CN1155876A - Borosilicate glass - Google Patents
Borosilicate glass Download PDFInfo
- Publication number
- CN1155876A CN1155876A CN 96190542 CN96190542A CN1155876A CN 1155876 A CN1155876 A CN 1155876A CN 96190542 CN96190542 CN 96190542 CN 96190542 A CN96190542 A CN 96190542A CN 1155876 A CN1155876 A CN 1155876A
- Authority
- CN
- China
- Prior art keywords
- glass
- weight
- bao
- mgo
- cao
- 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.)
- Pending
Links
Landscapes
- Glass Compositions (AREA)
Abstract
The invention relates to a borosilicate glass with a linear thermal expansion between 20 and 300 DEG C of 3.9 to 4.5*10<-6> K<-1> for the production of laboratory, household, pharmaceutical container, lamp and flat glass and other special technical glasses which can be fully electrically melted and conditioned in cold-top conditions. For fixing the glass composition, this requires, besides the attainment of the desired glass properties, a consideration of the specifics of the fully electric melting process and therefore results in a limited range of variation of several glass oxides, the exclusion of the use of some raw materials, the choice of suitable refining agents, etc. The composition of the glass is SiO2 + ZrO2 77,0 to 81,0 % wt.; B2O3 + Na2O + K2O + CaO + MgO + BaO 16,0 to 18,5 % wt.; of which Na2O + K2O + CaO + MgO + BaO 5,4 to 7,0 % wt.; of which CaO + MgO + BaO to 0,9 % wt.; Al2O3 3,7 to 4,9 % wt.; Cl<-> 0,05 to 0,4 % wt.; CeO 0,0 to 1,0 % wt.; with the relations: ratio CaO + MgO + BaO / ZrO2 0,0 to 1,5; ratio Na2O + K2O + CaO + MgO + BaO / B2O3 + SiO2 + Al2O3 + ZrO2 0,060 to 0,075. Only NaC1 or KC1 is used as a refining agent. A change between this glass and borosilicate glass 3.3 is reversible, repeatable as often as desired and possible within a short time.
Description
The present invention relates to thermal linear expansion coefficient and between 20-300 ℃, be 3.9-4.5 * 10
-6K
-1Borosilicate glass.
This glass is used for preparing testing laboratory's glass, family expenses glass, medicament reservoir glass, lamp glass, sheet glass and other industry and optics high quality glass product.
According to the present invention, this novel glass adopts in the time of can preparing the borosilicate glass with above-mentioned performance in known full electrically heated melting unit (according to cold top principle).
Be known in the art multiple borosilicate glass.The performance of determining their use value is high chemical resistance, low-thermal-expansion, high thermal fatigue resistance and high mechanical stability.
Therefore, according to DIN ISO 3585, adopt borosilicate glass 3.3 usually as laboratory, family expenses and laboratory glass wares.This glass only contains a spot of alkali (being lower than 5%), surpasses 79% silicon-dioxide and until about 13% boron trioxide.Its thermal expansivity is approximately 3.3 * 10 between 20-300 ℃
-6K
-1
In addition, the seal glass that contains boron also is known.It contains higher alkali and/or alkaline earth metal content, and also contains some other oxide compound sometimes.The thermal expansivity of these glass is 3.6-5.2 * 10
-6K
-1Another kind of known glass is called neutral medicine borosilicate glass.Opposite with seal glass is that it obtains the highest chemical resistant properties.Its alkali content is approximately 6.5-8.5%, and alkaline-earth metal is 3.2-5.0%, and its thermal expansivity is 4.8-5.1 * 10
-6K
-1
As said in patent specification DE3722130, known can be 4.0-5.0 * 10 with a kind of thermal expansivity
-6K
-1And the glass that satisfies most requirement replaces the borosilicate glass of these kinds.People also know by a kind of optimized composition and partly use some additional oxide compounds, as ZnO, SrO, CsO, Li
2O or the like can improve borosilicate glass determine some features of purposes and these features become proprietary, for example as said among patent specification DE4230607, DE4012288 or the DE4325656.
Under the situation of suitability for industrialized production borosilicate glass 3.3, because improved energy efficiency quality and ecological dominance are very popular according to the all-electric melting technology of cold top technology.In this technology, the fusing heat produces in melting channel by electric current, and wherein the surface of melting channel has new admixtion to cover always.Usually can form a kind of stable, effective adiabatic layer, it can also make volatile material be kept and they are sent in the melting tank once more.Because this advantage and expense thereof reduce, people have carried out research to adopt this method and equipment thereof to produce to known borosilicate glass.
So far can't the all-electric melting neutral medicine borosilicate glass of people, its reason is required finings As
2O
3And/or Sb
2O
3Can destroy molybdenum bar heating electrode commonly used.The method of initial solution technological operation problem has been described in DE-PS4313217.
Thermal linear expansion coefficient is 3.6-4.8 * 10
-6K
-1Borosilicate glass only can be under the quality limitations of strictness all-electric melting.Owing to contain the higher dosage of fluxing (basic metal, alkaline-earth metal and boron oxide compound), it can be 3.3 * 10 than thermal expansivity
-6K
-1Obviously fast fusing of borosilicate glass.But for glass formation completely, homogenizing and clarification, although higher fusing assistant content is arranged, still need approximately identical temperature of fusion, melting process required effective thermal insulation, the cold cooperation bed of material in the cold top of all-electric melting can not produce with stationary mode, and thermal equilibrium has been disturbed.The worst situation is that this technology no longer can reach required temperature, thereby makes the glass or the unfused particle of band bubble leave kiln.
If alkali and alkaline-earth metal add (these carbonate can be doped with vitriol according to its source) as carbonate, carbonic acid gas that then produces in melting process and sulfurous gas just can not be removed from smelting furnace fully.On the one hand, the gas volume that is discharged for hard borosilicate glass is quite high.The high resolution of carbonic acid gas and sulfurous gas can cause too high gas resistates in glass on the other hand.The solubleness that can know carbonic acid gas and sulfurous gas from other glass increases along with the increase of alkaline modulus (ratio of excessive organizer of network and network organizer).If this rule is transferred on the borosilicate glass, just can understand that the solubleness that the borosilicate glass that contains more basic metal and alkaline-earth metal and borosilicate glass 3.3 compare its carbonic acid gas or sulfurous gas is higher.As the glass that boils again, carbonic acid gas and sulfurous gas are released once more and appear in the final glass as small bubbles or bubble the latest.Suitable finings can be removed these gas with other oxygenant as white arsenic and/or antimonous oxide, but these finingss are owing to their destruction uses to molybdenum electrode are not suitable in the all-electric melting heating kiln.Because their high alkaline earth metal content, there is this fatal shortcoming in said glass in patent specification DE4230607, DE3722130 and DE4325656.
In addition, the oxide compound that other parts are used is as PbO, SnO, CuO, NiO, CdO, FeO, Cr
2O
3Can produce corrosive nature to the molybdenum heating electrode with ZnO, as the means of guard electrode, for example known direct current passivation is owing to adopting known precious metal device to abandon in feed appliance.
In addition, known in the melting process of the cold top of all-electric melting that the temperature of fusion of each glass is that determine and high especially for borosilicate glass, so this technology only is used for the glass viscosity and the electroconductibility of specified range.The electroconductibility of glass under conventional temperature of fusion is too high will to cause high electric current and energy density owing to high-alkali or alkaline earth metal content make, and will cause excessive heat, export license and bubble.When electroconductibility is too low, just has more electric current and flow through the calculus material.Excessive glass viscosity requires too high temperature to clarify or makes this process incomplete, and in the glass of book too, Rong particle or unclarified material usually can not sneaked in the glass that makes.Therefore the cold top of the all-electric melting method that is used for borosilicate glass 3.3 other glass (these glass have different viscosity and electroconductibility under comparable temperature of fusion) of can not migrating, its DeGrain.Many known thermal linear expansion coefficients are greater than 3.9 * 10
-6K
-1Its basic metal of borosilicate glass and the summation of alkaline earth metal content at (equally from patent specification DE3722130) more than 7%.Adopt the cold top of above-mentioned all-electric melting technology can not bubble-freely melt in required surpassing under 1550 ℃ the temperature of fusion.
In known method, the indication that is used for fixing and controls the oxidation-reduction potential of borosilicate it be unclear that.
The object of the present invention is to provide a kind ofly have high chemical resistance, thermal expansivity is 3.9-4.5 * 10
-6K
-1Soft borosilicate glass, this glass can be made under the useful ecology of the cold top of known all-electric melting technology and economic condition.
According to the present invention, this purpose has obtained solution, and its technological temperature is 10
4DPas is 1200-1270 ℃ down, and viscosity is 10 under 1550 ℃
2.6-10
2.8DPas is 20-33 than resistance down at 1550 ℃ ... centimetre, electric conductivity is 3.0-5.0S/m down at 1550 ℃, is melting with the 0.3-0.5 mm/min under about 1600 ℃ under the condition of cold top, and is having following essentially consist: SiO
2+ ZrO
277.0-81.0 weight %B
2O
3+ Na
2O+K
2O+CaO+MgO+16.0-18.5 weight %BaO is Na wherein
2O+K
2O+CaO+MgO+BaO 5.4-7.0 weight % is CaO+MgO+BaO-0.9 weight %Al wherein
2O
33.7-4.9 weight %Cl 0.05-0.4 weight % also meets following relationship: ratio
0.0-1.5 ratio
0.060-0.075
Under the situation of borosilicate glass of the present invention, can see the specific experience relevant with said technology and equipment thereof.Although the relation of the principle between glass properties and borosilicate glass are formed is known, some qualifications relevant with technology will cause a kind of brand-new, distinct and unusual purpose.
This novel glass belongs to the chemical resistant properties borosilicate glass, it is characterized in that following properties :-coefficient of linear expansion is between 20 ℃-300 ℃: 3.9-4.5 * 10
-6K
-1-transition temperature: more than 540 ℃;-according to the resistance to hydrolysis of DIN 12111: one-level;-according to the acid resistance of DIN 12116: one-level;-according to the alkali resistance of DIN 52322: secondary;
Because as medicine and/or family expenses glass, this glass must not have the toxic heavy metal oxide compound.It contains the component that can increase brightness and can stablize.For it can be melted by all-electric melting in known kiln, it does not allow to contain PbO, SnO, CuO, NiO, CdO, FeO, Cr
2O
3, ZnO, As
2O
3And/or Sb
2O
3
For ecological consideration, do not adopt fluorochemical as finings.In order in glass, to keep lower bubbles volume, in the fusing process, only discharge seldom or not release of carbon dioxide and sulfurous gas.
For fear of precious metal generation conglomeration, this glass does not have reduced state.In all-electric melting heat fused device, do not regulate the ability that impacts by conventional oxidizing fire device.For ecological consideration, because nitrate can discharge NO
x, therefore do not add nitrate (O
2The oxidation of decomposition and polyvalent ion).
Except the glass physicochemistry performance, the composition of borosilicate that can all-electric melting under the condition of cold top also can cause the requirement relevant with technology.
According to the present invention, if high-temperature physical property, near borosilicate 3.3, then the cold top of this all-electric melting technology is applicable to that thermal expansion is until 4.5 * 10 as viscosity and electroconductibility (for technological reason)
-6K
-1Borosilicate glass and make it to have good glass properties.In order to set up stable cold top condition, admixtion Ying Zaiyu is used for melting under the roughly the same speed of borosilicate glass 3.3.
In fusion test, confirmed following numerical value :-10
4Technological temperature under the dPas: 1200-1270 ℃-viscosity under 1550 ℃: 10
2.6-10
2.8The ratio resistance of dPas-under 1550 ℃: the batch melting speed during the molten again glass of 20-33 ohmcm-: 0.35-0.45 mm/min.
By fusion test, show by making SiO
2+ ZrO
2Amount surpass 77% and Al
2O
3Content be that 3.5-5.0% can realize relevant with technology predetermined technological temperature and 1550 ℃ of viscosity.But work as SiO
2+ ZrO
2Amount surpass at 81% o'clock, technological temperature and 1550 ℃ of viscosity can be increased to uncontrollable degree, and need consider the appearance of the resistates of these infusibility compositions.Work as SiO
2+ ZrO
2Amount 77% when following, its linear expansion is at Al of the present invention
2O
3Content under exceed 4.5 * 10
-6K
-1
In addition, verified relevant predetermined electroconductibility and than total amount and the SiO of resistance with basic metal and alkaline-earth metal with technology
2+ B
2O
3+ Al
2O
3+ ZrO
2The ratio of sum is fixed as 0.060-0.075.Surpass this value, the mistake high conductivity more than 1550 ℃ of following 5S/m will cause high current density, is lower than this value, below 3S/m, flows through stone material with regard to having too many electric current.
All oxides (basic metal+alkaline-earth metal+B as fusing assistant
2O
3) accelerated fusing.In order to keep required cold top state under the needed temperature of fusion more than 1550 ℃ of clarification, promptly being used for heat insulation admixtion surface does not melt, and the amount of these fusing assistants should not surpass 18.5%.For make when this value admixtion surface and borosilicate glass 3.3 quite, at least 0.6% in the required silicon oxide will replace with zirconium dioxide, the latter puts off fusing greatly.When the amount of fusing assistant was lower than 16%, this glass was slower than borosilicate glass 3.3 fusings, and this just requires excessive high temperature and can increase the danger that produces residual quartz.According to the variable content of the alkaline-earth metal that hereinafter will make an explanation, melting properties can be stablized by suitably increasing zirconium dioxide, and this moment, the ratio of alkaline-earth metal and zirconium dioxide remained on below 1.5.
As people were known, boron trioxide content influence chemical resistant properties and its lower limit were subjected to the restriction in the too high technological temperature more than 1300 ℃ and too high 1550 ℃ of viscosity.Consider alkali and the alkaline earth metal content that to explain hereinafter, in order to reach required chemical resistant properties, the content of boron oxide is defined as 10.5-12.5%.
Rule of thumb, linear thermal expansion is subjected to the very big influence of basic metal and alkaline earth metal content.Can determine, consider alkaline-earth metal to the qualification of electroconductibility and the adding of carbonate (it is described that it is discussed below literary composition), at least 5.4%, maximum 7.0% basic metal and alkaline-earth metal sum can be used for the linear thermal expansion between 20-300 ℃ is remained on 3.9-4.5 * 10
-6K
-1
In addition, have been found that if except 5.0-5.8%Na
2Also add 0.3-1.5%K beyond the O
2O or 0.6-0.9% alkaline-earth metal, or K
2O combines with alkaline-earth metal, then can reach required chemical resistant properties by using mixed alkali metal effect and additional mixed alkaline earth metallic appearance.Because in these alkaline-earth metal, BaO is verified to have required effect, and owing to following said advantage, barium oxide is preferred.Because Li
2O will increase crystallization trend, therefore without Lithium Oxide 98min.
As people were known, zirconium white was except the effect that postpones fusing, and it can also improve chemical resistant properties, particularly alkali resistance, physical strength, particularly therefore the scratch hardness of glass has increased use value, but has also increased the cost under the power operation situation.For this glass can be handled more economically, the content of zirconium dioxide is lower than 2.4%.Surprisingly, when this glass of mass production, when aluminum oxide is 3.7-4.9%, when this is worth, crystallization does not take place.In order to limit technological temperature, the content of aluminum oxide is preferably 4.1-4.5%, and the content of zirconium dioxide is preferably 0.8-1.0%.
In the industrial melting test of in the cold top fusing kiln of all-electric melting heating, carrying out and the mensuration of gas content subsequently, also find to work as Na
2O+K
2O+CaO+MgO+BaO and SiO
2+ Al
2O
3+ ZrO
2+ B
2O
3Ratio be lower than at 0.075 o'clock, carbonic acid gas and content of sulfur dioxide in the glass obviously reduce.In order to keep the carbonic acid gas and the content of sulfur dioxide of lower introducing, according to the present invention, just the consumption of alkaline-earth metal is limited in 0.9% and only can use carbonate to these alkaline-earth metal.Other carbonate or vitriol or contain carbonate or the raw material of vitriol need not, this be because they can discharge carbonic acid gas or sulfurous gas.Magnesium oxide has increased tendency towards devitrification, therefore also not as material composition.Different with calcium oxide is that barium oxide has increased specific refractory power and increased the brightness of glass (as desired as family expenses glass the time).Owing to this performance and to acid proof favourable influence, use barium oxide as unique alkaline-earth metal composition.This can be understood as has only calcium oxide and magnesium oxide impurity to allow, and they can enter glass with the amount below 0.1%.In order to avoid the tendency of boiling again fully, glass preferably according to the present invention does not have alkaline-earth metal, except the impurity that can allow.
If this glass must be stable, it is favourable introducing a certain amount of cerium oxide (IV) for soda-lime glass, because it can make the oxidation of multivalence foreign ion.Have been found that the oxygen that discharges from cerium oxide (IV) can not destroy the molybdenum bar electrode in side direction or bottom installation, this is because the oxygen that is discharged no longer contacts with these rods.In addition, also find, although there is not the existing temperature of fusion height of the borosilicate glass of vitriol, by As
2O
3Or Sb
2O
3The known corrosive nature that causes can not take place under the situation of the amount of cerium oxide used according to the invention.Simultaneously, required redox state can be adjusted and control with it.But the CeO content in the glass is no more than 1%, otherwise except meeting increases the molybdenum loss, also can have a negative impact to chemical resistant properties.
According to borosilicate glass of the present invention, its thermal linear expansion coefficient is 3.9-4.5 * 10 down at 20-300 ℃
-6K
-1, its transition temperature is 540-575 ℃, technological temperature is 10
4DPas is 1200-1270 ℃ down, and the viscosity under 1550 ℃ is 10
2.65DPas, be the 20-33 ohmcm than resistance down at 1550 ℃, electric conductivity is 3.0-5.0S/m down at 1550 ℃, it also satisfies the resistance to hydrolysis of one-level according to DIN 12111 simultaneously, one-level is according to the acid resistance of DIN 12116, with the alkali resistance of secondary according to DIN 52322, this glass has following composition: SiO
276.6-78.0 weight %B
2O
310.5-12.5 weight %Al
2O
33.7-4.9 weight %Na
2O 5.0-5.8 weight %K
2O 0.3-1.5 weight %CaO and/or MgO (impurity) are lower than 0.1% weight %BaO 0.0-0.9 weight %CeO 0.0-1.0 weight %ZrO
20.6-2.4 weight %Cl 0.05-0.4 weight %
Only adopt sodium-chlor and Repone K as finings, without As
2O
3Or Sb
2O
3Can adopt the raw material that contains calcium oxide, magnesium oxide, vitriol or fluorochemical that only contains minimum impurity.
Borosilicate glass of the present invention does not need alkaline-earth metal (except unavoidable impurities), so it is fully without carbonate.This point has reduced the tendency of boiling again.Basic metal is introduced as just borate, aluminate or silicate.The preferred glass of the present invention is characterized in that having following composition: SiO
276.6-77.7 weight %B
2O
311.0-12.0 weight %Al
2O
34.1-4.5 weight %Na
2O 5.1-5.6 weight %K
2O 0.8-1.2 weight %CeO 0.0-0.5 weight %ZrO
20.8-1.0 the special advantage of weight %Cl 0.05-0.2 weight % is that the borosilicate glass with its chemical constitution and its physicals of the present invention can adopt the melting process production of the cold top of all-electric melting, this technology is on the ecology, on the energy and be high efficiency in the operation.In this glass melting kiln, (its thermal linear expansion coefficient is 4.0-4.4 * 10 down at 20-300 ℃ to borosilicate glass of the present invention
-6K
-1, its transition temperature is 550-575 ℃, technological temperature is 10
4DPas is down for 1215-1260 ℃, and have the resistance to hydrolysis of one-level according to DIN12111, one-level is according to the acid resistance of DIN 12116 and the secondary alkali resistance according to DIN 52322) can and handle with the high quality fusing, thus can be fast and successfully interim and reversibly substituted by borosilicate glass 3.3.
Hereinafter, will describe the present invention in detail by embodiment.
Glass 5-19 represents the embodiment of the all-electric melting heats cold top smelting furnace of non-stop run in following table.
Glass 9-11 adopts the molten again glass of 20-30% to melt.
Glass 1-4 and can adopt cold top technology to come all-electric melting fusing as a comparison.
Glass 1 relates to the borosilicate glass 3.3 according to DIN ISO 3585.
Glass 20 is used as contrast, and can not adopt the cold top of all-electric melting technology bubble-freely to make (total amount of basic metal and alkaline-earth metal is too high, and is too lower than resistance, and alkaline modulus is too high).Mark in the table: the glass oxide compound is in weight %; α: the coefficient of linear expansion under 20-300 ℃, with 10
-6/ K meter; Tg: transition temperature, ℃; Ep: sink point or 10
4Technological temperature under the dPas, ℃; Ew: 10
7.6Fusing point under the dPas, ℃; R: at 1550 ℃ ratio resistance, ohmcm; V: burn-off rate, mm/min; Visk.: at the logarithm of 1550 ℃ of following viscosity (dPas).
Embodiment (routine 1-4 and 20 is used for contrast) No. SiO2 B2O3 Al2O3 Na2O K2O CaO MgO BaO ZrO2 Cl SlO2 B2O3
+ +
ZrO2 R2O
+RO1 80.40 13.0 2.25 3.70 0.55 0.02 0.01 0.03 0.05 80.43 17.282 79.80 12.40 3.00 4.20 0.66 0.01 0.05 0.55 80.35 17.323 79.00 11.00 3.75 4.95 0.80 0.01 0.05 0.85 0.05 78.85 16.814 78.90 10.65 4.10 4.45 1.40 0.01 0.05 0.85 0.05 79.75 16.565 77.50 11.93 3.77 5.06 0.83 0.05 0.86 0.06 78.36 17.876 77.70 11.00 4.10 5.20 0.90 0.01 0.05 0.90 0.08 78.60 17.167 77.60 11.00 4.25 5.20 0.091 0.01 0.05 0.90 0.09 78.50 17.178 76.90 11.30 4.37 5.45 0.92 0.02 0.01 0.92 0.10 77.82 17.709 76.60 11.39 4.40 5.58 0.95 0.02 0.02 0.93 0.07 77.53 17.9610 76.90 11.44 4.25 5.25 1.05 0.02 0.05 0.91 0.10 77.81 17.8111 76.90 11.58 4.15 5.22 1.06 0.05 0.01 0.89 0.09 77.79 17.7912 76.60 11.00 4.25 5.20 0.91 0.01 0.05 1.90 0.10 78.50 17.1713 77.10 11.64 4.15 5.30 0.30 0.05 0.05 0.80 0.63 0.10 77.73 18.1114 77.00 11.89 4.21 5.45 0.40 0.01 0.01 0.63 0.10 77.63 17.7615 76.63 12.00 4.25 5.45 0.83 0.02 0.02 0.80 0.10 77.43 18.3216 77.46 10.80 4.80 5.25 0.75 0.02 0.02 0.90 0.10 78.36 16.8417 76.66 12.20 4.30 5.70 0.40 0.02 0.02 0.70 0.10 77.36 18.3418 76.69 11.90 4.25 5.12 1.40 0.02 0.02 0.60 0.10 77.29 18.4619 76.60 11.20 4.15 5.06 0.95 0.02 0.02 2.00 0.10 78.60 17.2520 75.32 12.20 3.68 5.98 0.01 0.07 0.01 1.01 1.10 0.12 76.42 19.28140.40％CeO,200.33％CeO R2O ROROAlkalescence α Tg Ew Ep R Vlsk. v
+RO ZrO3 1 4.28 0.03 1.00 0.045 3.30 535 815 1245 32.0 2.7 0.422 4.92 0.06 0.11 0.051 3.63 559 825 12343 5.81 0.06 0.07 0.062 3.90 557 1233 26.2 0.364 5.91 0.06 0.07 0.063 3.85 559 12455 5.94 0.05 0.06 0.063 4.07 567 815 1231 25.8 2.65 0.366 6.16 0.06 0.07 0.066 4.18 570 818 1228 25.0 2.657 6.17 0.06 0.07 0.066 4.18 569 820 1228 25.0 2.65 0.398 6.40 0.03 0.03 0.068 4.30 566 809 1222 23.6 2.65 0.389 6.57 0.04 0.04 0.070 4.33 807 1219 23.2 2.65 0.4710 6.37 0.07 0.08 0.068 4.26 571 813 1227 24.0 2.65 0.4411 6.34 0.06 0.07 0.068 4.27 1227 24.0 2.65 0.4312 6.17 0.06 0.03 0.066 4.12 554 122813 6.50 0.90 1.43 0.070 4.00 553 122614 5.87 0.02 0.03 0.063 4.05 552 122215 6.32 0.04 0.05 0.067 4.19 552 122216 6.04 0.04 0.04 0.064 4.07 555 122717 6.14 0.04 0.06 0.065 4.16 551 121718 6.56 0.04 0.07 0.070 4.22 553 123019 6.05 0.04 0.02 0.064 4.06 555 121820 7.08 1.09 0.99 0.077 4.25 540 799 1176 13.6 2.45 0.54
Claims (6)
1. thermal linear expansion coefficient is 3.9-4.5 * 10 down at 20-300 ℃
-6K
-1Borosilicate glass, wherein its technological temperature is 10
4DPas is 1200-1270 ℃ down, and viscosity is 10 under 1550 ℃
2.6-10
2.8DPas is the 20-33 ohmcm than resistance down at 1550 ℃, and electric conductivity is 3.0-5.0S/m down at 1550 ℃, is melting with the 0.3-0.5 mm/min under about 1600 ℃ under the condition of cold top, and is having following essentially consist: SiO
2+ ZrO
277.0-81.0 weight %B
2O
3+ Na
2O+K
2O+CaO+MgO+BaO 16.0-18.5 weight % is Na wherein
2O+K
2O+CaO+MgO+BaO 5.4-7.0 weight % wherein CaO+MgO+BaO until 0.9 weight %Al
2O
33.7-4.9 weight %Cl-0.05-0.4 weight % also meets following relationship: ratio
Ratio
2. the borosilicate glass of claim 1 is characterized in that, its transition temperature is 540-575 ℃, corresponding to the resistance to hydrolysis of one-level according to DIN 12111, one-level is according to the acid resistance of DIN 12116 and the secondary alkali resistance according to DIN 52322, and this glass has following composition: SiO
276.6-78.0 weight %B
2O
310.5-12.5 weight %Al
2O
33.7-4.9 weight %Na
2O 5.0-5.8 weight %K
2O 0.3-1.5 weight %CaO and/or MgO (impurity) are lower than 0.1% weight %BaO 0.0-0.9 weight %ZrO
20.6-2.4 weight %Cl
-0.05-0.4 weight %
3. claim 1 or 2 borosilicate glass, wherein cerium oxide (IV) joins in the admixtion as discoloring agent and redox-stable agent, and its amount is for existing the CeO until 1.0 weight % in glass
2
4. according to one borosilicate glass among the claim 1-3, wherein only adopt sodium-chlor or Repone K as finings, without As
2O
3Or Sb
2O
3If, and adopt sodium-chlor or Repone K, then Cl in the glass
-Measuring the amount that should be taken into account any chlorine impurity in raw material and the molten again glass determines.
5. according to one borosilicate glass among the claim 1-4, wherein it has following composition: SiO
276.6-77.7 weight %B
2O
311.0-12.0 weight %Al
2O
34.1-4.5 weight %Na
2O 5.1-5.6 weight %K
2O 0.8-1.2 weight %CeO
20.0-0.5 weight %ZrO
20.8-1.0 weight %Cl
-0.05-0.2 weight %
6. according to one the purposes of borosilicate glass among the claim 1-5, be used to make testing laboratory's glass, family expenses glass, medicine glass, lamp glass, sheet glass and other industry and optics high quality glass product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96190542 CN1155876A (en) | 1995-04-28 | 1996-04-06 | Borosilicate glass |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19515608.0 | 1995-04-28 | ||
| CN 96190542 CN1155876A (en) | 1995-04-28 | 1996-04-06 | Borosilicate glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1155876A true CN1155876A (en) | 1997-07-30 |
Family
ID=5128078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96190542 Pending CN1155876A (en) | 1995-04-28 | 1996-04-06 | Borosilicate glass |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1155876A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838106B (en) * | 2010-05-14 | 2012-01-04 | 北京工业大学 | Borosilicate glass tube for photo-thermal power generation |
| CN101405232B (en) * | 2006-03-14 | 2012-05-30 | 肖特公开股份有限公司 | Optical glass for fiber optic light guide as core glass and fiber optic step-index optical fiber having the core glass |
| CN104261676A (en) * | 2014-09-04 | 2015-01-07 | 东莞市长安东阳光铝业研发有限公司 | Neutral borosilicate glass and application thereof |
| US9417701B2 (en) | 2004-09-13 | 2016-08-16 | Microsoft Technology Licensing, Llc | Flick gesture |
| CN107601873A (en) * | 2017-11-01 | 2018-01-19 | 怀来天元特种玻璃有限公司 | A kind of white jade color high-boron-silicon glass and preparation method thereof |
| CN107848871A (en) * | 2015-07-17 | 2018-03-27 | 日本电气硝子株式会社 | Medical container borosilicate glass |
| CN108137382A (en) * | 2016-05-03 | 2018-06-08 | 株式会社Lg化学 | Borosilicate glass, the light guide plate and its manufacturing method for including it |
| CN109437560A (en) * | 2018-12-28 | 2019-03-08 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of ultraviolet high borosilicate glass and preparation method thereof thoroughly |
| CN110255895A (en) * | 2019-07-16 | 2019-09-20 | 醴陵旗滨电子玻璃有限公司 | Containing alkali borosilicate glass and preparation method thereof |
| CN110342816A (en) * | 2019-08-27 | 2019-10-18 | 江西理工大学 | A kind of glassy solids electrolyte and preparation method thereof |
| CN110963708A (en) * | 2019-12-21 | 2020-04-07 | 山东省药用玻璃股份有限公司 | Small dose injection is with borosilicate glass injection bottle |
| CN112266166A (en) * | 2020-10-10 | 2021-01-26 | 中建材蚌埠玻璃工业设计研究院有限公司 | Composite auxiliary agent for preparing neutral medical glass tube |
| CN112811813A (en) * | 2021-01-15 | 2021-05-18 | 河北光兴半导体技术有限公司 | Borosilicate glass composition, borosilicate glass, and preparation method and application thereof |
| CN113860729A (en) * | 2021-10-25 | 2021-12-31 | 北京工业大学 | Medical glass of medium borosilicate |
-
1996
- 1996-04-06 CN CN 96190542 patent/CN1155876A/en active Pending
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9417701B2 (en) | 2004-09-13 | 2016-08-16 | Microsoft Technology Licensing, Llc | Flick gesture |
| CN101405232B (en) * | 2006-03-14 | 2012-05-30 | 肖特公开股份有限公司 | Optical glass for fiber optic light guide as core glass and fiber optic step-index optical fiber having the core glass |
| CN101838106B (en) * | 2010-05-14 | 2012-01-04 | 北京工业大学 | Borosilicate glass tube for photo-thermal power generation |
| CN104261676A (en) * | 2014-09-04 | 2015-01-07 | 东莞市长安东阳光铝业研发有限公司 | Neutral borosilicate glass and application thereof |
| CN107848871B (en) * | 2015-07-17 | 2021-12-07 | 日本电气硝子株式会社 | Borosilicate glass for medical containers |
| CN107848871A (en) * | 2015-07-17 | 2018-03-27 | 日本电气硝子株式会社 | Medical container borosilicate glass |
| US10710925B2 (en) | 2015-07-17 | 2020-07-14 | Nippon Electric Glass Co., Ltd. | Borosilicate glass for pharmaceutical container |
| CN108137382A (en) * | 2016-05-03 | 2018-06-08 | 株式会社Lg化学 | Borosilicate glass, the light guide plate and its manufacturing method for including it |
| CN108137382B (en) * | 2016-05-03 | 2020-12-18 | 株式会社Lg化学 | Borosilicate glass, light guide plate comprising borosilicate glass and manufacturing method of borosilicate glass |
| US10662107B2 (en) | 2016-05-03 | 2020-05-26 | Lg Chem, Ltd. | Borosilicate glass, light guide plate comprising the same and fabricating methods thereof |
| CN107601873B (en) * | 2017-11-01 | 2022-08-30 | 怀来天元特种玻璃有限公司 | White jade-colored high borosilicate glass and preparation method thereof |
| CN107601873A (en) * | 2017-11-01 | 2018-01-19 | 怀来天元特种玻璃有限公司 | A kind of white jade color high-boron-silicon glass and preparation method thereof |
| CN109437560A (en) * | 2018-12-28 | 2019-03-08 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of ultraviolet high borosilicate glass and preparation method thereof thoroughly |
| CN110255895B (en) * | 2019-07-16 | 2021-04-13 | 湖南旗滨医药材料科技有限公司 | Alkali-containing borosilicate glass and preparation method thereof |
| CN110255895A (en) * | 2019-07-16 | 2019-09-20 | 醴陵旗滨电子玻璃有限公司 | Containing alkali borosilicate glass and preparation method thereof |
| CN110342816B (en) * | 2019-08-27 | 2021-11-02 | 江西理工大学 | A kind of glassy solid electrolyte and preparation method thereof |
| CN110342816A (en) * | 2019-08-27 | 2019-10-18 | 江西理工大学 | A kind of glassy solids electrolyte and preparation method thereof |
| CN110963708A (en) * | 2019-12-21 | 2020-04-07 | 山东省药用玻璃股份有限公司 | Small dose injection is with borosilicate glass injection bottle |
| CN112266166A (en) * | 2020-10-10 | 2021-01-26 | 中建材蚌埠玻璃工业设计研究院有限公司 | Composite auxiliary agent for preparing neutral medical glass tube |
| CN112811813A (en) * | 2021-01-15 | 2021-05-18 | 河北光兴半导体技术有限公司 | Borosilicate glass composition, borosilicate glass, and preparation method and application thereof |
| CN113860729A (en) * | 2021-10-25 | 2021-12-31 | 北京工业大学 | Medical glass of medium borosilicate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100406021B1 (en) | Alkali-free glass and method for producing the same | |
| US3876481A (en) | Glass compositions, fibers and methods of making same | |
| CN105776849B (en) | Glass with improved toughness and scratch resistance | |
| CN1155876A (en) | Borosilicate glass | |
| KR100929099B1 (en) | Glass manufacturing method using outgassed frit | |
| US6686304B1 (en) | Glass fiber composition | |
| JP3800440B2 (en) | Alkali-free glass and method for producing the same | |
| CN1592722A (en) | Method for producing borosilicate glass | |
| CA2375719C (en) | Glass fiber composition | |
| JP2001080933A (en) | Crystal glass not containing lead and barium | |
| JP3800443B2 (en) | Non-alkali glass substrate for display and method for producing the same | |
| KR20160053986A (en) | Ion exchangeable glasses with high crack initiation threshold | |
| US8168552B2 (en) | Method of refining glass and product obtained | |
| JP2020518543A (en) | Method for reducing the oxidation state of metals during melting of glass compositions | |
| AU659272B2 (en) | Alkali-free glass compositions | |
| JP3861271B2 (en) | Alkali-free glass and method for producing the same | |
| WO2002057195A1 (en) | Zinc phosphate glass compositions | |
| JP4306044B2 (en) | Alkali-free glass and method for producing the same | |
| JP3897194B2 (en) | Alkali-free glass and method for producing the same | |
| WO2007106274A2 (en) | Method of making glass including use of boron oxide for reducing glass refiting time | |
| Zhao et al. | Glass formation and crystallization in alkali-containing fluoride glasses | |
| SE429852B (en) | COMPOSITION FOR PREPARATION OF GLASS WITH HIGH SCRATCH INDEX | |
| CN1187176A (en) | Boron-free glass fibers | |
| DE19515608C1 (en) | Borosilicate glass with linear thermal expansion | |
| JPH10231139A (en) | Non-alkali glass and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) |