The application is that application number is 201110060915.8, and name is called dividing an application of " a kind of preparation technology that the low-viscosity glass of high-intensity energy-conserving and environment-protective is arranged ".
Embodiment
The first embodiment
According to one embodiment of the invention, a kind of preparation technology of glass, it comprises the following steps:
Step 1: by the composition of this glass bag silicon oxide, calcium oxide, magnesium oxide, aluminum oxide, ferric oxide, sodium oxide, count as weight percents, in this glass, the content of boron oxide is 0-1%, the content of sodium oxide is 0.01-14%, iron oxide content is 0.01-5%, the content of fluorine oxide is 0-1%, content of magnesia is 8.1-20.2%, alumina content is 8-30%, 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; Prepare the raw material of required making glass by above requirement;
Step 2: by standby they all kinds of raw materials of institute, be positioned among material container separately, make various raw materials by the raw material transfer limes, after metering, send in the raw material mixed stirring device in required ratio, enter after being uniformly mixed in the aniseed pipe or feed bin that loads batching;
Step 3: the raw material of working good is entered in molten bath, according to the sodium oxide in predetermined requisite special scope, ferric oxide, aluminum oxide, silicon oxide, calcium oxide, magnesium oxide or also have titanium oxide, barytic composition and predetermined silicon oxide, calcium oxide, magnesium oxide between the ratio of composition of specific proportions relation, in the temperature of fusion corresponding to each glass formula, melt, form the glass metal of predetermined viscosity, homogenizing again, clarification, discharge bubble, forms flowable molten mass;
Step 4: three kinds of selections are arranged:
One of select, use the trombone slide moulding process: the melten glass body formed in step 3 is drawn into to Glass tubing and moulding through tube-pulling apparatus, through annealing, cooling, can make the described low-viscosity glass that high-intensity energy-conserving and environment-protective are arranged, and this glass water-intake rate is in the scope of 0-0.3%, and the folding strength of this glass reaches 70-180Mpa;
Two of selection, use blow molding technique: the melten glass body formed in step 3 is adopted to the technological process for blowing moulding, through annealing, cooling, can make the described low-viscosity glass that high-intensity energy-conserving and environment-protective are arranged, and this glass water-intake rate is in the scope of 0-0.3%, and the folding strength of this glass reaches 70-180Mpa;
Three of selection, use compression moulding technique: to the melten glass body component that forms in step 3 or after cutting, compression moulding in mould, through annealing, cooling, can make the described low-viscosity glass that high-intensity energy-conserving and environment-protective are arranged, and this glass water-intake rate is in the scope of 0-0.3%, and the folding strength of this glass reaches 70-180MPa.
The technique effect of the new product property of below the present invention being found is explained as follows.(in addition, in this manual, unless specialized, in glass, the content of various compositions all is weight percentage.)
Viscosity performance
The mensuration of embodiment of the present invention medium viscosity adopts U.S. THETA rotation high temperature viscosimeter.
From the example of table 1, table 2, table 3, from the viscosity data of several keys, comparatively speaking (at alumina content, reach 28% when following):
(1), temperature of fusion: be 10 according to the low-viscosity glass viscosity that high-intensity energy-conserving and environment-protective are arranged of the embodiment of the present invention
0.5Temperature when (handkerchief second) is 1540 ℃-1620 ℃; Viscosity is 10
1Temperature when (handkerchief second) is 1450 ℃-1520 ℃.
And above-mentioned prior art alkali-free boron glass cup, dish, pipe, bottle, the tank class glasswork such as use as solar energy glass pipe, medical, light fixture with, chemical industry, due to viscosity 10
0.5(handkerchief second) and 10
1The temperature of fusion of (handkerchief second) is much higher than 1650 ℃-1700 ℃, so adopt U.S. THETA rotation high temperature viscosimeter not measure at all.Especially the viscosity 10 that the goods (salic only 1-5%) such as conventional calcium sodium class vial, cup, dish, pipe can only be measured
1.5The temperature of fusion that temperature when (handkerchief second) is 1580 ℃, all exceed 150 ℃-300 ℃ of the present invention.
Viscosity 10 from clarification exhaust bubble
2Temperature when (handkerchief second), aluminum oxide of the present invention each example in 28% time is 1230 ℃-1300 ℃, and the low above-mentioned glasswork of calcium sodium class of above-mentioned prior art is at 1380 ℃-1400 ℃, and alkali-free high boron glass class said products reaches 1500 ℃-1550 ℃, also all exceed 150 ℃-200 ℃ of the present invention.
From moulding viscosity 10
3Temperature when (handkerchief second), alumina content of the present invention each example in 28% time is 1090 ℃-1160 ℃, and the above-mentioned glasswork of existing calcium sodium class is 1210 ℃-1250 ℃, alkali-free high boron glass class said products all reaches 1300 ℃-1320 ℃.Because viscosity performance of the present invention is well a lot, thus the insider all know, can be than prior art production, control out still less air blister defect, still less surface smoothness and the quality of quarrel point.
Strength property
Aforesaid existing as pipe, cup, bottle etc., and the goods such as glass insulator, solar water organ pipe for electrical network, aluminum oxide is only 1% left and right or 1-5% left and right, and its technical scheme is difficult for adding aluminum oxide, otherwise can not implement because viscosity is too high to produce, intensity is only also the 45-50MPa left and right.
And according to the embodiment of the present invention, as described in front viscosity part, can know when aluminum oxide is added to 20-25% or 25-30%, viscosity is also 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.
Environmental-protecting performance
As existing sun power Glass tubing, high temperature lantern pane, medical glasswares etc., melt especially moulding viscosity temperature in order to reduce, all adopt the content composition that adds boron oxide 8-15%, and the advantage of boron-free glass goods of the present invention is: (1) is due to traditional flux material that can not add boron, so the serious poison gas discharge that does not have boron to produce in environmental protection; (2) and when having added the aluminum oxide of 18-25%, the viscosity that is easy to control better than existing non-alkali glass material also can be arranged, and can reach the intensity of 100-160MPa or 130-160MPa.
Reduce costs performance
The equipment of the boron-free glass goods of technical scheme of the present invention, due to the composition that there is no boron, to the refractory corrosion in molten bath seldom, greatly increased equipment work-ing life 2-3 doubly.
Coefficient of expansion linear feature is outstanding, and the interval variation of differing temps is minimum.
According to the coefficient of expansion of the glass of the embodiment of the present invention, according to standard GB/T7320.1-2000, measure.
(1), conventional art prejudice is mainly to promote strain point temperature (lower limit that strain point temperature is the temperature of when glass ware forming, glass being annealed) with adding the aluminum oxide composition, reach 550 ℃-600 ℃ or reach 600 ℃-650 ℃ or the purpose more than 650 ℃ and be to solve at higher temperature and promote strain point, goods are sharply heated or are not had too much distortion or explosion occurs when cooling.But the present invention's technical scheme 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 the two ends numerical value of 150 ℃-300 ℃; Difference at the two ends numerical value of 550 ℃-600 ℃ is 1,000,000/1-2.8/1000000ths; For non-alkali glass, in the difference of the two ends numerical value of 600 ℃-650 ℃, be 1,000,000/1-3.0/1000000ths.The goods of these inventive features, for especially new forms of energy, medical treatment, light fixture, Chemicals the time, be difficult for explosion, and security is good.
Below, provide the concrete sample of filling a prescription of difference according to a kind of glass of the embodiment of the present invention, to understand better technical scheme of the present invention.
In order to describe in more detail the technical scheme according to the embodiment of the present invention, list formula and the corresponding performance of the obtained sample of the preparation technology of a kind of glass according to an embodiment of the invention below in table 1.
Table 2 (prior art)
* do not measure with the High Temperature Rotating viscometer, obtain through reckoning.
As seen from Table 1, the technical scheme of the present invention's 1-11 sample, all among the scope of embodiment 1, this glass has comprised silicon oxide, calcium oxide, magnesium oxide, aluminum oxide, ferric oxide, titanium oxide, barium oxide, the composition of sodium oxide, count as weight percents, in this glass, the content of boron oxide is 0-3.9%, the content of sodium oxide is 0.01-14%, iron oxide content is 0.01-5%, titanium oxide is 0.0003-4.9%, content of magnesia is 8.1-20.2%, alumina content is 8-30%, the content of its silicon oxide is 1.9 times-4.1 times of calcium oxide content, the content of calcium oxide is 1.2 times-1.6 times of magnesian content.Its viscosity is low than prior art table 2 all, especially temperature of fusion (table 1 sample 5,6,7,8,9,10) when having added the aluminum oxide of 20-30%, than all prior aries and comparative example (table 21,2,3,4) while only having added the composition below 10%, 10
0.5(handkerchief second) and 10
1Low 150 ℃-250 ℃ of melting process temperature when (handkerchief second).And its silicon, magnesium, calcium, iron, titanium, sodium content and ratio be not within the technical solution of the present invention scope.
Technical solution of the present invention is under the same equipment state of prior art, can energy-conservation 30% left and right (because the high temperature melting stage is the maximum stage of energy consumption), also from the contrast of table 1 and table 2, can improve intensity 2-3 doubly, mold temperature also hangs down 150 ℃ more than-250 ℃ simultaneously, and this is conducive to control the Forming Quality of product.As seen from Table 1 simultaneously, it is in the goods below 28% that sample of the present invention contains at 10 aluminum oxide, all do not add boron oxide, in the technique of this solar energy glass pipe for technology especially now and medical vessel etc., boracic reaches the boron poison gas volatilization in the production of product of 8-12%, can reach the environment protecting that is entirely zero.
From the sample the 6,7,8,9, the 10th of table 1, iron content, sodium, magnesium and silicon be calcium 2.1-2.3 doubly, calcium is doubly salic at the very high preferred version more than 20% of 1.3-1.5 of magnesium, its viscosity, intensity are very good as seen.And sample the 1,2,3, the 4th, adopt in technical solution of the present invention the sample of limit, lower limit on silicon, calcium, magnesium ratio.Various prior arts or comparative sample from table 2, its technical scheme, being comprised of silicon, calcium, magnesium, iron, sodium composition, reaches 8.1-20.2% at magnesium oxide, at silicon, is 1.9-4.1 times of calcium, calcium is that the 1.2-1.6 of magnesium doubly waits on whole invention technology contents, has 2-5 place or 3-5 place different.Just because of the innovation of the novelty of technical solution of the present invention, thus just produced the comparison prior art environmental protection, energy-conservation, reduction of discharging, viscosity, intensity, be conducive to the technique effect such as technical qualities control.
The sample 10 and 11 of table 1, and sample 10, 11, due to iron level 1 to 1.3, and higher barium oxide arranged, titanium oxide content and can become opaque brown Huang or brown color, to adapt in intensity, the feature such as viscosity temperature and strain point is all than well a lot of goods of prior art glass, relating to the cup of glass, dish, bottle, cylinder, the goods such as pipe, can or add again appropriate barium oxide at the ferric oxide that adds 1-1.5%, titanium oxide, manganese oxide, cobalt oxide isochrome and produce opaque blue or green blue, blue green, yellowish-brown, brown, the colors such as black for or drinks, beverage class and senior daily bottle, dish, the senior dark class glasswork with magnificent decorative value is arranged with practical value such as cup.
On the basis of above-mentioned the first embodiment, to count as weight percents, the content of aluminum oxide is 19-30%, and the content of boron oxide is 0-1%, and the content of sodium oxide is 0.01-2%, and the content of fluorine oxide is 0-1%; The annealing temperature lower limit of this glass (being the endotherm(ic)peak origin temp) is 610 ℃-710 ℃; This glass is 10 in viscosity
0.5Temperature when (handkerchief second) is 1510 ℃-1680 ℃; Viscosity is 10
1Temperature when (handkerchief second) is 1420 ℃-1600 ℃; Viscosity is 10
2Temperature when (handkerchief second) is 1270 ℃-1360 ℃; Viscosity is 10
3Temperature when (handkerchief second) is 1160 ℃-1280 ℃; The folding strength of this glass is 120-180MPa.
Preferred embodiment one
Referring to shown in Fig. 1, is the normal section schematic diagram of the prepared Glass tubing goods of preparation technology embodiment of a kind of glass of the present invention.Label 1 means a kind of Glass tubing goods of tube-pulling craft moulding.
Referring to shown in Fig. 2, is the process flow diagram that the preparation technology embodiment of a kind of glass of the present invention prepares Glass tubing.From scheming, the flow process of its moulding process is: (1), the raw material that will be scheduled to prepare are put into feeding warehouse, (2), then from feeding warehouse, raw material is transported in the kiln of molten bath, (3) enter molten bath and carried out melting clarification discharge bubble by preset temperature, (4), be then liquid molten mass, draw moulding through tube-pulling apparatus, make the low-viscosity glass tubing products that high-intensity energy-conserving and environment-protective are arranged of the present invention.
Referring to shown in Fig. 3, is that the preparation technology of a kind of glass of the present invention selects the normal section schematic diagram with the prepared vial goods of the embodiment of blow molding technological forming.Label 2 means a kind of vial goods of technological process for blowing moulding.
Referring to shown in Fig. 4, is that preparation technology's selection of a kind of glass of the present invention prepares the process flow diagram of vial with the embodiment of blow molding technological forming.From scheming, the flow process of its moulding process is: (1), the raw material that will be scheduled to prepare are put into feeding warehouse, (2), then from feeding warehouse, raw material is transported in the kiln of molten bath, (3) enter molten bath and carried out melting clarification discharge bubble by preset temperature, (4), be then liquid molten mass, through the technological process for blowing moulding, make the low-viscosity glass bottle product that high-intensity energy-conserving and environment-protective are arranged of the present invention.
Referring to shown in Fig. 5, is that the preparation technology of a kind of glass of the present invention selects the normal section schematic diagram with the prepared glass cylinder goods of the embodiment of compression moulding technological forming.Label 3 means a kind of glass cylinder goods of pressing process moulding
Referring to shown in Fig. 6, is that preparation technology's selection of a kind of glass of the present invention prepares the process flow diagram of glass cylinder with the embodiment of compression moulding technological forming.From scheming, the flow process of its moulding process is: (1), the raw material that will be scheduled to prepare are put into feeding warehouse, (2), then from feeding warehouse, raw material is transported in the kiln of molten bath, (3) enter molten bath and carried out melting clarification discharge bubble by preset temperature, (4), be then liquid molten mass, through the superfusion component or cut after, compression moulding in mould, make the low-viscosity glass cup goods that high-intensity energy-conserving and environment-protective are arranged of the present invention.
Now the preparation technology of a kind of glass of the present invention being adopted the tube-pulling craft moulding to prepare Glass tubing is that example is described further, and its manufacturing processed comprises following steps:
(1), at first, preparation raw material, form to calculate proportioning raw materials according to the low-viscosity glass by high-intensity energy-conserving and environment-protective of above-mentioned the first embodiment and various modification and example.
(2), be ready to comprise raw material cabin, molten bath kiln, the required product line device of trombone slide moulding process.
(3), press the Production Flow Chart of the technique shown in Fig. 2, the predetermined raw material of (1) step preparation is put into to feeding warehouse, then from feeding warehouse, raw material is transported in the kiln of molten bath, has entered and carried out melting by preset temperature behind molten bath and bubble is discharged in clarification, form liquid molten mass;
(4), adopt the device of trombone slide moulding process, by liquid glass melt, be drawn into Glass tubing and moulding, through annealing, cooling, make its water-intake rate of the present invention in the scope of 0-0.3%, folding strength reaches the low-viscosity glass pipe (as shown in Figure 1) that high-intensity energy-conserving and environment-protective are arranged of 70-180Mpa.
Now adopt the blow molding method take in a kind of glass of the present invention to prepare vial to be described further as example, its manufacturing processed comprises following steps:
(1), at first, preparation raw material, form to calculate proportioning raw materials according to the low-viscosity glass by high-intensity energy-conserving and environment-protective of above-mentioned the first embodiment and various modification and example.
(2), be ready to comprise raw material cabin, molten bath kiln, the required product line device of blow molding technique.
(3), press the Production Flow Chart of the technique shown in Fig. 2, the predetermined raw material of (1) step preparation is put into to feeding warehouse, then from feeding warehouse, raw material is transported in the kiln of molten bath, has entered and carried out melting by preset temperature behind molten bath and bubble is discharged in clarification, form liquid molten mass;
(4), adopt the device of blow molding technique, by liquid glass melt, through the technological process for blowing moulding, again through annealing, cooling, make its water-intake rate of the present invention in the scope of 0-0.3%, folding strength reaches the low-viscosity glass bottle (as shown in Figure 3) that high-intensity energy-conserving and environment-protective are arranged of 70-180Mpa.
Now the employing briquetting process of a kind of glass of the present invention be take and prepare glass cylinder and be described further as example, its manufacturing processed comprises following steps:
(1), at first, preparation raw material, form to calculate proportioning raw materials according to the low-viscosity glass by high-intensity energy-conserving and environment-protective of above-mentioned the first embodiment and various modification and example.
(2), be ready to comprise raw material cabin, molten bath kiln, the required product line device of compression moulding technique.
(3), press the Production Flow Chart of the technique shown in Fig. 2, the predetermined raw material of (1) step preparation is put into to feeding warehouse, then from feeding warehouse, raw material is transported in the kiln of molten bath, has entered and carried out melting by preset temperature behind molten bath and bubble is discharged in clarification, form liquid molten mass;
(4), adopt the device of compression moulding technique, by liquid glass melt, through component or after cutting, compression moulding in mould, through annealing, cooling, can make its water-intake rate of the present invention in the scope of 0-0.3%, folding strength reaches the low-viscosity glass cup (as shown in Figure 5) that high-intensity energy-conserving and environment-protective are arranged of 70-180Mpa.
Application
Due to the preparation technology of the above-mentioned a kind of glass according to the embodiment of the present invention, can, at the technical barrier that solves three aforementioned quasi-traditions, can be applied to solar energy glass pipe and medical and industrial Glass tubing etc. as be applied to solar water heater.
All prior arts all do not have open or disclose and use overcome various traditional composition hydrotropy compositions and the technology prejudice that is total to the solution composition of the present invention, and the product strength rising 1-3 that can produce unforeseeable hydrotropy or altogether solution function and generation doubly, environmental protection, the technique effect of energy-saving and emission-reduction etc., and for the trombone slide moulding of non-conventional glass goods or the technical scheme of blow molding or press technology for shaping, the pipe of scale glass, cup, bottle, the glasswork of one classes such as dish, and electrical network power station glass insulator, the glassworks such as ambetti hollow brick, so technical scheme of the present invention has novelty.
Below according to the preparation technology's of a kind of glass of the embodiment of the present invention characteristics, to technical solution of the present invention, do in a word bright.Technical scheme of the present invention relates to a kind of new product composition and the processing method of newfound product property and generation product.
It comprises the following steps:
Step 1: by the composition of this glass bag silicon oxide, calcium oxide, magnesium oxide, aluminum oxide, ferric oxide, sodium oxide, count as weight percents, in this glass, the content of boron oxide is 0-1%, the content of sodium oxide is 0.01-14%, iron oxide content is 0.01-5%, the content of fluorine oxide is 0-1%, titanium oxide is 0.0003-4.9%, content of magnesia is 8.1-20.2%, alumina content is 8-30%, 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; Prepare the raw material of required making glass by above requirement;
Step 2: by standby they all kinds of raw materials of institute, be positioned among material container separately, make various raw materials by the raw material transfer limes, after metering, send in the raw material mixed stirring device in required ratio, enter after being uniformly mixed in the aniseed pipe or feed bin that loads batching;
Step 3: the raw material of working good is entered in molten bath, according to the sodium oxide in predetermined requisite special scope, ferric oxide, aluminum oxide, silicon oxide, calcium oxide, magnesium oxide or also have titanium oxide, barytic composition and predetermined silicon oxide, calcium oxide, magnesium oxide between the ratio of composition of specific proportions relation, in the temperature of fusion corresponding to each glass formula, melt, form the glass metal of predetermined viscosity, homogenizing again, clarification, discharge bubble, forms flowable molten mass;
Step 4: three kinds of selections are arranged:
One of select, use the trombone slide moulding process: the melten glass body formed in step 3 is drawn into to Glass tubing and moulding through tube-pulling apparatus, through annealing, cooling, can make the described low-viscosity glass that high-intensity energy-conserving and environment-protective are arranged, and this glass water-intake rate is in the scope of 0-0.3%, and the folding strength of this glass reaches 70-180Mpa;
Two of selection, use blow molding technique: the melten glass body formed in step 3 is adopted to the technological process for blowing moulding, through annealing, cooling, can make the described low-viscosity glass that high-intensity energy-conserving and environment-protective are arranged, and this glass water-intake rate is in the scope of 0-0.3%, and the folding strength of this glass reaches 70-180Mpa;
Three of selection, use compression moulding technique: to the melten glass body component that forms in step 3 or after cutting, compression moulding in mould, through annealing, cooling, can make the described low-viscosity glass that high-intensity energy-conserving and environment-protective are arranged, and this glass water-intake rate is in the scope of 0-0.3%, and the folding strength of this glass reaches 70-180MPa.
The feature of the product of the bottle of the various abnormity that the tube-pulling craft that technical solution of the present invention adopts or technological process for blowing or pressing process produce, cup, pipe, tank based article has following level:
One, for the glass of all prior aries, be a kind of high aluminium content composition the composition scope that silicon, calcium, magnesium, iron, sodium are also arranged selection invention and between silicon, calcium, magnesium composition, the type of the change of the proportionlity of these technology essential factors invention.
They are two years old, the convert invention type of new purposes of the new character that the present invention has disclosed the product of finding, be also produced unforeseeable effect invention (by various glass processing methods, in the discovery of the invention of the new character of glasswork and new purposes, as the low-viscosity in the different process stage, high strength, the lightweight character of the high-quality technology controlling and process under better viscosity temperature condition of the new aluminium when high alumina content, silicon, calcium, magnesium eutectic character and generation, reach the unforeseeable effects such as energy-saving and environmental protection.
And, in the selection invention of the change of the present invention's factor proportion relation, its technical scheme is silicon: calcium is 2.0-4.1, calcium: magnesium is 1.2-1.6 scope doubly.And the glassy product of all employing tube-pulling crafts of prior art, technological process for blowing, pressing process, 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 namely the present invention is above-mentioned, there is novelty.And in the purposes of the bottle of the various abnormity that adopt tube-pulling craft or technological process for blowing or pressing process to produce, cup, pipe, tank based article, in technique, found new following product property, produced following unforeseeable technique effect.
(A), because one of discovery of the new character of product is to have overcome conventional art prejudice, thereby a kind of key element of the technology of the sodium oxide to the calcium soda glass produced is omitted invention: the goods such as the soda glass class vessel of prior art, cup, light fixture, it all contains the sodium of 10-13% left and right, be mainly used to flux, to fluxing of silicon composition, form the reduction that can 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 due to silicon, calcium, the variation invention of the element relationship between magnesium, in the purposes of glass, the product new property produced, when sodium content is in 0-1%, can be than low 150 ℃-250 ℃ of the viscosity temperature of several operation stages of the high soda glass of prior art, this will produce a large amount of energy-conservation glass stones with being conducive to the bad generation of melting process of high-quality control product, the defects such as bubble rate of quarrel point and the bad generation of row's bubble technique, especially for reducing the quarrel point, the calculus rate, bubble rate, the defects such as underproof formed product distortion also provide a good large technology controlling and process scope.
Prior art is in operation, if once produce the defect of any one operation stage, the mode that all is easy to increase the temperature of each operation stage in operation solves, but this just is prone to the top that collapses, the molten bath made in technique very much, greatly shortens molten bath work-ing life.And the invention provides the viscosity variable range that a technology that is conducive to control very much technique is controlled.Fundamentally solved the technical barrier of the product property (" material property " said in the industry) of the existing sodium that the insider thinks always (high sodium) glass " material property is short ".
(B), due to two of the discovery of the new character of product, overcome the prejudice of conventional art, produced to as adopted the glass-tube of the solar water heater that tube-pulling craft produces or the lamp a kind of key element elliptical technical solution of the present invention by " boron oxide " technology essential factor of a kind of alkali-free boron glass of all glass of pipe: existing alkali-free boron glass, it is because be no more than 1% sodium general containing, make the fusing assistant composition so all adopted the boron composition of 8-15% content, could form fluxing to silicon, the technology prejudice of thinking to go in the side of being far from it is arranged, reduction with the viscosity temperature that can form high-quality each operation stage of glass is controlled.But the new property of technical scheme of the present invention and discovery, broken this technology prejudice, can be due to silicon, calcium, the variation invention of the element relationship between magnesium, find new product property, in new purposes, when there is no boron oxide content or being 0-1%, can be than the viscosity temperature of the product of the boron with 8-15% content of prior art, several operation stages at glass hang down 250 ℃-350 ℃, this will form an a wide range of control technique and reach the new technology platform of controlling quality product, for sun power, higher order light is used, the medical glass that waits, the high-level level of this requirement and almost without bubble, without the quarrel point, without the quality requirements of calculus defect and accuracy requirement and the finished product rate of moulding, the quality product rate, especially for exhaust bubble and clarification, the viscosity of the operation stage of homogenizing process stage and moulding, a kind of much better discharging without boron poison gas than prior art all is provided, the technology controlling and process scope of energy-saving and emission-reduction and technology controlling and process platform.
(C), due to three of the discovery of the new product property of product, overcome a kind of of traditional glass and thought that strengthening aluminum oxide certainly leads to the technology prejudice that viscosity temperature significantly rises.As prior art calcium soda glass, the aluminum oxide that can only add 1% left and right, and existing alkali-free boron glass also generally only adds 8% left and right aluminum oxide to improve intensity, added and will make the viscosity temperature of this each very high stage process higher, the QT Quality Target that uncontrollable technique should reach.Traditional technology prejudice is also thought at all and can't under can low-cost, high-quality controlled processing condition, be added to 25-30% to aluminum oxide, to improve the application performance of product strength.But the new glassy product character of technical scheme of the present invention and discovery, broken this technology prejudice, the present invention at boracic not, containing sodium, not during fluorine-containing composition when 0-1% (or), alumina content is 3.1% or 16% or 20% or large span during 25% left and right while changing, prior art thinks that viscosity can significantly rise, but the variation of viscosity temperature of the present invention is only 30 ℃-40 ℃, when aluminum oxide is 30% left and right, viscosity temperature also only rises 40 ℃-80 ℃ with interior (seeing attached list 11 sample examples of 1 and the sample Comparative Examples of table 2).
And viscosity temperature is than also low 100 ℃-200 ℃ of the glassy 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 technical scheme of the present invention, calcium, magnesium, energy and aluminum oxide produce a kind of new product property when 1-25% or 25-30% content, the eutectic character of the aluminium of a kind of new high alumina content that Here it is, silicon, magnesium, calcium, can produce unforeseeable technique effect and and then the product high strength, lightening, the light-weighted unforeseeable technique effect that produce of the low viscosity temperature of high aluminium content.
When the present invention especially reaches 19-28% due to the content that can strengthen aluminum oxide, intensity can reach about 140-160Mpa or 180Mpa, be much higher than the 2-3 of various prior art strength of glass doubly, and due to viscosity temperature also than only during the 1-25% alumina content low 150 ℃-250 ℃ of prior arts, if so, when technical solution of the present invention forms the viscosity of alkali-free high boron glass, that should be equivalent to add aluminum oxide in addition to the viscosity space that can dissolve of 29-39% and the larger space of intensity rising.(annotate: the folding strength of this specification sheets and embodiment of the present invention glass, by sample being cut into to little of 50mm * 50mm * 5mm, adopt the folding strength instrument, by standard GB/T3810,4-2006, measure.) the high boron goods of alkali-free of prior art, because of the volatilization process of boron oxide composition, can cause the inequality of composition, the netted structural damage of material that aluminum oxide is participated in, affect due intensity greatly.This is the alkali-free high boron glass containing the time also poor major reason of intensity of 7-15% aluminum oxide.
The present invention is when high aluminium content, because of the silicon that can have high alumina to contain, calcium, the eutectic character of magnesium, when can produce the intensity of 90-145Mpa or 145-180Mpa, can have concurrently again more energy-conservation, the more low-cost characteristic with the processing range of larger viscosity temperature is arranged, be the glasswork product technology of existing all trombone slides or blowing or compacting do less than, can melt at melting process viscosity temperature stage control, overcome calculus and prevent the quarrel point be not melted, when controlling clarification and controlling moulding, the formed precision of glass is (because viscosity is lower, the more soft scope that control is more arranged of the glassy product of this operation stage, otherwise viscosity is higher, this operation stage glassy product is harder, more bad control drawing trombone slide, or blowing, or the accuracy of the moulding process of compacting and the qualification rate of precision and product, quality product rate quality).
(D), add ferric oxide 0.01-4%, be a kind of component invention, can form new function, save high-quality resource, greatly reduce costs.
They are three years old, announcement and discovery due to the character of new the said products, overcome more than above-mentioned and planted prior art prejudice, in, daily pipe, cup, dish, bottle, tank class glass art for, medical, industrial, chemical industry for various new forms of energy, following unforeseeable following technique effect and new purposes have been produced.(1) formed the technique effect of molten quality, bubble quality, high-precision modeling quality, yield rate and the rising of quality product rate that can well promote and control technique due to viscosity temperature character, (2) the unforeseeable energy-saving effect more than 200 ℃ due to viscosity temperature decline, (3) unforeseeable because eutectic character adds a large amount of aluminium (from 1%, being added to 25-30%), the intensity rising 2-3 of generation technique effect doubly, (4) due to intensity rise producible glass thus can frivolous 2-3 doubly energy-conservation, economize on resources, save logistics, storage 2-3 unforeseeable technique effect doubly, (5) owing to having 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, under the prerequisite of formed precision quality control, technological temperature do not rise and can reduce and energy-conservation prerequisite under, the boron composition omits in province, the fusing of technique can be arranged, row's bubble, the folding strength character that the better character in each stage of moulding produces with adding more aluminum oxide, and the unforeseeable boron composition that can not add 8-15% to the alkali-free boron glass, the clean environment firendly production effect without the discharge of boron poison gas produced, with the not serious corrosion molten bath because of producing without boron production, the effect that can make plant efficiency increase more than 30%.(6) technical solution of the present invention compares with existing all glass technologies, there is the new revealed and disclosed new character that do not have, and this character is can't infer in advance, unpredictable and reasoning out, and overcome the technology prejudice of traditional glass technology, solve people and thirsted in the industry the above-mentioned significant problem solved, technique effect has produced " matter " and " amount " the two variation, illustrate that technical scheme is non-obvious, there is outstanding substantive distinguishing features, there is significant technical progress, creative.
The key distinction about the present invention and prior art:
(1), the glass composition of the general production technique of the glassware without the boron soda glass of prior art, one is alumina content lower (generally all only at 1-3%), because exist, think once strengthen aluminum oxide over more than 3%, the technology prejudice that must flux with a large amount of sodium or boron, can not effectively reduce the control of viscosity temperature, can not reach the purpose that has quality to ensure, so its product strength is very poor, be only generally in 50MPa, can not reach the present invention's 70-180Mpa and preferred 120-180Mpa, also more can not can reach the soundness that high aluminium content is arranged as intensity of the present invention, wearing quality and lightening 2-3 are doubly.As the SU581097A of prior art discloses a kind of emulsion opal glass, purposes is the turbid lacteous coloured silk on colour, but its aluminum oxide is only 1-3%, its product strength can only be below 50MPa, and alumina content of the present invention can reach 8-30%, intensity can reach 70-180MPa, due to its boracic not, sodium only has again 0.5-2%, so it is due to using without sodium less than discovery and announcement the present invention, without boron (or being only below 1%) composition and the high aluminium content of aluminum oxide during up to 8-30% or 19-30% and silicon, calcium, the various operation stages that magnesium eutectic character and the present invention disclose when the new purposes of special-shaped product, the trombone slide adopted or blowing or pressing process and in the revealed or disclosed critical nature never such as the viscosity temperature of each viscosity operation stage.As: 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%, and boron oxide is 0-1%, and the content of fluorine oxide is 0-1%; The annealing temperature lower limit of this glass (being the endotherm(ic)peak origin temp) is 610 ℃-680 ℃; This 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 glass is 75-180MPa.
Perhaps, 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%, and boron oxide is 0-1%, and the content of fluorine oxide is 0-1%; The annealing temperature lower limit of this glass (being the endotherm(ic)peak origin temp) is 610 ℃-680 ℃; This 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 glass is 130-180MPa.
So, also can not expect under the condition that is created in the process viscosity reduction, produce under the secure prerequisite of a fusing, exhaust bubble, formed precision quality, yield rate, quality product rate, also can have concurrently high strength surpass its soundness more than 2 times, wearing quality and can guarantee same during with prior art intensity lightening 2-3 doubly energy-conservation, economize on resources, save logistics, save the unforeseeable multiple simultaneous technique effect of warehouse cost 2-3 times.
(2), the product composition aspect of the goods such as existing alkali-free boron glass solar pipe and light fixture, the key distinction is to the invention belongs to a kind of a kind of omission key element invention by it boron oxide key element of fluxing to prior art.(1) can reach fusing, row bubble, moulding viscosity temperature lower, quality control is better; (2) under more controlled prerequisite, can add more aluminum oxide in viscosity, intensity is better; (3) can there is no the discharge of boron poison gas fully, thoroughly solve the large problem of environmental protection in boron glass production.
(3), energy-saving and emission-reduction, due to can be temperature of fusion than prior art in the situation that equal alumina content reduces by 150 ℃-300 ℃, high-temperature zone due to fusing is maximum energy consumption district again, so can save energy 30-40%, also can reduce Carbon emission 30-40%.
(4), owing to can under same viscosity temperature, adding aluminum oxide 15-20%, so the intensity 2-3 of the product that can rise doubly.Solved no matter at the product use properties of the glassworks such as sun power or industry as electrical network use insulator glass or daily or therapeutic medical pipe, bottle, cup, dish and soundness, wearing quality, damageability not, also help and make Glass tubing attenuation 1-2 times of rear transmitance that strengthens sun power, improving energy efficiency turnover ratio greatly for sun power.But and the security load installed and used of the not roof of very firm wooden frame structure that is particularly suitable for Europe, the United States, Australia, South East Asia after lightening.
(5), because product strength can rise 2-3 doubly, can make the frivolous 2-3 of goods doubly, the saving 2-3 that forms raw material resources doubly and the cost that can economize in raw materials, and can be in the inland of all logistics and seagoing transport because of light, thin 2-3 doubly, save transportation cost, logistics cost.
(6), due to can be on same technique platform, boron composition before producing reaches the glassy product of 8-12%, can be fully boracic composition not, and fundamentally solve, and the discharge of the boron poison gas in producing such as electrician, chemical industry, boron glass-tube for existing solar energy glass pipe, medical, advanced lighting, form nontoxic production technology scheme thoroughly.
The new product property that the variation of above-mentioned purposes of the present invention is found and produce unforeseeable technique effect, it is nearly ten to 20 years, the whole world is as be applied to new forms of energy, chemical industry, electrician's industry, medical treatment and sun power and industrial Glass tubing, bottle, dish, tank, cup and electrical network are with thousands of enterprises of the industries such as glass insulator and tens thousand of technician, all research and solve and the industrial technology development trend that never solves and people thirst for solving and the great technical barrier that never succeeds and this specification sheets are mentioned many other people that also have thirst for the various technical barriers that solve and do not succeed, and state technique effect on the present invention, can solve, this is also that those skilled in the art are non-obvious unforeseeable.
Above-mentioned unforeseeable technique effect, all because adopted a kind of selection invention of change technology essential factor proportionlity or the omission invention of the invention of purposes conversion and technology essential factor, also have with or trombone slide, or blowing, or the component invention type of the processing method of compacting, and changed and found new product property after the purposes, found at viscosity temperature of each operation stage of these product process etc., from undiscovered new feature, when new property and high aluminium content and silicon, calcium, the new eutectic feature that the technical solution of the present invention of the appearance of magnesium discloses, and the product strength nature and characteristic produced therefrom, and a kind of omit key element invention type under without sodium or boron composition condition, low viscosity temperature profile and the high strength characteristics of high aluminium content, above new feature is never by prior art, to be disclosed or disclosed, and can produce unforeseeable technique effect, the character of these technical products can't inferred in advance, unpredictable, and overcome much technology prejudice, produced the variation of " matter " and " amount " of above-mentioned technique effect, illustrate that technical scheme is non-obvious, there is outstanding substantive distinguishing features and significant technical progress, creative.
The above, only for better preferred embodiment of the present invention is described, yet it is not limitation of the present invention, the anyone 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 by difference requirement and performance a kind of preparation technology of glass.Visible, within the every content that does not break away from technical solution of the present invention, especially claim, hold, any simple modification of above embodiment being done according to technical spirit of the present invention, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.