CN103274588B - A kind of Crystallization method utilizing deformation to regulate and control devitrified glass - Google Patents
A kind of Crystallization method utilizing deformation to regulate and control devitrified glass Download PDFInfo
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- CN103274588B CN103274588B CN201310161257.0A CN201310161257A CN103274588B CN 103274588 B CN103274588 B CN 103274588B CN 201310161257 A CN201310161257 A CN 201310161257A CN 103274588 B CN103274588 B CN 103274588B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P40/00—Technologies relating to the processing of minerals
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Abstract
The present invention relates to a kind of Crystallization method utilizing deformation to regulate and control devitrified glass, utilize deformation to regulate and control Na
2o-CaO-SiO
2-MgO-Al
2o
3(NCSMA) weave construction of Blast-furnace Slag Glass-ceramics, by loading the deformation of different distortion amount to the parent glass being heated to nucleation temperature and crystallization temperature, crystalline phase kind, grain-size, grain form in regulation and control devitrified glass, obtain uniform texture, crystalline phase composition and the different devitrified glass that distributes.The present invention, in the application in devitrified glass crystallization field, provides effective way for most devitrified glass system realizes overall rapid crystallization smoothly, for important basis has been established in the high-valued comprehensive utilization of large argument solid waste.
Description
Technical field
The present invention relates to a kind of control mode of devitrified glass crystallization, espespecially a kind of method utilizing deformation to regulate and control devitrified glass crystallization, object is to adopt deformation to replace interpolation nucleator, improves material property and (or) reduce costs while not affecting continuous production.
Background technology
At present, field of flow has been carried out both at home and abroad on the impact of organic polymer material crystallization, CaO-Al
2o
3-SiO
2or CaO-MgO-Al (CAS)
2o
3-SiO
2(CMAS) development work of Blast-furnace Slag Glass-ceramics, comprise the design of component system, key component or nucleator to work such as the impacts of crystallization property and weave construction, also do not relate to the research work of elastic stress field that deformation produces and plastic flow field regulation and control Blast-furnace Slag Glass-ceramics crystallization.
(1) field of flow research that organic polymer material crystallization is affected
A small amount of report is had about the crystallization of field of flow induction macromolecular material, the strain-crystallization effect of natural rubber in tensile deformation process, such as Shanghai Communications University is in meeting source etc. by applying differently strained sinusoidal oscillation shear field to isotatic polypropylene (iPP) subcooling films, under have studied large sstrain oscillatory shear flow field action, the flow-induced crystallization process of isothermal iPP.Result of study shows, apply the kinetics of crystallization that iPP obviously can be accelerated in large sstrain oscillatory shear flow field, and the strain applied can impel more greatly iPP kinetics of crystallization hastening phenomenon more obvious.
The rubber combined system of a polynite content has been constructed by study group of Sichuan University, the X-ray diffraction of NSRL and scattering experiment station is utilized to study it in tensile deformation process, polynite content, on the impact of natural rubber crystallization behavior, explores the enhanced mechanism of NR/montmorillonite Clay Nano-composite with this.Result of study shows, with the increase of tension strain, crystal diffraction arc intensity increases.And along with the increase of stretch ratio, the L200(of all samples and the grain-size of 200 crystal face vertical direction) and the grain-size of L120(and 120 crystal face vertical direction) all present the trend reduced gradually.In deformation process, crystal, under stress, is elongated along draw direction, so just there will be the phenomenon of size reduction perpendicular to draw direction.There is orientation in rubber, and drive rubber molecular chain preferred orientation interactional with it under less strain; In system, nucleation site increases, and grain-size also reduces.
Li Liangbin researcher seminar of Chinese University of Science and Technology has carried out the work of quantitative examination field of flow induction polymer crystallization, show that field of flow induced crystallization must utilize the means that combine of stream changes-synchrotron radiation just can throw a flood of light on form and the forming process of shish-kebab, and then the theoretical model of structure polymer field of flow induced crystallization.
The latest developments of the macromolecule melt Rheological Study of Akron university of the U.S., have studied the mechanism of shish-kebab in macromolecule melt quantitatively by stream change means.
Above-mentioned research work shows that the influence research work of field of flow to organic polymer material crystallization has achieved significant progress, but in field of inorganic nonmetallic material, related work is not also carried out in the crystallization control aspect of plastic flow field to devitrified glass that especially deformation produces.
(2) research of Blast-furnace Slag Glass-ceramics
Research at present to Blast-furnace Slag Glass-ceramics, focuses on blast-furnace slag to be the component system of main raw material development CAS or CMAS devitrified glass, crystallization property and weave construction.Such as old enter profit, Li Yuhua with blast furnace slag and cullet for main raw material, adopting sintering process to prepare principal crystalline phase is diopside (CaMgSi
2o
6) CMAS system high slag microcrystallite glass, and improve the over-all properties of devitrified glass by optimizing heat treatment process parameter.HongyuLiu, Yang Shumin, Lu Hongxia etc. with iron-smelting blast-furnace slag and potassium felspar sand for raw material, sintering process is adopted to prepare CMAS slag glass-ceramics, have studied the impact of heat treating regime on slag glass-ceramics crystallization behavior and performance, obtain best heat treatment process parameter.Yu Pingli, Zhang Wei etc. adopt sintering process to prepare the devitrified glass taking blast-furnace slag as main raw material, have studied respectively with the composition of diopside and the gehlenite cinder microcrystalline glass that is principal crystalline phase and preparation technology, analyze the relation of microstructure and performance.
In addition, Nan Xueli, Zhu Chunjiang, Liu Yang, Xiao Hanning etc. utilize melt casting method to be main raw material with blast-furnace slag, and have developed principal crystalline phase is wollastonite (CaSiO
3) and diopside (CaMg(SiO
3)
2) CaO-Al
2o
3-SiO
2-MgO slag glass-ceramics.Zhang Shengxiao, Yue Qinyan etc. analyze nucleating agent TiO
2on the impact of Blast-furnace Slag Glass-ceramics weave construction and crystallization property.
Wang Zhongjie, Ni Wen
[25]deng being that main raw material have developed with diopside and (CaMg (Si, Al, Fe) with nickel slag-blast-furnace slag mixing slag
2o
6) and hedenbergite (CaFe (Si, Al, Fe)
2o
6) be the cinder microcrystalline glass of principal crystalline phase.
YanZhao, G.A.Khater etc. affect in Blast-furnace Slag Glass-ceramics weave construction and crystallization property at nucleator and have carried out relevant work, and wherein YanZhao have studied CaF
2to with diopside and Ca
2siO
2f
2for the Blast-furnace Slag Glass-ceramics weave construction of principal crystalline phase and the impact of material property, G.A.Khater has inquired into Cr
2o
3, LiF, CaF
2and TiO
2multiple nucleator is on the impact of Blast-furnace Slag Glass-ceramics weave construction and crystallization property.
Above-mentioned research work shows the research work mainly component system design of Blast-furnace Slag Glass-ceramics, key component or nucleator are on the impact of weave construction, the aspects such as the relation of the optimization of heat treating regime and weave construction and performance, these work have important reference significance for utilizing sintering process and melt casting legal system for Blast-furnace Slag Glass-ceramics, but prepare Blast-furnace Slag Glass-ceramics for utilizing rolling process and then there is larger restriction, especially the method for organization of regulation control structure and crystallization property is only limitted to based on heat treating regime, adjust key component or nucleator.If the nucleating agent added is less, then more difficultly realize rapid crystallization; If add more nucleating agent, discharge port forms crystallization material, blocking outlet, as shown in Figure 2.Therefore, by regulating, the method for nucleating agent regulates and controls rapid crystallization, integrally crystallization has very large limitation.
Summary of the invention
The technology of the present invention is dealt with problems: overcome the deficiencies in the prior art, provides a kind of Crystallization method utilizing deformation to regulate and control devitrified glass, realizes Na
2o-CaO-SiO
2-MgO-Al
2o
3(NCSMA) integrally crystallization of microcrystalline glass in series and rapid crystallization, and improve weave construction by the method for deformation, improve crystallization velocity, overcome rolling process and prepare Na2O-CaO-SiO2-MgO-Al2O3(NCSMA) in Blast-furnace Slag Glass-ceramics process, when the nucleating agent added is few, more difficult rapid crystallization and weave construction is uneven; When adding more nucleating agent, constantly there is crystallization material in operate portions discharge port both sides, results in blockage.
The elastic stress field that the present invention utilizes deformation to produce or plastic flow field organization of regulation control structure and crystallization property, by crystalline phase kind, grain form, grain-size in deformation regulation and control NCSMA Blast-furnace Slag Glass-ceramics Crystallization Process, control weave construction by forming process design and improve product properties, realize the prerequisite of Blast-furnace Slag Glass-ceramics high performance, also be develop one of new forming method and theoretical important foundation, overall invention thinking as shown in Figure 4.
The technology of the present invention solution: a kind of Crystallization method utilizing deformation to regulate and control devitrified glass, as shown in Figure 4, step is as follows:
(1) requirement of integrally crystallization
Utilizing rolling process to prepare in the process of NCSMA microcrystalline glass in series to find product weave construction, uneven (shown in accompanying drawing 1, the principal crystalline phase in its mesexine M region is wollastonite (CaSiO
3), the principal crystalline phase in inner n-quadrant is combeite), top layer and middle part crystalline phase kind, grain-size, crystallization rate, grain form are different, and product performance decline, and occur the defects such as distortion warpage.
By taking to increase MgO, Na
2o etc. promote the oxide content of forming core or add ZrO
2, TiO
2etc. multiple nucleating agent, obtain the Blast-furnace Slag Glass-ceramics that top layer is consistent with the weave construction at middle part.Although the method for adding Nucleating Agent solves the uneven problem of weave construction, but crystallization material constantly appears in operate portions discharge port both sides, occur putty together with crystallization material condenses in discharge port pool wall, feed liquid cannot normally flow out, cause conforming product rate very low, cannot continuous seepage, even stop production.Therefore, by regulate main component or add nucleator improve NCSMA devitrified glass weave construction, realize integrally crystallization and have significant limitation.
For this reason, the present invention utilizes and carries out deformation to the parent glass of the NCSMA devitrified glass after calendering formation, by improving weave construction at coring warm area and the deformation of crystallization warm area, obtain uniform microtexture (comprising crystalline phase kind, crystallization rate, grain-size and grain form) in Blast-furnace Slag Glass-ceramics inside.
(2) demand of rapid crystallization
Current rolling process produces the crystallization and thermal treatment time of NCSMA system Blast-furnace Slag Glass-ceramics needs generally at 10-20 hour, and heat treatment time is long, production efficiency is low; The generation of solid waste blast-furnace slag is very big, if utilize the rolling process of current low speed to produce, then processing power is lower, and cost is higher.In order to enhance productivity, reduce production cost, the crystallization velocity of NCSMA Blast-furnace Slag Glass-ceramics need be improved, reach the object of rapid crystallization.
Concrete scheme is realized by following steps:
1, parent glass preparation
(1) prepare burden
First granular blast-furnace slag is ground into the powder being less than 20 orders (< 850 μm), and then add aluminum oxide, quartz sand, magnesium oxide, calcined soda for industry and ammonium nitrate five kinds of auxiliary materials, the proportioning of auxiliary material is that ((((17-21.0) ﹕ (1.0-3.5), mixes basis of formation admixtion by blast-furnace slag and auxiliary material to 3.0-7.0) ﹕ to 7.0-11.0) ﹕ to 1.0-3.0) ﹕.
(2) melt
The basic admixtion prepared is dropped into fusing kiln in batches, and in the scope of 1450-1600 DEG C, molten glass admixtion 1.0-4.0h, obtains uniform glass solution, then at 1350-1500 DEG C of insulation 1.0h, and homogenizing, fining glass liquid.
(3) shaping
Glass metal, through rolling press shaping formation high temperature parent glass plate, enters cooling annealing warm area subsequently, obtains parent glass.
2, the deformation process of parent glass
Parent glass plate enters coring warm area and crystallization warm area with transmission roller tables, and carry out calendering at coring warm area and crystallization warm area by deformation rolling press respectively and be out of shape, obtain the sheet glass of different thickness, the deformation process of parent glass plate as shown in Figure 3 and Figure 5.Wherein deformation process has three kinds of situations, is the following stated process (1) or (2) or (3) respectively.
Three kinds of deformation situations:
(1) coring warm area deformation (shown in Fig. 6)
Parent glass plate enters coring warm area (700-725 DEG C), and make sheet glass produce distortion through 1# deformation rolling press, thickness 0 < △ L≤40%(△ L of sheet glass represents deformation quantity), obtain the parent glass plate that thickness is 20.0-12.0mm.
Adopt 700-725 DEG C to be incubated 3h, and be incubated the heat treating regime of 2h at 850 DEG C, crystallization has the parent glass of different distortion amount, then obtains devitrified glass through 600 DEG C of insulation 3h annealing.
(2) crystallization warm area deformation (shown in Fig. 7)
Parent glass plate enters coring warm area (700-725 DEG C), after 700-725 DEG C of insulation 3h coring thermal treatment, obtain coring parent glass, then crystallization warm area (840-860 DEG C) is entered, sheet glass is made to produce distortion through 2# deformation rolling press, the thickness of coring parent glass plate reduces 0 < △ L≤40%(△ L and represents deformation quantity), obtain the coring sheet glass that thickness is 20.0-12.0mm.
Adopt the crystallization and thermal treatment system of 840-860 DEG C of identical insulation 2h, crystallization has the coring parent glass of different distortion amount, then obtains devitrified glass through 600 DEG C of insulation 3h annealing.
(3) coring warm area and crystallization warm area deformation (shown in Fig. 8)
Parent glass plate enters coring warm area (700-725 DEG C), sheet glass is made to produce distortion through 1# deformation rolling press, the thickness of sheet glass reduces 0 < △ L≤40%(△ L and represents deformation quantity), obtain the parent glass plate that thickness is 20.0-12.0mm.Adopt the coring heat treating regime of 700-725 DEG C of identical insulation 3h, coring has the parent glass of different distortion amount, obtains coring parent glass.
Enter crystallization warm area (840-860 DEG C), make sheet glass produce distortion through 2# deformation rolling press, the thickness of coring parent glass plate reduces 0-40%, obtains the coring sheet glass that thickness is 20.0-12.0mm.
Adopt the crystallization and thermal treatment system of 840-860 DEG C of identical insulation 2h, crystallization has the coring parent glass of different distortion amount, then obtains devitrified glass through 600 DEG C of insulation 3h annealing.
The present invention's beneficial effect is compared with prior art:
(1) person's character invention deformation promotes that NCSMA Blast-furnace Slag Glass-ceramics grain-size reduces, along with the increase of glass deformation amount, the difference of the average aspect ratio of devitrified glass top layer and internal grain first reduces rear increase (shown in Fig. 9), and the deflection increasing glass contributes to the formation suppressing the thick crystal in top layer.When glass deformation amount is 8-16%, devitrified glass mesexine and inner grain-size comparatively uniformity.
(2) deformation promotes that in cinder microcrystalline glass, crystalline phase kind increases, and crystallization rate improves.
(3) deformation promotes the column crystal layer eliminating top layer, and the weave construction of devitrified glass is more even.
(4) deformation improves the crystallization velocity of devitrified glass, significantly reduces the crystallization time of devitrified glass.
(5) utilize deformation in production process can organization of regulation control structure, improve the final performance of goods.
(6) deformation replaces interpolation nucleator, improves material property and (or) reduce costs while not affecting continuous production.
Accompanying drawing explanation
Fig. 1 is NCSMA system Blast-furnace Slag Glass-ceramics SEM pattern;
Fig. 2 is the blocking of discharge port crystallization, and 1 is discharge port; 2 is crystallization material;
Fig. 3 is NCSMA Blast-furnace Slag Glass-ceramics rolling process preparation flow;
Fig. 4 is Integral Thought of the present invention;
Fig. 5 is devitrified glass deformation process schematic diagram;
Fig. 6 is coring warm area deformation schematic diagram;
Fig. 7 is crystallization warm area deformation schematic diagram;
Fig. 8 is coring warm area and crystallization warm area deformation schematic diagram;
The relation of the difference of crystal grain average aspect ratio in glass deformation amount and devitrified glass based on Fig. 9;
The XRD diffraction peak intensity of Figure 10 to be deflection be devitrified glass sample different positions of 8%;
Figure 11 to be deflection be 8% devitrified glass cross-sectional scans Electronic Speculum pattern;
The XRD diffraction peak intensity of Figure 12 to be deflection be devitrified glass sample different positions of 16%;
Figure 13 to be deflection be 16% devitrified glass cross-sectional scans Electronic Speculum pattern;
The XRD figure spectrum of Figure 14 to be deflection be devitrified glass of 8%+24%;
Figure 15 is inside and the surface region port pattern of 8%+24% deflection;
The inner XRD figure spectrum of devitrified glass of Figure 16 to be deflection be 8%+32%;
Figure 17 is inside and the surface region port pattern of 8%+32% deflection.
1-parent glass plate 2-roller-way carrying roller 3-rolls top roll 4-and rolls lower roll.
Embodiment
The present invention is introduced in detail below in conjunction with drawings and the specific embodiments.But following embodiment is only limitted to explain the present invention, and protection scope of the present invention should comprise the full content of claim, is not limited only to the present embodiment.
Embodiment 1
1, parent glass preparation
(1) prepare burden
First granular blast-furnace slag is ground into the powder being less than 20 orders (< 850 μm), and then add aluminum oxide, quartz sand, magnesium oxide, calcined soda for industry and ammonium nitrate five kinds of auxiliary materials, the proportioning of auxiliary material is that ((((17-21.0) ﹕ (1.0-3.5), mixes basis of formation admixtion by blast-furnace slag and auxiliary material to 3.0-7.0) ﹕ to 7.0-11.0) ﹕ to 1.0-3.0) ﹕.
(2) melt
The basic admixtion prepared is dropped into fusing kiln in batches, and in the scope of 1450-1600 DEG C, molten glass admixtion 1.0-4.0h, obtains uniform glass solution, then at 1350-1500 DEG C of insulation 1.0h, and homogenizing, fining glass liquid.
(3) shaping
Glass metal, through rolling press shaping formation high temperature parent glass plate, enters cooling annealing warm area subsequently, obtains parent glass.
2, the deformation process of parent glass
Parent glass plate enters coring warm area (700-725 DEG C), makes sheet glass produce distortion through 1# deformation rolling press, and the thickness of sheet glass reduces 8%, obtains the parent glass plate that thickness is 18.4mm.
Adopt 700-725 DEG C to be incubated 3h, then be incubated the heat treating regime of 2h through 850 DEG C, crystallization has the parent glass of different distortion amount, then obtains devitrified glass through 600 DEG C of insulation 3h annealing.
Deflection is that the XRD diffraction peak intensity on the devitrified glass sample top layer of 8% obviously strengthens, and secondly top layer is basically identical with inner crystal type, is Na
5.27ca
3(Si
6o
18), Na
2ca
4mg
2si
4o
15and CaSiO
3three kinds of crystal (shown in Figure 10), and the difference of the average aspect ratio of sample top layer and internal grain significantly reduces.
The surface region of devitrified glass cross section fracture and the solid colour of interior region, without obvious column crystal layer (shown in Figure 11).
Embodiment 2
1, parent glass preparation
(1) prepare burden
First granular blast-furnace slag is ground into the powder being less than 20 orders (< 850 μm), and then add aluminum oxide, quartz sand, magnesium oxide, calcined soda for industry and ammonium nitrate five kinds of auxiliary materials, the proportioning of auxiliary material is that ((((17-21.0) ﹕ (1.0-3.5), mixes basis of formation admixtion by blast-furnace slag and auxiliary material to 3.0-7.0) ﹕ to 7.0-11.0) ﹕ to 1.0-3.0) ﹕.
(2) melt
The basic admixtion prepared is dropped into fusing kiln in batches, and in the scope of 1450-1600 DEG C, molten glass admixtion 1.0-4.0h, obtains uniform glass solution, then at 1350-1500 DEG C of insulation 1.0h, and homogenizing, fining glass liquid.
(3) shaping
Glass metal, through rolling press shaping formation high temperature parent glass plate, enters cooling annealing warm area subsequently, obtains parent glass.
2, the deformation process of parent glass
Parent glass plate enters coring warm area (700-725 DEG C), through after 700-725 DEG C of insulation 3h coring thermal treatment, obtain coring parent glass, then crystallization warm area (840-860 DEG C) is entered, sheet glass is made to produce distortion through 2# deformation rolling press, the thickness of coring parent glass plate reduces 16%, obtains the coring sheet glass that thickness is 16.8mm.
Adopt the 840-860 DEG C of crystallization and thermal treatment system being incubated 1.5h, crystallization has the coring parent glass of different distortion amount, then obtains devitrified glass through 600 DEG C of insulation 3h annealing.
Deflection is that the XRD diffraction peak intensity on the devitrified glass top layer of 16% is comparatively strong, and secondly top layer is consistent with inner crystal type, is Na
1.74(Mg
0.865si
1.135o
4), Na
7.15(Al
7.2si
8.8o
32) and Ca
7mgAl
10o
23three kinds of crystal (shown in Figure 12), the difference of its sample top layer and crystal inside length-to-diameter ratio is also less.
The surface region of devitrified glass cross section fracture and the solid colour of interior region, without obvious column crystal layer (shown in Figure 13).The difference of top layer and internal grain length-to-diameter ratio significantly reduces.
The crystallization time of devitrified glass shortens 25%.
Embodiment 3
1, parent glass preparation
(1) prepare burden
First granular blast-furnace slag is ground into the powder being less than 20 orders (< 850 μm), and then add aluminum oxide, quartz sand, magnesium oxide, calcined soda for industry and ammonium nitrate five kinds of auxiliary materials, the proportioning of auxiliary material is that ((((17-21.0) ﹕ (1.0-3.5), mixes basis of formation admixtion by blast-furnace slag and auxiliary material to 3.0-7.0) ﹕ to 7.0-11.0) ﹕ to 1.0-3.0) ﹕.
(2) melt
The basic admixtion prepared is dropped into fusing kiln in batches, and in the scope of 1450-1600 DEG C, molten glass admixtion 1.0-4.0h, obtains uniform glass solution, then at 1350-1500 DEG C of insulation 1.0h, and homogenizing, fining glass liquid.
(3) shaping
Glass metal, through rolling press shaping formation high temperature parent glass plate, enters cooling annealing warm area subsequently, obtains parent glass.
2, the deformation process of parent glass
Parent glass plate enters coring warm area (700-725 DEG C), makes sheet glass produce distortion through 1# deformation rolling press, and the thickness of sheet glass reduces 8%, obtains the parent glass plate that thickness is 18.4mm.Adopt the coring heat treating regime of 700-725 DEG C identical/3h, coring has the parent glass of different distortion amount, obtains coring parent glass.
Enter crystallization warm area (840-860 DEG C), make sheet glass produce distortion through 2# deformation rolling press, the thickness of coring parent glass plate reduces 24%, obtains the coring sheet glass that thickness is 14.0mm.
Adopt the crystallization and thermal treatment system of 840-860 DEG C of identical insulation 1.2h, crystallization has the coring parent glass of different distortion amount, then obtains devitrified glass through 600 DEG C of insulation 3h annealing.
Deflection be 24% devitrified glass top layer crystallization rate higher, between top layer and inside, define again " transition layer ", secondary top layer is mainly by CaNa
2al
4si
4o
16(01-084-1161), CaMgSi
2o
6, Ca
0.8mg
1.2(SiO
3)
2(01-076-0238) and Mg
0.944ca
0.056siO
3(01-076-0525) four kinds of crystal compositions (shown in Figure 14), and inside is by (Ca
0.94na
0.06) (Al
1.94si
2.06o
8) (01-084-0751), Na
2ca
4mg
2si
4o
15(00-042-1484) and CaAl
2si
2o
8(00-005-0528) three kinds of crystal compositions.And the difference of its sample top layer and crystal inside length-to-diameter ratio significantly increases.
Do not occur obvious column crystal region (shown in Figure 15), but there is the non-crystallized glass microcell of disperse in (in the scope of distance top layer vertical range 1-3mm) in microcrystallite body.The crystallization time of devitrified glass shortens 40%.
Embodiment 4
1, parent glass preparation
(1) prepare burden
First granular blast-furnace slag is ground into the powder being less than 20 orders (< 850 μm), and then add aluminum oxide, quartz sand, magnesium oxide, calcined soda for industry and ammonium nitrate five kinds of auxiliary materials, the proportioning of auxiliary material is that ((((17-21.0) ﹕ (1.0-3.5), mixes basis of formation admixtion by blast-furnace slag and auxiliary material to 3.0-7.0) ﹕ to 7.0-11.0) ﹕ to 1.0-3.0) ﹕.
(2) melt
The basic admixtion prepared is dropped into fusing kiln in batches, and in the scope of 1450-1600 DEG C, molten glass admixtion 1.0-4.0h, obtains uniform glass solution, then at 1350-1500 DEG C of insulation 1.0h, and homogenizing, fining glass liquid.
(3) shaping
Glass metal, through rolling press shaping formation high temperature parent glass plate, enters cooling annealing warm area subsequently, obtains parent glass.
2, the deformation process of parent glass
Parent glass plate enters coring warm area (700-725 DEG C), makes sheet glass produce distortion through 1# deformation rolling press, and the thickness of sheet glass reduces 8%, obtains the parent glass plate that thickness is 18.4mm.Adopt the coring heat treating regime of 700-725 DEG C of identical insulation 3h, coring has the parent glass of different distortion amount, obtains coring parent glass.
Enter crystallization warm area (840-860 DEG C), make sheet glass produce distortion through 2# deformation rolling press, the thickness of coring parent glass plate reduces 32%, obtains the coring sheet glass that thickness is 12.5mm.
Adopt the crystallization and thermal treatment system of 840-860 DEG C of identical insulation 1.2h, crystallization has the coring parent glass of different distortion amount, then obtains devitrified glass through 600 DEG C of insulation 3h annealing.
Kind of crystalline in the devitrified glass top layer of 8%+32% is more, and does not also form obvious column crystal (shown in Figure 17), but top layer, and secondary top layer is significantly different from the crystal in inside.As shown in Figure 16, secondary top layer is mainly by Na
0.622ca
0.368al
1.29si
2.71o
8(01-083-1938), Na
4ca
4(Si
6o
18) (01-079-1085) and CaSi
2o
5(00-015-0130) three kinds of crystal compositions, and inside is by (Ca
0.78na
0.22) (Al
1.78si
0.22) Si
2o
8(01-089-1480), Na
1.74mg
0.79al
0.15si
1.06o
4(00-047-1498) and Ca
2(Mg
0.25al
0.75) (Si
1.25al
0.75o
7) (01-079-2422) three kinds of crystal compositions, crystalline structure is seriously uneven, causes top layer to decline with inner combination.
The color in devitrified glass fracture cross section has significant difference, and the degree of crystallization of canescence part is higher, and the degree of crystallization of grey black part is poor.
In a word, the present invention utilizes deformation to regulate and control Na
2o-CaO-SiO
2-MgO-Al
2o
3(NCSMA) weave construction of Blast-furnace Slag Glass-ceramics, by loading the deformation of different distortion amount to the parent glass being heated to nucleation temperature and crystallization temperature, crystalline phase kind, grain-size, grain form in regulation and control devitrified glass, obtain uniform texture, crystalline phase composition and the different devitrified glass that distributes.The application of method in devitrified glass crystallization field of deformation organization of regulation control structure, provides effective way for most devitrified glass system realizes overall rapid crystallization smoothly, for important basis has been established in the high-valued comprehensive utilization of large argument solid waste.
It should be noted that, according to the various embodiments described above of the present invention, those skilled in the art are the four corners that can realize independent claim of the present invention and appurtenance completely, implementation procedure and the same the various embodiments described above of method; And non-elaborated part of the present invention belongs to techniques well known.
The above; be only part embodiment of the present invention, but protection scope of the present invention is not limited thereto, any those skilled in the art are in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.
Claims (8)
1. the Crystallization method utilizing deformation to regulate and control devitrified glass, it is characterized in that: parent glass plate enters 700-725 DEG C of coring warm area, sheet glass is made to produce distortion through 1# deformation rolling press, the thickness of parent glass plate reduces 0 < △ L≤40% (△ L represents deformation quantity), obtains the parent glass plate that thickness is 20.0-12.0mm; At 700-725 DEG C of insulation 3h, and then be warming up to the heat treating regime of 840-860 DEG C of insulation 2h, crystallization has the parent glass plate of different distortion amount, then obtains devitrified glass through 600 DEG C/3h annealing.
2. the Crystallization method utilizing deformation to regulate and control devitrified glass, it is characterized in that, parent glass plate enters 700-725 DEG C of coring warm area, after 700-725 DEG C of insulation 3h coring thermal treatment, obtain coring parent glass, then 840-860 DEG C of crystallization warm area is entered, sheet glass is made to produce distortion through 2# deformation rolling press, the thickness of coring parent glass plate reduces 0 < △ L≤40% (△ L represents deformation quantity), obtains the coring sheet glass that thickness is 20.0-12.0mm; Then in the crystallization and thermal treatment system of 840-860 DEG C of insulation 2h, crystallization has the coring parent glass plate of different distortion amount, then obtains devitrified glass through 600 DEG C/3h annealing.
3. the Crystallization method utilizing deformation to regulate and control devitrified glass, it is characterized in that, parent glass plate enters 700-725 DEG C of coring warm area, sheet glass is made to produce distortion through 1# deformation rolling press, the thickness of parent glass plate reduces 0 < △ L≤40% (△ L represents deformation quantity), and obtaining thickness is that 12mm is to the coring sheet glass being less than 20mm; There is in 700-725 DEG C of insulation 3h coring the parent glass of different distortion amount, obtain coring parent glass plate; Enter 840-860 DEG C of crystallization warm area, sheet glass is made to produce distortion through 2# deformation rolling press, the thickness of coring parent glass plate reduces 0 < △ L≤40%, there is 840-860 DEG C of insulation 2h crystallization the coring parent glass plate of different distortion amount, then obtain devitrified glass in 600 DEG C of insulation 3h annealing.
4. according to the arbitrary described a kind of Crystallization method utilizing deformation to regulate and control devitrified glass of claim 1-3, it is characterized in that: described deformation promotes that devitrified glass grain-size reduces, along with the increase of glass deformation amount, the difference of the average aspect ratio of devitrified glass top layer and internal grain first reduces rear increase, and the deflection increasing glass contributes to the formation suppressing the thick crystal in top layer.
5., according to the arbitrary described a kind of Crystallization method utilizing deformation to regulate and control devitrified glass of claim 1-3, it is characterized in that: described deformation can adjust the crystalline phase kind of devitrified glass, deformation promotes that in devitrified glass, crystalline phase kind increases.
6., according to the arbitrary described a kind of Crystallization method utilizing deformation to regulate and control devitrified glass of claim 1-3, it is characterized in that: described deformation can promote to eliminate or reduce the column crystal layer on top layer, the weave construction of homogenizing devitrified glass.
7., according to the arbitrary described a kind of Crystallization method utilizing deformation to regulate and control devitrified glass of claim 1-3, it is characterized in that: described deformation can adjust the crystal pattern of devitrified glass, is transformed into three dimensional growth by two-dimensional growth.
8., according to the arbitrary described a kind of Crystallization method utilizing deformation to regulate and control devitrified glass of claim 1-3, it is characterized in that: described deformation improves the crystallization velocity of devitrified glass, significantly shorten the crystallization time of devitrified glass.
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| CN101209892A (en) * | 2007-12-25 | 2008-07-02 | 山东建筑大学材料科学研究所 | Method for preparing special-shaped workable glass ceramic |
| CN102531339A (en) * | 2010-11-08 | 2012-07-04 | 湖州大享玻璃制品有限公司 | Method and apparatus of continuously forming crystallized glass |
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| CN101209892A (en) * | 2007-12-25 | 2008-07-02 | 山东建筑大学材料科学研究所 | Method for preparing special-shaped workable glass ceramic |
| CN102531339A (en) * | 2010-11-08 | 2012-07-04 | 湖州大享玻璃制品有限公司 | Method and apparatus of continuously forming crystallized glass |
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