 processing parameter sintering in air furnace, cause SiO
2with Li
2cO
3between reaction release CO
2form melten glass body, glass metal and gas be mixed to form porous organization, temperature-fall period makes this vesicular structure be retained, and produce a small amount of crystal in glass by phase-splitting, the porous devitrified glass that this stage obtains, pore size is 0.3-1.5mm, and density is 0.8-1.3g/cm
3, porosity is 50-70%, and crystalline content is 30-50%, and ultimate compression strength is 5-20MPa, and Young's modulus is 80-120Gpa.Kind of crystalline comprises lithium aluminosilicate (LiAlSi
3o
8), lithium bisilicate (Li
2si
2o
5), lithium metasilicate (Li
2siO
3), three kinds of crystal proportions are suitable.
(3) in his-and-hers watches 2, the porous devitrified glass body of embodiment 8 carries out two levels of thermal process, and processing parameter is see table 3.By the further crystallization of microcrystallite body, improve crystalline content and also adjust kind of crystalline and ratio, improve and regulate the performance of porous devitrified glass structure.Performance index according to table 3 sample can be found out, along with the carrying out of subordinate phase thermal treatment process, the pore property of sample remains unchanged, and thermal treatment process only changes hole wall crystal inside kind and ratio targetedly.Along with the insulation rising of platform temperature, the prolongation of soaking time, the mechanical property of porous devitrified glass body improves, and under embodiment 8-8 treatment process, sample mechanical property reaches best.The porous devitrified glass pore size that sample obtains after two levels of thermal process is 0.3-1.5mm, and density is 0.9-1.4g/cm
3, porosity is 50-70%, and crystalline content is 50-75%, and ultimate compression strength is 20-40MPa, and Young's modulus is 130-170GPa.Kind of crystalline comprises lithium aluminosilicate (LiAlSi
3o
8), lithium bisilicate (Li
2si
2o
5), lithium metasilicate (Li
2siO
3), wherein lithium metasilicate (Li
2siO
3) crystalline content is less.
The formula of table 1 Li-Al-Si system of the present invention porous devitrified glass
| Numbering | Li 2O(％) | SiO 2(％) | Al 2O 3(％) | ZrO 2(％) | CaO(％) | K 2O(％) | Na 2O(％) |
| 1 | 8 | 80 | 8 | 0.5 | 0.5 | 2 | 1 |
| 2 | 8 | 80 | 8 | 1 | 0.5 | 1 | 0.5 |
| 3 | 10 | 70 | 16 | 0.5 2 | 0.5 | 2 | 1 |
| 4 | 10 | 70 | 16 | 1 | 0.5 | 1 | 0.5 |
| 5 | 15 | 70 | 10 | 0.5 | 0.5 | 3 | 1 |
| 6 | 15 | 70 | 10 | 0.5 | 1 | 3 | 0.5 |
| 7 | 18 | 68 | 9 | 0.5 | 1 | 3 | 0.5 |
| 8 | 18 | 68 | 9 | 0.5 | 0.5 | 3 | 1 |
Table 2 once shaped stage process for preparing of the present invention parameter
Table 3 heat treatment stages processing parameter of the present invention
The various sample that two stages obtain adopts backscattered electron imagine (BSE), scanning electron microscope (SEM), X-ray diffraction (XRD), universal testing machine, resonant Young's modulus testing apparatus to test the structural characterization of sample, porous morphology characterization, composition analysis and mechanical property respectively respectively.
As seen from Figure 1, embodiment 8 sample is after once shaped, inside mostly is little bulk crystals (Figure 1A), after thermal treatment then there is a large amount of bar-shaped crystalline substances in (Figure 1B), composed as can be seen from the XRD figure in Fig. 2, the crystalline component after once shaped in matrix is mainly lithium aluminosilicate (LiAlSi
3o
8), lithium bisilicate (Li
2si
2o
5), lithium metasilicate (Li
2siO
3) three kinds, and wherein lithium metasilicate (Li
2siO
3) content is more.Kind of crystalline after thermal treatment is substantially constant, but lithium bisilicate (Li
2si
2o
5) amount significantly increase, be predominant crystal tissue.Because the mechanical property of lithium bisilicate is higher, before the mechanical property therefore after thermal treatment comparatively processes, there is raising by a relatively large margin.As seen from Figure 3, Li-Al-Si system porous devitrified glass uniform pore diameter prepared by the inventive method, stability and mechanical property higher, end article pore size is 0.3-1.5mm, density is 0.9-1.4g/cm3, and porosity is 50-70%, and crystalline content is 30-50%, ultimate compression strength is 20-40MPa, and Young's modulus is 130-170GPa.
Claims (5)
1. a preparation method for Li-Al-Si system porous devitrified glass, is characterized in that, comprise the steps:
(1) by mass percentage, by the LiO of 10-25%
2, the SiO of 68-80%
2, the Al of 8%-16%
2o
3, the %ZrO of 0.5-1
2, the K of 1-3%
2the CaO of O, 0.5-1%
2, the Na of 0.5-1%
2o carries out weighing and mixing, wherein LiO
2, K
2o, CaO
2, Na
2o all introduces with the form of carbonate;
(2) compound is loaded in crucible, be rapidly heated to 850-970 DEG C in air furnace, furnace cooling, form porous devitrified glass body;
(3) porous devitrified glass body is carried out two levels of thermal process, first stage thermal treatment temp is 400-500 DEG C, insulation 15-25 hour; Subordinate phase thermal treatment temp is 750-900 DEG C, insulation 20-30 hour.
2. the preparation method of Li-Al-Si system as claimed in claim 1 porous devitrified glass, is characterized in that, the described mixing of step (1) adopts ball milling, and ball-milling medium is dehydrated alcohol, and the ratio of ball, material, medium is 2:1:1.
3. the preparation method of Li-Al-Si system as claimed in claim 1 porous devitrified glass, is characterized in that, the type of feed of step (2) described compound in crucible is pine dress.
4. the preparation method of Li-Al-Si system as claimed in claim 1 porous devitrified glass, is characterized in that, described in be rapidly heated, temperature rise rate is 20-50 DEG C/min.
5. the preparation method of Li-Al-Si system as claimed in claim 1 porous devitrified glass, it is characterized in that, the described two levels of thermal process of step (3), temperature rise rate is 2-5 DEG C/min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977094A (en) * | 2017-04-18 | 2017-07-25 | 杭州余杭振华日化玻璃有限公司 | Crystal glass and preparation method thereof |
| CN113429196A (en) * | 2021-04-15 | 2021-09-24 | 西安交通大学 | Reaction sintering method for preparing porous Li2Si2O5Method for producing ceramic |
| CN114436536A (en) * | 2020-11-02 | 2022-05-06 | 毛闻达 | Spodumene microcrystalline foam glass and preparation method thereof |
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| JPH05139781A (en) * | 1991-11-22 | 1993-06-08 | Res Dev Corp Of Japan | Crystallized lithium glass |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977094A (en) * | 2017-04-18 | 2017-07-25 | 杭州余杭振华日化玻璃有限公司 | Crystal glass and preparation method thereof |
| CN106977094B (en) * | 2017-04-18 | 2019-05-21 | 杭州余杭振华日化玻璃有限公司 | Crystal glass and preparation method thereof |
| CN114436536A (en) * | 2020-11-02 | 2022-05-06 | 毛闻达 | Spodumene microcrystalline foam glass and preparation method thereof |
| CN113429196A (en) * | 2021-04-15 | 2021-09-24 | 西安交通大学 | Reaction sintering method for preparing porous Li2Si2O5Method for producing ceramic |
| CN113429196B (en) * | 2021-04-15 | 2022-08-05 | 西安交通大学 | Reaction sintering method for preparing porous Li 2 Si 2 O 5 Method for producing ceramic |
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