Background technology
The type material that devitrified glass is comprised of glassy phase and crystallization phases.Its physicochemical property are by the relative content of these two kinds of phases and performance is common determines.The Application Areas of devitrified glass is extensive.As building and ornament materials, many-sided performances such as its mechanical property, chemical stability, the feature of environmental protection, aberration consistence are all better than stone material, thereby are described as " finishing material of 21 century ".
The production method of devitrified glass mainly comprises two kinds of sintering process and rolling processes.The present invention innovates and forms on the basis producing at fluorcanasite calendering microcrystal glass plate.The chemical formula of fluorcanasite is Na
4-3k
2-3ca
5(Si
12o
30) F
4, the calendering microcrystal glass plate that it is principal crystalline phase of take is the high-grade glass material of a kind of high tenacity, high whiteness.But, mainly there is the deficiency of following three aspects: in this calendering microcrystal glass plate: (i) this calendering microcrystal glass plate gas hole defect is still on the high side, affected the stability of quality product; (ii) this calendering microcrystal glass plate, in life-time service process, is subject to the impact of atmospheric water, and easily water suction enters the larger lattice voids in its inside, causes crystal volumetric expansion, causes cracking.Its acid resistance is not strong simultaneously, easily by sour stripping SiO
2; (iii) composition of this calendering microcrystal glass plate must contain a certain amount of potassium oxide (K
2o), even the fluorcanasite (Na of minimum potassium oxide content
4k
2ca
5<Si
12o
30>F
4) K
2o content is also more than 7.5%.Introduce K
2the price of the salt of wormwood of O (normally 8400 yuan/ton of left and right), than introducing Na
2the price of the soda ash of O (conventionally 1500 yuan/ton of left and right) height.As building and ornament materials, high expensive is the unfavorable factor of its market competitiveness.In view of above 3 points, it is principal crystalline phase (NaCa that the present invention attempts researching and developing the fluorine silico-calcium sodium stone of take containing sodium oxide suboxide potassium content (even non-oxidation potassium), pure
2<Si
2o
5>
2f) calendering microcrystal glass plate.
For the gas hole defect that overcomes old product, gas is mainly subject to the impact of the viscosity of glass melt from the discharge of glass melt, and Na
2o falls low viscous effect and is much better than K
2o.Undoubtedly, significantly reduce K
2the content of O, increases the viscosity that sodium oxide content can reduce glass melt, and the gas that is conducive to the fusion stage is discharged, and is conducive to the clarification of liquation.
For fluorcanasite (Na
4-3k
2-3ca
5<Si
12o
30>F
4) the calendering microcrystal glass plate of principal crystalline phase, its crystalline structure is loose, spacious, and proportion is less, is 2.7 grams/cc, and this structure makes it to be easy to water suction, and the volume of crystal is expanded, and causes cracking.Meanwhile, its acid resistance is not strong, easily by sour stripping SiO
2, after long-term weathering, easily tarnish.And for fluorine silico-calcium sodium stone (NaCa
2<Si
2o
5>
2f) the calendering microcrystal glass plate of principal crystalline phase, its crystalline structure is dense, and proportion is 2.9 grams/cc.This structure is not easy planar water, does not also just have crystal volume to expand the possibility that causes cracking.And its acid resistance is better, life-time service can keep light.From economy aspect, the composition of fluorine silico-calcium sodium stone obtains owing to need not adding the salt of wormwood that comparatively price is high again.
The Chinese patent that on February 19th, 2014 announces: the floride-free calendering of a kind of white devitrified glass that CN 103588394A " a kind of white floride-free calendering devitrified glass and production method thereof " produces, the SiO that it comprises
2content is 35%~46.5%, Al
2o
3content is that 24%~35%, MgO content is 7%~13%, Na
2o+K
2o content is 4%~10%; A kind of calendering microcrystal glass plate that the present invention produces, the SiO that it comprises
2content is 47~65%, Al
2o
3content is that 0~5%, MgO content is 0~2%, K
2o content is 0~3%, Na
2o content is 5~20%.This shows, chemical composition feature of the present invention is different from the Chinese patent of announcing on February 19th, 2014.
More than find out, the superiority of the calendering microcrystal glass plate that fluorine silico-calcium sodium stone is principal crystalline phase is many-sided.
Summary of the invention
The object of the invention is to, a kind of calendering microcrystal glass plate and production method thereof are provided, described microcrystal glass plate is fluorine silico-calcium sodium stone crystalline phase, and its surface porosity reduces, and does not ftracture, and acid resistance is good, and cost is lower.
The solution of the present invention is: the microcrystal glass plate that the fluorine silico-calcium sodium stone of take is main crystalline phase, and by weight percentage, it comprises following component and content:
SiO
2:47~65%;
Al
2O
3:0~5%;
CaO:11~26%;
MgO:0~2%;
K
2O:0~3%;
Na
2O:5~20%;
F:3~8%;
Finings: 0.5~1%.
Preferably, described take in the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, Al
2o
3content be 3%.
Preferably, described take in the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, the content of CaO is 15%.
Preferably, described take in the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, K
2the content of O is 0.6%.
Preferably, described take in the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, Na
2the content of O is 9%.
Preferably, described take in the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, SiO
2content be 60.3%.
Preferably, described take in the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, described finings is arsenic oxide arsenoxide and SODIUMNITRATE.
Preferably, described take in the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, the principal crystalline phase of described microcrystal glass plate is fluorine silico-calcium sodium stone crystalline phase.
Produce described method of take the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, comprise the following steps:
Step 1, according to said components, weigh, prepare burden, mix, obtain admixtion;
Step 2, described admixtion is added to melting furnaces, by the first temperature-control device, controlling glass melting temperature is 1400~1500 ℃, the uniform glass liquation generating is via dog-hole, uptake, material road, enter rolling press, by the second temperature-control device being arranged on rolling press, control the temperature that passes in and out rolling press, the temperature of entering described rolling press is 1050~1150 ℃, and the temperature of extruder-calender is 850~950 ℃, the sheet glass that formation thickness is 3~35mm;
Step 3, described sheet glass is entered into thermal treatment roller-way kiln through transition roller table, at 600~700 ℃ of nucleation temperatures, coring 60~150min; At 700~800 ℃ of strong nucleation temperatures, strong coring 45~90min; At 800~900 ℃ of crystallization temperatures, crystallization 30~60min;
Step 4, the microcrystal glass plate obtaining is annealed, then cut, rough polishing, essence throw, and obtains the qualified microcrystal glass plate building and ornament materials that fluorine silico-calcium sodium stone is main crystalline phase of take.
Preferably, in described production method of take the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, in described step 2, glass melting temperature is 1470 ℃.
Preferably, in described production method of take the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, in described step 3, nucleation temperature is 680 ℃, and nucleation time is 100min.
Preferably, in described production method of take the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, in described step 3, strong nucleation temperature is 760 ℃, and strong nucleation time is 73min.
Preferably, in described production method of take the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, in described step 3, crystallization temperature is 845 ℃, and crystallization time is 56min.
The invention has the advantages that:
1, the principal crystalline phase of described microcrystal glass plate is fluorine silico-calcium sodium stone crystalline phase;
2, the fracture toughness property of described microcrystal glass plate is 2.1Mpa.m
1/2, belong to higher toughness material, be conducive to the reprocessing such as cutting;
3, described microcrystal glass plate surface porosity reduces, and does not ftracture, and acid resistance is good;
4, described devitrified glass plate producing process cost is lower, and the market competitiveness is strong.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail, to make those skilled in the art can implement according to this with reference to specification sheets word.
The microcrystal glass plate that the fluorine silico-calcium sodium stone of take is main crystalline phase, by weight percentage, it comprises following component and content:
SiO
2:47~65%;
Al
2O
3:0~5%;
CaO:11~26%;
MgO:0~2%;
K
2O:0~3%;
Na
2O:5~20%;
F:3~8%;
Finings: 0.5~1%.
Described take in the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, Al
2o
3content be 3%.
Described take in the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, the content of CaO is 15%.
Described take in the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, K
2the content of O is 0.6%.
Described take in the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, Na
2the content of O is 9%.
Described take in the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, SiO
2content be 60.3%.
Described take in the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, described finings is arsenic oxide arsenoxide and SODIUMNITRATE.
Described take in the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, the principal crystalline phase of described microcrystal glass plate is fluorine silico-calcium sodium stone crystalline phase.
Produce described method of take the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, comprise the following steps:
Step 1, according to said components, weigh, prepare burden, mix, obtain admixtion;
Step 2, described admixtion is added to melting furnaces, by the first temperature-control device, controlling glass melting temperature is 1400~1500 ℃, the uniform glass liquation generating is via dog-hole, uptake, material road, enter rolling press, by the second temperature-control device being arranged on rolling press, control the temperature that passes in and out rolling press, the temperature of entering described rolling press is 1050~1150 ℃, and the temperature of extruder-calender is 850~950 ℃, the sheet glass that formation thickness is 3~35mm;
Step 3, described sheet glass is entered into thermal treatment roller-way kiln through transition roller table, at 600~700 ℃ of nucleation temperatures, coring 60~150min; At 700~800 ℃ of strong nucleation temperatures, strong coring 45~90min; At 800~900 ℃ of crystallization temperatures, crystallization 30~60min;
Step 4, the microcrystal glass plate obtaining is annealed, then cut, rough polishing, essence throw, and obtains the qualified microcrystal glass plate building and ornament materials that fluorine silico-calcium sodium stone is main crystalline phase of take.
In described production method of take the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, in described step 2, glass melting temperature is 1470 ℃.
In described production method of take the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, in described step 3, nucleation temperature is 680 ℃, and nucleation time is 100min.
In described production method of take the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, in described step 3, strong nucleation temperature is 760 ℃, and strong nucleation time is 73min.
In described production method of take the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase, in described step 3, crystallization temperature is 845 ℃, and crystallization time is 56min.
The present invention is not because additionally add and mainly contain Al
2o
3, MgO and K
2the raw material of O, so its content is far smaller than Al in Chinese patent CN 103588394 A of announcement
2o
3, MgO and K
2the content of O, thus the calendering microcrystal glass plate of fluorine silico-calcium sodium stone crystalline phase could be formed, fluorcanasite crystalline phase that simultaneously neither original product, this is that this patent obtains the basic of many-sided advantage.
Described fracture toughness property of take the microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase is 2.1Mpa.m
1/2, belonging to higher toughness material, this both can keep certain opposing mechanical external force performance, can be beneficial to the mechanical workouts such as cutting again.And the fracture toughness property of the original product that principal crystalline phase is fluorcanasite is at 4Mpa.m
1/2although its opposing mechanical external force is strong, it is difficult to very much cutting, is unfavorable for deep processing.
And describedly take the microcrystal glass plate surface porosity that fluorine silico-calcium sodium stone is main crystalline phase and reduce, acid resistance is good, and life-time service does not ftracture.And the surface porosity of original product is on the high side, acid resistance does not reach Expectation of Glass-Ceramics Used as Decorated Materials building material industry standard (JC/T 872-2000) sometimes.According to this standard, product soaks 650 hours at 1% sulphuric acid soln, and mass loss rate is less than or equal to 0.2%, and outward appearance is unchanged.For excellent product, not only acid resistance is qualified, and the pore that is greater than 1mm is unallowed.The pore of 0.5mm-1mm does not allow to surpass 2/m
2, the pore that is less than 0.5mm is not subject to quantity limitation, only needs not intensive.
Tracking by nearly 1 year detects, and product acid resistance of the present invention all reaches building material industry standard, and gas hole defect rate is no more than 4%.And original product usually can't pass acid resistance standard detection the whole year, and gas hole defect rate generally all surpasses 4%, and maximum reaches 20% sometimes.
Meanwhile, describedly take microcrystal glass plate that fluorine silico-calcium sodium stone is main crystalline phase owing to not adopting the salt of wormwood of higher price to make raw materials cost lower, is 800 yuan/ton.And the raw materials cost of raw produce is 1400 yuan/ton, declined 43%.
Embodiment 1
By weight percentage, take SiO
260.7%, Al
2o
33.7%, CaO 17.7%, and MgO 0.3%, K
2o 0.8%, Na
2o 11%, and F 5%, and finings arsenic oxide arsenoxide and SODIUMNITRATE resultant are 0.8%, mix, and obtain admixtion; Described admixtion is added to melting furnaces, and glass melting temperature is 1470 ℃, and uniform glass liquation is via dog-hole, uptake, material road, enter rolling press, entering described rolling press temperature is 1100 ℃, and going out described rolling press temperature is 900 ℃, the sheet glass that formation thickness is 20mm; Described sheet glass is entered into thermal treatment roller-way kiln through transition roller table, at 680 ℃ of nucleation temperatures, coring 100min; At 760 ℃ of strong nucleation temperatures, strong coring 73min; At 845 ℃ of crystallization temperatures, crystallization 56min; The microcrystal glass plate obtaining is annealed, cutting, rough polishing, essence throw, obtain the qualified microcrystal glass plate building and ornament materials that fluorine silico-calcium sodium stone is main crystalline phase of take.This product acid resistance reaches national building material industry standard, and gas hole defect rate is 2.8%, and fracture toughness property is 2.11Mpa.m
1/2.
X-ray diffraction curve display as shown in Figure 1, the curve of figure a indication is the X-ray diffraction curve of the microcrystal glass plate that obtains of embodiment 1, figure b is the PDF standard diffraction card of fluorine silico-calcium sodium stone, figure c is the PDF standard diffraction card of Calcium Fluoride (Fluorspan) (also claiming fluorite), as can be seen from Figure 1, PDF standard diffraction card (65-0535) data of the PDF standard diffraction card (41-1441) of the diffraction peak of resulting microcrystal glass plate and fluorine silico-calcium sodium stone and Calcium Fluoride (Fluorspan) (also claiming fluorite) are substantially identical, the crystalline phase that described microcrystal glass plate is described is fluorine silico-calcium sodium stone and fluorite, main crystalline phase is fluorine silico-calcium sodium stone.
Embodiment 2
By weight percentage, take SiO
257.8%, Al
2o
33%, CaO 17.2%, and MgO 1%, K
2o 2%, Na
2o 12.7%, and F 5.5%, and finings arsenic oxide arsenoxide and SODIUMNITRATE 0.8%, mix, and obtains admixtion; Described admixtion is added to melting furnaces, and glass melting temperature is 1460 ℃, and uniform glass liquation is via dog-hole, uptake, material road, enter rolling press, entering described rolling press temperature is 1090 ℃, and going out described rolling press temperature is 890 ℃, the sheet glass that formation thickness is 20mm; Described sheet glass is entered into thermal treatment roller-way kiln through transition roller table, at 650 ℃ of nucleation temperatures, coring 110min; At 750 ℃ of strong nucleation temperatures, strong coring 75min; At 863 ℃ of crystallization temperatures, crystallization 40min; The microcrystal glass plate obtaining is annealed, cutting, rough polishing, essence throw, obtain the qualified microcrystal glass plate building and ornament materials that fluorine silico-calcium sodium stone is main crystalline phase of take.The acid resistance of this product reaches national building material industry standard, and gas hole defect rate is 2.8%, and fracture toughness property is 2.06Mpa.m
1/2.
Embodiment 3
By weight percentage, take SiO
252.5%, Al
2o
33.5%, CaO 20.4%, and MgO 1%, K
2o 1.6%, Na
2o 15.7%, and F 4.5%, and finings arsenic oxide arsenoxide and SODIUMNITRATE 0.8%, mix, and obtains admixtion; Described admixtion is added to electric melting furnace, and glass melting temperature is 1480 ℃, and uniform glass liquation is via dog-hole, uptake, material road, enter rolling press, entering described rolling press temperature is 1110 ℃, and going out described rolling press temperature is 910 ℃, the sheet glass that formation thickness is 20mm; Described sheet glass is entered into thermal treatment roller-way kiln through transition roller table, at 660 ℃ of nucleation temperatures, coring 105min; At 770 ℃ of strong nucleation temperatures, strong coring 70min; At 870 ℃ of crystallization temperatures, crystallization 35min; The microcrystal glass plate obtaining is annealed, cutting, rough polishing, essence throw, obtain the qualified microcrystal glass plate building and ornament materials that fluorine silico-calcium sodium stone is main crystalline phase of take.The acid resistance of this product reaches national building material industry standard, and gas hole defect rate is 3.3%, and fracture toughness property is 2.05Mpa.m
1/2.
Embodiment 4
By weight percentage, take SiO
251.3%, Al
2o
33%, CaO 18.7%, and MgO 1%, K
2o 2%, Na
2o 16.9%, and F 6.5%, and finings arsenic oxide arsenoxide and SODIUMNITRATE 0.6%, mix, and obtains admixtion; Described admixtion is added to melting furnaces, and glass melting temperature is 1490 ℃, and uniform glass liquation is via dog-hole, uptake, material road, enter rolling press, entering described rolling press temperature is 1120 ℃, and going out described rolling press temperature is 920 ℃, the sheet glass that formation thickness is 20mm; Described sheet glass is entered into thermal treatment roller-way kiln through transition roller table, at 670 ℃ of nucleation temperatures, coring 103min; At 780 ℃ of strong nucleation temperatures, strong coring 67min; At 880 ℃ of crystallization temperatures, crystallization 33min; The microcrystal glass plate obtaining is annealed, cutting, rough polishing, essence throw, obtain the qualified microcrystal glass plate building and ornament materials that fluorine silico-calcium sodium stone is main crystalline phase of take.The acid resistance of this product reaches national building material industry standard, and gas hole defect rate is 3.4%, and fracture toughness property is 2.05Mpa.m
1/2.
Embodiment 5
By weight percentage, take SiO
249.5%, Al
2o
34.2%, CaO 20%, and MgO 0.5%, K
2o 1.5%, Na
2o 18.4%, and F 5.2%, and finings arsenic oxide arsenoxide and SODIUMNITRATE 0.7%, mix, and obtains admixtion; Described admixtion is added to electric melting furnace, and glass melting temperature is 1500 ℃, and uniform glass liquation is via dog-hole, uptake, material road, enter rolling press, entering described rolling press temperature is 1130 ℃, and going out described rolling press temperature is 930 ℃, the sheet glass that formation thickness is 20mm; Described sheet glass is entered into thermal treatment roller-way kiln through transition roller table, at 690 ℃ of nucleation temperatures, coring 95min; At 780 ℃ of strong nucleation temperatures, strong coring 58min; At 890 ℃ of crystallization temperatures, crystallization 30min; The microcrystal glass plate obtaining is annealed, cutting, rough polishing, essence throw, obtain the qualified microcrystal glass plate building and ornament materials that fluorine silico-calcium sodium stone is main crystalline phase of take.The acid resistance of this product reaches national building material industry standard, and gas hole defect rate is 3.6%, and fracture toughness property is 2.02Mpa.m
1/2.
Although embodiment of the present invention are open as above, but it is not restricted to listed utilization in specification sheets and embodiment, for those skilled in the art, can easily realize other modification, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details and illustrates here and the embodiment describing.