CN104817273B - Devitrified glass of nanocrystal cluster and preparation method thereof is distributed with glass phase - Google Patents
Devitrified glass of nanocrystal cluster and preparation method thereof is distributed with glass phase Download PDFInfo
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- CN104817273B CN104817273B CN201510139877.3A CN201510139877A CN104817273B CN 104817273 B CN104817273 B CN 104817273B CN 201510139877 A CN201510139877 A CN 201510139877A CN 104817273 B CN104817273 B CN 104817273B
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- 239000011521 glass Substances 0.000 title claims abstract description 171
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 38
- 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 35
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 16
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 16
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 16
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 13
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 12
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 8
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 19
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 17
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 13
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 12
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000006132 parent glass Substances 0.000 claims description 10
- 229910018557 Si O Inorganic materials 0.000 claims description 9
- 239000010881 fly ash Substances 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- 238000010504 bond cleavage reaction Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052611 pyroxene Inorganic materials 0.000 claims description 5
- 230000007017 scission Effects 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 238000005352 clarification Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 3
- 230000006378 damage Effects 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000470 constituent Substances 0.000 abstract description 2
- 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
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 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
- 239000005355 lead glass Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 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
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910052796 boron Inorganic materials 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
- 238000005266 casting Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 210000001787 dendrite Anatomy 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
- 230000005611 electricity 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
- 238000000465 moulding Methods 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
The present invention relates to devitrified glass of nanocrystal cluster and preparation method thereof is distributed with a kind of glass phase, the percentage by weight of the chemical constituent of devitrified glass is：35 65%SiO2, 10 30%CaO, 3 15%Al2O3, 3 15%MgO, 0 5%Na2O, 0 5%K2O, 2 5%B2O3, 1 8%CaF2, 5 15%Fe2O3, 0.01 5%Cr2O3With 0.1 8%REO, the crystal cluster that size is 1 5nm is distributed with the glass phase of the devitrified glass, the component of the crystal cluster includes Si, O, Ca, Mg, Al, Fe, RE and Na.The addition of rare earth oxide causes that above-mentioned crystal cluster is formed in glass phase, so as to improve the mechanical performance of devitrified glass.The devitrified glass low production cost, preparation method are simple, have wide range of applications, and can obtain the devitrified glass of better mechanical property.
Description
Technical field
The present invention relates to a kind of devitrified glass and preparation method thereof, nanocrystal is distributed with more particularly to a kind of glass phase
Devitrified glass of cluster and preparation method thereof, belongs to devitrified glass ceramics field.
Background technology
With economic fast development, the first resource such as mineral metal products, coal is petered out, in the urgent need to mine tailing,
The secondary resources such as blast furnace slag, flyash carry out higher value application, accelerate development recycling economy.The synthesis of current China metal tailings
Utilization rate less than 10%, therefore, improve mine tailing comprehensive utilization it is extremely urgent.Many researchers have carried out mine tailing again
The researchs such as choosing, backfill mine and production devitrified glass and practice, wherein with metal tailings, blast furnace slag, flyash and gangue etc.
Industrial solid castoff can prepare CaO-Al for primary raw material2O3-SiO2- MgO owners crystalline phase is augite or diopside
Devitrified glass, because the system devitrified glass has the characteristics such as high intensity, 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 species, crystallite dimension, the quantity of crystalline phase, but also with the property of glass phase
It is closely related with content.The crystalline phase of existing silicate glass-ceramics it is main by average-size be hundreds of nanometers to tens microns
Grain is brilliant or dendrite is constituted；And glass is mutually the non-crystalline solids of longrange disorder, seen under transmitted electron high-resolution microscope modes
Survey is the longrange disorder arrangement without crystal diffraction spot and atom, as shown in Figure 1；And the glass phase of silicate glass-ceramics
In in addition to Si and O, also often weaken the property of glass phase comprising the cation of the destruction Si-O keys such as Ca, Mg, Al, Fe, Na
Can, and ultimately cause the decline of whole microcrystal glass material performance.
The content of the invention
In view of the above mentioned problem in the presence of prior art, the invention provides a kind of crystallite with compared with high-mechanical property
Glass and preparation method thereof, is distributed with nanocrystal cluster in the glass phase of the devitrified glass, contained in nanocrystal cluster
Make SiO2Ca, Mg, Si, O, Al, Fe, RE and Na element of easy scission of link, increased the link of the bridging oxygen key of Si-O in glass phase, make
It is pure quartz glass that the glass of Bayan Obo tailing microcrystal glass is mutually purified, so as to improve the mechanical performance of devitrified glass.Micro-
Rare earth oxide is added in the preparing raw material of crystal glass so that the formation of above-mentioned crystal cluster, so as to improve devitrified glass
Mechanical performance.The devitrified glass low production cost, preparation method are simple, have wide range of applications, and can obtain better mechanical property
Devitrified glass.
To reach above-mentioned purpose, specific technical scheme of the invention is as follows：
The devitrified glass of nanocrystal cluster is distributed with a kind of glass phase, the devitrified glass is CaO-Al2O3-SiO2-
MgO microcrystalline glass in series, including principal crystalline phase and glass phase, it is characterised in that：The principal crystalline phase is pyroxene phase, and the glass is mutually stone
English glass, is distributed with the nanocrystal cluster that size is 1-5nm, the component bag of the nanocrystal cluster in the glass phase
Include Si, O, Ca, Mg, Al, Fe, RE and Na；
Further, the rare earth elements RE be La and Ce in one or two；
The devitrified glass of nanocrystal cluster is distributed with a kind of glass phase, it is characterised in that：The change of the devitrified glass
Learn component percentage by weight be：35-65%SiO2, 10-30%CaO, 3-15%Al2O3, 3-15%MgO, 0-5%Na2O、0-
5%K2O, 2-5%B2O3, 1-8%CaF2, 5-15%Fe2O3, 0.01-5%Cr2O3And 0.1-8%REO, the nanocrystal group
The size of cluster is 1-5nm；
Further, the component of the nanocrystal cluster includes Si, O, Ca, Mg, Al, Fe, RE and Na；
Further, the crystal cluster has Ca, Mg, Al, La, Fe and the Na for destroying Si-O keys in having digested glass phase
Cation so that SiO is only included in glass phase2, it is pure quartz glass that the glass of devitrified glass is mutually purified, and improves crystallite glass
The mechanical performance of glass；
Further, the rare earth elements RE be La and Ce in one or two；
The method for preparing above-mentioned devitrified glass, it is characterised in that：The method comprises the following steps：
(1) percentage composition weighs primary raw material by weight, and the weight percentage of each primary raw material is：40-60% mine tailings,
10-20% flyash, 10-25%SiO2, 5-10%CaO, 2-5% borax, 1-6%CaF2, 0.01-5%Cr2O3And 0.1-8%
REO；
(2) above-mentioned primary raw material is ground to below 40 mesh, is then melted at 1400-1500 DEG C, clarification, it is uniform after pour
Type casting moulding, prepares parent glass sample；
(3) room temperature is cooled to the furnace after above-mentioned parent glass sample is annealed 2-4 hours at 500-650 DEG C；
(4) parent glass sample annealing it is cold go after coring 2-4 hours at 600-700 DEG C；
(5) by the furnace cooling after crystallization 2-4 hours at 800-900 DEG C of the glass sample after coring；
(6) it is devitrified glass that the crystal cluster is distributed with pyroxene phase and glass phase to prepare including principal crystalline phase；
Further, the mine tailing selection Bayan Obo mine tailing；
Further, the REO is rare earth oxide La2O3、CeO2In one or two mixing；
One kind improves CaO-Al2O3-SiO2The method of-MgO microcrystalline glass in series mechanical strengths, it is characterised in that：Using molten
The method of melting prepares the rare earth oxide of the 0.1-8% that raw material weight is added in the raw material of devitrified glass, and the addition of rare earth oxide makes
Generation nanocrystal cluster in the glass phase of devitrified glass is obtained, easily making in addition to Si, O element is contained in nanocrystal cluster
SiO2The Ca of scission of link, Mg, Al, Fe, RE and Na element, increased the link of the bridging oxygen key of Si-O in glass phase, make devitrified glass
Glass mutually to purify be pure quartz glass, so as to improve the mechanical performance of devitrified glass.
Beneficial effects of the present invention：The present invention is by adding rare earth oxide La2O3、CeO2CaO-Al can be made2O3-
SiO2Form the crystal cluster of 1-5nm in the glass phase of-MgO microcrystalline glass in series, the crystal cluster digested Ca in glass phase,
The cation with destruction Si-O keys such as Mg, Al, RE, Fe and Na so that SiO is only included in glass phase2, therefore by devitrified glass
Glass mutually to purify be pure quartz glass, improve the mechanical performance of devitrified glass.
Brief description of the drawings
Fig. 1 is the existing CaO-Al for being not added with REO2O3-SiO2The high-resolution transmission electricity of glass phase in-MgO microcrystalline glass in series
Sub- micro-image；
Fig. 2 is the high-resolution transmission electron microscope image of glass phase in the devitrified glass of the embodiment of the present invention 1；
The power spectrum collection of illustrative plates of the nanocrystal cluster that Fig. 3 mutually contains for glass in the devitrified glass in the embodiment of the present invention 1；
Fig. 4 is the power spectrum collection of illustrative plates of glass 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 glass phase in the devitrified glass of the embodiment of the present invention 2；
Fig. 6 is the power spectrum collection of illustrative plates of glass phase non-nano crystal Cluster zone in the devitrified glass in the embodiment of the present invention 2.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and detailed description.It should be noted that following
Embodiment is only example, is not limit the scope of the invention, and all are equal based on the simple deformation scheme that thought of the invention is made
Fall within the scope of the present invention.
Mine tailing in primary raw material of the invention can select Bayan Obo mine tailing, also can select other mine tailings, can freely select
Select.The Bayan Obo mine tailing and the chemical composition of flyash that the present invention is selected are shown in Table 1.
The Bayan Obo mine tailing of table 1 and chemical composition of PCA (Wt%)
Specific embodiment is given below.
Embodiment 1
The preparation method of the devitrified glass of nanocrystal cluster is distributed with a kind of glass phase：
(1) according to the chemical constituent weight proportion of devitrified glass：50%SiO2, 20%CaO, 5.04%Al2O3, 7.73%
MgO, 0.55%Na2O, 2%B2O3, 3%CaF2, 3.43%Fe2O3, 0.25%Cr2O3And 8%La2O3, weight is carried out to raw material
Proportioning：50% Bayan Obo mine tailing, 15% flyash, 15%SiO2, 6.75%CaO, 2% borax, 3%CaF2, 0.25%
Cr2O3And 8%La2O3；
(2) batch mixing：The raw material that will have been matched is put into ball milling 60min in ball mill, is ground to below 40 mesh；
(3) melt：Well mixed raw material is fitted into crucible, is melted at 1400-1500 DEG C using high temperature resistance furnace, clear
Clearly, uniformly；
(4) it is molded and anneals：The glass solution melted after clarification is poured to cast to be molded on stainless steel mould and prepares basis
Glass sample, furnace cooling after parent glass sample is annealed 4 hours at 600 DEG C, eliminates stress in sample；
(5) it is heat-treated：Parent glass sample in 680 DEG C of coring 2 hours, in 860 DEG C of crystallization 2 hours, will prepare after annealing
Go out principal crystalline phase for pyroxene phase, the devitrified glass of nanocrystal cluster is distributed with glass phase.
(6) microcell of the devitrified glass sample inlayed to molybdenum ring using transmission electron microscope is observed (due to sample
It is smaller, so being inlayed using molybdenum ring to devitrified glass sample), Fig. 2 is addition 8%La2O3Glass in Bayan Obo tailing microcrystal glass
The high-resolution electronic micro-image of glass phase, can be observed from Fig. 2, and most of region is atom longrange disorder row in glass phase
Row, the i.e. structure type of glass phase, and the atomic rule of 1-5nm in the region intermediate distribution that these atom longrange disorders are arranged
The region of arrangement, the atom of the nano-area is analogous to the regular of atom in crystal not being longrange disorder arrangement
Arrangement, therefore, the region is nanocrystal cluster, and the nanocrystal cluster is discrete, be distributed in glass phase to disperse.
Mo elements in Fig. 3 and Fig. 4 are not the elements in nanocrystal cluster, but the element of the molybdenum ring for inlaying samples.
(7) nanocrystal cluster is main during the glass phase of devitrified glass is obtained using the supporting energy depressive spectroscopy of transmission electron microscope
Composition is Ca, Mg, Al, Si, La, Fe and O element, as shown in Figure 3；Non-nano crystal Cluster zone in the glass phase of devitrified glass
Main component is Si and O elements as shown in figure 4, explanation with the addition of La2O3Devitrified glass by the Ca in glass phase, Mg, Al, Si,
La, Fe and O element aggregation have been arrived in nanocrystal cluster, and in remaining residual glass phase are Si and O elements.Due to glass phase
In Ca, Mg, Al, Si, La, Fe element play a part of scission of link, if largely there is above-mentioned element in glass phase, certainly will drop
The link of low silicon-oxy tetrahedron, slackens the mechanical property of glass phase.After nanocrystal cluster has digested above-mentioned element so that surplus
It is pure quartz glass in remaining residual glass phase, will so improves the mechanical performance of devitrified glass.
Embodiment 2
The preparation method of the devitrified glass of nanocrystal cluster is distributed with a kind of glass phase：
(1) raw material weight proportioning of soup processed：50% Bayan Obo mine tailing, 15% flyash, 22%SiO2, 7.05%CaO, 2% boron
Sand, 3%CaF2, 0.25%Cr2O3And 0.7%La2O3+CeO2；
(2) batch mixing：The raw material that will have been matched is put into ball milling 60min in ball mill, is ground to below 40 mesh；
(3) melt：Well mixed raw material is fitted into crucible, is melted at 1400-1500 DEG C using high temperature resistance furnace, clear
Clearly, uniformly；
(4) it is molded and anneals：The glass solution melted after clarification is poured to cast to be molded on stainless steel mould and prepares basis
Glass sample, furnace cooling after parent glass sample is annealed 4 hours at 600 DEG C, eliminates stress in sample；
(5) it is heat-treated：Parent glass sample in 680 DEG C of coring 2 hours, in 860 DEG C of crystallization 2 hours, will prepare after annealing
Go out principal crystalline phase for pyroxene phase, the devitrified glass of nanocrystal cluster is distributed with glass phase.
(6) microcell of the devitrified glass sample inlayed to molybdenum ring using transmission electron microscope is observed, and Fig. 5 is addition
0.7%La2O3+CeO2The high-resolution electronic displaing micro picture of glass phase in Bayan Obo tailing microcrystal glass, contains in its glass phase
Size is the crystal cluster of 1-5nm.Non-nano crystal Cluster zone main component is Si and O elements in the glass phase of devitrified glass
As shown in fig. 6, explanation with the addition of La2O3+CeO2Devitrified glass glass phase in form nanocrystal cluster so that it is surplus
Contain Si and O elements in remaining residual glass phase.Therefore the mechanical performance of devitrified glass is improved.
Using three-point bending method to being not added with rare earth oxide, addition 8%La2O3And 0.7%La2O3+CeO2Prepare
The rupture strength of Bayan Obo tailing microcrystal glass sample is detected that concrete outcome is shown in Table 2.Addition 8%La2O3With 0.7%
La2O3+CeO2The rupture strength of the Bayan Obo tailing microcrystal glass of preparation is respectively 170.32MPa and 250.13MPa, hence it is evident that
Higher than the devitrified glass rupture strength for being not added with rare earth oxide preparation.
The rupture strength testing result of the Bayan Obo tailing microcrystal glass sample of table 2
Addition 8%La2O3, 0.7%La2O3+CeO2Due to separating out nanometer in the glass phase of Bayan Obo tailing microcrystal glass
The crystal cluster of level, the crystal cluster is enriched easily makes SiO2Ca, Mg, Al, Si, RE and Fe element of scission of link, increased glass
The link of the bridging oxygen key of Si-O in glass phase, it is pure quartz glass the glass of Bayan Obo tailing microcrystal glass is mutually purified, and is improved
The mechanical performance of devitrified glass.
As can be seen here, when manufacturing devitrified glass, REO is added in the feed, can cause shape in the glass phase of devitrified glass
Into nano level crystal cluster, Ca, Mg, Al, Si, RE and Fe element present in the crystal cluster easily make SiO2Scission of link, because
For nanocrystal cluster has digested above-mentioned element, so that respective element is reduced in glass phase, therefore glass phase is increased
The link of the bridging oxygen key of Si-O, making the glass of Bayan Obo tailing microcrystal glass, mutually to purify be pure quartz glass, so as to improve micro-
The mechanical performance of crystal glass.
Claims (6)
1. the devitrified glass of nanocrystal cluster is distributed with a kind of glass phase, it is characterised in that：The chemistry of the devitrified glass
The percentage by weight of component is：35-65%SiO2, 10-30%CaO, 3-15%Al2O3, 3-15%MgO, 0-5%Na2O、0-
5%K2O, 2-5%B2O3, 1-8%CaF2, 5-15%Fe2O3, 0.01-5%Cr2O3And 0.1-8%REO, the nanocrystal group
The size of cluster is 1-5nm；The REO is rare earth oxide La2O3、CeO2In one or two mixing；The devitrified glass bag
Glass phase is included, the glass is mutually pure quartz glass.
2. devitrified glass according to claim 1, it is characterised in that：The component of the nanocrystal cluster includes
Si, O, Ca, Mg, Al, Fe, RE and Na；The RE be La and Ce in one or two.
3. devitrified glass according to claim 2, it is characterised in that：The nanocrystal cluster has in having digested glass phase
There are Ca, Mg, Al, RE, Fe and Na cation of destruction Si-O keys so that SiO is only included in glass phase2, by the glass of devitrified glass
It is pure quartz glass that glass is mutually purified.
4. the method for preparing the devitrified glass described in any one of claims 1 to 3, it is characterised in that：The method includes following step
Suddenly：
(1) percentage composition weighs primary raw material by weight, and the weight percentage of each primary raw material is：40-60% mine tailings, 10-
20% flyash, 10-25%SiO2, 5-10%CaO, 0-5% borax, 1-6%CaF2, 0.01-5%Cr2O3And 0.1-8%
REO；
(2) above-mentioned primary raw material is ground to below 40 mesh, is then melted at 1400-1500 DEG C, clarification, it is uniform after be cast into
Type, prepares parent glass sample；
(3) room temperature is cooled to the furnace after above-mentioned parent glass sample is annealed 2-4 hours at 500-650 DEG C；
(4) after parent glass sample annealing cooling coring 2-4 hours at 600-700 DEG C；
(5) by the furnace cooling after crystallization 2-4 hours at 800-900 DEG C of the glass sample after coring；
(6) it is devitrified glass that the nanocrystal cluster is distributed with pyroxene phase and glass phase to prepare including principal crystalline phase.
5. the method for preparing devitrified glass according to claim 4, it is characterised in that：The mine tailing selects Bayan Obo tail
Ore deposit.
6. it is a kind of to improve CaO-Al2O3-SiO2The method of-MgO microcrystalline glass in series mechanical strengths, it is characterised in that：Using melting
Method prepares the rare earth oxide of the 0.1-8% that raw material weight is added in the raw material of devitrified glass, and the addition of rare earth oxide is caused
Nanocrystal cluster is produced in the glass phase of devitrified glass, contained in nanocrystal cluster easily makes SiO in addition to Si, O element2
Ca, Mg, Al, Fe, RE and Na element of scission of link, increased the link of the bridging oxygen key of Si-O in glass phase, make the glass of devitrified glass
It is pure quartz glass that glass is mutually purified, so as to improve the mechanical performance of devitrified glass, the rare earth oxide is La2O3And CeO2In
One or two mixing, the RE be La and Ce in one or two.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510139877.3A CN104817273B (en) | 2015-03-27 | 2015-03-27 | Devitrified glass of nanocrystal cluster and preparation method thereof is distributed with glass phase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510139877.3A CN104817273B (en) | 2015-03-27 | 2015-03-27 | Devitrified glass of nanocrystal cluster and preparation method thereof is distributed with glass phase |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104817273A CN104817273A (en) | 2015-08-05 |
| CN104817273B true CN104817273B (en) | 2017-06-27 |
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| 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 |
| 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 |
| EP3685864A1 (en) * | 2019-01-22 | 2020-07-29 | Fabrica Nacional De Moneda Y Timbre - Real Casa De La Moneda | Use of feldspar based particles as security-markers |
| JP7325275B2 (en) * | 2019-09-12 | 2023-08-14 | 株式会社ニッカトー | 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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| Cr2O3对白云鄂博西尾矿微晶玻璃显微结构及性能的影响;李保卫等;《人工晶体学报》;20140331;第43卷(第3期);第642-647页 * |
| Crystallization Characteristics and Properties of High-Performance Glass-Ceramics Derived from Baiyunebo East Mine Tailing;Li Baowei et al.;《Environmental Progress & Sustainable Energy》;20140613;第34卷(第2期);第420-426页 * |
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