CN102260045A - Environment-friendly, energy-saving and low-melting-point color glaze decoration flat glass with high annealing temperature and strength and preparation method thereof - Google Patents

Environment-friendly, energy-saving and low-melting-point color glaze decoration flat glass with high annealing temperature and strength and preparation method thereof Download PDF

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CN102260045A
CN102260045A CN2011100609139A CN201110060913A CN102260045A CN 102260045 A CN102260045 A CN 102260045A CN 2011100609139 A CN2011100609139 A CN 2011100609139A CN 201110060913 A CN201110060913 A CN 201110060913A CN 102260045 A CN102260045 A CN 102260045A
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杨德宁
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Abstract

The invention relates to environment-friendly, energy-saving and low-melting-point color glaze decoration flat glass with high annealing temperature and strength. The melting point of color glaze layers in 1 to 10 colors on the surface of substrate glass is between 540 and 730 DEG C, and the substrate glass of the product is characterized by comprising the following components in percentage by weight: 0 to 3.9 percent of boron oxide, 0.01 to 14 percent of sodium oxide, 0.01 to 5 percent of iron oxide, 0 to 2.8 percent of fluorine oxide, 8.1 to 22.2 percent of magnesium oxide, 0.01 to 39 percent of aluminum oxide, silicon oxide in an amount which is 1.9 to 4.1 times that of calcium oxide, and the calcium oxide in an amount which is 1.2 to 1.6 times of the magnesium oxide, wherein the thickness difference of the substrate glass is less than 0.3mm, the water absorption rate of the substrate glass is in the range of 0 to 0.3 percent, the breaking strength of the substrate glass is 50 to 180MPa, and the lower limit of the annealing temperature of the substrate glass (namely the starting point temperature of an endothermic peak) is between 550 and 710 DEG C.

Description

The low melting point colored glaze decorative flat glass and the preparation method of the high-intensity environment-friendly and energy-efficient of high annealing temperature
Technical field
The present invention relates to be used for the especially ambetti of prior art, and alternative ceramic plate, ceramic tile and aluminium-plastic panel, decorate plastic veneer, resinous artificial stone plate, and be used for interior exterior wall, ground and deck plate, various decorative sheet materials during household such as kitchen cabinet panel and engineering are used sodium oxide in the predetermined requisite special scope arranged, ferric oxide, aluminum oxide, silicon oxide, calcium oxide, magnesium oxide, or also has titanium oxide, barytic composition and predetermined silicon oxide, calcium oxide, the factor proportion relationship change invention of the composition of specific proportions between magnesium oxide relation and to the multiple innovative technology schemes such as omission invention technical scheme of boron or sodium composition, the various traditional technology prejudice [the annealing temperature lower limit (being the endotherm(ic)peak origin temp) that accounts for the soda-lime glass of existing sheet glass ultimate production 99.9% only is 490 ℃] that must form hydrotropy composition and eutectic composition with a large amount of sodium or boron composition have been overcome, and can produce unforeseeable at low sodium, come economy in the composition of no boron, hang down with becoming produce colored glazed glass exceed 50 ℃-200 ℃ base plate glass that can preferably exceed 150 ℃-200 ℃ of prior art annealing temperature lower limit (being the endotherm(ic)peak origin temp), though again than the glass of existing unique sheet glass alkali-free boron glass technical scheme with high annealing temperature lower limit (being the endotherm(ic)peak origin temp), but calcium sodium sheet glass appears in the cost height reaches 80-100 product doubly, as seen has only the present invention just to have the cost economic feasibility of making the colored glazed glass finishing material; And intensity of the present invention can rise 1-3 doubly, makes the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature and preparation method can have real big controllable costs of producing, can ensure unprecedented the two technological property that has concurrently that carries out the glaze sintering and the yield rate of normally not breaking is arranged below annealing point again.
Background technology
The kind of modern wall floor decorative material plate or brick is many, but significant deficiency is separately all arranged, as:
(1), the major defect of common calcium soda glass and ambetti and glass mosaic is, [1] it does not have the linear change feature because of the coefficient of expansion, so it is big to change difference, the annealing point lower limit is endotherm(ic)peak starting point (being generally about 490 ℃), because the insider knows, be difficult to make the inorganic glaze of the fusing point that is lower than 490 ℃, if again owing to come the printed decoration pattern with the inorganic glaze that is higher than 490 ℃, will produce the distortion of glasswork, especially it is extremely wayward and occur that burst rate is greatly arranged to produce second annealing technology, the insider also knows, about strain point temperature, glass can produce expansion jumpy, and this is the major technique obstacle that present all calcium soda glass can not form meticulous applicable inorganic glaze agglomerating pattern printed matter at all.Thereby can only do the minimum mosaic goods of size (the following size of minimum 5cm just can be because of the bad explosion that produces of annealing); [2] and now can only be used for unicolor tempering printed glass (can overcome the problem that annealing occurs) with the formation surface tension.And technology tempering goods cannot make as next other size that can be cut into arbitrarily in final user's hand of various on-gauge plates such as 2400 * 1200mm now; [3] fusing point of the glaze of existing colored glaze toughened glass and all mosaic glass is all at 760 ℃-820 ℃, because softeningly will adapt to glass tempering the time have the temperature of point deformation and the softening corner of using of mosaic glass to become circle, this is a technique known; [4] its hardness and wear resistance are very poor, and intensity only is about 45-50MPa, can not be used for household and engineering ground and use; [5] its viscosity is 10 0.5(handkerchief second) and 10 1(handkerchief second) melting temperature adopts the basic survey of U.S. THETA rotation high temperature viscosimeter not go out, and can only measure viscosity 10 1.5Temperature when (handkerchief second) is about 1580 ℃ temperature of fusion, thus have in producing not meltable, the defective that energy consumption is big (fusing of per kilogram and moulding energy consumption reach 1500 kilocalories); [6] flameproof effect is poor, and is explosive.
(2), existing aluminium-plastic panel finishing material, it is generally formed by two layers of aluminium book plate therebetween one deck plastic plate, its defective is, [1] since the intermediary plastic layer out of doors the use meeting drench with rain because of exposing to the weather and the variation of the temperature difference, and the generation gross distortion, and because soft, the book of plastic-aluminum flitch, planeness, poor flatness; Can not make it fully to reach and reach the smooth and smooth finish of minute surface as glass and ceramic.[2] its surface printing bag pattern can only use organic materials, just inevitable easily aging, easy to change, so can only be indoor application, more can not do outdoor use;
(3), decorate plastics class thick china, its defective is that [1] impossible construction case reaches the smooth and smooth finish of minute surface; [2] can not do ground, not wear-resisting because of it; [3] there is not the fire protection flame retarding effect; [4] product must not be done outdoor use, and is not so very easily aging, very easily distortion.So, major defect is arranged all no matter be used for decorative engineering veneer or house ornamentation engineering or wooden furniture veneer.
(4), ceramic plate and ceramic tile, its defective is, [1] present all ceramic plates, owing to adopt extrude or be pressed into base drying or firing process more argillaceous, volume production can not be produced 0.3mm-1.6mm or the super book goods of 2-3mm, and the volume production size can only accomplish the mm of 1800 * 900mm * (5-6), can not produce 2400 * 1200mm * (2-3) mm or the above product of 3mm size; [2] and its product strength less than 50MPa, rapid wear in construction and transportation, and the thickness of 99.99% ceramic tile product all is 9-15mm; [3] its water-intake rate is bigger, reaches 0.5-0.1%, easily soil pick-up; [4] during its goods glaze stamp because firing temperature reaches 1100 ℃-1200 ℃, so can not keep the crystalline phase (because of it can melt) of quartz crystal, so its goods difference of hardness is not wear-resisting; [5] its technology has determined that the energy consumption of its production is big especially, dust and carbonic acid gas, the discharging of sulfurous gas is big, the weight of raw material and finished product is big, the transportation cost height, make that the energy consumption of transportation is all very big, water resource waste is big, floor space is big, efficient is low, its production of articles is to adopt the water law ball-milling technology, spray tower technology, ceramic press technology, the change system of the advanced ceramics production of compositions such as water law polishing and edging technology is produced, its energy consumption is big, dust and dusty gas discharging are big, the water consumption height, so advocate green economy in the whole world, energy-conserving and environment-protective, today of low-carbon economy, the production technique of the ceramic under this conventional equipment system has significant limitation and shortcoming, has the upgrading of being badly in need of the new invention product to substitute.
(5), lithotome, its defective is that [1] not environmental protection has radioelement; [2] weight is big, especially in exterior wall is used, must could do the wall surface dry-hang use by the thickness more than the 25mm by standard; [3] high-grade natural stone resource reduces day by day.
(6), rostone and ambetti, the output and the effect of rostone are low, the cost height; And the pattern glaze of ambetti all is an organic materials, easy to change, the utmost point is not wear-resisting, and (not can be used as exterior wall and ground uses, and the printed patterns stained glass of tempering can not be made the goods of specified size, can not cut, present inorganic glaze figured plate glass, also can only make the 5cm size with interior glass mosaic, doing greatly a bit will influence its second annealing because of about 490 ℃ annealing point of calcium soda glass, can produce the explosion phenomenon, because it is impossible being lower than the batch process of 490 ℃ unorganic glass glaze, so industry all wishes to occur overcoming technical barrier greater than the standard-sized goods that can cut arbitrarily of the fine pattern of the glass mosaic of 5cm.
(7), in addition, existing a kind of publication number is " crystal glass and production method thereof with natural-marble-like surface patterns " patent application of CN 1053047A, its technology has just determined its inevitable product defects, rather than the defective of its product that determines on the product composition.
1, its technology is expressed as the pieces of glass material is preserved in moulding box, makes ... crystallization enters inside from glass surface, and frit fuses each other--combination, feed glass material size ..., obtain to have the outward appearance of marble, granite decorative pattern.And this file has the mould frame of the statement of mass crystallization technological process, and what as seen it adopted is the technology of a kind of color decorative pattern devitrified glass of the sticking liquate crystalline substance of particle.
A, its chromatic pattern and opaque product feature are not obviously determined by material composition, be the crystal, colour and the decorative pattern that decide its product from each glass particle surface to inside that add in the processing method by application documents statements, so its each particulate material all overgrows with crystal from outside to inside, be never transparent, may not reach the goods of the visible transmission ratio that good 40%-95% is arranged, and need overcome these defectives.
B, owing to be to be undertaken on its technology by the particles with different sizes material, make the softening and distortion of its frit, and adhere is integral each other ... the glass crystallization of separating out simultaneously meets the size and the shape (seeing its 7th page) of pieces of glass material.The insider knows, topmost defective is loose when being product cloth particle, so burn till the back product plane a large amount of uneven places is arranged, this particulate crystal, as all devitrified glasses, to grow up, the various granular roughness on surface that make are all at 0.5mm-1.5mm, and this framed moulding process, product plane is very uneven, framedly in addition again all fire with refractory materials, surface and four jiaos irregularity degree be with firing deformation is increasing each time, thus the thickness difference of its finished product all at 1.5mm-2mm, all products are wanted pros and cons to wipe off to polish, the minimum 1mm-2mm thickness of skimming of respectively scraping, even and after scraping throwing positive and negative two, the thickness difference of its product also can reach more than the 1mm, so its defective and waste are all big.Differ greatly with internal-phase ratio at 0.3mm with the thickness difference of glass of the present invention and normal sheet glass.This defective is also caused by its processing method fully, rather than the material composition generation, so need overcome these defectives.
(8), the PDP of prior art and alkali-free boron glass, representational is the US2002/0011080A1 patent, though it has the improved strain point, but defective is in its technical scheme: one, because it is finished product contains boron oxide level and reaches 5-20%,, not only very big to environmental protection harm so the volatilization of its many 2 times boron can form the inequality of composition, and its product strength is not high, only reaches 45-50MPa; Its two, its production cost is high, because its viscosity height, fusing and row's bubble and moulding be difficulty all, so only, not can be used as ambetti, never be used for the publicity or the example of colored glazed glass yet as the electronic console glass of price than the high 50-100 multiple of the dull and stereotyped calcium soda glass of existing float glass process.
Because the defective and the deficiency of above-mentioned prior art, the inventor is based on being engaged in this type of product design manufacturing pragmatic experience and expertise for many years, actively studied innovation, in the hope of overcoming the deficiencies in the prior art and defective, after having solved complicated production technique problem, a kind of sodium oxide that has in the predetermined requisite special scope has been proposed, ferric oxide, aluminum oxide, silicon oxide, calcium oxide, magnesium oxide, or also has titanium oxide, barytic composition and predetermined silicon oxide, calcium oxide, the innovative technology scheme of the composition of the specific proportions relation between the magnesium oxide, and the various traditional composition hydrotropy compositions and the technology prejudice of eutectic composition have been overcome, and the product strength rising 1-3 that can produce unforeseeable hydrotropy or eutectic function and generation doubly, environmental protection, the technique effect of energy-saving and emission-reduction etc., and on glass substrate, adhere to fusing point the present invention at the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of 540 ℃-730 ℃ colored glaze.
Summary of the invention
First embodiment of the invention discloses the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature, the fusing point of the glazed colour layer of the 1-10 kind color on its base plate glass surface is at 540 ℃-730 ℃, the base plate glass of its goods is characterised in that: this base plate glass comprises silicon oxide, calcium oxide, magnesium oxide, aluminum oxide, ferric oxide, the composition of sodium oxide, count as weight percents, the content of boron oxide is 0-3.9% in this base plate glass, the content of sodium oxide is 0.01-14%, iron oxide content is 0.01-5%, the content of fluorine oxide is 0-2.8%, content of magnesia is 8.1-22.2%, alumina content is 0.01-39%, the content of its silicon oxide is 1.9 times-4.1 times of calcium oxide content, and the content of calcium oxide is 1.2 times-1.6 times of magnesian content; The thickness difference of this base plate glass is less than 0.3mm; The water-intake rate of its base plate glass is in the scope of 0-0.3%; The folding strength of its base plate glass reaches 50-180Mpa; The annealing temperature lower limit of its base plate glass (being the endotherm(ic)peak origin temp) is 550 ℃-710 ℃.
According to the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that: meter as weight percents, alumina content is 3.1-39%.
According to the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that: meter as weight percents, the content of titanium oxide is 0.0003-4.9%.
Low melting point colored glaze decorative flat glass according to the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that: count as weight percents, its silicon oxide, calcium oxide, magnesium oxide three's content summation is 51-99.8%, and barytic content is 0.01-14%.
Low melting point colored glaze decorative flat glass according to the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that: by heavy percentage, the content of aluminum oxide is 0.01-30%, silicon oxide: calcium oxide is 2.0-3.6 times, calcium oxide: magnesium oxide is 1.3-1.49 times, sodium oxide is 0.01-2%, and boron oxide is 0-1%, and the content of fluorine oxide is 0-1%; The annealing temperature lower limit of this base plate glass (being the endotherm(ic)peak origin temp) is 610 ℃-710 ℃; This base plate glass is 10 in viscosity 0.5Temperature when (handkerchief second) is 1500 ℃-1640 ℃; Viscosity is 10 1Temperature when (handkerchief second) is 1450 ℃-1580 ℃; Viscosity is 10 2Temperature when (handkerchief second) is 1210 ℃-1350 ℃; Viscosity is 10 3Temperature when (handkerchief second) is 1070 ℃-1230 ℃; The folding strength of this base plate glass is 50-180MPa.
Low melting point colored glaze decorative flat glass according to the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that: by heavy percentage, the content of aluminum oxide is 8-30%, silicon oxide: calcium oxide is 2.0-3.6 times, calcium oxide: magnesium oxide is 1.3-1.49 times, sodium oxide is 0.01-2%, and boron oxide is 0-1%, and the content of fluorine oxide is 0-1%; The annealing temperature lower limit of this base plate glass (being the endotherm(ic)peak origin temp) is 610 ℃-680 ℃; This base plate glass is 10 in viscosity 0.5Temperature when (handkerchief second) is 1520 ℃-1640 ℃; Viscosity is 10 1Temperature when (handkerchief second) is 1450 ℃-1580 ℃; Viscosity is 10 2Temperature when (handkerchief second) is 1210 ℃-1350 ℃; Viscosity is 10 3Temperature when (handkerchief second) is 1070 ℃-1230 ℃; The folding strength of this base plate glass is 75-180MPa.
Low melting point colored glaze decorative flat glass according to the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that: by heavy percentage, the content of aluminum oxide is 19-30%, silicon oxide: calcium oxide is 2.0-3.6 times, calcium oxide: magnesium oxide is 1.3-1.49 times, sodium oxide is 0.01-2%, and boron oxide is 0-1%, and the content of fluorine oxide is 0-1%; The annealing temperature lower limit of this base plate glass (being the endotherm(ic)peak origin temp) is 610 ℃-680 ℃; This base plate glass is 10 in viscosity 0.5Temperature when (handkerchief second) is 1550 ℃-1640 ℃; Viscosity is 10 1Temperature when (handkerchief second) is 1450 ℃-1580 ℃; Viscosity is 10 2Temperature when (handkerchief second) is 1210 ℃-1350 ℃; Viscosity is 10 3Temperature when (handkerchief second) is 1080 ℃-1230 ℃; The folding strength of this base plate glass is 130-180MPa.
Low melting point colored glaze decorative flat glass according to the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that: by heavy percentage, the content of aluminum oxide is 0.01-19%, silicon oxide: calcium oxide is 2.0-3.6 times, calcium oxide: magnesium oxide is 1.3-1.49 times, sodium oxide is 0.01-2%, and boron oxide is 0-1%, and the content of fluorine oxide is 0-1%; The annealing temperature lower limit of this base plate glass (being the endotherm(ic)peak origin temp) is 610 ℃-680 ℃; This base plate glass is 10 in viscosity 0.5Temperature when (handkerchief second) is 1500 ℃-1580 ℃; Viscosity is 10 1Temperature when (handkerchief second) is 1450 ℃-1520 ℃; Viscosity is 10 2Temperature when (handkerchief second) is 1210 ℃-1310 ℃; Viscosity is 10 3Temperature when (handkerchief second) is 1070 ℃-1160 ℃; The folding strength of this base plate glass is 50-145MPa.
Low melting point colored glaze decorative flat glass according to the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that: count as weight percents, the content of calcium oxide is 1.3 times-1.6 times of magnesian content, the content of silicon oxide is 2.0 times-3.6 times of content of calcium oxide, magnesian content is 10.1-19.9%, and the content of aluminum oxide is 19-39%.
According to the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that:
(1), counts as weight percents, in its base plate glass content: 1. magnesium oxide accounts for 7-20%, 2. calcium oxide is in magnesian 1.0 times-1.8 times scope, 3. silicon oxide is in magnesian 2.6 times-5.6 times scope, 4. silicon oxide is in 2.2 times-3.8 times the scope of calcium oxide, 5. aluminum oxide is 0.1-30%, and 6. sodium oxide is 0-18%, and 7. barium oxide is 0-5%;
(2), the strain point temperature of the base plate glass of its goods is in 560 ℃-720 ℃ scope;
(3), the water-intake rate of the base plate glass of its goods is in the scope of 0-0.001%;
(4), as weight percents the meter, the content summation of the middle magnesium oxide of the base plate glass of its goods, calcium oxide, three kinds of compositions of silicon oxide reaches 51%-100%.
According to the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, it is characterized in that: the composition board of its goods is by compound composition of sheet metal (3) of low melting point colored glaze decorative flat glass (1) and bonding material layer (2) and the 0.1-1mm or the 1-5mm thickness of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature.
Low melting point colored glaze decorative flat glass according to the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that: count as weight percents, the content of aluminum oxide is smaller or equal to 30% in its base plate glass, and this base plate glass is 10 in viscosity 0.5Temperature when (handkerchief second) is 1480 ℃-1640 ℃; Viscosity is 10 1Temperature when (handkerchief second) is 1410 ℃-1600 ℃; Viscosity is 10 2Temperature when (handkerchief second) is 1180 ℃-1340 ℃; Viscosity is 10 3Temperature when (handkerchief second) is 1040 ℃-1220 ℃; The thickness difference of this base plate glass is less than 0.3mm; The water-intake rate of this base plate glass is in the scope of 0-0.3%; The annealing temperature lower limit of this base plate glass (being the endotherm(ic)peak origin temp) is in 550 ℃-710 ℃ the scope; The folding strength of this base plate glass is 50-180MPa; The thermal expansivity of this base plate glass is 1,000,000/1.0-3.0/1000000ths in the difference of 150 ℃-300 ℃ two ends numerical value; Difference at 550 ℃-600 ℃ two ends numerical value is 1,000,000/1.0-2.8/1000000ths.
According to the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, its goods are characterised in that: the quartz crystal or the alpha-alumina crystals that contain 20-70% in the glaze layer on its top layer.
According to the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that:
(1), counts as weight percents, in its goods content: 1. magnesium oxide accounts for 7-20%, 2. calcium oxide is in magnesian 1.0 times-1.8 times scope, 3. silicon oxide is in magnesian 2.6 times-5.6 times scope, 4. silicon oxide is in 2.2 times-3.8 times the scope of calcium oxide, 5. aluminum oxide is 0.1-30%, and 6. sodium oxide is 0-18%, and 7. barium oxide is 0-5%;
(2), the strain point temperature of its goods is in 560 ℃-720 ℃ scope;
(3), the water-intake rate of its goods is in the scope of 0-0.001%;
(4), as weight percents the meter, the content summation of magnesium oxide, calcium oxide, three kinds of compositions of silicon oxide reaches 51%-100% in its goods.
According to the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that:
(1), counts as weight percents, in its goods content: 1. the content of calcium oxide is 0.6 times-2.4 times of magnesian content, 2. the content of silicon oxide is 1.3 times-5.8 times of magnesian content, 3. the content of silicon oxide is 1.3 times-5.8 times of content of calcium oxide, 4. aluminum oxide is 0.1-30%, 5. sodium oxide is 0-18%, and 6. barium oxide is 0-20%;
(2), wherein the content summation of magnesium oxide, calcium oxide, three kinds of compositions of silicon oxide reaches 51%-99.9%;
(3), the water-intake rate of its goods is in the scope of 0-0.001%.
According to the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that:
(1), counts as weight percents, in its goods content: 1. magnesium oxide accounts for 7-20%, 2. the content of calcium oxide is 1.0 times-1.8 times of magnesian content, 3. the content of silicon oxide is 2.6 times-5.6 times of magnesian content, 4. the content of silicon oxide is 2.2 times-3.8 times of content of calcium oxide, 5. aluminum oxide is 0.1-30%, and 6. sodium oxide is 0-18%, and 7. barium oxide is 0-5%;
(2), the strain point temperature of its goods is in 560 ℃-720 ℃ scope;
(3), the water-intake rate of its goods is in the scope of 0-0.001%;
(4), as weight percents the meter, the content summation of magnesium oxide, calcium oxide, three kinds of compositions of silicon oxide reaches 51%-99.9% in its goods.
Low melting point colored glaze decorative flat glass according to the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that: count as weight percents, in its goods content: calcium oxide is magnesian 1.15 times-1.8 times.
According to the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that:
(1), counts as weight percents, in its goods content: 1. magnesium oxide accounts for 9.1-22%, 2. the content of calcium oxide is 0.6 times-2.0 times of magnesian content, 3. the content of silicon oxide is 2.8 times-5.6 times of magnesian content, 4. the content of silicon oxide is in 2.3 times-3.8 times the scope of content of calcium oxide, 5. aluminum oxide is 0.1-30%, and 6. sodium oxide is 0-18%, and 7. barium oxide is 0-5%;
(2), the strain point temperature of its goods is in 560 ℃-720 ℃ scope;
(3), the water-intake rate of its goods is in the scope of 0-0.001%;
(4), as weight percents the meter, the content summation of magnesium oxide, calcium oxide, three kinds of compositions of silicon oxide reaches 51%-99.9% in its goods.
According to the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that: meter as weight percents, when alumina content reached 0-3.8% in the goods: viscosity was 10 1The melting process temperature of (handkerchief second) is 1300 ℃-1400 ℃; Viscosity is 10 2The clarification of (handkerchief second), exhaust bubble technological temperature are 1120 ℃-1260 ℃; Viscosity is 10 3The moulding process temperature of (handkerchief second) is 1010 ℃-1060 ℃; The folding strength of its goods reaches 60-100MPa.
Low melting point colored glaze decorative flat glass according to the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that: count as weight percents, when alumina content reached 3.8-15% in the goods: viscosity was 10 1The melting process temperature of (handkerchief second) is 1320 ℃-1430 ℃; Viscosity is 10 2The clarification of (handkerchief second), exhaust bubble technological temperature are 1140 ℃-1290 ℃; Viscosity is 10 3The moulding process temperature of (handkerchief second) is 1040 ℃-1130 ℃; The folding strength of its goods reaches 80-130MPa.
According to the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that: meter as weight percents, when alumina content reached 15-23% in the goods: viscosity was 10 1The melting process temperature of (handkerchief second) is 1360 ℃-1550 ℃; Viscosity is 10 2The clarification of (handkerchief second), exhaust bubble technological temperature are 1250 ℃-1430 ℃; Viscosity is 10 3The moulding process temperature of (handkerchief second) is 1060 ℃-1200 ℃; The folding strength of its goods reaches 100-180MPa.
Low melting point colored glaze decorative flat glass according to the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that: this base plate glass comprises silicon oxide, magnesium oxide and calcium oxide, wherein, count as weight percents, the content of silicon oxide is 2.1 times-6.5 times of magnesian content in this base plate glass, and the content of silicon oxide is 1.8 times-4.6 times of content of calcium oxide;
The thickness difference of this base plate glass is less than 0.3mm;
Its water-intake rate is in the scope of 0-0.3%;
Its folding strength reaches 50-180MPa.
Low melting point colored glaze decorative flat glass according to the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that: count as weight percents, in this base plate glass, the content of silicon oxide is 2.6 times-5 times of magnesian content, and the content of silicon oxide is 2.4 times-3.4 times of content of calcium oxide.
Low melting point colored glaze decorative flat glass according to the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that: count as weight percents, the content of calcium oxide is 1.0 times-1.6 times of magnesian content, more preferably 1.2 times-1.5 times.
According to the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the thickness of the base plate glass of its goods is 0.3-1.8mm.
According to the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the thickness of the base plate glass of its goods is 1.8-5mm.
According to the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the thickness of the base plate glass of its goods is 5-20mm.
According to the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that: meter as weight percents, the content of sodium oxide is 0.01-2%.
According to the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the base plate glass of its goods is characterised in that: meter as weight percents, the content of sodium oxide is 2.1-5%.
Second embodiment of the invention provides the preparation method of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature, it is characterized in that:
Step 1, the required various sodium oxides that have in the predetermined requisite special scope of base plate glass component configuration according to each described goods of claim 1-6, ferric oxide, aluminum oxide, silicon oxide, calcium oxide, magnesium oxide, or also has titanium oxide, barytic composition and predetermined silicon oxide, calcium oxide, the raw material of the innovative technology scheme of the composition of the specific proportions relation between the magnesium oxide, temperature of fusion corresponding to each glass formula after mixing stirring melts, form the controlled viscosity and the low viscous glass metal of optimization, homogenizing again, clarification, discharge bubble, form flowable molten mass;
Step 2, any technology is carried out moulding to glass in employing floating process, horizontal drawing technology, lattice-method process, calendering technology, the press over system technology, makes the base plate glass of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature through refrigerating work procedure;
Step 3 is to the surface printing of the base plate glass of the goods of moulding or to execute the cloth last layer be that 540 ℃-730 ℃ colored glaze forms ornament layer by the fusing point of a kind or 2-10 kind color.
The low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of according to an embodiment of the invention high annealing temperature, colored glaze pattern decorative layer on its product surface, be by the 2-100 cover is set, the monolith articles printing device unit that every cover is made up of 1-10 plane wire mark or roll printing device or ink jet printing device, mode with layout in parallel, surface to the base plate glass of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of described high annealing temperature, carry out the printing of colored glaze material, carry out the glaze sintering circuit again, the prepared low melting point colored glaze decorative flat glass goods that in same batch of production of articles, make 2-100 piece product surface produce the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of every default different printing pattern that 1-10 kind color arranged or color glaze ornament layer.
Processing method according to the embodiment of the invention, wherein: the 2-4 bar limit of the metal sheet of the back of the body bottom surface of the composition board of its goods, the distance that 10-30mm has stretched out in the limit portion of the low melting point colored glaze decorative flat glass goods of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature in the top layer of proportion poststack.
Description of drawings
Fig. 1 is the floor map of base plate glass of low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the present invention and preparation method's embodiment.
Fig. 2 is the schematic flow sheet of floating process moulding of base plate glass of low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the present invention and preparation method's embodiment.
Fig. 3 is the side diagrammatic cross-section of state of floating process moulding of base plate glass embodiment of low melting point colored glaze decorative flat glass of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the present invention and preparation method's the high-intensity environment-friendly and energy-efficient of high annealing temperature.
Fig. 4 is that the size of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the present invention and preparation method embodiment is that the colored glaze material that prints predetermined three look districts of 1220mm * 2440mm forms the floor map of low melting point colored glaze decorative flat glass goods that the top layer is the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of predetermined colored glaze material pattern decorative layer.
Fig. 5 is that the size of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the present invention and preparation method embodiment is that the colored glaze material that prints predetermined three look districts of 1220mm * about 2-5mm of 2440mm thickness forms the diagrammatic cross-section of low melting point colored glaze decorative flat glass goods of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature that the top layer is the predetermined colored glaze material pattern decorative layer of about 0.1-1mm thickness.
Fig. 6 is that the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the present invention and the top layer of preparation method embodiment are the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature, the back side is the aluminium sheet that overlapping back portion does not exceed surface silicon hydrochlorate colored glaze ambetti size, the NEW TYPE OF COMPOSITE sheet material cross-sectional view of pasting compound composition by tackiness agent mutually.
Fig. 7 is that the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the present invention and the top layer of preparation method embodiment are the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature, the back side is to have 2 limits separately the aluminium sheet that has stretched out the 10-30mm distance than surface silicon hydrochlorate colored glaze ambetti size, the NEW TYPE OF COMPOSITE sheet material cross-sectional view of pasting compound composition mutually more.
Fig. 8 is that the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the present invention and the employing top layer of preparation method embodiment are the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature, the back side is to have after overlapping 2 limits separately the aluminium sheet that has stretched out 10-30mm than surface silicon hydrochlorate colored glaze ambetti size more, paste the NEW TYPE OF COMPOSITE sheet material of compound composition mutually, after the punching of the predetermined position on the 10-30mm extension, can carry out the upright two dimensional structure synoptic diagram that the metope screw is installed.
Description of reference numerals
1: the base plate glass of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature
2: the feed bin opening for feed
3: feed bin
4: the mixing raw material of predetermined preparation
5: raw material enters the molten bath kilneye in molten bath
6: the molten bath kiln
7: diversion trench
8: molten tin bath
9: the transition roller platform
10: annealing furnace
11: the cutting portioning station
12: float glass process production line matrix
21: oblique line is partly represented the first look district colored glaze material pattern area of having printed
31: wire cross is partly represented the second look district colored glaze material pattern area of having printed
41: pore is partly represented the tertiary color district colored glaze material pattern area of having printed
123: the glaze pattern decorative layer that has printed predetermined three pattern colour district colored glaze material on expression upper strata
13: expression has the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature of glazed colour layer
14: represent that overlapping back portion does not exceed the aluminium sheet of the low melting point colored glaze decorative flat glass limit portion of the high-intensity environment-friendly and energy-efficient of the high annealing temperature in top layer
141: represent to have after overlapping 2 limits separately the aluminium sheet that has stretched out the 10-30mm distance than the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of the high annealing temperature in top layer more
15: the tackiness agent that expression is predetermined
16: the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of the high annealing temperature in ratio top layer of aluminium sheet stretches out the screw open holes in the limit portion of 10-30mm at the bottom of the back of the body of expression composite sheet
Embodiment
The present invention has initiated (1) novelty, creationary environment-friendly type glass substrate technical scheme, make it have (2) linear thermal expansion feature, it is annealing temperature lower limit (being the endotherm(ic)peak origin temp) that high annealing point is arranged, the glass that high strength characteristics arranged and (3) are limited to the new function colored glazed glass goods of three technology essential factor characteristics combination of (annotate: the glaze of simple glass mosaic and all glass is all 760 ℃ of temperature of fusion more than-820 ℃) glazed colour layer of 540 ℃-730 ℃ temperature of fusion, under the economically viable prerequisite of cost, solved the technical barrier that prior art sheet glass can not be used for the big plate face multicolor printing ambetti of non-tempering.
Because it is low-cost to have only the present invention to initiate in the prior art, make to high efficiency production base plate glass annealing temperature lower limit (being the endotherm(ic)peak origin temp) rise to minimum 540 ℃ from 490 ℃ of ordinary plate glass, be preferably more than 600 ℃ or 650 ℃ or (annotate: existing sheet glass has only indicating meter alkali-free boron glass that this performance is just arranged more than 700 ℃, factors such as technology and material but the insider knows it, market price is 250,000-300,000 yuans/ton, ratio is built about 2000 yuans/ton expensive 100 times of soda glass), the present invention exceeds 150 ℃-220 ℃ than 490 ℃ of prior art calcium soda glass, again owing to have very good thermal expansion linear feature, promptly the warm area expansion changes minimum near annealing point, so, one, can adopt fusing point at 540 ℃-730 ℃ glaze, the glaze of preferred 600 ℃ of-650 ℃ or 650 ℃-700 ℃ of fusing points, and this glaze can the not big production in highland of cost, and fusing point cannot be produced greatly at the glaze below 540 ℃, and serious environmental issue arranged) and since the present invention can be under the annealing point temperature sintering printed with fine pattern.So need not take second annealing technology, just can produce meticulous colored glaze bag, grain pattern printing color or the one color product of the low melting point colored glaze decorative flat glass of stone materials such as 2400 * 1200mm, 3000 * 1800mm or the various high-intensity environment-friendly and energy-efficients of a kind of high annealing temperature of the present invention as pattern decorative on-gauge plate sizes such as aluminium plate, layer of wood sheet material, plastic-aluminum sheet material, composite wood board, wood powder density board, resin plates, and product can cut as above-mentioned first technological standard sheet material is any by the construction requirement size unprecedentedly.
Below, embodiments of the invention are described in detail.
First embodiment:
According to one embodiment of the invention, the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature, the fusing point of the glazed colour layer of the 1-10 kind color on its base plate glass surface is at 540 ℃-730 ℃, the base plate glass of its goods is characterised in that: this base plate glass comprises silicon oxide, calcium oxide, magnesium oxide, aluminum oxide, ferric oxide, the composition of sodium oxide, count as weight percents, the content of boron oxide is 0-3.9% in this base plate glass, the content of sodium oxide is 0.01-14%, iron oxide content is 0.01-5%, the content of fluorine oxide is 0-2.8%, content of magnesia is 8.1-22.2%, alumina content is 0.01-39%, the content of its silicon oxide is 1.9 times-4.1 times of calcium oxide content, and the content of calcium oxide is 1.2 times-1.6 times of magnesian content; The thickness difference of this base plate glass is less than 0.3mm; The water-intake rate of its base plate glass is in the scope of 0-0.3%; The folding strength of its base plate glass reaches 50-180Mpa; The annealing temperature lower limit of its base plate glass (being the endotherm(ic)peak origin temp) is 550 ℃-710 ℃.
Count as weight percents, the content of aluminum oxide is smaller or equal to 30% in this base plate glass, and this base plate glass is 10 in viscosity 0.5Temperature when (handkerchief second) is 1480 ℃-1640 ℃; Viscosity is 10 1Temperature when (handkerchief second) is 1410 ℃-1600 ℃; Viscosity is 10 2Temperature when (handkerchief second) is 1180 ℃-1340 ℃; Viscosity is 10 3Temperature when (handkerchief second) is 1040 ℃-1220 ℃; The thickness difference of this base plate glass is less than 0.3mm; The water-intake rate of this base plate glass is in the scope of 0-0.3%; The strain point temperature of this base plate glass is in 560 ℃-720 ℃ scope; The folding strength of this base plate glass is 50-180MPa; The thermal expansivity of this base plate glass is 1,000,000/1.0-3.0/1000000ths in the difference of 150 ℃-300 ℃ two ends numerical value; Difference at 550 ℃-600 ℃ two ends numerical value is 1,000,000/1.0-2.8/1000000ths.
In addition, the adding aluminum oxide can make the intensity of base plate glass improve but can increase the temperature of fusion of glass and the temperature under other various viscosity.Can add the aluminum oxide of proper content according to requirement according to the base plate glass of present embodiment to the demand and the temperature under the various viscosity of intensity.(in addition, in this manual, unless specialize, the percentage composition of various compositions all is weight percentage in the base plate glass.)
The performance characteristic of product of the present invention
The annealing temperature performance
Annotate: the described annealing temperature lower limit of this specification sheets (being the endotherm(ic)peak origin temp) is to adopt comprehensive thermal analyzer to measure.
The annealing temperature lower limit of base plate glass of the present invention (being the endotherm(ic)peak origin temp) is 550 ℃-710 ℃.The annealing temperature lower limit of the base plate glass of the embodiment of the invention (being the endotherm(ic)peak origin temp) preferably is to solve under higher temperature in the purpose of 600 ℃ or 650 ℃ or 650 ℃-700 ℃, under annealing point, the existing easy explosion technical barrier that always perplexs the second annealing of colored glazed glass production just can not appear in agglomeration glaze.
Strength property
Aforesaid (A) existing industry, building glass, as calcium sodium sheet glass, LCD glass, only be about aluminum oxide about 1% or 1-3%, and its technical scheme is difficult for adding aluminum oxide, otherwise can not implement because of viscosity is too high to produce, intensity also only is 45-60MPa.
And according to base plate glass embodiment of the present invention, as described in preceding viscosity part, in the time of can knowing aluminum oxide adding 20-25%, viscosity also is lower than prior art, and the platform of a good technology span of control arranged, aspect the intensity of goods, goods of the present invention can very easily reach 100-160MPa or 130-180MPa.The folding strength that relates to the glass of the embodiment of the invention in this specification sheets by sample being cut into little of 50mm * 5mm * 5mm, adopts the folding strength instrument, measures by standard GB/T3810.4-2006.
The strain point height, coefficient of expansion linear feature is outstanding, and the interval expansion changing value of differing temps is minimum
The coefficient of expansion according to the glass of the embodiment of the invention is measured according to standard GB/T7320.1-2000.
Especially goods do not have too much modification or explosion occurs during the colored glaze sintering when can sharply heat or cool off.But the technical scheme according to the base plate glass of the embodiment of the invention can have better coefficient of expansion linear feature, produce very little glass visco-elasticity sudden change, specifically the thermal expansivity of its goods is 1,000,000/1-3.0/1000000ths in the difference of 150 ℃-300 ℃ two ends numerical value; Difference at 550 ℃-600 ℃ two ends numerical value is 1,000,000/1-2.8/1000000ths; Being used for non-alkali glass is 1,000,000/1-3.0/1000000ths in the difference of 600 ℃-650 ℃ two ends numerical value.Than the thermal expansion of 550 ℃-600 ℃ in prior art calcium sodium float glass and PDP or TFT glass is that the difference of two ends numerical value is 16/1000000ths will get well and 5-16 doubly, is that the difference of two ends numerical value is 20/1000000ths will get well and 7-20 doubly than the thermal expansion of 550 ℃-600 ℃ of LCD calcium soda glass.
This also provides one to use under the colored glaze pattern sintering process of rise suddenly temperature or quench and building and ornament materials fp environment for use, having than existing various glass has better distortion little, stable and do not suddenly change, extremely be difficult for explosion, the little very big advantage of the glass visco-elasticity sudden turn of events when rising suddenly cooling.
Water-intake rate
According to the water-intake rate of the base plate glass of the embodiment of the invention in the scope of 0-0.3%.In addition, the base plate glass of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high according to an embodiment of the invention annealing temperature, it can select to have good transparent feature and water-repellancy.
Water-intake rate according to the base plate glass of the embodiment of the invention is to measure according to standard GB/T3810.3-2006.
Thickness is poor
According to the thickness difference of the base plate glass of the embodiment of the invention in the scope of 0.3mm.
Thickness difference according to the base plate glass of the embodiment of the invention is to measure according to standard GB/T1216.
In order to describe technical scheme in more detail, list the prescription and the corresponding performance of the sample of the base plate glass under the glazed colour layer according to an embodiment of the invention below in the table 1 according to embodiment of the invention base plate glass.
The convenience of controllable economy, stdn and working design
Base plate glass of the present invention can be under the condition than low tens times of existing alkali-free boron sheet glass cost, conform with color glaze glass not under the secondary annealed condition at annealing temperature lower limit (being the endotherm(ic)peak origin temp), (be under the high tens times condition of production efficiency because the alkali-free sheet glass of existing boracic condition can only be with expensive platinum channel device row bubble, article one, 8 tons production line of daily output will be invested and be reached more than 10 hundred million Renminbi, but also essential factor boron composition was to the annual cold repair of the corrosion in molten bath three months, so reach 250,000-300,000 Renminbi/tons, and the present invention's technical scheme can reach same various qualities, especially quality intensity can also exceed 1-2 doubly, and adopt large-tonnage can produce 300 tons-800 tons processing method production daily, investment is 3-4 hundred million Renminbi, so the low 50-80 of cost doubly.) high-quality big production the in reasonable Financial cost ground of energy.This be not very conspicuous just can be the character of sheet glass and annealing temperature lower limit (being the endotherm(ic)peak origin temp), intensity, solve at low cost, this is a kind of technical scheme that unexpected effect is arranged that the essential technique difficult problem of sheet glass on market of inorganic glaze printing prior art never occurred.The insider knows, this has produced new broad-spectrum advantage, and (and tempering glaze panel is inapplicable, can not be as ceramic tile on-site cutting, and as the impression case, the steel plate edge must be the width pattern defect that has about 1-2mm, behind the tempering can not be as ceramic tile edging, and the present invention can be printed as big on-gauge plates such as 2400 * 1200mm, can edging, cutting as ceramic tile, ensure the zero defect and the big plate stdn of product of pattern and use the cutting judicial convenience.
Vide infra and be subordinate list 1
Figure BSA00000450314200181
Table 2 (prior art)
Figure BSA00000450314200201
*Do not go out with high temperature rotary viscosity instrumentation, obtain through reckoning.
From last table 1 as seen:
For the boron oxide of being set forth among the embodiment at 0-3.9%, ferric oxide is at 0.01-5%, titanium oxide is at 0.0003-4.9%, sodium oxide at 0.02-8.8% and magnesium oxide at 8.1-22.2%, and silicon oxide: calcium oxide is 1.9-4.1 times, calcium oxide: magnesium oxide is interior the sample of scope of 1.2-1.6 technical solution of the present invention doubly, at first on viscosity, all be better than have now an incision technology 10 0.5(handkerchief second), 10 1Melt viscosity when (handkerchief second), 10 2Exhaust bubble when (handkerchief second), clarification, homogenizing viscosity are all than 150 ℃-400 ℃ of prior aries (can with reference to comparison sheet 2 and table 3).And its coefficient of linear thermal expansion 150 ℃-300 ℃, at 550 ℃-600 ℃ and in the difference of 600 ℃-650 ℃ two ends numerical value, also good with high boron glass than existing calcium soda glass, PDP glass, alkali-free liquid crystal display.
Sample the 6,7,8,9, the 10th, being in a preferred calcium oxide is magnesian 1.3-1.5 times, silicon oxide be calcium oxide 2.1-3.3 doubly and also alumina content among the more excellent scope of 19-30%, especially technique effect indexs such as the difference of viscosity and linear expansivity and temperature index are best.
And sample 1,2,3,4,5,11, all be within the content of technical solution of the present invention, as seen its viscosity, intensity, the coefficient of expansion should be than TFT liquid crystal display boron glass, PDP plasma panel glass and all prior art sheet glass of all prior aries.
And sample the 1,2,3, the 4th, the upper limit of the magnesium of the present technique invention scheme that adopts, calcium, silicon ratio, lower limit and the example of proportional range of bound of intersecting, and sample 1 and 5 be silicon, calcium, magnesium summation is the example of the upper and lower limit of 59.5-99.8%.
From sample 10,11, because iron level is 1 to 1.3, and higher barium oxide arranged, titanium oxide content and can become opaque brown Huang or pale brown look, with adapt to when produce each outside surface of glaze layer as glasswork the time (as the color glazed brick of pottery, brick modelled after an antique), owing to do not mind the light transmission of glass, so fall cost, expand as the former favourable range of application of common quartz sand of the unavailable big hundreds of times of transparent glass, technology of saving resources effect and the effect (high-grade silicon materials than common price more than high ten times) of about 10 times of main raw material costs of reducing are just fairly obvious.
Table 2 has been listed the glass formula and the relevant performance of some prior aries.As can be seen from Table 2, at first because four kinds of boron that sample contains, iron, titanium, sodium, scope and the present invention of magnesium are different, again because silicon and calcium, and the proportionlity between calcium oxide and the magnesium oxide is all different fully with specific proportions relation of the present invention, its silicon oxide and calcium oxide and calcium oxide and magnesium oxide ratio exceed the present invention greatly, ratio of the present invention is that calcium oxide is 1.2 times-1.6 times of content of magnesia, silicon oxide is 1.9 times-4.1 times of calcium oxide content, and the silicon oxide of these products all is different fully than calcium oxide and calcium oxide than magnesian content.As seen from Table 2 on its technology prejudice always all silicon be as the skeleton of glass and be melted and also be the infusible matrix, so its viscosity, especially 10 0.5(handkerchief second), 10 1Melting process temperature when (handkerchief second), adopt the rotational viscosimeter of standard all to survey to go out at all (because of its viscosity too high), as seen it will overcome energy consumption in fusing, overcomes quarrel point, calculus, the difficulty of lifting production efficiency more greatly or very big.It is 10 of normal exhaust bubble and homogenizing 2Temperature when (handkerchief second) also exceeds 150 ℃-300 ℃ than table 1 sample of the present invention, and the visible energy-conservation and easy to control comparative advantages of the difficulty of its exhaust bubble and homogenizing and technique platform of the present invention are for 10 3The moulding process temperature of (handkerchief second), the present invention is for moulding, planeness, thickness difference for goods also have the manageable comparative advantages of very big technology, and aspect product strength, goods of the present invention also are its 2-3 times, at coefficient of linear expansion, especially be related to the advantage that on the difference of several important warm areas of the linear feature of agglomeration glaze on glass or fire-proof and explosion-proof visco-elasticity value changes, also has very greatly.
Example 1
On the basis of above-mentioned first embodiment, limit by heavy percentage, the content of aluminum oxide is 0.01-30%, silicon oxide: calcium oxide is 2.0-3.6 times, calcium oxide: magnesium oxide is 1.3-1.49 times, and sodium oxide is 0.01-2%, boron oxide is 0-1%, and the content of fluorine oxide is 0-1%; The annealing temperature lower limit of this base plate glass (being the endotherm(ic)peak origin temp) is 610 ℃-710 ℃; This base plate glass is 10 in viscosity 0.5Temperature when (handkerchief second) is 1500 ℃-1640 ℃; Viscosity is 10 1Temperature when (handkerchief second) is 1450 ℃-1580 ℃; Viscosity is 10 2Temperature when (handkerchief second) is 1210 ℃-1350 ℃; Viscosity is 10 3Temperature when (handkerchief second) is 1070 ℃-1230 ℃; The folding strength of this base plate glass is 50-180MPa.
Example 2
On the basis of above-mentioned first embodiment, limit by heavy percentage, the content of aluminum oxide is 8-30%, silicon oxide: calcium oxide is 2.0-3.6 times, calcium oxide: magnesium oxide is 1.3-1.49 times, and sodium oxide is 0.01-2%, boron oxide is 0-1%, and the content of fluorine oxide is 0-1%; The annealing temperature lower limit of this base plate glass (being the endotherm(ic)peak origin temp) is 610 ℃-680 ℃; This base plate glass is 10 in viscosity 0.5Temperature when (handkerchief second) is 1520 ℃-1640 ℃; Viscosity is 10 1Temperature when (handkerchief second) is 1450 ℃-1580 ℃; Viscosity is 10 2Temperature when (handkerchief second) is 1210 ℃-1350 ℃; Viscosity is 10 3Temperature when (handkerchief second) is 1070 ℃-1230 ℃; The folding strength of this base plate glass is 75-180MPa.
Example 3
On the basis of above-mentioned first embodiment, limit by heavy percentage, the content of aluminum oxide is 19-30%, silicon oxide: calcium oxide is 2.0-3.6 times, calcium oxide: magnesium oxide is 1.3-1.49 times, and sodium oxide is 0.01-2%, boron oxide is 0-1%, and the content of fluorine oxide is 0-1%; The annealing temperature lower limit of this base plate glass (being the endotherm(ic)peak origin temp) is 610 ℃-680 ℃; This base plate glass is 10 in viscosity 0.5Temperature when (handkerchief second) is 1550 ℃-1640 ℃; Viscosity is 10 1Temperature when (handkerchief second) is 1450 ℃-1580 ℃; Viscosity is 10 2Temperature when (handkerchief second) is 1210 ℃-1350 ℃; Viscosity is 10 3Temperature when (handkerchief second) is 1080 ℃-1230 ℃; The folding strength of this base plate glass is 130-180MPa.
Example 4
On the basis of above-mentioned first embodiment, limit by heavy percentage, the content of aluminum oxide is 0.01-19%, silicon oxide: calcium oxide is 2.0-3.6 times, calcium oxide: magnesium oxide is 1.3-1.49 times, and sodium oxide is 0.01-2%, boron oxide is 0-1%, and the content of fluorine oxide is 0-1%; The annealing temperature lower limit of this base plate glass (being the endotherm(ic)peak origin temp) is 610 ℃-680 ℃; This base plate glass is 10 in viscosity 0.5Temperature when (handkerchief second) is 1500 ℃-1580 ℃; Viscosity is 10 1Temperature when (handkerchief second) is 1450 ℃-1520 ℃; Viscosity is 10 2Temperature when (handkerchief second) is 1210 ℃-1310 ℃; Viscosity is 10 3Temperature when (handkerchief second) is 1070 ℃-1160 ℃; The folding strength of this base plate glass is 50-145MPa.
Example 5
On the basis of above-mentioned first embodiment, to the composition of base plate glass, limit meter as weight percents, the content of titanium oxide is 0.0003-4.9%.
Example 6
On the basis of above-mentioned first embodiment, to the composition of base plate glass, limit meter as weight percents, barytic content is 0.01-14%.
Example 6
On the basis of above-mentioned first embodiment, to the composition of base plate glass, limit meter as weight percents, its silicon oxide, calcium oxide, magnesium oxide three's content summation is 51-99.8%.
Example 7
On the basis of above-mentioned first embodiment, composition to base plate glass, limit meter as weight percents, the content of calcium oxide is 1.3 times-1.6 times of magnesian content, the content of silicon oxide is 2.0 times-3.6 times of content of calcium oxide, magnesian content is 10.1-19.9%, and the content of aluminum oxide is 19-39%.
Example 8
On the basis of above-mentioned first embodiment,, limit the composition of base plate glass:
(1), counts as weight percents, in its base plate glass content: 1. magnesium oxide accounts for 7-20%, 2. calcium oxide is in magnesian 1.0 times-1.8 times scope, 3. silicon oxide is in magnesian 2.6 times-5.6 times scope, 4. silicon oxide is in 2.2 times-3.8 times the scope of calcium oxide, 5. aluminum oxide is 0.1-30%, and 6. sodium oxide is 0-18%, and 7. barium oxide is 0-5%; Count as weight percents, the content summation of the middle magnesium oxide of the base plate glass of its goods, calcium oxide, three kinds of compositions of silicon oxide reaches 51%-100%; Its performance is as follows:
The strain point temperature of the base plate glass of its goods is in 560 ℃-720 ℃ scope;
The water-intake rate of the base plate glass of its goods is in the scope of 0-0.001%;
Example 9
On the basis of above-mentioned first embodiment, to the composition of base plate glass, limit meter as weight percents, the content of aluminum oxide is smaller or equal to 30% in its base plate glass, and this base plate glass is 10 in viscosity 0.5Temperature when (handkerchief second) is 1480 ℃-1640 ℃; Viscosity is 10 1Temperature when (handkerchief second) is 1410 ℃-1600 ℃; Viscosity is 10 2Temperature when (handkerchief second) is 1180 ℃-1340 ℃; Viscosity is 10 3Temperature when (handkerchief second) is 1040 ℃-1220 ℃; The thickness difference of this base plate glass is less than 0.3mm; The water-intake rate of this base plate glass is in the scope of 0-0.3%; The strain point temperature of this base plate glass is in 560 ℃-720 ℃ scope; The folding strength of this base plate glass is 50-180MPa; The thermal expansivity of this base plate glass is 1,000,000/1.0-3.0/1000000ths in the difference of 150 ℃-300 ℃ two ends numerical value; Difference at 550 ℃-600 ℃ two ends numerical value is 1,000,000/1.0-2.8/1000000ths.
Example 10
On the basis of above-mentioned first embodiment, apply the quartz crystal or the alpha-alumina crystals that contain 20-70% in the glaze layer to the base plate glass top layer.
Example 11
According to the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the thickness of the base plate glass of its goods is 0.3-1.8mm.
Example 12
According to the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the first embodiment of the present invention, the thickness of the base plate glass of its goods is 1.8-20mm.
Example 13
On the basis of above-mentioned first embodiment, to the composition of base plate glass, limit meter as weight percents, the content of sodium oxide is 0.01-2%.
Example 14
On the basis of above-mentioned first embodiment, to the composition of base plate glass, limit meter as weight percents, the content of sodium oxide is 2.1-5%.
Example 15
On the basis of above-mentioned first embodiment, to the composition of base plate glass, limit meter as weight percents, the content of sodium oxide is 2.1-8%.
Example 16
On the basis of above-mentioned first embodiment, to the composition of base plate glass, limit meter as weight percents, the content of sodium oxide is 2.1-14%.
Example 17
On the basis of above-mentioned first embodiment, to the composition of base plate glass, limit meter as weight percents, the content of aluminum oxide is 1-19%.
More than be to composition and characteristic thereof, the method for manufacturing according to the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature of the embodiment of the invention is described below according to the base plate glass of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature of the embodiment of the invention.
Second embodiment
Seeing also shown in Figure 1ly, is the base plate glass goods floor map of low melting point colored glaze decorative flat glass of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of according to an embodiment of the invention high annealing temperature and preparation method's the high-intensity environment-friendly and energy-efficient of high annealing temperature.From scheming as seen the base plate glass of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of label 1 a kind of high annealing temperature of expression.
Seeing also shown in Figure 2ly, is the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the present invention and the preparation method schematic flow sheet to the floating process moulding that base plate glass adopted of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature.From scheming as seen; the flow process of its moulding process is that the raw material of predetermined preparation is put into feeding warehouse; from feeding warehouse, raw material is transported in the kiln of molten bath then; entered the molten bath and carried out fusion and vent gas bubble by preset temperature; it then is liquid molten mass; enter into molten tin bath (next door of molten tin bath is provided with the shielding gas station of nitrogen hydrogen to molten tin bath input protection gas); on the tin face of molten tin bath, drop down flat; through drawing the limit; traction; form the smooth work in-process band of polishing; enter into the annealing furnace cooling of lowering the temperature from the transition roller platform; and obtain goods; on the cutting portioning station, enter the cutting packing of predetermined size again, obtain the base plate glass work in-process of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature.
Seeing also shown in Figure 3ly, is the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the present invention and preparation method adopt the state of floating process moulding to the base plate glass of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature side diagrammatic cross-section.From scheming as seen, label 2 expression feed bin opening for feeds, label 3 expression feed bins, the mixing raw material of the predetermined preparation of label 4 expressions, label 5 expression mixing raw materials enter the molten bath kilneye (mixing raw material of the predetermined preparation shown in the label 4 is transported in the molten bath of molten bath kiln thus) in molten bath, label 12 expression float glass line matrixes, label 6 expression molten bath kilns, liquid molten raw material body in the label 7 expression baths enters the diversion trench of molten tin bath, the molten tin bath of label 8 expression floating process, the work in-process band that forms in the label 9 expression molten tin baths enters the transition roller platform of annealing furnace, label 10 expression annealing furnaces, and the cutting portioning station of packing is cut moulded products in label 11 expressions.
See also shown in Figure 4ly, the size that is the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the present invention and preparation method embodiment is that the colored glaze material that prints predetermined three look districts of 1220mm * 2440mm forms the floor map of low melting point colored glaze decorative flat glass goods that the top layer is the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of predetermined colored glaze material pattern decorative layer.From scheming as seen, the base plate glass of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of label 1 a kind of high annealing temperature of expression, label 21 oblique lines are partly represented the first look district colored glaze material pattern area of having printed, label 31 wire cross represent that partly the second look district colored glaze material pattern area of having printed, label 41 pores partly represent the tertiary color district colored glaze material pattern area of having printed.
See also shown in Figure 5ly, the size that is the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the present invention and preparation method embodiment is that the colored glaze material that prints predetermined three look districts of 1220mm * about 2-5mm of 2440mm thickness forms the diagrammatic cross-section of low melting point colored glaze decorative flat glass goods of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature that the top layer is the predetermined colored glaze material pattern decorative layer of about 0.1-1mm thickness.From scheming as seen the base plate glass of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of label 1 a kind of high annealing temperature of expression, the glaze pattern decorative layer that has printed predetermined three pattern colour district colored glaze material on label 123 expression upper stratas.
See also shown in Figure 6, be that the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the present invention and the top layer of preparation method embodiment are the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature, the back side is the aluminium sheet that overlapping back portion does not exceed surface silicon hydrochlorate colored glaze ambetti size, the NEW TYPE OF COMPOSITE sheet material cross-sectional view of pasting compound composition by tackiness agent mutually.From scheming as seen, label 13 expressions have the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature of glazed colour layer, the overlapping back of label 14 expressions portion does not exceed the aluminium sheet of the low melting point colored glaze decorative flat glass limit portion of the high-intensity environment-friendly and energy-efficient of the high annealing temperature in top layer, the predetermined tackiness agent of label 15 expressions.
See also shown in Figure 7, be that the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the present invention and the top layer of preparation method embodiment are the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature, the back side is to have 2 limits separately the aluminium sheet that has stretched out the 10-30mm distance than surface silicon hydrochlorate colored glaze ambetti size, the NEW TYPE OF COMPOSITE sheet material cross-sectional view of pasting compound composition mutually more.From scheming as seen, label 13 expressions have the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature of glazed colour layer, there are 2 limits separately the aluminium sheet that has stretched out the 10-30mm distance than the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of the high annealing temperature in top layer, the tackiness agent that label 15 expressions are scheduled to after label 141 expression is overlapping more.
See also shown in Figure 8, be that the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the present invention and the employing top layer of preparation method embodiment are the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature, the back side is to have after overlapping 2 limits separately the aluminium sheet that has stretched out 10-30mm than surface silicon hydrochlorate colored glaze ambetti size more, paste the NEW TYPE OF COMPOSITE sheet material of compound composition mutually, after the punching of the predetermined position on the 10-30mm extension, can carry out the upright two dimensional structure synoptic diagram that the metope screw is installed.From scheming as seen, label 13 expressions have the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature of glazed colour layer, have 2 limits separately the aluminium sheet that has stretched out the 10-30mm distance than the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of the high annealing temperature in top layer after label 141 expression is overlapping, label 16 represents that the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of the high annealing temperature in ratio top layer of aluminium sheet at the bottom of the back of the body of composite sheets stretches out the screw open holes in the limit portion of 10-30mm more.
Now with the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the present invention and the making its glasswork and print colored glaze ornament layer formation goods of preparation method with the float glass process moulding technique, be described further, its manufacturing processed comprises following steps:
[1], at first, preparation raw material is calculated proportioning raw materials according to the various compositional range of the glass of first embodiment.
[2], be ready to the float glass process production line that comprises facilities such as former feed bin, molten bath kiln, the tin kiln that contains tin liquor and edge machine, tractor, transition roller platform, annealing furnace cooling system, cutting portioning station of floating process as shown in Figure 3.
[3], press the Production Flow Chart of Fig. 3 and floating process shown in Figure 2, the compound of the predetermined preparation shown in the label 4 of [1] step preparation, from the feed bin opening for feed shown in the label 2 of Fig. 3, be conveyed in the former feed bin shown in the label 3 in raw material conveying belt mode, again through the molten bath kilneye shown in the label 5, [1] step prepared mixture is sent in the molten bath of the predetermined resistant to elevated temperatures molten bath kiln shown in the label 6, progressively (for alumina content is situation below 30% corresponding to the humidity province of the temperature of fusion of each glass formula the time, temperature of fusion can be in the scope of 1360 ℃-1460 ℃ temperature or 1460 ℃-1680 ℃) form the liquid melting body of good fluidity, progressively discharge bubble in the liquid raw material through the high-temperature zone, promptly formed the flowability mixing raw material molten mass preferably that can enter molding procedure.
[4], by the Production Flow Chart of floating process shown in Figure 2 and shown in Figure 3, the flowable that makes [3] step is the mixing raw material molten mass preferably, from the folder mouth of the molten bath kiln shown in the label 6 through the diversion trench shown in the label 7, flow on the tin face of the molten tin bath (also can be described as the tin kiln) shown in the label 8 of float glass process production line, flat through dropping down again, draw the traction of limit and tractor through edge machine, polishing is thrown flat on the tin liquor face, after formation work in-process band goes out the tin kiln by the transition roller platform shown in the label 9, enter the annealing furnace cooling of the cooling cooling system of the roller-way shown in the label 10, enter into the cutting portioning station shown in the label 11 again, through cutting, packing, the fusing point of glazed colour layer of 1-10 kind color that can make its base plate glass surface of the present invention as shown in Figure 1 is at 540 ℃-730 ℃, this base plate glass comprises silicon oxide, calcium oxide, magnesium oxide, aluminum oxide, ferric oxide, titanium oxide, the composition of sodium oxide, count as weight percents, the content of boron oxide is 0-3.9% in this base plate glass, the content of sodium oxide is 0.01-14%, iron oxide content is 0.01-5%, the content of fluorine oxide is 0-2.8%, titanium oxide is 0.0003-4.9%, content of magnesia is 8.1-22.2%, alumina content is 0.01-39%, the content of its silicon oxide is 1.9 times-4.1 times of calcium oxide content, and the content of calcium oxide is 1.2 times-1.6 times of magnesian content; The thickness difference of this base plate glass is less than 0.3mm; The water-intake rate of its base plate glass is in the scope of 0-0.3%; The folding strength of its base plate glass reaches 50-180Mp; This base plate glass is 10 in viscosity 0.5Temperature when (handkerchief second) is 1480 ℃-1640 ℃; Viscosity is 10 1Temperature when (handkerchief second) is 1410 ℃-1600 ℃; Viscosity is 10 2Temperature when (handkerchief second) is 1180 ℃-1340 ℃; Viscosity is 10 3Temperature when (handkerchief second) is 1040 ℃-1220 ℃; The thickness difference of this base plate glass is less than 0.3mm; The water-intake rate of this base plate glass is in the scope of 0-0.3%; The annealing temperature lower limit of this base plate glass (being the endotherm(ic)peak origin temp) is in 550 ℃-710 ℃ scope; The folding strength of this base plate glass is 50-180MPa; The thermal expansivity of this base plate glass is 1,000,000/1.0-3.0/1000000ths in the difference of 150 ℃-300 ℃ two ends numerical value; It in the difference of 550 ℃-600 ℃ two ends numerical value the base plate glass of low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of 1,000,000/1.0-2.8/1000000ths.
[5], the base plate glass of low melting point colored glaze decorative flat glass that top layer shown in the label 1 is not had a high-intensity environment-friendly and energy-efficient of high annealing temperature of glaze pattern enters the printing position on the transfer limes successively, by the predetermined pattern requirement, adopt successively and be equipped with predetermined first, second and the colored glaze material printing equipment of tertiary color district printed patterns version, respectively white enamel is printed onto the base plate glass top layer of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature shown in the label 1 by the printed patterns district shown in the label 21 oblique lines part of the first look district printed patterns version; Dark orange glaze is printed onto the base plate glass top layer of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature shown in the label 1 by the printed patterns district shown in the label 31 wire cross part of the second look district printed patterns version; Shallow orange glaze is printed onto the base plate glass top layer of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature shown in the label 1 by the printed patterns district shown in the label 41 pores part of tertiary color district printed patterns version; So far promptly finished predetermined white, the printing of three look district colored glaze material of orange, shallow orange deeply, in operating procedure, the printing of control glaze layer is about the thickness of 0.1-1mm.
[6], to be printed with predetermined white, dark orange, the base plate glass of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature of the pattern decorative layer that three look district colored glaze material of shallow orange form, enter into the roller kiln of glaze sintering circuit by transfer limes, under the processing condition by the base plate glass distortion softening point temperature of the known low melting point colored glaze decorative flat glass that should be lower than the high-intensity environment-friendly and energy-efficient of high annealing temperature in the industry, make the different process required different humidity province of silicate glaze to set, progressively carry out preheating and heat up firing, through cooling, can make as shown in Figure 4 surface again by white, dark orange, it is 2-5mm that three glaze looks of shallow orange district composition pattern is of a size of 1220mm * 2440mm thickness, the thermal strain temperature spot is the annealing temperature lower limit within 550 ℃-600 ℃ or 600 ℃ of-650 ℃ of scopes, folding strength reaches the goods of low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature of 50-160MPa.From Fig. 4 as seen, label 1 expression top layer does not have the base plate glass of low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature of glaze pattern, label 21 oblique lines are partly represented the first look district colored glaze material pattern area of having printed, label 31 wire cross represent that partly the second look district colored glaze material pattern area of having printed, label 41 pores partly represent the tertiary color district colored glaze material pattern area of having printed.And from its section, then be as shown in Figure 5, the top layer of the about 2-5mm thickness of its label 1 expression do not have the base plate glass of low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature of glaze pattern, the glaze pattern decorative layer of the colored glaze material of the about 0.1-1mm thickness that has printed predetermined white, dark orange, three look districts of shallow orange composition pattern on label 123 expression upper stratas.
The modification 1 of second embodiment
In the selection to the preparation method of the base plate glass of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature of above-mentioned second embodiment, the following processing method that can also select to adopt is carried out, as:
Also can select 1, adopt horizontal drawing technology: the flowable molten mass that forms is had that drawing of horizontal drawing technology characteristics is thin, moulding, annealing, cools off, cuts making, through glaze and the sintering of bedying, make the base plate glass of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature again;
Perhaps also can select 2, adopt lattice-method process: the flowable molten mass that forms is adopted lattice-method process moulding, annealing, cools off, cuts making, through glaze and the sintering of bedying, make the base plate glass of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature again;
Perhaps also can select 3, adopt calendering technology: the flowable molten mass that forms is adopted that calendering technology rolls, moulding, annealing, cools off, cuts making, through glaze and the sintering of bedying, make the base plate glass of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature again;
Perhaps also can select 4, adopt press over system technology: the flowable molten mass that forms is adopted that press over system technology is drawn down, moulding, annealing, cools off, cuts making, through glaze and the sintering of bedying, make the base plate glass of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature again;
Above technology also all can make the fusing point of glazed colour layer of 2-10 kind color on its base plate glass surface of the present invention at 540 ℃-730 ℃, this base plate glass comprises silicon oxide, calcium oxide, magnesium oxide, aluminum oxide, ferric oxide, titanium oxide, the composition of sodium oxide, count as weight percents, the content of boron oxide is 0-3.9% in this base plate glass, the content of sodium oxide is 0.01-14%, iron oxide content is 0.01-5%, the content of fluorine oxide is 0-2.8%, titanium oxide is 0.0003-4.9%, content of magnesia is 8.1-22.2%, alumina content is 0.01-39%, the content of its silicon oxide is 1.9 times-4.1 times of calcium oxide content, and the content of calcium oxide is 1.2 times-1.6 times of magnesian content; The thickness difference of this base plate glass is less than 0.3mm; The water-intake rate of its base plate glass is in the scope of 0-0.3%; The folding strength of its base plate glass reaches 50-180Mp; This base plate glass is 10 in viscosity 0.5Temperature when (handkerchief second) is 1480 ℃-1640 ℃; Viscosity is 10 1Temperature when (handkerchief second) is 1410 ℃-1600 ℃; Viscosity is 10 2Temperature when (handkerchief second) is 1180 ℃-1340 ℃; Viscosity is 10 3Temperature when (handkerchief second) is 1040 ℃-1220 ℃; The thickness difference of this base plate glass is less than 0.3mm; The water-intake rate of this base plate glass is in the scope of 0-0.3%; The annealing temperature lower limit of this base plate glass (being the endotherm(ic)peak origin temp) is in 550 ℃-710 ℃ scope; The folding strength of this base plate glass is 50-180MPa; The thermal expansivity of this base plate glass is 1,000,000/1.0-3.0/1000000ths in the difference of 150 ℃-300 ℃ two ends numerical value; It in the difference of 550 ℃-600 ℃ two ends numerical value the base plate glass of low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of 1,000,000/1.0-2.8/1000000ths.
The modification 2 of second embodiment
Colored glaze pattern decorative layer on its product surface, be by the 2-100 cover is set, the monolith articles printing device unit that every cover is made up of 1-10 plane wire mark or roll printing device or ink jet printing device, mode with layout in parallel, surface to the base plate glass of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of described high annealing temperature, carry out the printing of colored glaze material, carry out the glaze sintering circuit again, the prepared low melting point colored glaze decorative flat glass goods that in same batch of production of articles, make 2-100 piece product surface produce the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of every default different printing pattern that 1-10 kind color arranged or color glaze ornament layer.
The modification 3 of second embodiment
Contain in the glaze of its product surface ornament layer or corundum crystal or quartz crystal or gehlenite crystal or nepheline crystal or merwinite crystal or calcio-akermanite crystal or mullite crystal or diopside crystal or wollastonite crystal or willemite crystal or cordierite crystal or monticellite crystal or enstatite crystal or contain crystalline lithium or spinel crystal or rutile crystal.
The modification 4 of second embodiment
The composition board of its goods is by compound composition of sheet metal (3) of low melting point colored glaze decorative flat glass goods (1) and bonding material layer (2) and the 0.1-1mm or the 1-5mm thickness of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature.
The modification 5 of second embodiment
The 2-4 bar limit of the metal sheet of the back of the body bottom surface of the composition board of its goods, the distance that 10-30mm has stretched out in the limit portion of the low melting point colored glaze decorative flat glass goods of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature in the top layer of proportion poststack.
Application of the present invention and be different from the characteristics of prior art:
To low melting point colored glaze decorative flat glass according to the high-intensity environment-friendly and energy-efficient of high annealing temperature of the embodiment of the invention, the fundamental difference of itself and prior art just, conclude again and be summarized as follows:
The present invention has the technical scheme of novelty to be in dull and stereotyped colored glazed glass field: the fusing point of the glazed colour layer of the 1-10 kind color on its base plate glass surface is at 540 ℃-730 ℃, the base plate glass of its goods is characterised in that: this base plate glass comprises silicon oxide, calcium oxide, magnesium oxide, aluminum oxide, ferric oxide, the composition of sodium oxide, count as weight percents, the content of boron oxide is 0-3.9% in this base plate glass, the content of sodium oxide is 0.01-14%, iron oxide content is 0.01-5%, the content of fluorine oxide is 0-2.8%, content of magnesia is 8.1-22.2%, alumina content is 0.01-39%, the content of its silicon oxide is 1.9 times-4.1 times of calcium oxide content, and the content of calcium oxide is 1.2 times-1.6 times of magnesian content; The thickness difference of its base plate glass is less than 0.3mm; The water-intake rate of its base plate glass is in the scope of 0-0.3%; The folding strength of its base plate glass reaches 50-180Mp; The annealing temperature lower limit of its base plate glass (being the endotherm(ic)peak origin temp) is 550 ℃-710 ℃.
The present invention has annealing temperature lower limit (being the endotherm(ic)peak origin temp) and different necessary 550 ℃ of higher-710 ℃ of character of existing calcium sodium sheet glass, and the annealing temperature lower limit (being the endotherm(ic)peak origin temp) of can be under the prerequisite of economy preferred 600 ℃ or 650 ℃ or 700 ℃, the present invention at first is a kind of component invention, for colored glaze sheet glass, at first be, the temperature of fusion of the glazed colour layer of 1-10 kind color of the present invention has been selected 540 ℃-730 ℃ scope, and the sheet glass that must cooperate with it has the new property feature different with prior art sheet glass of following level.
One, sheet glass for all prior aries under the glazed colour layer, importantly use a kind of to aluminium, silicon, calcium, magnesium, iron, the selection invention of the composition scope of sodium and to silicon, calcium, between the magnesium composition, the technical scheme of the change invention of the proportionlity of these technology essential factors is a silicon: calcium is 2.0-4.1, calcium: magnesium is 1.2-1.6 scope doubly, and all sheet glass of prior art, two end values of the rarest factor proportion relation, outside the scope of the invention, within the close limit that is chosen in all prior aries of the factor proportion relation that the present invention just is above-mentioned, has novelty.And in the present invention's glazed colour layer sheet glass purposes, in the technology, found new following product property, produced following unforeseeable technique effect.
They are two years old, the migrate invention type of new purposes of the new character that the present invention has disclosed the product of finding, also be produced unforeseeable effect (promptly by various sheet glass working methods, aspect new sheet glass purposes, the outstanding new viscosity temperature and the product in [1] the different process stage that can produce, [2] thickness is poor, [3] water-intake rate, [4] folding strength, [5] visible transmission ratio, [6] percent ripple, sheet glass new properties such as [7] thermal linear expansion coefficient feature, new purposes feature).
Especially in new purposes, the present invention has found the new reduction viscosity temperature and the eutectic character of the product that prior art never disclosed, melting process stage viscosity temperature, homogenizing, row's bubble, clarification process stage viscosity temperature is especially controlled the planeness of percent ripple or thickness is poor, the viscosity temperature that draws thin (or the polishing in the floating process) technology in moulding process stage.
(A), because a kind of key element to the sodium oxide technology of dull and stereotyped calcium soda glass that one of discovery of the new character of product has overcome that conventional art prejudice produces is omitted invention: the sheet glass of prior art, almost all building glasses more than 99.9%, general industry glass, it all contains the sodium about 13%, be mainly used to flux, especially to the fluxing of silicon composition, form the reduction that to control viscosity of each operation stage.But the new property of the product of technical scheme of the present invention and discovery, broken this technology prejudice, can be owing to silicon, calcium, the variation invention of the element relationship between the magnesium, in the purposes of sheet glass, the product new property that produces, when sodium content is in 0-1%, can be than low 150 ℃-250 ℃ of the viscosity temperature of several operation stages of the high sodium sheet glass of prior art, this will produce a large amount of energy-conservation and to help high-quality control product thickness poor, percent ripple, sheet glass calculus with the bad generation of melting process, the defectives such as bubble rate of quarrel point and the bad generation of row's bubble technology, especially can significantly promote the quality that has certain requirements as the ultrafine sheet glass of LCD display of 0.5-1.1mm, reduce the quarrel point, the calculus rate, bubble rate, reduce defective thickness rate and defective percent ripple rate.
Prior art is in operation, if in case produce the defective of any one operation stage, prior art all is easy to increase the temperature of each operation stage in operation mode solves, but this just is prone to the molten bath is collapsed top, reduction of service life greatly very much.And the invention provides the viscosity variable range that a technology that helps controlling very much technology is controlled.Fundamentally solved the technical barrier of the product property (" material " promptly said in the industry) of the existing sodium that the insider thinks always (high sodium) sheet glass " material property is short ".
(B), because two of the discovery of the character that product is new, overcome the prejudice of conventional art, produced a kind of key element omission invention: the existing alkali-free boron sheet glass that is particularly useful for liquid-crystal display to " boron oxide " technology essential factor of alkali-free boron glass, it surpasses 1% sodium owing to not containing, adopted the boron composition of 8-15% content to make the fusing assistant composition, the technology prejudice of thinking to go in the side of being far from it is arranged, especially form fluxing to silicon, with the reduction control of the viscosity temperature that can form high-quality each operation stage of sheet glass, and the annealing temperature lower limit (being the endotherm(ic)peak origin temp) that can produce base plate glass reaches 600 ℃-730 ℃ technique effect.But the new property of technical scheme of the present invention and discovery, broken this technology prejudice, can be owing to silicon, calcium, the variation invention of the element relationship between the magnesium, in the sheet glass purposes, produce new product property, when not having boron oxide content or only being 0-1%, not only can make the annealing temperature lower limit (being the endotherm(ic)peak origin temp) of base plate glass reach 600 ℃-730 ℃, can also be than the viscosity temperature with the product of the boron of 8-15% content of prior art, than low 250 ℃-350 ℃ of several operation stages of the sheet glass of existing alkali-free boron glass, this will form the new technology platform that a very large-scale CONTROL PROCESS reaches the control quality product, compare prior art glass, it is poor to reach the higher level thickness, percent ripple level and almost do not have bubble, there is not the quarrel point, the yield rate of the ultra-thin product of the 0.5-2mm thickness of the quality requirements of no calculus defective, the quality product rate, especially for exhaust bubble and clarification, homogenizing process stage and moulding, draw the viscosity of thin operation stage, a kind of technology controlling and process scope and the technology controlling and process platform more much better than prior art all are provided.
The proportionlity of the present invention's silicon, calcium, magnesium key element changes the technical scheme of invention, has overcome prior art and has only added the technology prejudice that the great talent has generation annealing temperature lower limit (being the endotherm(ic)peak origin temp) to rise by aluminium or boron composition.Technique scheme of the present invention can be created in boron and aluminium and be lower than 1% annealing temperature lower limit when following (endotherm(ic)peak origin temp) and also can rise about 100 ℃, and sodium content is lower than 2% annealing temperature lower limit when following (endotherm(ic)peak origin temp) and also has bigger rising (the sample example of seeing attached list).If on above technical scheme, also add alumina content more certainly, can form the technique effect that annealing temperature lower limit (being the endotherm(ic)peak origin temp) is risen again.Make it to reach the character requirement of the low cost of core of the present invention, high annealing point.
(C), (1), of the present inventionly a kind ofly the existing a kind of above-mentioned key element that accounts in the calcium sodium sheet glass of sheet glass total amount more than 99% 13% sodium content is omitted invention to have produced the annealing temperature lower limit (being the endotherm(ic)peak origin temp) that can make base plate glass is 610 ℃-710 ℃ product properties that are preferably 650 ℃-680 ℃, and the annealing temperature lower limit of all present dull and stereotyped calcium soda glass (being the endotherm(ic)peak origin temp) only is 490 ℃.And the annealing temperature lower limit (being the endotherm(ic)peak origin temp) of the sheet glass of the no boron of the present invention's alkali-free (or only being the sodium of 0.01-1%) is 610 ℃-710 ℃, because minimum by technical scheme magnesium of the present invention is 8.1% (generally reaching 12-18%), calcium is minimum to be 9.6% (being generally 15-18%), this composition is the major cause that the annealing temperature lower limit (being the endotherm(ic)peak origin temp) of base plate glass significantly rises, can exceed 120 ℃-200 ℃ than the annealing temperature lower limit (being the endotherm(ic)peak origin temp) of common existing dull and stereotyped calcium soda glass, this is that this is very important on the technique effect of colored glazed glass of the present invention for the discovery of another new product property, just because of the annealing temperature lower limit of existing calcium sodium sheet glass (being the endotherm(ic)peak origin temp) only is 490 ℃, so if make the sintering of inorganic colored glaze, a kind of selection is as existing mosaic glass, can only make the fritter of 2-5cm size, and use cost is hanged down the low temperature glaze (fusing point approximately) of some, its area is little, second annealing is less demanding, does not just split.
(2) if second select, to make 10cm, 20cm and let alone and make 60cm * 60cm's or large size more, second annealing is difficulty very, and rupture rate is high, and the big production of product never successfully occurred on prior art and the market.Large size is all used the organic resin typography, and it has certain out of doors variable color and combines not well problem with glass, again cannot be bonding as ceramic tile, and because of glue for tile can corrode color resin, also sticking insecure.The sheet glass of prior art can not be used the size product of light, thin glass colored glaze flat board, substitutes the thick and heavy tile product of high energy consumption.
(3), the 3rd selection is the glaze (annotate: ceramic tile glaze fusing point is about 950 ℃-1200 ℃) that adopts existing 490 ℃ of left and right sides fusing points, as make the little lines of the applique product on normal cup, the bottle, minimum area account for refute use high, can not use in a large number, there are not finishing material big area, large-tonnage economy to say, so without any examples of applications.
(4) and the 4th be chosen as and adopt existing alkali-free boron sheet glass, promptly because the glass of liquid-crystal display, its prior art production cost is high, about 300,000 yuan/ton of existing market price, if 0.7mm thickness to reach 600 yuans/m 2, PDP plasma glass 1.8-2.8mm is thick also reaches 1000 yuans/m 2So though its ANNEALING OF GLASS lowest temperature (being the endotherm(ic)peak origin temp) can reach 580 ℃-680 ℃ or 700 ℃, can be with the glaze of 600 ℃-650 ℃ the fusing point that economy is arranged, but its glass cost does not have the substrate as finishing material, substitute ceramic tile, even the economic feasibility of most significant end ceramic tile.And the newfound annealing temperature lower limit (being the endotherm(ic)peak origin temp) of the sheet glass of a kind of key element omission invention of above-mentioned no boron alkali-free of the present invention can reach 600 ℃-730 ℃, and can foregoingly there be Financial cost low, and quality better, the mode of production that output is big, production the present invention's glass substrate can adopt 600 ℃-730 ℃ colored glaze material of economic feasibility to carry out combinations produce again.So this alternative ceramic tile that has been a kind of solution that unforeseeable technique effect arranged, the people that solve existing finishing material thirst for for a long time solving and not have a difficult problem of solution.
(5), here be noted that, though increasing calcium, the content of magnesium is as reaching the calcium soda glass that surpasses prior art of 19-50% (calcic+magnesium altogether 10-12%), can omit the boron composition just can make ANNEALING OF GLASS lowest temperature (being the endotherm(ic)peak origin temp) rise greatly, and have sodium oxide to reach 2-13% also can to rise greatly, just smaller than annealing temperature lower limit (the being the endotherm(ic)peak origin temp) rising of the product of no sodium or low sodium, but be not that the composition of adding calcium and magnesium just can reach the purpose of production, because also want to have simultaneously the processing condition of the viscosity temperature that is appropriate to the especially lower exhaust bubble of sheet glass.The sheet glass of prior art, if only strengthen the content of calcium and magnesium, rather than have strengthening its viscosity temperature of calcium-magnesium content exactly than all prior aries and still can being higher than 150 ℃-300 ℃ of the present invention of mutual proportionlity between the present invention's the silicon, calcium, magnesium, again such as alkali-free boron sheet glass, it has added the fusing assistant boron composition of 8-15%, the aluminum oxide that has just only added 8-10% is 10 in viscosity 2Row when (handkerchief second) steeps the temperature of technology up to more than 1500 ℃, must finish exhaust bubble operation with the high platinum row bubble passage of a kind of shallow pool (depth of metal is 5-10cm only), and produce only several tons daily.So itself and low viscosity of the present invention, can the comparing of technical scheme that high annealing temperature lower limit (being the endotherm(ic)peak origin temp) is arranged again with hundreds of ton day output explained hereafter (Pai Pao district pool depth reaches 70-100cm), its quantum of output differs from tens times, and to reach large-tonnage production capacity of the present invention, to go up tens lines, and invest many tens times of meeting.Just say, in the rising that solves annealing temperature lower limit (being the endotherm(ic)peak origin temp), make it to conform with the requirement of various display plate glass and colored glaze and sheet glass such as fire-proof and explosion-proof, an existing incision technology sheet glass, or just strengthen the technical scheme that calcium+magnesium reaches 20-50%, rather than take the variation invention of the present invention's factor proportion relation, the technical scheme of selection invention, all be the unforeseeable combination technique effect that can not take into account cost and annealing temperature lower limit (being the endotherm(ic)peak origin temp).
(6), it produces that unforeseeable technique effect not only is can be in annealing temperature lower limit (the being the endotherm(ic)peak origin temp) character of the goods of the present invention of the low aluminium of no sodium or boron and high alumina with at 150 ℃-300 ℃ and in the coefficient of linear expansion value of 600 ℃-650 ℃ or 680 ℃, fully can high-quality in addition, low-cost, high tens times of production efficiencys etc. can reach the technical requirements of the high-quality dull and stereotyped colored glazed glass of production simultaneously with taking into account and form better Financial cost target.
(D), since the discovery of the new product property of product four, overcome a kind of of classic flat-plate glass and thought that strengthening aluminum oxide certainly leads to the technology prejudice that viscosity temperature significantly rises.As prior art calcium soda glass, can only add the aluminum oxide about 1%, and existing alkali-free boron sheet glass, also generally only add 8% left and right sides aluminum oxide and improve strain point, added and to make the viscosity temperature of this very high each stage process higher, the QT Quality Target that uncontrollable technology should reach.Also think and to be added to 25-30% to aluminum oxide, to improve product strength under can controlled cheaply processing condition.But the new sheet glass product property of technical scheme of the present invention and discovery, broken this technology prejudice, the present invention at boracic not, do not contain sodium, not (during 0-1%) during fluorine-containing composition, when the large span when alumina content is 3.1% or 16% or 20% or 25% left and right sides changes, prior art thinks that viscosity can significantly rise, but the variation of viscosity temperature of the present invention only is, viscosity temperature also only rise about 80 ℃ (see attached list 1 11 sample examples) when aluminum oxide is 30% left and right sides.
And viscosity temperature is than also low 100 ℃-200 ℃ of the sheet glass products that has added 13% sodium oxide or 8-15% boron oxide.This has proved the invention technical scheme of the factor proportion relationship change scope of silicon in the technical scheme of the present invention, calcium, magnesium, energy and aluminum oxide produce a kind of new product property when 25% or 30% content, the eutectic character of the aluminium of a kind of new high alumina content that Here it is, silicon, magnesium, calcium can produce the unforeseeable technique effect and and then the high-intensity unforeseeable technique effect of height product that produces of the low viscosity temperature of high aluminium content.
When the present invention especially reaches 19-28% owing to the content that can strengthen aluminum oxide, intensity can reach about 140-160Mpa or 180Mpa, the 2-3 that is much higher than various prior art sheet glass intensity doubly, and since viscosity temperature also than only during the 1-25% alumina content low 150 ℃-250 ℃ of prior arts, when so if technical solution of the present invention forms the viscosity of alkali-free high boron glass, that should be equivalent in addition to add aluminum oxide to the viscosity space that can dissolve of 29-39% and intensity rise than the large space (folding strength of this specification sheets and embodiment of the invention glass, by sample being cut into little of 50mm * 50mm * 5mm, adopt the folding strength instrument, by standard GB/T3810,4-2006 measures.)。The high boron goods of the alkali-free of prior art because of the volatilization process of boron oxide composition, can cause the inequality of composition, and the netted structural damage of material that aluminum oxide is participated in influences due intensity greatly.This is the time also relatively poor major reason of intensity that the alkali-free high boron glass contains the 7-15% aluminum oxide.
So the present invention can be when having high aluminium content and no boron content, produce the folding strength of 90-145MPa or 145-180MPa, and have concurrently more energy-conservation, more low-cost and the processing range of bigger viscosity temperature arranged, this be now all colored glaze sheet glass do less than, and the present invention also can be in the control fusing of melting process viscosity temperature stage, overcome calculus and prevent to produce the quarrel point that is not melted, the thickness of sheet glass is poor (because viscosity is low more when clarification and control moulding, the soft more scope that control is arranged more of the sheet glass product of this operation stage, otherwise viscosity is high more, this operation stage sheet glass product is hard more, gets over not drawing fortunately, horizontal drawing, or calendering, or float glass process drop down flat, draw thin, operation stages such as polishing control thickness difference and percent ripple).
Can reach higher 2 times in above-mentioned better quality and intensity than existing sheet glass with prior art, the discovery and the generation of this new product property, make component invention with glazed colour layer produce the metope product of enough intensity of the thickness that can produce 1-2mm and this product invention ground product of 2-3mm thickness, high strength, lightening substituting to the thick ground product of the thick product of the exterior wall cladding 12mm of the national standard of existing pottery and various other 10mm produce several times saving worker's of the energy, resource, logistics, storage unforeseeable effect.
(E), owing to adopted the invention of a kind of technology essential factor elliptical, to prior art as the alkali-free boron glass, and can be than the better calculus of prior art, the quarrel point, bubble rate, the Flatness degree, under the prerequisite of the quality control of thickness difference, before technological temperature does not rise, reduce and energy-conservation prerequisite under, the boron composition omits in province, the fusing of dull and stereotyped technology can be arranged, row's bubble, moulding, draw the better character in thin each stage and can add more aluminum oxide and the folding strength character that produces, and the unforeseeable boron composition that can not add 8-15% to flat-panel monitor alkali-free boron glass, and guarantee that bubble rate is high-quality, Flatness, thickness is poor, the guarantee of the product quality of percent ripple, can solve the technology prejudice that prior art alkali-free boron glass production equipment can only add the technology of platinum channel with press over system technology, higher is to adopt floating process, ensureing that thickness is poor, Flatness, under the quality prerequisite of percent ripple, can enhance productivity tens of times, can save tens times of investments, save the unforeseeable effect of 20 times in soil factory building.So cost descends greatly, it is the component invention of colored glaze sheet glass of the present invention, can equally with the alkali-free boron display glass of prior art conform with under the prerequisite of the big production of colored glazed glass at annealing temperature lower limit (being the endotherm(ic)peak origin temp), and the colored glaze that produces new character base plate glass, thereby reduce cost greatly, produce the unforeseeable effect of the technical foundation generation of unforeseeable economic feasibility.
They are three years old, because the announcement and the discovery of the character of new the said products, overcome and planted prior art prejudice more than above-mentioned, in various architectural decoration colored glaze sheet glass field, produced (1) of following unforeseeable technique effect because the viscosity temperature temperature property has formed the technique effect that can well promote with molten quality, bubble quality, Flatness, thickness difference and the percent ripple quality of CONTROL PROCESS; (2) unforeseeable because energy-conservation about 30% the effect more than 200 ℃ that viscosity temperature descends; (3) unforeseeable because eutectic character add a large amount of aluminium (from 1% be added to 25% or 25-30%), the intensity rising 2-3 of generation technique effect doubly; (4) because intensity rises producible thus colored glaze sheet glass can frivolous 2-3 doubly energy-conservation, economize on resources, save logistics, storage 2-3 unforeseeable technique effect doubly; (5) the new technique effect of the present invention also is, strengthens owing to can be used for finishing material sheet glass opaque or that transparency is not high on iron oxide content, can save the high-quality frit resource that reduces day by day, and main frit cost descends 10 times.Conventional art thinks that the higher raw material of iron-holder influences glass and produces blue green defective, but the present invention can be in sheet glass, can promote intensity 2-3 doubly, so can approach 2-3 doubly, transmittance can rise on the contrary, blue greenness is not obvious all the better, does not influence transparent and the use colored glazed glass that makes progress.And colored glaze more can use the high iron material of big hundred times of equivalent when last, did not more mind transparency, more can save the raw material and the resource of the various medium levels of glass, saved cost greatly.So this component invention is can produce a kind of unforeseeable light, thin, high strength, save the colored glaze sheet glass product of the net effect of the high-end resource of glass, the cost that economizes in raw materials greatly.This is the inaccessible existing high strength of other prior art, thin, the economize in raw materials technique effect of resource but also 10 times of the costs of economizing in raw materials greatly not only not only gently not only.(6) owing to adopted the invention of a kind of technology essential factor elliptical, to prior art as the alkali-free boron glass, and can be than the better calculus of prior art, the quarrel point, bubble rate, Flatness, under the prerequisite of the quality control of thickness difference, before technological temperature does not rise, reduce and energy-conservation prerequisite under, the boron composition omits in province, the fusing of dull and stereotyped technology can be arranged, row's bubble, moulding, draw the better character in thin each stage and can add more aluminum oxide and the folding strength character that produces, and the unforeseeable boron composition that can not add 8-15% to dull and stereotyped alkali-free boron glass, and guarantee that bubble rate is high-quality, Flatness, thickness is poor, the guarantee of the product quality of percent ripple, can solve the only technology prejudice of the technology of 6-8 ton of daily output that prior art alkali-free boron glass production equipment can only add platinum channel with press over system technology, higher is to adopt 400-800 ton large-tonnage made in Japan such as float glass process, horizontal drawing, calendering or the like technology, ensureing that thickness is poor, under the quality prerequisite of Flatness, can enhance productivity tens times, can save tens times of investments, save the unforeseeable effect of 20 times in soil factory building.Technical solution of the present invention compares with existing all sheet glass or colored glaze sheet glass technology, has never revealed and disclosed new character, and this character is can't infer in advance, unpredictable and reasoning is come out, and overcome the technology prejudice of traditional sheet glass technology, solve people and thirsted for the above-mentioned significant problem that solves in the industry, technique effect has produced " matter " and " amount " the two variation, illustrate that technical scheme is non-obvious, has outstanding substantive distinguishing features, have significant technical progress, creative.
(F), because goods of the present invention can be at sintering glazed colour layer below 700 ℃, so can sintering screen printing glaze layer, can add a large amount of various crystal quartz that especially cost is low or diamond spar crystal powder or grain at the glaze layer as 30-80%, (quartz can reach 7 grades hardness to form the wearing coat high rigidity of beyond example 0.2-3mm, add diamond spar and then can reach 9 grades of hardness), and this in Production of Ceramics, do less than, because the firing temperature of pottery is at 1100 ℃-1200 ℃, this moment, the quartz or the diamond spar of ceramic surface can only become glassy phase, and below 730 ℃, quartz or diamond spar crystal also can keep crystallization phases, this quartz crystal hardness that just can form beyond example ambetti polishing reaches 7 grades of wear-resistant surface top layers or corundum crystal hardness reaches 9 grades wearing coat, wear resistance to pottery or stone material, zero water-intake rate, zero soil pick-up rate, high slip, be revolutionaryly challengingly (anti-skiddingly can be used for bathroom, kitchen surface, subway, the ground, public place that harbour and all flows of the people are big), wherein quartzy top layer can be polished because of 7 grades of hardness, become optimum top layer quartzy glaze combination polishing high abrasion goods, and 9 grades of hardness of diamond spar can not be polished, but can against expectation become optimum competent anti-skidding or wear-resisting diamond spar glaze component invention goods, so the present invention can form energy-conserving and environment-protective, the attrition resistant alternative upgrade technique of low-cost high-quality.And can substituting challenge be proposed to highly energy-consuming, high pollution, high dust discharge, high water consumption, low output, inferior goods and the whole equipment process system of ceramics.
(G), the present invention can make the 0.5-5mm ultrathin, under the state that the surface stress that does not carry out tempering is handled, what folding strength reached 50-180MPa preferably is the low melting point colored glaze decorative flat glass goods of the high-intensity environment-friendly and energy-efficient of ultrathin high annealing temperature of 90-145MPa or 145-180MPa, and be used for and the metal sheet of thin layer is compounded to form novel composite sheet with it, with purpose light, thin, high-intensity decorative effect, reach and satisfy better functional user demand.
But also the distance that 10-30mm has stretched out in the limit portion of low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of the high annealing temperature in top layer that can adopt the 2-4 bar limit proportion poststack of the bottom surface sheet metal that makes composite sheet, the easy mounting means that punches and afterwards adopt screw directly to hammer into body of wall or use in the limit portion that this stretches out with the metope of the hard-wired innovation of body of wall keel frame, the breakage rate that fractures is reduced greatly, the existing better unforeseeable technique effect of new product property is arranged.
(H), the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the present invention, the thickness of the base plate glass of its goods is 0.3-1.8mm.Frivolous especially, be particularly suitable for metope and use, energy-conservation especially, and equipment output capacity height.
(I), the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the present invention, the thickness of the base plate glass of its goods is 1.8-20mm.The intensity height is fit to ground, and especially the exterior wall of super large plate uses goods.
(J), the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature of the present invention, when the content of aluminum oxide was 19-39% in the composition of the base plate glass of its goods, product strength was the highest, especially was fit to the special goods that high strength requires.
Decorative effect such as the senior imitative stone material at colored glazed glass of the invention described above technical scheme, imitative timber also has the discovery of the various new character under the prerequisite of lower cost, produce unforeseeable technique effect, especially solved a major technique great difficult problem that people thirst for solving in the building and ornament materials industry for a long time and that do not have to succeed and be:
One, the annual over ten billion m that produces per year in the whole world 2Ceramic tile and sheet material in.The ceramic tile product has 3,000,000,000 m annual every year 2Be used for metope market.But the thickness of its product is at 8-15mm, indoor wall be 8-10mm, outdoor 12-15mm.And printed patterns of the present invention (no matter monochrome or 2-10 kind look) product can be made the product of 0.5-1.5mm, can make the lightening 6-10 of ceramic wall face product doubly.
Have an appointment every year 7000000000 m in market, ceramic tile product ground 2Be used for market, ground.But the thickness of its product is at 9-12mm.And colored glaze printed patterns of the present invention (no matter monochrome or 2-10 kind look) product, because intensity can reach three times of pottery, so as long as 3-4mm just has the same intensity.Wherein, transparent glass simultaneously is placed on the surface, the effect of printing the colored glaze pattern behind just is equivalent to existing throwing glazed brick (add the layer of transparent glaze on the ceramic pattern surface, polishing forms a glass glaze again).There are 1,000,000,000 m in the whole world 2Output.Wherein of the present invention at glass surface formation one deck colored glaze pattern, just be equivalent to the brick modelled after an antique of pottery, 3,000,000,000 m have an appointment global every year 2Output.Wherein the surface low-temperature sintering at glass of the present invention forms the glazed colour layer that one deck contains crystal such as quartz etc., polishing again, (but quartz content crystal of the present invention reaches 50%-60% just to be equivalent to ceramic now polished tile, fastness to rubbing, hardness, antifouling property are well more a lot of than ceramic polished brick), there is 3,000,000,000 m every year in the whole world 2About.Say that just the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of the high annealing temperature of the present invention can make annual 6000000000-10,000,000,000 m 2The backward production technique of ceramic product change.
[1], can be than furring tile thin 6 times with the invention described above product, can be than floor tile thin 3 times.This just can solve the long-term light-weighted resource that economizes in raw materials of thirsting for solution in the past of ceramic tile industry, saves oil, electric energy, the industrial strategy difficult problem of minimizing carbon emission and dust discharge.Say that just the present invention can make annual 10000000000 m of building decoration pottery 2And by annual industry of growing up 10% or more at the production link 70%-80% that saves material, energy-conservation 70%-80%, minimizing carbon emission 70%-80%.(if according to calculating the change of global tooling by the present invention's floating process, the energy consumption that can save the generated energy in year power station, three Yangtze River Gorges)
[2], owing to can produce large-sized light sheets such as 2400 * 1200mm or 3000 * 1800mm, can also substitute many metopes and fit up with aluminium sheet or standard-sized aluminium-plastic panel, save bauxite resource, and resource of the present invention most ten thousand times than bauxite resource reserves, cost is also much lower, and product is more corrosion-resistant again, and is more smooth well-pressed, the pattern decorative expressive force is more arranged, can print patterns such as all stone materials, wood grain.And the present invention is also convenient than ceramic plate, slabstone, aluminium sheet, aluminium-plastic panel on the metope installation method, cost is low.
[3], because can be under the secure performance condition of intensity, adopt existing all potteries and glass work less than the product of the 1-2mm thickness that programmable wood grain, bag and color are arranged again, be used for the veneer on the plank of exterior wall in house of wooden structures in America and Europe and Australia, Russia, East Asia, South Asia, substitute the non-bearing metope that brick and cement analyses and reach top grade, fire prevention, frivolous sun-resistant again, sleet erosive effect, and be used for the magnificent frivolous again good waterproof effect attractive in appearance of having of wooden structures metope upstairs new use value is also arranged.
(2), for the ambetti of prior art, it is owing to can only do the selection of colored glaze substrate with present common calcium soda glass, but its annealing point is about 490 ℃, the glaze that can not can manufacture again below 480 ℃ (must be introduced a large amount of lead first severe toxicity is arranged, two is high by cost), so can only on the glass Bo Saike below the 5cm size, print (, when annealing, being difficult for explosion), so inorganic glaze sheet glass of the printing of never production oversized dimensions in history because its size is minimum.Useful in addition tempering technology melts glaze at 750 ℃ more than-830 ℃, adopts reinforcing process to solve annealing stress problem.But this kind product size is specific, can not cut, and can not adapt to requirement in decorative engineering is used, and the intensity difference of calcium soda glass, can not make Ground Application.
And the technology of the present invention, [1] owing to can make base plate glass annealing temperature lower limit (being the endotherm(ic)peak origin temp) preferably rise to 600 ℃ or 650 ℃ or 730 ℃, exceed 150 ℃-200 ℃ than calcium soda glass, again owing to have very good thermal expansion linear feature, promptly the warm area expansion changes minimum near annealing point, so, one, (this glaze is different from the glaze below 480 ℃ at 540 ℃-730 ℃ glaze can to adopt fusing point, this glaze can the not big production in highland of cost, and do not have an environmental issue), the fine pattern of sintering printing under the annealing point temperature.So need not take second annealing technology, just can produce meticulous colored glaze bag, the grain pattern product of the various on-gauge plate sizes commonly used of decorative sheet such as 2400 * 1200mm, 3000 * 1800mm or stone material or glass unprecedentedly, and product can cut by the construction requirement size arbitrarily, but the present invention has just formed the full-range convenience, high efficiency of standard size order, production, supply and sales, logistics cutting construction and feature cheaply.[2] because the present invention can exceed 2-3 times than the intensity of about 50MPa of the calcium sodium sheet glass of prior art and ceramic plate, brick, can preferably reach 90-145MPa or 145-180MPa.So product can make book 2-3 doubly, and same intensity is arranged.Especially substitute ceramic product, this be existing all colored glaze agates hold high up gram or tempering colored glazed glass do less than.
(3), because goods of the present invention can be at 540 ℃ of-730 ℃ of agglomeration glazes, so can sintering screen printing glaze layer, can add a large amount of quartz or corundum crystal powder or grain at the glaze layer as 20-65%, the wearing coat high rigidity (reaching 7 grades) of beyond example formation 0.2-3mm, and this in pottery be do less than, because the firing temperature of pottery is at 1100 ℃-1200 ℃, this moment, the quartz of ceramic surface can only become glassy phase, and at 600 ℃, 650 ℃, 700 ℃, quartz or corundum also can keep crystalline phase, this is the quartz crystal face top layer of the beyond example formation ambetti polishing of energy just, or non-polished surface forms the wear-resisting non-skid finish of corundum crystal, [1] wear resisting property to pottery and stone material, [2] non-skid property, [3] especially almost zero water-intake rate and the high antifouling property of surface of polished, [4] high strength and ultra-thin performance, [5] ultralight super large plate flour products size characteristic, [6] go up the technical progress that wall and cladding mode etc. have formed six great revolutions, and the insider knows, the dust of glass smelting technology lacks tens times than ceramic preparation method, and the generation of waste material will be lacked hundreds of times.This can be to the efficient of whole ceramic process equipment, the progress of energy-saving and environmental protection.The present invention has revolutionary meaning to the progressive trend of the highly energy-consuming of ceramics, high pollution, high dust discharge, high water consumption, low output, inferior whole ceramic equipment manufacturing industry system industry in environmental protection.
In sum, more than three in the building decoration industry, especially in pottery and ambetti industry product and technology, the technical scheme of the present invention and the processing method of three great technical barriers that people thirst for solving always and that do not succeed, be not in the field technician only by general reasoning from logic person's simple experiment technical scheme that can form conspicuous technique effect that maybe can reach in other words, this explanation the present invention has remarkable substantial technical progress, so the present invention is creative.
Prior art especially in household such as exterior wall, ground and deck plate, kitchen cabinet panel and engineering ambetti material and the ambetti of the present invention used compare:
1, for the ambetti of prior art, itself since the annealing point of common calcium soda glass about 490 ℃, and the technical glaze that can not can manufacture below 540 ℃ (must be introduced a large amount of lead first severe toxicity is arranged, second cost is high, can not produce greatly for three), so can only on the glass Bo Saike below the 5cm size, print (, when annealing, being difficult for explosion), so inorganic glaze sheet glass of the printing of never production oversized dimensions in history because its size is minimum.Useful in addition tempering technology is melting glaze more than 750 ℃, adopts reinforcing process to solve annealing stress problem.But this kind product size is specific, can not cut, and can not adapt to the requirement of the accessibility feature requirement such as the application and construction that can cut arbitrarily, collocation of popular on-gauge plate in decorative engineering is used.And the intensity difference of calcium soda glass, can not make Ground Application, sharp, the unsafe defective of damaged posterior border is arranged again.
And the technology of the present invention:
[1], can unprecedented ground high rate of finished products, less energy-consumption, high value, high strength, light and thin type (0.5-3mm thickness), modular size ground produce the high precision screen printing glaze pattern of 2400 * 1200mm, 3000 * 1800mm, comprise stone material line, wood grain, all kinds of senior carpet pattern (this existing pottery and ambetti technology are not accomplished at all).
[2], because goods of the present invention can be at sintering more than 650 ℃, so can sintering screen printing glaze layer, can add a large amount of various crystal quartz that especially cost is low or diamond spar crystal powder or grain at the glaze layer as 30-80%, form the wearing coat high rigidity (reaching 7 grades or 9 grades of hardness) of beyond example 0.2-3mm, especially quartz or diamond spar are through 540 ℃ to 700 ℃ fire, can be very white, the extremely attrition resistant three that this hardness that can also initiate the ultrawhite of zero water-intake rate reaches the 7-9 level unprecedentedly is characterized as the Ground Application product of one.And the upper layer that contains quartz crystal can be finished to the high abrasion goods of bright and clean layer, and the not polished product that contains the diamond spar top layer can be the new functional decoration material product of best anti-skid wearable.And this is in the existing technology of all ceramic products, technology and ambetti product, definitely be do less than, the present invention is beyond example, because the firing temperature of pottery is at 1100 ℃-1200 ℃, this moment, the quartz or the diamond spar of ceramic surface can only become glassy phase, can become fragile, become the effect of not wear-resisting, as to become transparent area impossible ultrawhite; And burn till warm area at 540 ℃-730 ℃ of the present invention, quartz also can keep crystallization phases, this just can form the quartz crystal face top layer of beyond example ambetti polishing, wear resistance, zero water-intake rate, zero soil pick-up rate, high slip to pottery or stone material or ambetti top layer, be revolutionary challenging (anti-skidding can be used for the big ground, public place of bathroom, kitchen surface, subway, harbour and all flows of the people), can form energy-conserving and environment-protective, the attrition resistant alternative upgrade technique of low-cost high-quality.And can substituting challenge be proposed to highly energy-consuming, high pollution, high dust discharge, high water consumption, low output, inferior goods and the whole equipment process system of ceramics.And all potteries of prior art, ambetti technology, never open or paid close attention to above technical solution of the present invention and the non-obvious substantive technique effect of energy.
2, top layer printing more of the present invention or cloth crystal layer product, the rostone based article of prior art, its output and effect are low, and cost height, one bar are given birth to not line daily output only at 200-300m 2, can reach 30,000-80,000 m and float glass line technology adds the daily output of double-firing process 2
3, existing aluminium-plastic panel finishing material, and the present invention adds the composition board of aluminium, can overcome it to be printed as organic materials because of moulding plate by Exposure to Sunlight after contraction gross distortion and pattern in the exterior wall use, so can not make the defective of exterior wall.The composition board that the present invention adds aluminium has pattern meticulous, and will never fade, planeness is fabulous, and the same simple installation with aluminium-plastic panel of energy, the advantage that cost descends greatly, work efficiency rises greatly.But also can save a large amount of installing materials and man-hour more easily without the dry-hanging keel frame, and directly be fixed on the body of wall with expandable nail, play glue in side seam again, form stone material dry suspending finishing effect.And all potteries of prior art, ambetti technology, never open or paid close attention to above technical solution of the present invention and the non-obvious substantive technique effect of energy.
4, for the decorative pattern plastics class panel of prior art, the present invention is 0.3mm-1.6mm ultrathin goods especially, be used for table top, defend the kitchen panel, sliding door face, furniture veneer, there is intensity good, hardness height, ultra-thin, ultralight, fastness to rubbing is good, pattern effect is good, and planeness very degree of scraping is good, comprehensive advantage such as corrosion resistant, waterproof, moisture proof aliquation, fire-retardant, safety, environmental protection.
Existing all colored glaze base plate glass technology is arranged earlier, all never open or pay attention to or disclose glaze character of the present invention and the overall technical architecture of a kind of component invention of forming according to the technical scheme of base plate glass of the present invention.Especially existing all colored glaze base plate glass technology is arranged earlier, from " contrasting principle separately " convention, all never open or pay attention to or disclosed technical scheme according to first embodiment of the invention, especially about the technical scheme of the fusing point of the technical scheme of base plate glass and ANNEALING OF GLASS lowest temperature (being the endotherm(ic)peak origin temp) feature and glaze, so goods of the present invention not only can replace many architectural pottery products, because its manufacturing process is different from international and domestic advanced ceramics production-line technique equipment technology fully, does not especially adopt water law ball milling operation wherein, the spraying operation, the ceramic press operation, high energy consumptions such as polishing process, high pollution, the link of high water consumption; Also because the innovation and the maturity of technology, intensity is 2-3 times of (the ceramic 50MPa of being of pottery, goods of the present invention can reach 130-160MPa), can produce the only ultra-thin product of 2-2.3mm thickness, just replace the product (the mass-produced ceramic tile of modern mature technology is the product of 9-15mm thickness) that the modern architecture ceramic plate can only be produced the thinnest technology for 6mm thickness.So technology of the present invention is for advanced ceramics, can: 1. energy-conservation [oil, electricity, coal] reaches 60%-80%; 2. since product only thick for 2-5mm, to polish the advanced ceramics product of the 10mm that grinds off 1mm thickness than traditional technology, 50-80% saves material; 3. water saving reaches 80%; 4. the GDP Carbon emission reduces 60-80%; 5. owing to can adopt the big wooden frame packing of big plate, carton, the bubble chamber of pottery are saved packing cost more than 50% relatively now.
So the present invention not only technical scheme is not the technical scheme with novelty that simple reasoning from logic of a kind of usefulness of thinking or simple experiment just can form afterwards, and the technique effect that its technique effect neither obviously reach.And these nearly just ten to 20 years, the enterprise of thousands of family of global architectural decorative glass industry, building decoration ceramic industry, decorative sheet industry and hundreds thousand of technician, all research and solve and the problem that never solves.Because solving, the present invention's technical scheme on glass substrate, adheres to fusing point at 540 ℃-730 ℃ colored glaze; Sodium oxide, ferric oxide, aluminum oxide, silicon oxide, calcium oxide, magnesium oxide in the predetermined requisite special scope is arranged or also have titanium oxide, barytic composition and predetermined silicon oxide, calcium oxide, magnesium oxide between the innovative technology scheme of composition of specific proportions relation; Overcome the various traditional composition hydrotropy compositions and the technology prejudice of eutectic composition, and the product strength rising 1-3 that can produce unforeseeable hydrotropy or eutectic function and generation doubly, the technique effect of environmental protection, energy-saving and emission-reduction etc.; When not adding the boron oxide composition that environmental protection harm is arranged, the present invention except that the existence of viscosity advantage and strength advantage, can produce the environmental protection of practicality, a large amount of is energy-conservation, reduce Carbon emission, make various sheet glass goods lightening, especially compare the alkali-free high boron glass, the saving cost that raising equipment production life-span 6-10 doubly produces and the 10-20 that enhances production capacities are doubly, and the several times saving of the raw material resources after product lightweight 3-6 times, the logistics of landlocked and seagoing transport and 3-6 energy-conservation and following degradation technique effect cost doubly of storage are that the people to the technology trends of the industrial field of the above-mentioned ambetti novel material that global decorative building material industry is opened up of the great technical contribution of the difficult problem of industry and professional and alternative ceramic plate brick product thirst for solving and the great technical barrier of never succeeing and this specification sheets are mentioned also have many other people to thirst for solving and do not succeed because the fusing point of colored glaze material is innovated and the good coefficient of linear expansion feature of strain point of this base plate glass, low viscosity, high strength characteristics could realize the large size on-gauge plate of product, big plate, ultra-thin plate, high-strength plate, the sheet material of not only zero water-intake rate of ultrawhite but also the antifouling feature of the extremely wear-resisting height of high rigidity, fine pattern printing sheet material, fine pattern printing wearable plate, the various technical barriers of unexampled each characteristic new decorative materials such as ultra-thin high strength glass composite sheet.
Above-mentioned unforeseeable technique effect, overcome multiple prior art prejudice, especially at low boron, the technology prejudice that low aluminium (as content when 1-2% is following) annealing temperature can not rise, especially by the invention of the technology essential factor elliptical of boron and aluminium and sodium and above-mentioned key element being changed invention and having found the renewal technology character of the ANNEALING OF GLASS lowest temperature (being the endotherm(ic)peak origin temp) of generation, and owing to adopted a kind of change invention of the proportionlity that changes technology essential factor and selection invention and because of finding that having produced product innovation in a kind of invention of migrating in colored glaze sheet glass purposes founds, row's bubble, clarification, homogenizing, moulding and the viscosity temperature that draws thin operation stage such as grade, intensity, thickness difference and newfound fluxing or character such as eutectic, make the intensity 1-2 character doubly that can rise with the consequent alumina content that strengthens, and these several product properties can also have concurrently in producing plate colored glaze product simultaneously, and glaze layer a kind of who adds special temperature of fusion the generation of component invention of unforeseeable technique effect is arranged and the coloured lustre ware of the present invention of realizing and all prior aries relatively, produced multi-level invention and added that a kind of of component invention can't infer in advance, the above-mentioned multiple technologies effect that unpredictable and reasoning is come out, produced the variation of " matter " and " amount " of technique effect, illustrate that technical scheme is non-obvious, have outstanding substantive distinguishing features and significant technical progress, so the present invention is creative.
The above, only be for the preferable preferred embodiment of the present invention is described, it is not to be limitation of the present invention, any personnel that are familiar with this technology may utilize the technology contents of above-mentioned announcement to be changed or be modified to the equivalent embodiment of equivalent variations, can implement the low melting point colored glaze decorative flat glass and the preparation method of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature by difference requirement and performance.As seen, hold within the every content that does not break away from technical solution of the present invention, the especially claim, to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical solution of the present invention according to technical spirit of the present invention.

Claims (10)

1. the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature, the fusing point of the glazed colour layer of the 1-10 kind color on its base plate glass surface is at 540 ℃-730 ℃, the base plate glass of its goods is characterised in that: this base plate glass comprises silicon oxide, calcium oxide, magnesium oxide, aluminum oxide, ferric oxide, the composition of sodium oxide, count as weight percents, the content of boron oxide is 0-3.9% in this base plate glass, the content of sodium oxide is 0.01-14%, iron oxide content is 0.01-5%, the content of fluorine oxide is 0-2.8%, content of magnesia is 8.1-22.2%, alumina content is 0.01-39%, the content of its silicon oxide is 1.9 times-4.1 times of calcium oxide content, and the content of calcium oxide is 1.2 times-1.6 times of magnesian content;
The thickness difference of its base plate glass is less than 0.3mm;
The water-intake rate of its base plate glass is in the scope of 0-0.3%;
The folding strength of its base plate glass reaches 50-180Mp;
The annealing temperature lower limit of its base plate glass (being the endotherm(ic)peak origin temp) is 550 ℃-710 ℃.
2. the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature according to claim 1, the base plate glass of its goods is characterised in that: by heavy percentage, the content of aluminum oxide is 0.01-30%, silicon oxide: calcium oxide is 2.0-3.6 times, calcium oxide: magnesium oxide is 1.3-1.49 times, sodium oxide is 0.01-2%, and boron oxide is 0-1%, and the content of fluorine oxide is 0-1%; The annealing temperature lower limit of this base plate glass (being the endotherm(ic)peak origin temp) is 610 ℃-710 ℃; This base plate glass is 10 in viscosity 0.5Temperature when (handkerchief second) is 1500 ℃-1640 ℃; Viscosity is 10 1Temperature when (handkerchief second) is 1450 ℃-1580 ℃; Viscosity is 10 2Temperature when (handkerchief second) is 1210 ℃-1350 ℃; Viscosity is 10 3Temperature when (handkerchief second) is 1070 ℃-1230 ℃; The folding strength of this base plate glass is 50-180MPa.
3. the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature according to claim 1, the base plate glass of its goods is characterised in that: by heavy percentage, the content of aluminum oxide is 8-30%, silicon oxide: calcium oxide is 2.0-3.6 times, calcium oxide: magnesium oxide is 1.3-1.49 times, sodium oxide is 0.01-2%, and boron oxide is 0-1%, and the content of fluorine oxide is 0-1%; The annealing temperature lower limit of this base plate glass (being the endotherm(ic)peak origin temp) is 610 ℃-680 ℃; This base plate glass is 10 in viscosity 0.5Temperature when (handkerchief second) is 1520 ℃-1640 ℃; Viscosity is 10 1Temperature when (handkerchief second) is 1450 ℃-1580 ℃; Viscosity is 10 2Temperature when (handkerchief second) is 1210 ℃-1350 ℃; Viscosity is 10 3Temperature when (handkerchief second) is 1070 ℃-1230 ℃; The folding strength of this base plate glass is 75-180MPa.
4. the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature according to claim 1, the base plate glass of its goods is characterised in that: by heavy percentage, the content of aluminum oxide is 19-30%, silicon oxide: calcium oxide is 2.0-3.6 times, calcium oxide: magnesium oxide is 1.3-1.49 times, sodium oxide is 0.01-2%, and boron oxide is 0-1%, and the content of fluorine oxide is 0-1%; The annealing temperature lower limit of this base plate glass (being the endotherm(ic)peak origin temp) is 610 ℃-680 ℃; This base plate glass is 10 in viscosity 0.5Temperature when (handkerchief second) is 1550 ℃-1640 ℃; Viscosity is 10 1Temperature when (handkerchief second) is 1450 ℃-1580 ℃; Viscosity is 10 2Temperature when (handkerchief second) is 1210 ℃-1350 ℃; Viscosity is 10 3Temperature when (handkerchief second) is 1080 ℃-1230 ℃; The folding strength of this base plate glass is 130-180MPa.
5. the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature according to claim 1, the base plate glass of its goods is characterised in that: by heavy percentage, the content of aluminum oxide is 0.01-19%, silicon oxide: calcium oxide is 2.0-3.6 times, calcium oxide: magnesium oxide is 1.3-1.49 times, sodium oxide is 0.01-2%, and boron oxide is 0-1%, and the content of fluorine oxide is 0-1%; The annealing temperature lower limit of this base plate glass (being the endotherm(ic)peak origin temp) is 610 ℃-680 ℃; This base plate glass is 10 in viscosity 0.5Temperature when (handkerchief second) is 1500 ℃-1580 ℃; Viscosity is 10 1Temperature when (handkerchief second) is 1450 ℃-1520 ℃; Viscosity is 10 2Temperature when (handkerchief second) is 1210 ℃-1310 ℃; Viscosity is 10 3Temperature when (handkerchief second) is 1070 ℃-1160 ℃; The folding strength of this base plate glass is 50-145MPa.
6. the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature according to claim 1, the base plate glass of its goods is characterised in that:
(1), counts as weight percents, in its base plate glass content: 1. magnesium oxide accounts for 7-20%, 2. calcium oxide is in magnesian 1.0 times-1.8 times scope, 3. silicon oxide is in magnesian 2.6 times-5.6 times scope, 4. silicon oxide is in 2.2 times-3.8 times the scope of calcium oxide, 5. aluminum oxide is 0.1-30%, and 6. sodium oxide is 0-18%, and 7. barium oxide is 0-5%;
(2), the strain point temperature of the base plate glass of its goods is in 560 ℃-720 ℃ scope;
(3), the water-intake rate of the base plate glass of its goods is in the scope of 0-0.001%;
(4), as weight percents the meter, the content summation of the middle magnesium oxide of the base plate glass of its goods, calcium oxide, three kinds of compositions of silicon oxide reaches 51%-100%.
7. according to the preparation method of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of the described a kind of high annealing temperature of each claim of claim 1-6, it is characterized in that:
Step 1, the required various sodium oxides that have in the predetermined requisite special scope of base plate glass component configuration according to each described goods of claim 1-6, ferric oxide, aluminum oxide, silicon oxide, calcium oxide, magnesium oxide, or also has titanium oxide, barytic composition and predetermined silicon oxide, calcium oxide, the raw material of the innovative technology scheme of the composition of the specific proportions relation between the magnesium oxide, temperature of fusion corresponding to each glass formula after mixing stirring melts, form the controlled viscosity and the low viscous glass metal of optimization, homogenizing again, clarification, discharge bubble, form flowable molten mass;
Step 2, any technology is carried out moulding to glass in employing floating process, horizontal drawing technology, lattice-method process, calendering technology, the press over system technology, makes the base plate glass of the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of high annealing temperature through refrigerating work procedure;
Step 3 is to the surface printing of the base plate glass of the goods of moulding or to execute the cloth last layer be that 540 ℃-730 ℃ colored glaze forms ornament layer by the fusing point of a kind or 2-10 kind color.
8. the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature according to claim 1 is characterized in that: the composition board of its goods is by compound composition of sheet metal (3) of low melting point colored glaze decorative flat glass (1) and bonding material layer (2) and the 0.1-1mm or the 1-5mm thickness of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature.
9. the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature according to claim 1, it is characterized in that: count as weight percents, the content of aluminum oxide is smaller or equal to 30% in its base plate glass, and this base plate glass is 10 in viscosity 0.5Temperature when (handkerchief second) is 1480 ℃-1640 ℃; Viscosity is 10 1Temperature when (handkerchief second) is 1410 ℃-1600 ℃; Viscosity is 10 2Temperature when (handkerchief second) is 1180 ℃-1340 ℃; Viscosity is 10 3Temperature when (handkerchief second) is 1040 ℃-1220 ℃; The thickness difference of this base plate glass is less than 0.3mm; The water-intake rate of this base plate glass is in the scope of 0-0.3%; The strain point temperature of this base plate glass is in 560 ℃-720 ℃ scope; The folding strength of this base plate glass is 50-180MPa; The thermal expansivity of this base plate glass is 1,000,000/1.0-3.0/1000000ths in the difference of 150 ℃-300 ℃ two ends numerical value; Difference at 550 ℃-600 ℃ two ends numerical value is 1,000,000/1.0-2.8/1000000ths.
10. the low melting point colored glaze decorative flat glass of the high-intensity environment-friendly and energy-efficient of a kind of high annealing temperature according to claim 1 is characterized in that: the quartz crystal or the alpha-alumina crystals that contain 20-70% in the glaze layer on its top layer.
CN2011100609139A 2010-03-18 2011-03-15 Environment-friendly, energy-saving and low-melting-point color glaze decoration flat glass with high annealing temperature and strength and preparation method thereof Pending CN102260045A (en)

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