CN1218893C - Method for mfg. high strength fireproof signle sheet cesium potash glass - Google Patents
Method for mfg. high strength fireproof signle sheet cesium potash glass Download PDFInfo
- Publication number
- CN1218893C CN1218893C CNB2004100056450A CN200410005645A CN1218893C CN 1218893 C CN1218893 C CN 1218893C CN B2004100056450 A CNB2004100056450 A CN B2004100056450A CN 200410005645 A CN200410005645 A CN 200410005645A CN 1218893 C CN1218893 C CN 1218893C
- Authority
- CN
- China
- Prior art keywords
- glass
- manufacture method
- masking liquid
- sylvite
- cesium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000011521 glass Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 30
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 title claims description 15
- 229910052792 caesium Inorganic materials 0.000 title claims description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 title description 2
- 235000015320 potassium carbonate Nutrition 0.000 title description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 title 1
- 229940072033 potash Drugs 0.000 title 1
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 238000005507 spraying Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 33
- 230000000873 masking effect Effects 0.000 claims description 31
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 24
- 239000001103 potassium chloride Substances 0.000 claims description 22
- 235000011164 potassium chloride Nutrition 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000000137 annealing Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 8
- 239000013543 active substance Substances 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- 150000003606 tin compounds Chemical class 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 5
- 229920000159 gelatin Polymers 0.000 claims description 5
- 235000019322 gelatine Nutrition 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical group [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001828 Gelatine Substances 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims 1
- 235000010981 methylcellulose Nutrition 0.000 claims 1
- 239000001488 sodium phosphate Substances 0.000 claims 1
- 229910000162 sodium phosphate Inorganic materials 0.000 claims 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 11
- 238000005187 foaming Methods 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 238000004383 yellowing Methods 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 11
- 230000035882 stress Effects 0.000 description 10
- 238000005496 tempering Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 7
- 230000009970 fire resistant effect Effects 0.000 description 6
- 239000005329 float glass Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000005357 flat glass Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000005341 toughened glass Substances 0.000 description 5
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000005388 borosilicate glass Substances 0.000 description 3
- 238000007688 edging Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- -1 polyethylene terephthalate Polymers 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 208000006558 Dental Calculus Diseases 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000007495 chemical tempering process Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 229940093916 potassium phosphate Drugs 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 2
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 241000206753 Gloiopeltis Species 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- QYIJPFYCTROKTM-UHFFFAOYSA-N [Sn].P(O)(O)(O)=O Chemical compound [Sn].P(O)(O)(O)=O QYIJPFYCTROKTM-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- 229960004839 potassium iodide Drugs 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Landscapes
- Glass Compositions (AREA)
Abstract
The present invention relates to a manufacturing technique and a method for single-sheet fireproof glass, which is realized by simultaneously carrying out physical toughening and chemical toughening in a horizontal toughening furnace, wherein the chemical toughening is realized by hot spraying a salt solution with specific components. The surface pressure stress of the product of the present invention is not less than 140MPa and is not greater than 180MPa. The product of the present invention has a fireproof function and overcomes the disadvantages of poor weather resistance, easy yellowing and foaming under the condition of ultraviolet irradiation and low strength of grouting fireproof glass, and the grouting fireproof glass can not be used for the outer walls of buildings.
Description
Technical field
The present invention relates to the manufacturing process and the method for single-sheet fire-resistant glass, belong to sheet glass deep processing field.
Background technology
According to State Standard of the People's Republic of China's " shatter proof glass flame resistant glass for building " definition and classification (GB15763.1-2001), flame resistant glass is divided into single-sheet fire-resistant glass and composite fireproof glass.Single-sheet fire-resistant glass (DFB) is made of single-glass, and satisfies the special glass of associated refractory class requirement.Be divided into A, B, C three classes by fire performance.Wherein C class flame resistant glass is the flame resistant glass that satisfies the fire integrity requirement.
At present, single-sheet fire-resistant glass mainly contains following two types both at home and abroad:
1, borosilicate glass: contain boron oxide, the aluminum oxide of higher composition in the glass, the thermal expansivity of glass is reduced greatly, thereby can bear rapid heating and cooling, have the fp function.Shortcoming is that the founding of borosilicate glass, moulding particularly are drawn into sheet glass for building, complex process, and the cost height, yield rate is low.So borosilicate glass is used for making chemistry special-shaped glass goods such as laboratory glass wares, flameproof ware mostly.
2, high-intensity toughened glass: because glass is a kind of brittle glass, resistance to compression is not anti-opens, and its actual strength has only 1/1000 of theoretical strength, often by sheet glass being carried out the method raising strength of glass that tempering is handled, the thermal stresses that produces when making glass can bear anxious heat (or chilling), thus the fp function had.Common toughened glass has certain fire-proof function, but can't be used for mineral wool glass, mainly is that its bearing stress is not high enough, and intensity is not high.Have only high-intensity toughened glass could be used as flame resistant glass.
In the glass production of domestic each producer, the physical toughened processing with chemical tempering carried out respectively.Number of patent application be the manufacture method of 01124523.9 patent application introduction comprise to glass cut in order, edging, chemical tempering, physical toughened manufacture method.The salts solution that wherein uses in the chemical tempering process mainly contains saltpetre, potassium silicate, Potassium monofluoride, aluminium sesquioxide and cerium oxide in forming.
Number of patent application is that 02117908.5 manufacture method of introducing is that glass carries out the potassium salt soln spraying earlier behind cutting, edging, and chemical tempering is carried out in dry back in heat treatment furnace, and is then physical toughened and paste PET (polyethylene terephthalate) low-radiation film.Its thermal treatment temp is 400-600 ℃, and the treatment time is 0.25～3 hour, and glass stands up.The salts solution that wherein uses in the chemical tempering process mainly contains sylvite, sodium salt, Potassium monofluoride, masking liquid tackifier, stripper and anion surfactant in forming.
More than two disclosed chemical temperings of patent application all in the fused salt reactive tank, carry out, glass is immersed in the solution tank ion exchange reaction takes place.Shortcoming is that chemical time is oversize, can not large-scale continuously produce, and production efficiency is not high, the cost height.
Basic identical abroad about the production technique of the production technique of high strength glass and domestic employing, but disclose in the glass production process among the clear 56-50145A of Japanese JP, physical toughened and chemical tempering carries out simultaneously, sheet glass is heated to 550 ℃ by room temperature in stove after, to glass surface spraying salts solution, 470-580 ℃ the insulation several hours after, continue to be warming up to 550-700 ℃, chilling obtains strengthened glassy product then, the salts solution that uses can be the alkali-metal salts solution of ionic radius greater than the surface layer of glass ionic radius, potassiumiodide for example, vitriolate of tartar, salt of wormwood, Repone K and Potassium Bromide, specifically the salts solution that uses is potassiumphosphate and tin chloride mixing solutions.And the mixed powder that spraying process uses fused saltpetre powder or saltpetre and is selected from sylvite such as Repone K, vitriolate of tartar, potassiumphosphate disclosed among the clear 56-164036A of the Japanese JP of another piece.
Though adopt physical toughened and the simultaneously treated technology of chemical tempering, can improve strength of glass, but sheet glass need be handled the long period in stove, for solving the problem that exists in the above-mentioned single-sheet fire-resistant glass manufacturing process, realize scale operation, enhance productivity, the invention provides a kind of special complete processing, promptly in physical toughened, spray the salts solution of specific composition, thereby obtain high-intensity refractory Cs-K glass.
Summary of the invention
Concrete production method of the present invention is that glass is put into temperature is 650-735 ℃ of annealing furnace, in to the glass rapid heating, the caesium sylvite masking liquid of spraying specific composition, caesium sylvite masking liquid proportioning is as follows: sylvite: 35～65%, sodium salt: 1～6%, cesium salt: 0.5～1.5%, masking liquid tackifier: 0.2～10%, tin compound stripper: 2～20%, anion surfactant: 0.2～1.2%, water: 25～50%, press every millimeter thickness heating of glass 30-65 second heat-up time, after heating was finished, glass entered the cooling section rapid quench.
Wherein sylvite is phosphoric acid salt (K
3PO
4, K
2HPO
4, KH
2PO
4), halogenide (KF, KCl, KBr, KI), vitriol (K
2SO
4, KHSO
4), nitrate (KNO
3), carbonate (K
2CO
3, KHCO
3), borate (K
3BO
3, K
4B
2O
7) or the mixture between them.In the above-mentioned reinforced effects, K
3PO
4Reinforced effects as sylvite is best, is KCl and KNO secondly
3Combination, moreover be K
2SO
4And KNO
3Combination, KCl and KNO
3The effect of using is the poorest separately.Wherein KCl and KNO
3When both used, its ratio of mixture was that 5: 1～1: 1 an o'clock effect reaches maximum value; K
2SO
4With KNO
3When both used, its ratio of mixture was that 3: 1～1: 1 o'clock effect is best.The optimum concn of potassium borate solution is 30%-55%, is better than K when potassium borate and saltpetre combination
3PO
4Adopt under the situation of borate and nitrate combination KNO when sylvite
3In mixing salt proportion be 60%～70% o'clock for best.
Cesium salt is cesium nitrate or cesium carbonate, introduces a small amount of Cs in the masking liquid
+Be because Cs
+Radius ratio K
+Bigger, the Na in the exchange glass
+, formed effect is better, makes the stress of glass improve greatlyyer, and intensity is higher, thereby improves the fire resistance of glass.
For hot spray process, when adding a small amount of sodium salt in masking liquid, the intersection of potassium sodium ion exchange rate improves.When adopting K
3PO
4Ion-exchanger and K in the masking liquid
3PO
4Weight percent is 50% o'clock, and the sodium salt of suitable adding 4%～13% is (as Na
3PO
4).The weight percent concentration of sodium ion is 1%～6% in the corresponding solution.Guarantee the ratio＜Na of the na concn in the masking liquid
+/ (Na
++ K
+) be controlled at below 7%, experiment showed, that 0.5%～4% is the optimum range value.
The viscosity that adds tackifier increase masking liquid in masking liquid overcomes the phenomenon of masking liquid at the mobile and masking liquid maldistribution of glass surface.The masking liquid tackifier often adopt organic compound such as starchy compounds, gelatin, gelatine, gloiopeltis compounds of group, Viscogum BE, methylcellulose gum, yellow starch gum, the content of tackifier in masking liquid is 0.2%～10%, and corresponding pasty state fluid viscosity scope is 0.01～2PaS.Because tackifier are bicarbonate compounds, so simultaneously can selectivity add proper amount of oxidant such as potassium manganate (sodium), potassium permanganate (sodium), potassiumchromate (sodium), potassium bichromate (sodium), Potcrate (sodium), can guarantee that the fully burning of tackifier in heat-processed lose.
Adding stripper in masking liquid makes glasswork remain sylvite behind tempering to peel off automatically easily from the surface etc.Stripper commonly used is tin compound (as tin chloride, tin protochloride, stannic oxide, phosphoric acid tin or their mixture), wherein with SnCl
4Be the best.When using K
3PO
4For ion-exchanger and coating liquid concentration are 10～193g/100ml H
2During O, corresponding tin compound concentration is 1～50g/100ml solution.The residue coating substance is peeled off easily, also can be improved reinforced effects simultaneously.
In order to improve the wettability of sylvite coating liquid and glass surface, obtain thickness and evenly, also must in masking liquid, add tensio-active agent in conjunction with good sylvite solid phase coating.Tensio-active agent divides cats product such as RN
+(CH
3)
3Cl and anion surfactant such as ROSO
3Na, the tensio-active agent optimal addn in masking liquid is 0.2%～1.2% of a masking liquid gross weight.
Where necessary, also can apply wear-resistant coating thing (tin compound commonly used or organic polymer) so that stress is protected at glass surface.Before glass advances annealing furnace, to finish grind edge polishing to glass and handle, glass edge portion wears into round edge, and the bight is carried out the rounding limit and is handled.Because technology of the present invention improves the stress of glass surface, thereby makes glass have the possibility of self-destruction, the limit portion of glass often becomes the weakest position, if glass edging is of low quality, thereby will cause stress concentration to make glass self-explosion.Glass of the present invention will make quality product of the present invention more stable advancing to carry out rounding limit and the processing of rounding angle before annealing furnace is handled.Big 2～3 times blast of common toughened glass is made in use than usual cools off glass rapidly.
Embodiment
Embodiment 1:
Preparation caesium potassium salt soln consists of: K as masking liquid
+: 40% (by K
2SO
4With KNO
3Formed by 3: 1), Na
+(Na
3PO
4): Cs 1%,
+(CsNO
3): masking liquid tackifier (starch) 0.5%: stripper (SnCl 10%,
4): tensio-active agent (ROSO 18%,
3Na): water 0.5%: 30%, get the thick 610 * 610mm float glass of 6mm, finish grind the limit all around, annealing furnace is put in rounding limit and fillet and polishing then, is 220-300 second in the annealing furnace internal heating time, spray the salts solution of preparation simultaneously to glass surface, after heating was finished, glass entered the cooling section rapid quench, measured the bearing stress value (MPa) of glass.The detailed process parameter sees Table 1.
Embodiment 2:
Preparation caesium potassium salt soln consists of: K as masking liquid
+: 60% (by KCl and KNO
3Formed by 1: 1), Na
+(Na
3PO
4): Cs 5%,
+(Cs
2CO
3): masking liquid tackifier (gelatine) 1.5%: stripper (SnCl 1%,
4): tensio-active agent (ROSO 3%,
3Na): water 1%: 28.5%, get the thick 610 * 610mm float glass of 8mm, finish grind the limit all around, annealing furnace is put in rounding limit and fillet and polishing then, is 300-360 second in the annealing furnace internal heating time, spray the salts solution of preparation simultaneously to glass surface, after heating was finished, glass entered the cooling section rapid quench, measured the bearing stress value (MPa) of glass.The detailed process parameter sees Table 1.
Embodiment 3:
Preparation caesium potassium salt soln consists of: K as masking liquid
+: 50% (K
3PO
4), Na
+(Na
3PO
4): Cs 5%,
+(CsNO
3): masking liquid tackifier (starch) 1%: stripper (SnCl 0.5%,
4): tensio-active agent (Rn 15%,
+(CH
3)
3Cl): water 1.2%: 27.3%, get the thick 610 * 610mm float glass of 10mm, finish grind the limit all around, annealing furnace is put in rounding limit and fillet and polishing then, is 380-450 second in the annealing furnace internal heating time, spray the salts solution of preparation simultaneously to glass surface, after heating was finished, glass entered the cooling section rapid quench, measured the bearing stress value (MPa) of glass.The detailed process parameter sees Table 1.
Embodiment 4:
Preparation caesium potassium salt soln is as masking liquid, forms identically with embodiment 1, gets the thick 610 * 610mm float glass of 12mm and handles, and the detailed process parameter sees Table 1.
Embodiment 5:
Preparation caesium potassium salt soln is as masking liquid, forms identically with embodiment 2, gets the thick 610 * 610mm float glass of 15mm and handles, and the detailed process parameter sees Table 1.
Embodiment 6:
Preparation caesium potassium salt soln is as masking liquid, forms identically with embodiment 3, gets the thick 610 * 610mm float glass of 19mm and handles, and the detailed process parameter sees Table 1.
Table 1 annealing furnace technic index
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Thickness | 6mm | 8mm | 10mm | 12mm | 15mm | 19mm |
| Heat-up time (second) | 220～300 | 300～360 | 380～450 | 400～550 | 600～1000 | 750～1200 |
| Head temperature (℃) | 695～705 | 690～705 | 690～705 | 685～700 | 650～690 | 650～685 |
| Bottom temp (℃) | 735 | 735 | 735 | 735 | 700～735 | 700～735 |
| Cooling wind pressure (* 10 5Pa) | 1.2～1.8 | 0.5～0.8 | 0.25～0.35 | 0.15～0.25 | 0.06～0.1 | 0.02～0.06 |
| The cooling tuyere is from glass distance (mm) | 35 | 40 | 40～45 | 45～50 | 55～60 | 60～65 |
| Transmission speed (cm/s) | 50 | 45 | 40 | 35 | 25 | 20 |
| The unloading piece temperature (℃) | 40～60 | 40～60 | 40～60 | 40～60 | 40～60 | 40～60 |
| Heating tube thermal equilibrium pressure (* 10 5Pa) | 3～5 | 2～4 | 2～3 | 2～2.5 | 1.5～2.2 | 1.0～1.5 |
Single-sheet fire-resistant glass by the inventive method is made detects according to GB15763.1 " shatter proof glass flame resistant glass for building " through national fire-proof construction material quality supervision and test center, and its index is as follows:
| The thickness processing parameter | 6mm | 8mm | 10mm | 12mm | 15mm | 19mm |
| The fire integrity time (minute) | 183 | 96 | 128 | 135 | 74 | 84 |
| Bearing stress value (MPa) | 151 | 162 | 174 | 158 | 150 | 149 |
Because glass itself contains nickel sulphide inclusions, behind glass tempering, owing to exist higher prestress can cause glass easily to be revealed, therefore the prestress value of feed glass also is necessary, bearing stress by the glass after this art breading is not more than 180Mpa, be not less than 140Mpa, guarantee that the safety performance of high-strength refractory Cs-K glass is stable.
Product of the present invention has superior fire resistance, and it is poor to have overcome grouting flame resistant glass weathering resistance, and easily jaundice is bubbled under uviolizing, and intensity is low, can not be used for the deficiency of external wall.Because effect is greatly improved glass intensity in the time of physical toughened and chemical tempering.By detecting, use the glass of this method manufacturing, its bending strength is more than 1.5 times of common toughened glass of stack pile.
Claims (8)
1, a kind of manufacture method of high-strength refractory Cs-K glass, it is characterized in that it is 650-735 ℃ of annealing furnace that glass is put into temperature, in to the glass rapid heating, the caesium sylvite masking liquid of spraying specific composition, caesium sylvite masking liquid proportioning is: sylvite: 35～65%, sodium salt: 1～6%, cesium salt: 0.5～1.5%, masking liquid tackifier: 0.2～10%, tin compound stripper: 2～20%, tensio-active agent: 0.2～1.2%, water: 25～50%, press every millimeter thickness heating of glass 30-65 second heat-up time, after heating was finished, glass entered the cooling section rapid quench.
2, manufacture method as claimed in claim 1 is characterized in that the sylvite that uses is K
3PO
4
3, manufacture method as claimed in claim 1 is characterized in that the sylvite that uses is KCl and KNO
3Weight ratio is 5: 1～1: 1 a mixture, or K
2SO
4And KNO
3Weight ratio is 3: 1～1: 1 a mixture.
4, manufacture method as claimed in claim 1 is characterized in that the sodium salt that uses is a sodium phosphate, and cesium salt is cesium nitrate or cesium carbonate, and the tin compound stripper is a tin tetrachloride.
5, manufacture method as claimed in claim 1 is characterized in that the masking liquid tackifier that use are one or more mixtures that are selected from starch, gelatin, gelatine, methylcellulose gum, the yellow starch gum.
6, manufacture method as claimed in claim 1 is characterized in that the surface pressure of the glass for preparing should be worth greater than 140Mpa, less than 180Mpa.
7, manufacture method as claimed in claim 1, the thickness of its glass are 6mm, 8mm, 10mm, 12mm, 15mm, 19mm.
8, as any described manufacture method of claim 1-7, it is characterized in that to carry out rounding edge polishing and the polished finish of rounding angle to glass.
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| CNB2004100056450A CN1218893C (en) | 2004-02-21 | 2004-02-21 | Method for mfg. high strength fireproof signle sheet cesium potash glass |
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| CNB2004100056450A CN1218893C (en) | 2004-02-21 | 2004-02-21 | Method for mfg. high strength fireproof signle sheet cesium potash glass |
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| CN1218893C true CN1218893C (en) | 2005-09-14 |
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