CN104817273A - Microcrystalline glass with nanocrystal clusters distributed in glass phase, and preparation method thereof - Google Patents
Microcrystalline glass with nanocrystal clusters distributed in glass phase, and preparation method thereof Download PDFInfo
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- CN104817273A CN104817273A CN201510139877.3A CN201510139877A CN104817273A CN 104817273 A CN104817273 A CN 104817273A CN 201510139877 A CN201510139877 A CN 201510139877A CN 104817273 A CN104817273 A CN 104817273A
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- 239000011521 glass Substances 0.000 title claims abstract description 101
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims description 19
- 229910052746 lanthanum Inorganic materials 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 239000006132 parent glass Substances 0.000 claims description 12
- 229910018557 Si O Inorganic materials 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000010881 fly ash Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 238000010504 bond cleavage reaction Methods 0.000 claims description 6
- 229910052611 pyroxene Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 230000007017 scission Effects 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 4
- 238000005352 clarification Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 239000004328 sodium tetraborate Substances 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 abstract 1
- 229910001634 calcium fluoride Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000013081 microcrystal Substances 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000006017 silicate glass-ceramic Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052639 augite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003001 depressive effect Effects 0.000 description 1
- 229910052637 diopside Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
The invention relates to a microcrystalline glass with nanocrystal clusters distributed in the glass phase, and a preparation method thereof. The microcrystalline glass contains 35-65wt% of SiO2, 10-30wt% of CaO, 3-15wt% of Al2O3, 3-15wt% of MgO, 0-5wt% of Na2O, 0-5wt% of K2O, 2-5wt% of B2O3, 1-8wt% of CaF2, 5-15wt% of Fe2O3, 0.01-5wt% of Cr2O3 and 0.1-8wt% of REO. Rare earth oxide (REO) is added to make crystal clusters formed in the glass phase in order to improve the mechanical performances of the microcrystalline glass. The microcrystalline glass prepared through the method has the advantages of low production cost, simple preparation method, wide application range and good mechanical performances.
Description
Technical field
The present invention relates to a kind of devitrified glass and preparation method thereof, be particularly distributed with devitrified glass of nanocrystal cluster and preparation method thereof in a kind of glassy phase, belong to devitrified glass ceramics field.
Background technology
Along with the fast development of economy, petering out of the first resource such as mineral metal products, coal, in the urgent need to carrying out higher value application to secondary resources such as mine tailing, blast furnace slag, flyash, accelerates development recycling economy.The comprehensive utilization ratio of current China metal tailings is less than 10%, and therefore, the comprehensive utilization improving mine tailing is extremely urgent.Many researchers have carried out spoil reclaming, backfill mine and have produced the Researching and practicing such as devitrified glass, wherein with industrial solid castoffs such as metal tailings, blast furnace slag, flyash and coal gangues for main raw material can prepare CaO-Al
2o
3-SiO
2-MgO owner crystalline phase is the devitrified glass of augite or diopside, because this system devitrified glass has the characteristics such as high strength, high-wearing feature and high rigidity, can be widely used in the fields such as machinery, chemical industry, building.
The performance of devitrified glass is not only decided by kind, grain-size, the quantity of crystalline phase, but also closely related with content with the character of glassy phase.The crystalline phase of existing silicate glass-ceramics is primarily of the mean sizes brilliant or dentrite composition that is hundreds of nanometer to the particle of tens microns; And glassy phase is the non-crystalline solids of longrange disorder, is observed under transmitted electron high resolution microscope modes and does not have the longrange disorder of crystal diffraction spot and atom to arrange, as shown in Figure 1; And in the glassy phase of silicate glass-ceramics except Si and O, also often comprise the positively charged ion that Ca, Mg, Al, Fe, Na etc. destroy Si-O key, weaken the performance of glassy phase, and finally cause the decline of whole microcrystal glass material performance.
Summary of the invention
In view of the problems referred to above existing in prior art, the invention provides a kind of devitrified glass and preparation method thereof had compared with high-mechanical property, be distributed with nanocrystal cluster in the glassy phase of this devitrified glass, contain in nanocrystal cluster and make SiO
2ca, Mg, Si, O, Al, Fe, RE and Na element of easy scission of link, adds the link of the bridging oxygen key of Si-O in glassy phase, and the glassy phase purification making Bayan Obo tailing microcrystal glass is pure silica glass, thus improves the mechanical property of devitrified glass.In the raw materials of devitrified glass, add rare earth oxide, make the formation of above-mentioned crystal cluster, thus improve the mechanical property of devitrified glass.This devitrified glass low production cost, preparation method be simple, have wide range of applications, and can obtain the devitrified glass of better mechanical property.
For achieving the above object, concrete technical scheme of the present invention is as follows:
Be distributed with a devitrified glass for nanocrystal cluster in glassy phase, this devitrified glass is CaO-Al
2o
3-SiO
2-MgO microcrystalline glass in series, comprise principal crystalline phase and glassy phase, it is characterized in that: described principal crystalline phase is pyroxene phase, described glassy phase is silica glass, be distributed with the nanocrystal cluster being of a size of 1-5nm in described glassy phase, the component of this nanocrystal cluster comprises Si, O, Ca, Mg, Al, Fe, RE and Na;
Further, described rare earth elements RE is one or both in La and Ce;
Be distributed with a devitrified glass for nanocrystal cluster in glassy phase, it is characterized in that: the weight percent of the chemical composition of described devitrified glass is: 35-65%SiO
2, 10-30%CaO, 3-15%Al
2o
3, 3-15%MgO, 0-5%Na
2o, 0-5%K
2o, 2-5%B
2o
3, 1-8%CaF
2, 5-15%Fe
2o
3, 0.01-5%Cr
2o
3and 0.1-8%REO, described nanocrystal cluster is of a size of 1-5nm;
Further, the component of described nanocrystal cluster comprises Si, O, Ca, Mg, Al, Fe, RE and Na;
Further, described crystal cluster has digested in glassy phase Ca, Mg, Al, La, Fe and Na positively charged ion having and destroy Si-O key, makes only to comprise SiO in glassy phase
2, be pure silica glass by the purification of the glassy phase of devitrified glass, improve the mechanical property of devitrified glass;
Further, described rare earth elements RE is one or both in La and Ce;
Prepare the method for above-mentioned devitrified glass, it is characterized in that: the method comprises the steps:
(1) percentage composition takes main raw material by weight, and the weight percentage of each main raw material is: 40-60% mine tailing, 10-20% flyash, 10-25%SiO
2, 5-10%CaO, 2-5% borax, 1-6%CaF
2, 0.01-5%Cr
2o
3and 0.1-8%REO;
(2) above-mentioned main raw material is ground to below 40 orders, then melting at 1400-1500 DEG C, clarification, evenly rear cast molding, prepare parent glass sample;
(3) room temperature is cooled to the furnace after being annealed at 500-650 DEG C 2-4 hour by above-mentioned parent glass sample;
(4) parent glass sample annealing cold go after at 600-700 DEG C coring 2-4 hour;
(5) by the furnace cooling after crystallization 2-4 hour at 800-900 DEG C of the glass sample after coring;
(6) prepare and comprise principal crystalline phase and be pyroxene phase and the devitrified glass being distributed with described crystal cluster in glassy phase;
Further, described mine tailing selects Bayan Obo mine tailing;
Further, described REO is rare earth oxide La
2o
3, CeO
2in one or both mixing;
A kind of raising CaO-Al
2o
3-SiO
2the method of-MgO microcrystalline glass in series physical strength, it is characterized in that: the rare earth oxide adopting scorification to prepare the 0.1-8% adding raw material weight in the raw material of devitrified glass, adding of rare earth oxide makes to produce nanocrystal cluster in the glassy phase of devitrified glass, contains easily to make SiO in nanocrystal cluster except Si, O element
2ca, the Mg of scission of link, Al, Fe, RE and Na element, add the link of the bridging oxygen key of Si-O in glassy phase, the glassy phase purification making devitrified glass is pure silica glass, thus improves the mechanical property of devitrified glass.
Beneficial effect of the present invention: the present invention is by adding rare earth oxide La
2o
3, CeO
2caO-Al can be made
2o
3-SiO
2form the crystal cluster of 1-5nm in the glassy phase of-MgO microcrystalline glass in series, this crystal cluster has digested Ca, Mg, Al, RE, Fe and Na etc. in glassy phase and has had the positively charged ion destroying Si-O key, makes only to comprise SiO in glassy phase
2, therefore the glassy phase of devitrified glass is purified as pure silica glass, improves the mechanical property of devitrified glass.
Accompanying drawing explanation
Fig. 1 is the existing CaO-Al not adding REO
2o
3-SiO
2the high resolution transmission electron microscope image of glassy phase in-MgO microcrystalline glass in series;
Fig. 2 is the high resolution transmission electron microscope image of glassy phase in the devitrified glass of the embodiment of the present invention 1;
Fig. 3 is the power spectrum collection of illustrative plates of the nanocrystal cluster that in the devitrified glass in the embodiment of the present invention 1, glassy phase contains;
Fig. 4 is the power spectrum collection of illustrative plates of glassy phase non-nano crystal Cluster zone in the devitrified glass in the embodiment of the present invention 1;
Fig. 5 is the high resolution transmission electron microscope image of glassy phase in the devitrified glass of the embodiment of the present invention 2;
Fig. 6 is the power spectrum collection of illustrative plates of glassy phase non-nano crystal Cluster zone in the devitrified glass in the embodiment of the present invention 2.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.It should be noted that, following examples are only examples, do not limit the scope of the invention, and all simple deformation schemes of making based on thought of the present invention all fall within the scope of the present invention.
Mine tailing in main raw material of the present invention can select Bayan Obo mine tailing, also can select other mine tailing, can unrestricted choice.The Bayan Obo mine tailing that the present invention selects and the chemical composition of flyash are in table 1.
Table 1 Bayan Obo mine tailing and chemical composition of PCA (Wt%)
Provide specific embodiment below.
Embodiment 1
The preparation method of the devitrified glass of nanocrystal cluster is distributed with in a kind of glassy phase:
(1) according to the chemical composition weight proportion of devitrified glass: 50%SiO
2, 20%CaO, 5.04%Al
2o
3, 7.73%MgO, 0.55%Na
2o, 2%B
2o
3, 3%CaF
2, 3.43%Fe
2o
3, 0.25%Cr
2o
3and 8%La
2o
3, weight proportion is carried out to raw material: 50% Bayan Obo mine tailing, 15% flyash, 15%SiO
2, 6.75%CaO, 2% borax, 3%CaF
2, 0.25%Cr
2o
3and 8%La
2o
3;
(2) batch mixing: the raw material that proportioning is good is put into ball mill ball milling 60min, be ground to below 40 orders;
(3) melting: the raw material that mixes loaded in crucible, utilizes high temperature resistance furnace in 1400-1500 DEG C of melting, clarification, evenly;
(4) shaping and annealing: the glass solution after melting being clarified waters to cast from shapingly on stainless steel mould prepares parent glass sample, by parent glass sample at 600 DEG C of annealing furnace cooling after 4 hours, eliminates stress in sample;
(5) thermal treatment: after annealing, parent glass sample was 680 DEG C of coring 2 hours, 860 DEG C of crystallization 2 hours, preparing principal crystalline phase was pyroxene phase, is distributed with the devitrified glass of nanocrystal cluster in glassy phase.
(6) utilize the microcell of transmission electron microscope to the devitrified glass sample that molybdenum ring is inlayed to observe (because sample is less, so adopt molybdenum ring to inlay to devitrified glass sample), Fig. 2 is for adding 8%La
2o
3the high-resolution electronic micro-image of glassy phase in Bayan Obo tailing microcrystal glass, can be observed from Fig. 2, in glassy phase, most of region is the arrangement of atom longrange disorder, the i.e. structure formation of glassy phase, and the region of the atomic rule arrangement of 1-5nm in the region intermediate distribution of these atom longrange disorder arrangement, the atom of this nano-area is being not longrange disorder arrangement, but be similar to the regular arrangement of crystal Atom, therefore, this region is nanocrystal cluster, and this nanocrystal cluster discrete, be distributed in glassy phase to disperse.Mo element in Fig. 3 and Fig. 4 is not the element in nanocrystal cluster, but the element of molybdenum ring in order to inlaying samples.
(7) it is Ca, Mg, Al, Si, La, Fe and O element that the energy depressive spectroscopy utilizing transmission electron microscope supporting obtains nanocrystal cluster main component in the glassy phase of devitrified glass, as shown in Figure 3; In the glassy phase of devitrified glass non-nano crystal Cluster zone main component be Si and O element as shown in Figure 4, illustrate and with the addition of La
2o
3devitrified glass Ca, Mg, Al, Si, La, Fe and O element aggregation in glassy phase has been arrived in nanocrystal cluster, and remaining residual glass mutually in be Si and O element.Because Ca, Mg, Al, Si, La, Fe element in glassy phase all plays the effect of scission of link, if there is above-mentioned element in a large number in glassy phase, the link of silicon-oxy tetrahedron certainly will be reduced, slacken the mechanical property of glassy phase.After nanocrystal cluster has digested above-mentioned element, be pure silica glass in making remaining residual glass mutually, the mechanical property of devitrified glass will have been improved like this.
Embodiment 2
The preparation method of the devitrified glass of nanocrystal cluster is distributed with in a kind of glassy phase:
(1) raw material weight proportioning: 50% Bayan Obo mine tailing, 15% flyash, 22%SiO
2, 7.05%CaO, 2% borax, 3%CaF
2, 0.25%Cr
2o
3and 0.7%La
2o
3+ CeO
2;
(2) batch mixing: the raw material that proportioning is good is put into ball mill ball milling 60min, be ground to below 40 orders;
(3) melting: the raw material that mixes loaded in crucible, utilizes high temperature resistance furnace in 1400-1500 DEG C of melting, clarification, evenly;
(4) shaping and annealing: the glass solution after melting being clarified waters to cast from shapingly on stainless steel mould prepares parent glass sample, by parent glass sample at 600 DEG C of annealing furnace cooling after 4 hours, eliminates stress in sample;
(5) thermal treatment: after annealing, parent glass sample was 680 DEG C of coring 2 hours, 860 DEG C of crystallization 2 hours, preparing principal crystalline phase was pyroxene phase, is distributed with the devitrified glass of nanocrystal cluster in glassy phase.
(6) utilize the microcell of transmission electron microscope to the devitrified glass sample that molybdenum ring is inlayed to observe, Fig. 5 is for adding 0.7%La
2o
3+ CeO
2the high-resolution electronic displaing micro picture of glassy phase in Bayan Obo tailing microcrystal glass, containing the crystal cluster being of a size of 1-5nm in its glassy phase.In the glassy phase of devitrified glass non-nano crystal Cluster zone main component be Si and O element as shown in Figure 6, illustrate and with the addition of La
2o
3+ CeO
2devitrified glass glassy phase in define in nanocrystal cluster, containing Si and O element in making remaining residual glass mutually.Therefore the mechanical property of devitrified glass is improved.
Utilize three-point bending method to not adding rare earth oxide, adding 8%La
2o
3and 0.7%La
2o
3+ CeO
2the folding strength of the Bayan Obo tailing microcrystal glass sample of preparation detects, and concrete outcome is in table 2.Add 8%La
2o
3and 0.7%La
2o
3+ CeO
2the folding strength of Bayan Obo tailing microcrystal glass of preparation is respectively 170.32MPa and 250.13MPa, apparently higher than the devitrified glass folding strength not adding rare earth oxide and prepare.
The folding strength detected result of table 2 Bayan Obo tailing microcrystal glass sample
Add 8%La
2o
3, 0.7%La
2o
3+ CeO
2owing to separating out nano level crystal cluster in the glassy phase of Bayan Obo tailing microcrystal glass, this crystal cluster is enriched and easily makes SiO
2ca, Mg, Al, Si, RE and Fe element of scission of link, adds the link of the bridging oxygen key of Si-O in glassy phase, and the glassy phase purification making Bayan Obo tailing microcrystal glass is pure silica glass, improves the mechanical property of devitrified glass.
As can be seen here, when manufacturing devitrified glass, add REO in the feed, can make to form nano level crystal cluster in the glassy phase of devitrified glass, Ca, Mg, Al, Si, RE and Fe element existed in this crystal cluster easily makes SiO
2scission of link, because nanocrystal cluster has digested above-mentioned element, so make respective element in glassy phase reduce, because this increasing the link of the bridging oxygen key of Si-O in glassy phase, the glassy phase purification making Bayan Obo tailing microcrystal glass is pure silica glass, thus improves the mechanical property of devitrified glass.
Claims (10)
1. be distributed with a devitrified glass for nanocrystal cluster in glassy phase, this devitrified glass is CaO-Al
2o
3-SiO
2-MgO microcrystalline glass in series, comprise principal crystalline phase and glassy phase, it is characterized in that: described principal crystalline phase is pyroxene phase, described glassy phase is silica glass, be distributed with the nanocrystal cluster being of a size of 1-5nm in described glassy phase, the component of this nanocrystal cluster comprises Si, O, Ca, Mg, Al, Fe, RE and Na.
2. devitrified glass according to claim 1, is characterized in that: described rare earth elements RE is one or both in La and Ce.
3. be distributed with a devitrified glass for nanocrystal cluster in glassy phase, it is characterized in that: the weight percent of the chemical composition of described devitrified glass is: 35-65%SiO
2, 10-30%CaO, 3-15%Al
2o
3, 3-15%MgO, 0-5%Na
2o, 0-5%K
2o, 2-5%B
2o
3, 1-8%CaF
2, 5-15%Fe
2o
3, 0.01-5%Cr
2o
3and 0.1-8%REO, described nanocrystal cluster is of a size of 1-5nm.
4. devitrified glass according to claim 3, is characterized in that: the component of described nanocrystal cluster comprises Si, O, Ca, Mg, Al, Fe, RE and Na.
5. devitrified glass according to claim 4, is characterized in that: described nanocrystal cluster has digested in glassy phase Ca, Mg, Al, RE, Fe and Na positively charged ion having and destroy Si-O key, makes only to comprise SiO in glassy phase
2, be pure silica glass by the purification of the glassy phase of devitrified glass.
6. according to the devitrified glass one of claim 3 to 5 Suo Shu, it is characterized in that: described rare earth elements RE is one or both in La and Ce.
7. prepare the method for the devitrified glass described in any one of claim 1 to 5, it is characterized in that: the method comprises the steps:
(1) percentage composition takes main raw material by weight, and the weight percentage of each main raw material is: 40-60% mine tailing, 10-20% flyash, 10-25%SiO
2, 5-10%CaO, 0-5% borax, 1-6%CaF
2, 0.01-5%Cr
2o
3and 0.1-8%REO;
(2) above-mentioned main raw material is ground to below 40 orders, then melting at 1400-1500 DEG C, clarification, evenly rear cast molding, prepare parent glass sample;
(3) room temperature is cooled to the furnace after being annealed at 500-650 DEG C 2-4 hour by above-mentioned parent glass sample;
(4) parent glass sample annealing cold go after at 600-700 DEG C coring 2-4 hour;
(5) by the furnace cooling after crystallization 2-4 hour at 800-900 DEG C of the glass sample after coring;
(6) prepare and comprise principal crystalline phase and be pyroxene phase and the devitrified glass being distributed with described nanocrystal cluster in glassy phase.
8. the method preparing devitrified glass according to claim 7, is characterized in that: described mine tailing selects Bayan Obo mine tailing.
9. the method preparing devitrified glass according to claim 7, is characterized in that: described REO is rare earth oxide La
2o
3, CeO
2in one or both mixing.
10. one kind is improved CaO-Al
2o
3-SiO
2the method of-MgO microcrystalline glass in series physical strength, it is characterized in that: the rare earth oxide adopting scorification to prepare the 0.1-8% adding raw material weight in the raw material of devitrified glass, adding of rare earth oxide makes to produce nanocrystal cluster in the glassy phase of devitrified glass, contains easily to make SiO in nanocrystal cluster except Si, O element
2ca, the Mg of scission of link, Al, Fe, RE and Na element, add the link of the bridging oxygen key of Si-O in glassy phase, the glassy phase purification making devitrified glass is pure silica glass, thus improves the mechanical property of devitrified glass.
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399331A (en) * | 2015-10-27 | 2016-03-16 | 广东省生态环境与土壤研究所（广东省土壤科学博物馆） | Glass ceramization method for dual fixed detoxification of chromium in chromium slag |
| CN106430982A (en) * | 2016-09-19 | 2017-02-22 | 内蒙古科韵环保材料股份公司 | Recycling method of glass ceramic material |
| CN108409143A (en) * | 2018-06-13 | 2018-08-17 | 合肥协耀玻璃制品有限公司 | A kind of warping resistance devitrified glass |
| CN109160742A (en) * | 2018-11-14 | 2019-01-08 | 西南科技大学 | It is a kind of using flyash as the devitrified glass of raw material |
| CN109160741A (en) * | 2018-11-14 | 2019-01-08 | 西南科技大学 | A kind of direct sintering coal ash for manufacturing for devitrified glass method |
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| TWI751689B (en) * | 2019-09-12 | 2022-01-01 | 日商日化陶股份有限公司 | Wear-resistant alumina sintered body |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399331A (en) * | 2015-10-27 | 2016-03-16 | 广东省生态环境与土壤研究所（广东省土壤科学博物馆） | Glass ceramization method for dual fixed detoxification of chromium in chromium slag |
| CN105399331B (en) * | 2015-10-27 | 2018-06-29 | 广东省生态环境与土壤研究所（广东省土壤科学博物馆） | A kind of glass ceramics method for the dual fixed removing toxic substances of chromium in chromium slag |
| CN106430982A (en) * | 2016-09-19 | 2017-02-22 | 内蒙古科韵环保材料股份公司 | Recycling method of glass ceramic material |
| CN108409143A (en) * | 2018-06-13 | 2018-08-17 | 合肥协耀玻璃制品有限公司 | A kind of warping resistance devitrified glass |
| CN109160742A (en) * | 2018-11-14 | 2019-01-08 | 西南科技大学 | It is a kind of using flyash as the devitrified glass of raw material |
| CN109160741A (en) * | 2018-11-14 | 2019-01-08 | 西南科技大学 | A kind of direct sintering coal ash for manufacturing for devitrified glass method |
| CN109160742B (en) * | 2018-11-14 | 2022-03-01 | 西南科技大学 | Microcrystalline glass using fly ash as raw material |
| CN109160741B (en) * | 2018-11-14 | 2022-03-01 | 西南科技大学 | Method for preparing microcrystalline glass by directly sintering fly ash |
| CN113518632A (en) * | 2019-01-22 | 2021-10-19 | 国家造币印钞厂-皇家造币厂 | Raman mark |
| TWI751689B (en) * | 2019-09-12 | 2022-01-01 | 日商日化陶股份有限公司 | Wear-resistant alumina sintered body |
| CN113264682A (en) * | 2021-05-22 | 2021-08-17 | 内蒙古科技大学 | Solid waste-based nanocrystalline cluster magnetic glass ceramic and preparation method thereof |
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