CN102875026A - Black building decorative glass ceramics and preparation method thereof - Google Patents
Black building decorative glass ceramics and preparation method thereof Download PDFInfo
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- CN102875026A CN102875026A CN201210439133XA CN201210439133A CN102875026A CN 102875026 A CN102875026 A CN 102875026A CN 201210439133X A CN201210439133X A CN 201210439133XA CN 201210439133 A CN201210439133 A CN 201210439133A CN 102875026 A CN102875026 A CN 102875026A
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Abstract
The invention provides a black building decorative glass ceramics which comprises the following components by weight: 70 to 90 percent of aegirine-augite slag, 5 to 20 percent of inferior quartz, and 5 to 10 percent of inferior limestone. The black building decorative glass ceramics provided by the invention is pure in color development, and has outstanding performances. The invention also provides a preparation method of the black building decorative glass ceramics. With the adoption of the preparation method provided by the invention, the producing cost is reduced, and the environmental pollution is decreased.
Description
Technical field:
The invention belongs to building material technical field, what relate to is a kind of architectural decorative glass and preparation method thereof, particularly be the preparation method of a kind of black building decoration devitrified glass and this devitrified glass.
Background technology:
Devitrified glass claims again glass-ceramic, is the parent glass with specific composition, in heat-processed by controlling crystallizing, and make a kind ofly contain the polycrystalline solids material that a large amount of crystallites reach glassy phase mutually.It is generally acknowledged that crystalline content is conducive to improve physical strength, hardness and wear resistance, the chemical stability of glass more.Devitrified glass both had been different from pottery, also was different from glass, with ceramic difference be that crystalline phase in crystallization process is from single uniform glass phase or has produced the zone that is separated, the dense material that produces by nucleation and crystal growth; Be that with the glass difference devitrified glass is the composite diphase material that microcrystal and residual glass form, the fundamental property of its existing glass, the polycrystalline feature that has again pottery, the characteristics of glass and pottery have been concentrated, combining glass melting, ceramic tile shaping, crystallization and thermal treatment technique and stone polishing, cutting technique in one, is the type material of a class uniqueness.Devitrified glass has formed a kind of material of special class at present, and it is various in style, and performance is different, has very widely purposes.Crystallizing glass sheet material is a kind of in the numerous kinds of devitrified glass, it is a kind of novel high-grade building and ornament materials, have the intensity height, resistance to wear, corrosion-resistant, weather resistance, do not absorb water, do not fade, physicochemical property and the uniform hue such as cleaning convenience, no radioactivity pollute, gloss is soft sparkling and crystal-clear, gorgeous elegance, clean mark, surface compact have no time to wait excellent appearance characteristics.As " high-end " product in the building and ornament materials, the crystallizing glass sheet material various aspects of performance all is better than lithotome, so be widely used in now in the high-grade fitting-out works such as building inside and outside wall, ground and corridor post.
The earliest to the research of devitrified glass, from utilizing industrial waste, slag and slag etc.U.S. CORNING glasswork at first developed devitrified glass in 1957, and the development of devitrified glass is had historical contribution.Nineteen sixty, USSR (Union of Soviet Socialist Republics) Kitaigocodski succeeded in developing cinder microcrystalline glass, and the 1st roll-in method glass line in 1966 builds up and go into operation.In 20 century 70 mid-terms, Nippon Electric Glass Co., Ltd has successfully developed the devitrified glass of different varieties and specification with sintering process.China has also added the research ranks of devitrified glass since the eighties in 20th century, has stepped into the industrial test stage beginning of the nineties, although, the research and development of sintered glass-ceramics dalle are started late, obtained in the short period of time very much progress.
The technology of preparing of devitrified glass changes according to the requirement that its raw materials used kind, characteristic reach product performance, mainly contains scorification, sintering process, melten gel-gel method, rolling process, secondary forming process, toughening technology etc.For the mine tailing waste residue microcrystal glass, the technology of preparing that present industrial production is mature on the whole is mainly scorification, sintering process, and is domestic take sintering process as main.
Scorification is the traditional method of preparation devitrified glass.This method is at high temperature founded admixtion and is first straight forming, annealing behind the glass, then carries out at a certain temperature coring and crystallization, to obtain the crystallized glass article that crystal grain is tiny and even structure is fine and close.Determining of heat treating regime is the key problem in technology of this method.Thermal treatment generally minute two processes is carried out, with the glass heats of annealing to the nucleus formation temperature
T Nuclear, and the insulation certain hour, make it form a large amount of nucleus, then be warming up to crystal growth temperature with certain temperature rise rate
T Brilliant, and insulation certain hour forms the tiny and even structure of crystal grain, fine and close devitrified glass.The advantage of scorification is: 1. can adopt any glass forming method, such as calendering, compacting, blowing, drawing etc., be convenient to goods and the mechanization production of production traits complexity; 2. goods pore-free, density is high; 3. the glass compositing range is wide.The problem that scorification exists mainly contains: 1. glass melting temperature is too high, and usually at 1400-1600 ℃, energy consumption is large; 2. heat treating regime is difficult to control in actual production; 3. crystallization temperature is high, and the time is long.
Produce devitrified glass with sintering process and at first proposed the sixties in 20th century by H a surname Bonn, and realize industrialization in 20 century 70s in Japan.Sintering process is that fusion cast glass pellet and crystallization are made two bites at a cherry, it is cold with shrend after high temperature melting is glass to be about to admixtion, it is pulverized be fine particle, adopt and the similar method of ceramic post sintering again after the moulding, allow glass powder densification and nucleation crystallization under the semi-melting state.1. the advantage of sintering process for need not passing through the forming of glass stage, the preparation that therefore is suitable for the glass that very high temperature founds and is difficult to form the devitrified glass of glass; 2. owing to the bonding of crystallization and pieces of glass is carried out simultaneously, therefore be difficult for bursting, the finished product rate is high, and crystallization time is short, energy-conservation, product thickness is adjustable, can produce easily special-shaped sheet material and various curved slab with similar lithotome decorative pattern, and its color variety is abundant, decorative effect is desirable, be more suitable for suitability for industrialized production, thickness is generally 18-22mm, is suitable for interior exterior wall and ground decoration and uses; 3. because glass powder particles is tiny, surface-area increases, thereby is easier to crystallization than the glass that scorification makes, and can not add or add less Nucleating Agent.The sintering process at present problem of maximum is upper layer densification depths shallow (about 2mm), and internal porosity is difficult to get rid of, and sheet material is out of shape (especially large specification) easily.Although domestic and international many scholars have carried out large quantity research to the problems referred to above, be not solved yet so far.
At present, the development general trend of crystallizing glass sheet material is technique simplification, functional diversities, with low costization.The problem that mainly faces in products production and research is: 1) by the devitrified glass composition Study, reduce the devitrified glass firing temperature; 2) weight of reduction unit surface product in the hope of reducing cost, makes the devitrified glass slimming.And the firing process relevant with its slimming, annealing schedule should have corresponding research and adjustment.
Utilize industrial residue and mine tailing to produce devitrified glass, can solve well wasting of resources problem and environmental problem that industrial residue and tailings impoundment bring.Along with fundamental research deeply and preparation technology's improvement; develop that cost is low, less energy consumption, excellent property; the mine tailing waste residue microcrystal glass of the diverse in function development trend that will be inevitable; utilize industrial tailings (ore deposit) preparation decorative devitrified glass material; can greatly reduce production costs, simultaneously the protection of environment and the target of the realization building materials industry strategy of sustainable development be had important meaning and effect.Along with country to increasing energy-conservation, the implementation dynamics that reduces discharging, utilize the research and development dynamics also increasing to solid waste such as the metallurgical slag such as scum, copper ashes, slag, titanium slag, chromium slag and tantalum niobium concentrate slag, phosphorus slag, complex ore slag, compound mine tailing, flyash, volcanic ash, coal gangues.Contain the compositions such as a large amount of silicon oxide, aluminum oxide, calcium oxide, magnesium oxide in various slags and flyash, volcanic ash, coal gangue, these compositions all are very useful in the building decoration devitrified glass.How to utilize above industrial slag, produce the higher finishing material of added value, have many technical problems to need research, also obtained certain new results.
Xiao Hanning etc. processing condition are on the microstructural impact of waste steel slag glass-ceramic [J]. Hunan University's journal, 2001,28 (1): 135-139. by the design to the material the Nomenclature Composition and Structure of Complexes, having obtained blast furnace slag and slag consumption is 55%-60%, take pyroxene as principal crystalline phase, the devitrified glass of excellent property.
Berry Na. the research of chromium slag microcrystallite glass crystallization behavior [J]. metallic substance and metallurgical engineering, 2008,36 (2): 19-21. take the chromium slag as raw material, adopt scorification to prepare devitrified glass, and studied the impact of chromium slag content on the ceramics behavior, for the comprehensive utilization of chromium slag provides reference.
Xiao Xingcheng etc. the research of Crystallization Process of Titanate-Slag Glass Ceramics [J]. glass and enamel, 1999,27 (2): 7-11. P to add
2O
5TiO with titanium slag itself
2Form Composite Nucleation Agents, developed (the SiO with CaMg
3)
2For principal crystalline phase, the titanium slag devitrified glass of better mechanical property and chemical stability is arranged.
It is new etc. that Cao builds. and utilize yellow phosphorus furnace slag to make the experimental study [J] of devitrified glass. Guizhou University of Technology's journal: natural science edition, carried out take yellow phosphorus furnace slag as main raw material at 2003,32 (1): 33-36., prepares the experimental study of devitrified glass with sintering process.
Wang Zhiqiang etc. the research of Acid Leaching Residue of Ascharite Glass-Ceramics [J]. glass and enamel, with 60% Acid leaching residue of ascharite developed the devitrified glass that be suitable for building and ornament materials aspect at 1999,27 (3): 9-13..
Liu's Xuan etc. produce devitrified glass research [J] with gold mine tailings. nonmetalliferous ore, 2007,30 (1): 35-36. take golden mine tailing as basic raw material, adopt sintering process to prepare devitrified glass, technique is simple and easy to control, and the mine tailing peak use rate can reach 70%, and the devitrified glass of producing is functional.
Yang Huizhi etc. bauxite gangue devitrified glass development [J]. the mining industry research and development, 2007,27 (6): 48-49. utilize bauxite, and through 1000 ℃ of sintering, having obtained principal crystalline phase is that wollastonite, crystal grain are needle-like, well behaved devitrified glass.
Kuang Jingzhong etc. the composition of tungsten tailing microcrystal glass and preparation [J]. the mineral products comprehensive utilization, 2003 (3): 37-40. take the tungsten mine tailing as main raw material, and adopting cast molding crystallization method to prepare principal crystalline phase is the tailing microcrystal glass of β-wollastonite.
Chinese patent 03128180.x discloses a kind of with standby cordierite glass-ceramic and the manufacture method thereof of coal ash for manufacturing, the main raw material of making devitrified glass is flyash, also must add alumina powder or magnesiumcarbonate or magnesium basic carbonate in addition, perhaps magnesite or brucite or magnesium oxide powder and methyl cellulose binder and water.Chinese patent 03111105.x discloses a kind of compound fly ash building manufacture method of glass-ceramic, take flyash as main raw material, adds in addition nucleator, toughner, tinted shade powder, mineral dye or light-storing and emitting material and makes devitrified glass.Chinese patent 200710010103.3 discloses take iron tailings, flyash and boron mud as prepared using scorification technique and has prepared microhardness 8-10Hv (0.98N), folding strength 160-194MPa, and apparent bulk density is 2.9-3.4g.cm
-3, acid resistance 97-99%, alkali resistance 99-100%, the devitrified glass of excellent performance.
Wang Qin. utilize thermal plasma melting incineration of refuse flyash to prepare the experimental study [D] of devitrified glass. 2009.7:170-180. adopts double anode direct current thermal plasma fusion technology melting flying dust rubbish, flying ash, utilize flying dust gained slag to be equipped with the research that other additives have carried out the preparation building microcrystalline glass, the brilliant particle size distribution in the devitrified glass is in the scope of 0.05-0.4 μ m.The devitrified glass color that makes is abundant, and ink black, black gray expandable, khaki color, storage stone, maroon and cyan etc. are arranged.After the micritization processing, the mechanical property of the devitrified glass that makes and soda acid erosion resistance all are better than its parent glass, can compare favourably with senior lithotomes such as grouan and marbles.
Zhao Boyan. experimental study [D] .2010.6:10-12. that the microwave method melting prepares the sludge ash devitrified glass uses the microwave-heating sludge ash to be main raw material, carried out the experimental study of high volume sludge ash devitrified glass technology, successfully made take the devitrified glass of lime feldspar as the densification of principal crystalline phase even structure.The devitrified glass that microwave method makes has the more crystal of even compact, and physicochemical property is better.
Chinese patent 96115271.0 " utilizes nepheline to prepare the Processes and apparatus of devitrified glass ", Chinese patent 200710011239.9 " utilizes the Processes and apparatus of nepheline glass ceramic Treating Municipal Sewage mud " and the disclosed content of Chinese patent 200910012207.x " a kind of nepheline glass ceramic and metal powder composite material and preparation method thereof " is take nepheline or nepheline syenite as major ingredient, adopts sintering process to prepare the matrix material of devitrified glass or devitrified glass and metal.
At present, utilize ore dressing slag, trade waste, the single tone building decoration devitrified glass of low-cost preparation becomes the main research tendency of devitrified glass, for realizing this goal, different ore dressing slag, trade waste in microcrystalline glass formula, have been introduced, reduce to a certain extent production cost, improved the over-all properties of devitrified glass.Up to now, do not find to utilize the aegirine augite slag to make raw material, adopt scorification to produce the report of black building decoration crystallized glass article.Building decoration devitrified glass main chemical compositions is SiO
2, CaO, Al
2O
3, MgO, TiO
2, Na
2O etc.The aegirine augite slag has SiO approximately
245%, Al
2O
316%, R
2O11%, Fe
2O
323%, its main component and building microcrystalline glass composition are very approaching, can directly replace frit to produce devitrified glass, and this not only can save the frit of high-quality, and can reduce discharging, saves the soil.
Summary of the invention:
The objective of the invention is in order to overcome above-mentioned deficiency, provide that a kind of low cost, color development are pure, the black building decoration devitrified glass of excellent performance.
Another object of the present invention is to reduce production costs in order to provide a kind of, the preparation method of environmental contamination reduction, the black building decoration devitrified glass of preserving the ecological environment.
The purpose of the present invention's invention is achieved like this:
Black building decoration devitrified glass of the present invention comprises following component by weight:
Aegirine augite slag 70-90,
Quartz 5-20 inferior,
Poor line stone 5-10,
Above-mentioned aegirine augite slag is by weight by SiO
240-50, Al
2O
315-20, CaO0.2-1, MgO0.1-0.5, Fe
2O
320-25, TiO
20.5-1.5, K
2O 2-4, Na
2O 7-9, Co
2O
30.3-1.5, MnO
20.5-1.5 form, wherein Fe
2O
3, TiO
2, Co
2O
3, MnO
2Nonferrous metal oxides weight part sum is 21.3-29.5; Quartz inferior is by weight by SiO
278-86, Al
2O
312-18, Fe
2O
31-2, TiO
20.5-1.5, K
2O 0-0.5, Na
2O 0-0.5 forms; Poor line stone is by weight by SiO
210-15, Al
2O
32-5, CaO65-76, MgO3-6, Fe
2O
33-5, K
2O 2-3, Na
2O 0.2-1 forms.
The preparation method of black building decoration devitrified glass of the present invention may further comprise the steps:
(1) raw material crushing: respectively aegirine augite slag, quartz inferior, poor line stone are crushed to the particulate that granularity is 0.154mm, it is stand-by to cross 100 mesh sieves;
(2) batching: get respectively the aegirine augite slag after sieving, quartzy, poor line stone, by weight aegirine augite slag inferior: inferior quartzy: poor line stone=(70-90): (5-20): the proportion ingredient of (5-10);
(3) batch mixing: the batching that will prepare adds ball mill for dry grinding, and dry grinding is to utilize the alumina balls masonry to be grinding medium, and the weight ratio of control abrading-ball, batching is (2-2.5): l, and milling time is 1-4h, forms compound, and compound is crossed 200 mesh sieves;
(4) found: compound is added in the High Temperature Furnaces Heating Apparatus found, 1250-1300 ℃ of charge temperatures, temperature of fusion is 1400-1600 ℃, soaking time is 60-240min;
(5) moulding: pour the glass metal after the melting into die for molding;
(6) coring and crystallization: the glass after the moulding is placed in the High Temperature Furnaces Heating Apparatus, at 700-800 ℃ of coring 20-120min, then the temperature rise rate with 5-30 ℃/min is warmed up to 850-1120 ℃, constant temperature crystallization 30-240min, at 500-700 ℃ of lower annealing 30-240min, sample is made black building decoration devitrified glass through cutting edge, polish, polishing at last.
Nepheline (Nepheline) is a kind of emerging (Na, K) (AlSiO
4) the lagoriolite non-metallic minerals, because in acid, decomposing the silica gel that generates the rosy clouds shape, therefore named nepheline.There is distribution more than 30 countries and regions in the world.China is from explored mineral deposit, and reserves are abundant, and are widely distributed.In areas such as Huili, Sichuan, Nan Jiang, Jinzhai County, Anhui, Area, Gejiu District, Yunnan Province, Suizhou, hubei, Linxian County, Shanxi Province, Jilin Yongsheng, Zhou Kou Dian, Hebei, Earthquake of Anyang station in Henan, Wan Xi the nepheline syenite ore deposit is arranged.Occurring in nature nepheline and aegirine augite coexist as in the alkali syenit, and the two becomes symbiotic relationship, and general nepheline content is nepheline syenite at the rock more than 15%.But most of mineral deposit iron-holder is more than 5%, will inevitably not affect use in Ceramic production if do not do special processing.The gordian technique of nepheline mineral products production is the reasonable classification of work in-process and high intensity magnetic separation deironing, and purpose is that iron-holder in the raw ore 〉=2% is dropped in iron-holder≤0.2%, and granularity could adapt to the large industrial standards such as glass, pottery at 200 orders-30 order.
After the fragmentation of nepheline raw ore process and the rod milling, pass through again size classification, granularity〉0.1mm through vacuum filtration, multi-stage magnetic separation, select respectively one-level, secondary, three grades, level Four nepheline fine powder, the magnetic separation of carrying out again aegirine augite with separate, the mine tailing waste residue that stays at last is the aegirine augite slag, contains abundant Fe in the aegirine augite slag
2O
3, TiO
2, Co
2O
3, MnO
2Be 20-30 Deng nonferrous metal oxides sum (parts by weight), the aegirine augite slag is the inferior raw material of a standard.The concept of " poor quality " refers to that main ingredient content is low in the composition of raw material, and the foreign matter contents such as iron, titanium are high, do not meet national standard, can't use in transparent glass or light pottery.Aegirine augite is for containing ferrosilicate (Na, Ca) (Fe
+ 3, Fe
+ 2, Mg, Al) and [Si
2O
6], aegirine augite is needle-like and is embedded among nepheline mineral, the potash feldspar thing in secondary rainbow rosy clouds syenite ore deposit.Aegirine augite content is 5-10% in the nepheline raw ore.
According to ligand field theory, material is painted mainly to be because electronics is caused at different transition between the energy levels and ion pair Optical Absorption and scattering.The transition metals such as cobalt, chromium, iron, nickel, copper, manganese, their ion outermost orbit is the d track, is non-spherically symmetrical orbitals.When these ions are in the difform ligand field, the coordination negative ion produces splitting of energy levels to the energy change of each track, and four d tracks that so original energy level is identical become different energy levels under the coordination ion effect, namely produce ligand-field effect, formed the spinel type rock steady structure.Electronics transition between the d of different energy levels track absorbs the light of certain wavelength, and its transition energy is between 1ev-4ev, and just corresponding optical range is visible region.
Ni
2+, Fe
3+, Cr
3+, Co
3+Deng containing unpaired electronics on the transition metal ion outermost layer, their ground state and excited energy are more approaching, generation absorbs the strong selectivity of visible light, its spectral absorption can suppress the light transmission rate of its ion mutually, when their ionic concn cooperate to be adjusted when suitable, can complementary visible light after their curve of spectrum stack all absorb and present black.When multiple spinel crystal mixing effect that chromium, cobalt, iron, nickel, copper, manganese form, the mixing principle of losing lustre according to color, in the situation that the crystal ratio is fit to, the various ion out-shell electron transition that is in different valence state and ligand field environment all absorbs 7 kinds of monochromatic ray in the visible light basically, makes sample present black.
The present invention prepares black building decoration devitrified glass with the aegirine augite slag as major ingredient.The slag mineral composition is take aegirine augite, albite, potash feldspar, perthite, magnetite, rhombohedral iron ore, fluorite, phosphatic rock, aspidelite, biotite, white mica etc. as main.The aegirine augite slag embodies at composition: poor silicon, rich aluminium, iron, titanium, manganese, potassium, sodium, and Fe
2O
3, TiO
2, Co
2O
3, MnO
2Be 20-30 Deng nonferrous metal oxides sum (parts by weight), showing in nature the feature of lower, the natural one-tenth porcelain of fusing point.Under the high temperature, aegirine augite slag both alternative feldspar plays the flux effect, effectively reduces the low eutectic point of compound, and the glass melting temperature of glass is reduced, and the sintering temperature of pottery is descended.On the other hand, provide again high temperature synthetic spinel crystallite required transitional pigment element, the spinel of different tones makes devitrified glass present the effect of black by complementary colors and stack.
The present invention adopts higher, the Fe of levels of transition metals
2O
3, TiO
2, Co
2O
3, MnO
2Be 20-30, form complicated, with low cost aegirine augite slag Deng nonferrous metal oxides sum (parts by weight), with it as major ingredient, add common frit inferior (quartzy, Wingdale), provide a kind of low cost to prepare the method for black building decoration devitrified glass; Providing simultaneously a kind of is major ingredient with the aegirine augite slag, add the simple glass material, take scorification as the basis, use that conventional glass, Production of Ceramics method and production unit prepare that color development is pure, the processing method of excellent performance, black building decoration crystallized glass article with low cost.The present invention does not change existing technique, does not increase any equipment, and the technical indicator of its product and use properties meet JC/T 872-2000 Expectation of Glass-Ceramics Used as Decorated Materials industry standards fully.
Utilize discarded aegirine augite slag and common frit to produce black glass ceramic as batching, compared with prior art, the industrial waste that the present invention will originally be difficult to utilize has carried out effective processing, obtained having the black building decoration devitrified glass of higher practicality and economic worth, change the conventional black devitrified glass and will introduce the way of expensive industrial glass raw material and tinting pigment, obtain stable black building decoration devitrified glass with less production cost, solved waste material and stacked the problem that takies a large amount of soils, surrounding enviroment are polluted.The used batching of the present invention is tailing waste thing or frit inferior, and wide material sources are with low cost, has realized the recycling of solid waste resource, and implementation result is desirable.
Advantage of the present invention is as follows:
(1) the used main raw material of the present invention is the aegirine augite slag of discarding, and this slag has poor silicon, aluminium, and potassium, sodium content are high, and iron, titanium foreign matter content are large, contain Fe
2O
3, TiO
2, Co
2O
3, MnO
2Be 20-30 characteristics Deng the nonferrous metal oxides sum, not only help to save natural resource, reduce production costs, also help environment protection.
(2) the aegirine augite slag that utilizes, add common frit, do not add any extra colorant, adopt scorification just can produce black building decoration crystallized glass article, started one for comprehensive development and utilization aegirine augite slag and turned harm into good and practicable approach.
(4) adopt scorification, utilize conventional equipment to produce, need not to increase or change any optional equipment.
(5) the microhardness 8.52-9.50Hv (0.98N) of the black glass ceramic goods of preparation, folding strength 160-190MPa, apparent bulk density is 291-3.26g/cm
3, acid resistance 95-98%, alkali resistance 96-99%, excellent performance has than high added value.Can be used as material of construction and be applied to architectural decoration, it is anticorrosion in chemical industry equipment also to can be used as anticorrosion ceramic applications.
Black aegirine augite slag building decoration devitrified glass sample has been carried out the main performance index analysis, the results are shown in Table 1, contrast finds that this building decoration devitrified glass meets JC/T 872-2000 industry standards fully, and black is pure, color development is stable.
?
The performance of table 1 aegirine augite slag black building decoration devitrified glass sample
| Sequence number | Project name | Measured value |
| 1 | Color colourity | L*=10.86；a*=—2.84；b*=—0.57 |
| 2 | Water-intake rate % | 0.00 |
| 3 | Density g/cm 3 | 2.91—3.26 |
| 4 | Microhardness Hv (0.98N) | 8.52—9.50 |
| 5 | Folding strength MPa | 160—190 |
| 6 | Acid resistance % | 95—98 |
| 7 | Alkali resistance % | 96—99 |
Embodiment:
Aegirine augite slag among following each embodiment is by weight by SiO
245.79, Al
2O
316.43, CaO0.54, MgO0.18, Fe
2O
323.50, TiO
20.91, K
2O 2.76, Na
2O 8.23, Co
2O
30.45, MnO
21.21 form, wherein Fe
2O
3, TiO
2, Co
2O
3, MnO
2Nonferrous metal oxides weight part sum is 26.07; Quartz inferior is by weight by SiO
282.02, Al
2O
315.09, Fe
2O
31.44, TiO
21.05, K
2O 0.19, Na
2O 0.21 forms; Poor line stone is by weight by SiO
213.94, Al
2O
32.30, CaO75.06, MgO4.53, Fe
2O
32.48, K
2O 2.33, Na
2O 0.36 forms.
EXAMPLE l:
(1) raw material crushing: respectively aegirine augite slag, quartz inferior, poor line stone are crushed to the particulate that granularity is 0.154mm, it is stand-by to cross 100 mesh sieves;
(2) batching: get respectively aegirine augite slag after sieving, quartzy, poor line stone, by weight aegirine augite slag inferior: inferior quartzy: the proportion ingredient of poor line stone=70: 20: 10;
(3) batch mixing: the batching that will prepare adds ball mill for dry grinding, and dry grinding is to utilize the alumina balls masonry to be grinding medium, and the weight ratio of control abrading-ball, batching is 2: l, and milling time is 240mim, forms compound, compound is crossed 200 mesh sieves;
(4) found: compound is added in the High Temperature Furnaces Heating Apparatus found, 1300 ℃ of charge temperatures, temperature of fusion is 1600 ℃, soaking time is 60min;
(5) moulding: pour the glass metal after the above-mentioned melting into die for molding;
(6) coring and crystallization: the glass after the moulding is placed in the High Temperature Furnaces Heating Apparatus, at 800 ℃ of coring 20min, then the temperature rise rate with 30 ℃/min is warmed up to 1120 ℃, constant temperature crystallization 30min, at 700 ℃ of lower annealing 30min, sample is made black building decoration devitrified glass through cutting edge, polish, polishing at last.
Embodiment 2:
(1) raw material crushing: respectively aegirine augite slag, quartz inferior, poor line stone are crushed to the particulate that granularity is 0.154mm, it is stand-by to cross 100 mesh sieves;
(2) batching: get respectively aegirine augite slag after sieving, quartzy, poor line stone, by weight aegirine augite slag inferior: inferior quartzy: the proportion ingredient of poor line stone=75: 15: 10;
(3) batch mixing: the batching that will prepare adds ball mill for dry grinding, and dry grinding is to utilize the alumina balls masonry to be grinding medium, and the weight ratio of control abrading-ball, admixtion is 2.4: l, and milling time is 90 mim, forms compound, compound is crossed 200 mesh sieves;
(4) found: compound is added in the High Temperature Furnaces Heating Apparatus found, 1290 ℃ ± 20 ℃ of charge temperatures, temperature of fusion is 1550 ℃ ± 40 ℃, soaking time is 90mim;
(5) moulding: pour the glass metal after the above-mentioned melting into die for molding;
(6) coring and crystallization: the glass after the moulding is placed in the High Temperature Furnaces Heating Apparatus, at 730 ℃ of coring 60min, then the temperature rise rate with 25 ℃/min is warmed up to 1080 ℃, constant temperature crystallization 60min, at 650 ℃ of lower annealing 60min, sample is made black building decoration devitrified glass through cutting edge, polish, polishing at last.
Embodiment 3:
(1) raw material crushing: respectively aegirine augite slag, quartz inferior, poor line stone are crushed to the particulate that granularity is 0.154mm, it is stand-by to cross 100 mesh sieves;
(2) batching: get respectively aegirine augite slag after sieving, quartzy, poor line stone, by weight aegirine augite slag inferior: inferior quartzy: the proportion ingredient of poor line stone=80: 10: 10;
(3) batch mixing: the batching that will prepare is put into ball mill for dry grinding, and dry grinding is to utilize the alumina balls masonry to be grinding medium, and the weight ratio of control abrading-ball, batching is 2.3: l, and milling time is 150mim, forms compound, compound is crossed 200 mesh sieves;
(4) found: compound is put into High Temperature Furnaces Heating Apparatus found, 1270 ℃ of charge temperatures, temperature of fusion is 1500 ℃, soaking time is 150mim;
(5) moulding: with the glass metal after the above-mentioned melting to entering die for molding;
(6) coring and crystallization: the glass after the moulding is placed in the High Temperature Furnaces Heating Apparatus, at 750 ℃ of coring 60min, then the temperature rise rate with 20 ℃/min is warmed up to 980 ℃, constant temperature crystallization 150min, at 600 ℃ of lower annealing 150min, sample is made black building decoration devitrified glass through cutting edge, polish, polishing at last.
Embodiment 4:
(1) raw material crushing: be the particulate of 0.154mm with aegirine augite slag, quartz inferior, limestone crushing to granularity respectively, it is stand-by to cross 100 mesh sieves;
(2) batching: get respectively aegirine augite slag after sieving, quartzy, poor line stone, by weight aegirine augite slag inferior: inferior quartzy: the proportion ingredient of poor line stone=85: 7: 8;
(3) batch mixing: the batching that will prepare adds ball mill for dry grinding, and dry grinding is to utilize the alumina balls masonry to be grinding medium, and the weight ratio of control abrading-ball, compound is 2.2: l, and milling time is 200mim, forms compound, compound is crossed 200 mesh sieves;
(4) found: compound is added in the High Temperature Furnaces Heating Apparatus found, 1260 ℃ ± 20 ℃ of charge temperatures, temperature of fusion is 1450 ℃ ± 40 ℃, soaking time is 200mim;
(5) moulding: pour the glass metal after the above-mentioned melting into die for molding;
(6) coring and crystallization: the glass after the moulding is placed in the High Temperature Furnaces Heating Apparatus, at 780 ℃ of coring 100min, then the temperature rise rate with 15 ℃/min is warmed up to 900 ℃, constant temperature crystallization 200min, at 600 ℃ of lower annealing 200min, sample is made devitrified glass through cutting edge, polish, polishing at last.
Embodiment 5:
(1) raw material crushing: respectively aegirine augite slag, quartz inferior, poor line stone are crushed to the particulate that granularity is 0.154mm, it is stand-by to cross 100 mesh sieves;
(2) batching: get respectively aegirine augite slag after sieving, quartzy, poor line stone, by weight aegirine augite slag inferior: inferior quartzy: the proportion ingredient of poor line stone=90: 5: 5;
(3) batch mixing: the batching that will prepare adds ball mill for dry grinding, and dry grinding is to utilize the alumina balls masonry to be grinding medium, and the weight ratio of control abrading-ball, batching is 2.5: l, and milling time is 60mim, forms compound, compound is crossed 200 mesh sieves;
(4) found: compound is added in the High Temperature Furnaces Heating Apparatus found, 1250 ℃ of charge temperatures, temperature of fusion is 1400 ℃, soaking time is 240mim;
(5) moulding: pour the glass metal after the above-mentioned melting into die for molding;
(6) coring and crystallization: the glass after the moulding is placed in the High Temperature Furnaces Heating Apparatus, at 700 ℃ of coring 120min, then the temperature rise rate with 5 ℃/min is warmed up to 850 ℃, constant temperature crystallization 240min, at 500 ℃ of lower annealing 240min, sample is made black building decoration devitrified glass through cutting edge, polish, polishing at last.
The various embodiments described above are that foregoing of the present invention is further described, but this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to above-described embodiment.All technology that realizes based on foregoing all belong to scope of the present invention.
Claims (2)
1. black building decoration devitrified glass comprises following component by weight:
Aegirine augite slag 70-90,
Quartz 5-20 inferior,
Poor line stone 5-10,
Above-mentioned aegirine augite slag is by weight by SiO
240-50, Al
2O
315-20, CaO0.2-1, MgO0.1-0.5, Fe
2O
320-25, TiO
20.5-1.5, K
2O 2-4, Na
2O 7-9, Co
2O
30.3-1.5, MnO
20.5-1.5 form, wherein Fe
2O
3, TiO
2, Co
2O
3, MnO
2Nonferrous metal oxides weight part sum is 21.3-29.5; Quartz inferior is by weight by SiO
278-86, Al
2O
312-18, Fe
2O
31-2, TiO
20.5-1.5, K
2O 0-0.5, Na
2O 0-0.5 forms; Poor line stone is by weight by SiO
210-15, Al
2O
32-5, CaO65-76, MgO3-6, Fe
2O
33-5, K
2O 2-3, Na
2O 0.2-1 forms.
2. the preparation method of black building decoration devitrified glass may further comprise the steps:
(1) raw material crushing: respectively aegirine augite slag, quartz inferior, poor line stone are crushed to the particulate that granularity is 0.154mm, it is stand-by to cross 100 mesh sieves;
(2) batching: get respectively the aegirine augite slag after sieving, quartzy, poor line stone, by weight aegirine augite slag inferior: inferior quartzy: poor line stone=(70-90): (5-20): the proportion ingredient of (5-10);
(3) batch mixing: the batching that will prepare adds ball mill for dry grinding, and dry grinding is to utilize the alumina balls masonry to be grinding medium, and the weight ratio of control abrading-ball, batching is (2-2.5): l, and milling time is 1-4h, forms compound, and compound is crossed 200 mesh sieves;
(4) found: compound is added in the High Temperature Furnaces Heating Apparatus found, 1250-1300 ℃ of charge temperatures, temperature of fusion is 1400-1600 ℃, soaking time is 60-240min;
(5) moulding: pour the glass metal after the melting into die for molding;
(6) coring and crystallization: the glass after the moulding is placed in the High Temperature Furnaces Heating Apparatus, at 700-800 ℃ of coring 20-120min, then the temperature rise rate with 5-30 ℃/min is warmed up to 850-1120 ℃, constant temperature crystallization 30-240min, at 500-700 ℃ of lower annealing 30-240min, sample is made black building decoration devitrified glass through cutting edge, polish, polishing at last.
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