CN101428966A - Borosilicate glass suitable for electric light source - Google Patents
Borosilicate glass suitable for electric light source Download PDFInfo
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- CN101428966A CN101428966A CNA2008102392280A CN200810239228A CN101428966A CN 101428966 A CN101428966 A CN 101428966A CN A2008102392280 A CNA2008102392280 A CN A2008102392280A CN 200810239228 A CN200810239228 A CN 200810239228A CN 101428966 A CN101428966 A CN 101428966A
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Abstract
The invention provides glass applicable to electric light source, which belongs to the field of borosilicate glass, in particular to a high-precision small-diameter glass tube through a public known pull tube forming process by using an environment-friendly fining agent to realize good melting quality, so as to meet the requirement of electric light source mechanical light manufacture. The swell factor of the glass is (38-76) multiplies 10<-7>/DEG C to fulfill sealing of tungsten, molybdenum and raft. The glass consists of the following chemical compositions in weight percentage: 55 to 75 percent of SiO2, 5 to 22 percent of B2O3, 2 to 6 percent of Al2O3, 0 to 8 percent of MgO, CaO, BaO and SrO, 5 to 12 percent of Li2O, Na2O and K2O, 0 to 1 percent of ZrO2, 0.5 to 4 percent of TiO2, 0 to 2 percent of ZnO, 0 to 1 percent of SnO 2, and 0 to 0.5 percent of Cl2. The glass is characterized by the borosilicate glass system. The glass product has the advantages of high transmission of visible light, ultraviolet resisting property and insolation resisting property without harmful elements.
Description
Technical field
The present invention relates to the glass material as electric light source products (cold-cathode lamp, luminescent lamp, halogen lamp, mercury lamp, sodium vapor lamp) use, this glass can be realized refining quality preferably through special finings.By known trombone slide, blowing, press forming technology, prepare high-accuracy glass pipe, glass shell, lens.
Background technology
Human research to electric light source started from for 18 end of the centurys, was accompanied by the development of electric light source, electric light source glass kind also constantly improve and evolution in.Along with electric light source has entered into New Times of miniaturization, energy-conservationization, electronization, environmental protectionization, long-actingization, have only electric light source glass to catch up with synchronously and could realize.
The luminous form of existing electric light source is divided into heat radiation light source, glow discharge spot lamp and electroluminescent source three classes, radiating light source be electric current by conducting electricity twinkler, make it radiation luminous energy at high temperature.Comprise two kinds of incandescent light and halogen tungsten lamps, can produce high temperature, generally need glass to have high-temperature stability, therefore requirement has higher strain point, (coefficient of expansion is less than 65 * 10 for low-coefficient glass
-7/ ℃) and the high-temperature dielectric characteristic, reduce near the glass dielectric loss of electrode, one can be energy-conservation, and the two can reduce because of the local pyrexia of glass conduction, produces potential safety hazard; Glow discharge spot lamp generally passes through excitaton source, it is luminous that its gas inside or medium are produced, good brightness, spectral range is wide, and electric light source glass does not have the ultraviolet cutoff ability mostly, such electric light source utensil of people's life-time service, dermatosis be can cause producing, even skin carcinoma, organic illuminating devices such as the plastics that fit together with it in addition produced, also will be subjected to ultraviolet influence, cause performance degradation.Some electric light source is tanning by the sun in the process at sunlight, electric light source glass colour generation xanthochromia or painted.Even electric light source glass also can variable color under the UV spectrum irradiation that self produces.It is bad that these phenomenons embody the anti-performance of tanning by the sun of glass.Especially traditional electric light source glass uses arsenic oxide arsenoxide, weisspiessglanz, cerium oxide in a large number in order to pursue good fusing effect.It can cause the anti-result who tans by the sun poor performance naturally, and simultaneous oxidation arsenic, weisspiessglanz also are the glass compositions that restriction is used, and it does not meet environmental requirement.Electric light source glass generally all needs to carry out repeatedly hot-work in system lamp process, when temperature during greater than glass softening point, if understand because of residual SO as the glass of finings is inner with vitriol
3And the generation small bubbles, even air pocket more, cause glass intensity and degradation.If adopt fluorochemical, can produce bigger erosion to the kiln refractory materials, and clarifying efficiency is lower, produces environmental pollution simultaneously as finings.
Summary of the invention
The object of the invention is, a kind of environment-friendly type borosilicate glass composition is provided, and has good electric property, satisfies as the electric light source service requirements, suitably coefficient of expansion scope (38～76) * 10
-7/ ℃, but can satisfy the sealing-in of tungsten, molybdenum raft electrode materials.
The object of the invention is, provides a kind of and can stop ultraviolet ray, can realize the anti-glass of performance that tans by the sun again; reduce appearance color and change possibility; reduce the influence of glass, reduce the ultraviolet radiation under the human habitat condition simultaneously, protection people's life safety the light efficiency decay.
The inventor has carried out a large amount of research work, found that: utilize the volatility oxymuriate and appraise at the current rate stannic oxide, can reach clear quality and the effect of traditional finings (finingss such as arsenic oxide arsenoxide, weisspiessglanz, fluorochemical, vitriol) electric light source glass as finings.Can effectively avoid the harm of these finingss, arsenic oxide arsenoxide, weisspiessglanz are poisonous element, belong to restriction and use kind; The fluorochemical clarifying effect is poor, and volatile quantity is big, and topsoil severity is serious to refractory corrosion in addition; Vitriol can remain in SO in the glass
3, carry out sealing-in and add and can produce bubble man-hour, influence glass machinery intensity and resistance to air loss.The anti-of the finings that these are traditional tans by the sun the performance extreme difference, and the present invention uses oxymuriate and stannic oxide finings that well anti-solarization is arranged.
Oxymuriate and stannic oxide realize that the clarifying effect method is, oxymuriate includes but not limited to NaCl, NH
4Cl, BaCl
2, ZnCl
2, add-on is 0.15～1.5%, the remaining Cl in the glass
2Amount is 0～0.5%; The stannic oxide add-on is 0～1.0%.Finings can use separately or both use jointly, when stannic oxide uses, should be used with 5～10 times of nitrate simultaneously, ratio was 1:1～5 when oxymuriate and stannic oxide were shared, be used with 5～10 times of nitrate simultaneously, can obtain preferable clarifying effect by this array mode.
The present invention forms by adjusting glass, can obtain glass melting and forming parameters preferably, makes it have relatively low forming temperature starting point, has long frit.At known glass tubing forming technique, can make the Glass tubing of high precision minor diameter, its minimum diameter can reach Φ 1.6mm, wall thickness 0.2mm, diameter and wall thickness deviation reach ± 0.02mm
Glass material of the present invention is characterized in that: constituted by the borosilicate glass that contains following composition, and by the quality percentage composition,
SiO
2 55～75
B
2O
3 5～22
Al
2O
3 2～6
Li
2O 0～1
Na
2O 1～5
K
2O 2～8
And Li wherein
2O+Na
2O+K
2O 5～12
MgO 0～2
CaO 0～5
BaO 0～3
SrO 0～3
And wherein MgO+CaO+BaO+SrO 0～8
ZrO
2 0～1
TiO
2 0.5～4
ZnO 0～2
SnO
2 0～1
Cl
2 0～0.5
And SnO wherein
2+ Cl
20.3～1.0
Glass material of the present invention, its serial intrinsic viscosity point temperature is 10
4The temperature of dPas viscosity (being called for short Tw) is below 1180 ℃; 10
7.6The temperature of dPas viscosity (being called for short Ts) is below 780 ℃; 10
11.5The temperature of dPas viscosity (being called for short Td) is 640 ℃, 10
13.4The temperature of dPas viscosity (being called for short Tg) is below 580 ℃.
Glass material of the present invention, the ultraviolet cut-on agent of employing is a titanium oxide, has uv absorption property preferably, it is obviously painted to be difficult for making simultaneously glass to produce again.254nm UV-light percent of pass is less than 10%, and by the coloring impurity ion content and the O/R value of feed glass raw material, the 587nm visible light transmissivity that makes glass is greater than 85% in addition.
In above-mentioned glass was formed, the scope reason of each composition of qualification was as described below.
SiO
2Be the composition that is used to constitute necessity of glass skeleton, its content increases more, and on the one hand, chemical durability is high more, and electric property is good more.On the other hand, have the tendency that improves viscosity, so, if too much just be difficult to obtain the long glass of expecting property.Its content is more than 55%, more than 60%, in addition, is below 75% preferably, preferably below 69%, is more preferably below 68%.If SiO
2Be more than 65%, but just can reach chemical durability, physical strength, the electric property of usage level.In addition, if SiO
2Be below 70%, the fusion of then selected quartz raw material does not just need the longer time, so, can not produce difficulty to refining quality, under the finings effect, obtain satisfied fining glass quality easily, can obtain the high electric light source Glass tubing of dimensional precision easily by rational tube-pulling craft.
B
2O
3Be the necessary composition that is used to improve glass structure stability, reduction glass viscosity, raising glass electric property, the reduction coefficient of expansion, its content increases more, and glass just shows and hangs down viscosityization.On the other hand, have the tendency that reduces chemical durability, its content is more than 5%, is preferably more than 8%, more preferably more than 12%.In addition, B
2O
3Be below 22%, be preferably below 18.5%, be more preferably below 17.5%.
Al
2O
3It is the necessary composition that greatly improves glass chemistry stability, reduce the devitrification of glass tendency, it is the necessary composition that improves glass hard (HRC65 and physical strength simultaneously, it is the composition that improves modulus in tension, but it has the tendency that improves viscosity and temperature of fusion, so if content is too much, just be difficult to obtain the long glass of expecting property.Its content is more than 2%, preferably more than 2.5%, is more preferably more than 3%.In addition, be below 6%, preferably below 5%, be more preferably below 4%.If more than 6%, then glass crystalline possibility is very little, and liquidus temperature lower (corresponding liquidus viscosity is bigger) helps the high electric light source Glass tubing of production dimensional precision.In addition, if Al
2O
3Be below 4%, then the viscosity of glass melting liquid can be not too high, and melting temperature (Tm) is then taken into account melting temperature (Tm), mold temperature, liquidus temperature, glass chemistry stability easily less than 1580 ℃.
Li as alkalimetal oxide
2O, Na
2O, K
2The content of O is 5～12%.Alkalimetal oxide makes the glass melting temperature descend as the flux composition.If the content of these compositions is more than 5%, just can expect to have the effect of the fusion that improves glass.In addition, can make the glass low viscosity, viscosity characteristics is elongated, can improve the stability of glass again.Preferably 5.5～11%, be more preferably 6～10%.When the content of alkali metal component is more than 5%, has the possibility of using the all-electric melting furnace fusing.Li
2O, Na
2O and K
2The content separately of O preferably is respectively Li
2O 0～1 (particularly 0.2～0.8%), Na
2O 1～5% (particularly 2.2～4.8%, further be 2.4～4.5%), K
2O 2～8% (the best is 2.5～7.5%).And, recommend Li
2O, Na
2O and K
2O is shared, perhaps uses two kinds at least, for using Na simultaneously
2O and K
2Content ratio during O, preferred K
2O and Na
2The mass ratio of O is 3～5, if in this scope, by the mixed base effect, can easily realize reducing viscosity, the requirement of raising electric property of glass.
MgO, CaO, SrO, BaO as the alkali earths glass ingredient can make stabilizationization, prevent to produce in glass crystallization.In addition, have moving of the alkali that suppresses in the glass.The total amount of its content is 0～8%, preferably 1～7%, further preferably 4～6%.If more than 3%, the effect that prevents that alkali from moving just appears, if contain more than 4%, has and suppresses the crystalline effect significantly.
ZrO
2Having the glass chemistry of improvement stability, prevent that the alkalies and alkaline earth ion from separating out effect, also is the composition that improves modulus in tension in addition.Its content is 0～1.0%, preferably 0.01～0.8%, be more preferably 0.1～0.6%, further preferably 0.2～0.5%.
ZnO has the viscosity that reduces glass, the outstanding effect composition that the inhibition crystallization is separated out.Its content is 0～3%, preferably 0.1～1%.If below 0.5%, just be difficult to generate the crystallization that contains Zn system.
TiO
2Be to prevent to tan by the sun and stop the good glass composition of ultraviolet, can improve the glass specific inductivity simultaneously.Use TiO
2Glass, the iron contamination that should reduce in the frit is introduced, the feed glass total iron content is less than 150PPm, can avoid the ferrotitanium glass coloring like this.TiO
2Content is 0.5～4%, preferably 1～3.5%.
The process of glass process is as follows:
At first, selector closes and states the frit that glass is formed, through weighing, making it become above-mentioned feature glass forms, behind the uniform mixing, fuse at glass-melting furnace, the fusion mode can adopt common flame glass furnace, pure oxygen glass furnace, all-electric melting glass furnace, flame+electricity fusing-aid glass furnace.Adopt known drawing, blowing, method for press forming, form Glass tubing, glass shell, lens product.
Embodiment
Embodiment 1
Based on embodiment the present invention is described, table 1 is the composition and the performance of embodiments of the invention and comparative example.At first, press table 1 embodiment 1 glass composition and select raw material, ingredient requirement, (150 μ m screen overflows are below 1% to quartz sand, 45 μ m screen underflows are below 30%), aluminium hydroxide or aluminum oxide (median size 50 μ m), (400 μ m screen overflows are below 10% for boric acid or borax, 63 μ m screen underflows are below 10%), lime carbonate (median size 250 μ m), Strontium carbonate powder (median size 20 μ m) screen overflow is below 1%, 50 μ m) screen underflow is below 5%), barium carbonate (median size 50 μ m), zinc oxide (median size 10 μ m screen overflows are below 1%), as other glass ingredient, use the magnesiumcarbonate of SILVER REAGENT, magnesium oxide, sodium-chlor, ammonia chloride, bariumchloride, zinc chloride, Quilonum Retard, lithium hydroxide, soda ash, zirconium white, zirconium silicate, stannic oxide, titanium oxide, SODIUMNITRATE.And, Fe in the frit
2O
3Carry out strictness control, require total content less than 100PPm, finished glass Fe
2O
3Content is less than 150PPm.
Embodiment 1 glass chemistry of pressing in the table 1 is formed, and every preparation 300g glass metal need be joined quartz sand 230g, boric acid 28.5g, aluminum oxide 6.1g, soda ash 21g, lime carbonate 21.9g, magnesiumcarbonate 7.1g, barium carbonate 9.9g, Strontium carbonate powder 10.4g, zirconium white 0.75g, zinc oxide 3.1g, titanium oxide 1.5g.The finings of selecting for use is sodium-chlor and stannic oxide, the sodium-chlor consumption is 0.75g, and the stannic oxide consumption is 0.75g, and the SODIUMNITRATE consumption is 3.75g, the glass chemistry that makes its batching satisfy table 1 embodiment 1 is formed, and uses platinum crucible fusion 24 hours under 1580 ℃ of temperature then.After fusion,, anneal then the plate glass goods of fused solution press forming for regulation.The fundamental property that has shown sample at table 1.
Remaining F in the glass
2And Cl
2Be the value of utilizing x-ray fluorescence analysis to obtain, remaining SO in the glass
3Be the value of obtaining by chemical analysis, the glass properties evaluation is carried out with reference to following method.
The evaluation of glass apparent density is to carry out like this.Specifically, use sink and float method, this method is to select Beta-bromo naphthalene and tetrabromoethane to mix the liquid that forms different specific weight by a certain percentage, glass sample is suspended in mixing test solution top, and along with variation of temperature, the density of test solution is done corresponding the variation, when the density of test solution is consistent with glass specimen, glass begins to sink, and according to the temperature factor of sinking temperature and test solution, just can measure the density of glass.
The expansion coefficient of glass thread evaluation is to carry out like this.Specifically, use the dilatometer method, this method is that sample is placed on the silica glass support, utilizes thermal expansivity different of glass specimen and silica glass, measures both relative elongations in heat-processed.And the coefficient of expansion of quartz glass tube is known, so the total elongation of glass specimen should be the elongation sum of the isometric silica glass frame of digital sensor reading and sample.With it divided by institute's intensification degree and sample length.Final expression glass is in the unit length of room temperature to 300 ℃ and the increment of unit length.
Glass material high-temperature insulation resistance T
K-100Be performed such, specifically, adopt the GB10581 standard.
Specific inductivity under the glass material power frequency condition is performed such, and specifically, adopts the GB1409 standard.
The glass refraction evaluation is to carry out like this.Specifically, use Abbe refractometer.
The evaluation of glass spectral transmittance is to carry out like this.Specifically, adopt GB5433-85, use spectrophotometer.
The glass viscosity evaluation is to carry out like this.Specifically, the measuring method and the instrument of the employing of different viscosity value are also different.10
4The dPas viscosity measurement is adopted the rotation high temperature viscosimeter with reference to ASTM C-965 standard; 10
7.6The dPas viscosity measurement is with reference to ASTM C-338, the Littleton softening point apparatus, adopt the glass yarn of Φ 0.65 ± 0.1mm length 230mm to carry out in process furnace, heating by 5 ℃/min speed, temperature when extension speed is 1mm/min is a softening point temperature, and it characterizes the softening unique point of glass at the deadweight state; 10
13.4The dPas viscosity measurement is used coefficient of expansion determinator with reference to ASTM E-228.
The glass clarifying effect assessment is performed such, and specifically, adopts 40 times of stereoscopic microscopes of band scale to observe, and every size, finally is converted into every hectogram glass and contains the bubble number as the counting number greater than 30 microns bubble.
It is anti-that to tan by the sun performance evaluation be to carry out like this.Specifically, adopt 40W emission 254nm UV-lamp, apart from sample 200mm, irradiation 6 hours adopts its transmitance at the 400nm place of spectrophotometer measurement to change then.Difference is more little, and the anti-performance of tanning by the sun is good more.
The glass ultraviolet that this group glass is formed stops excellent property, at the 254nm place 8.9% transmitance is only arranged, and comparative example 1 and comparative example 2 is respectively 26.8% and 24.4%, obviously is better than comparative example.
This glass intrinsic viscosity point corresponding temperature of organizing this group glass composition is very moderate, T
WdShow one of forming of glass material length judgement criteria, for trombone slide forming technology principle, T
WdBe worth big more, will very easy acquisition high quality, the high-accuracy glass pipe.T
WdJudge trombone slide fundamental principle: T
Wd〉=400 ℃, can access the good Glass tubing of dimensional precision; T
Wd〉=500 ℃, obtain the good Glass tubing of dimensional precision easily; T
Wd〉=570 ℃, very easily obtain the good and high forming speed of dimensional precision; This group glass belongs to and obtains the good Glass tubing of dimensional precision easily.
For electric light source glass, specific inductivity is greater than 5, high-temperature insulation resistance T
K-100Greater than 300 ℃, belong to operable electronic product, this group glass satisfies the working conditions requirement.
The anti-performance of tanning by the sun of this group glass, Δ T is 0.3, is better than 2.5 and 3.8 of comparative example.
In general, embodiment 1 is example relatively, and glass clarifying is effective, and hectogram glass blister number has good visible light transmissivity less than 1, and good ultraviolet stops characteristic, the moderate coefficient of expansion, but can adopt the raft alloy sealing.The temperature-viscosity characteristic is better, and frit is longer, presses T
WdEvaluation can production high precision small size Glass tubing.Electric property is good simultaneously, meets the electric light source service requirements.Anti-tan by the sun performance and be better than comparative example.The harmful element that does not contain artificial adding is an environment-friendly type electric light source glass.
Embodiment 2
The actual composition of glass is with reference to table 1 embodiment 2, and embodiment 2 glass chemistries of pressing in the table 1 are formed, and every preparation 300g glass metal need be joined quartz sand 205.5g, borax 18.9g, boric acid 78.6g, aluminium hydroxide 13.8g, lithium hydroxide 3g, salt of wormwood 26.3g, titanium oxide 10.7g.The finings of selecting for use is calcium chloride and stannic oxide, the calcium chloride consumption is 0.15g, the stannic oxide consumption is 0.75g, the saltpetre consumption is 7.5g, the glass chemistry that makes its batching satisfy table 1 embodiment 2 is formed, use and embodiment 1 identical preparation technology and evaluation method, shown the fundamental property of sample at table 1.
In general, embodiment 2 is example relatively, and glass clarifying is effective, and hectogram glass blister number has good visible light transmissivity less than 1, and good ultraviolet stops characteristic, and the moderate coefficient of expansion can adopt the sealing-in of molybdenum group.The temperature-viscosity characteristic is better, and frit is longer, presses T
WdEvaluation can be easy to production high precision small size Glass tubing.Electric property is good simultaneously, meets the electric light source service requirements.Anti-tan by the sun performance and be better than comparative example, tan by the sun not easy to change for a long time.The harmful element that does not contain artificial adding is an environment-friendly type electric light source glass.
Embodiment 3
Embodiment 3 glass chemistries of pressing in the table 1 are formed, and every preparation 300g glass metal need be joined quartz sand 166.5g, borax 23.6g, boric acid 52g, aluminium hydroxide 11.7g, lithium hydroxide 18g, salt of wormwood 35.9g, lime carbonate 16.4g, magnesium oxide 6.2g, barium carbonate 11.9g, Strontium carbonate powder 12.4g, zirconium silicate 4.7g, zinc oxide 6.1g, titanium oxide 4.5g.The finings of selecting for use is a stannic oxide, and the stannic oxide consumption is 3g, and the SODIUMNITRATE consumption is 12g, and the glass chemistry that makes its batching satisfy table 1 embodiment 3 is formed, and uses and embodiment 1 identical preparation technology and evaluation method, has shown the fundamental property of sample at table 1.
In general, embodiment 3 is example relatively, and glass clarifying is effective, and hectogram glass blister number has good visible light transmissivity less than 1, and good ultraviolet stops characteristic, the moderate coefficient of expansion, but can adopt the raft alloy sealing.The temperature-viscosity characteristic is better, and frit is longer, presses T
WdEvaluation can easily production high precision small size Glass tubing.Electric property is good simultaneously, meets the electric light source service requirements.Anti-tan by the sun performance and be better than comparative example, tan by the sun not easy to change for a long time.The harmful element that does not contain artificial adding is an environment-friendly type electric light source glass.
Embodiment 4
Embodiment 4 glass chemistries of pressing in the table 1 are formed, and every preparation 300g glass metal need be joined quartz sand 208.4g, borax 29.8g, boric acid 106.1g, aluminum oxide 18g, Quilonum Retard 3.8g, salt of wormwood 13.4g, lime carbonate 27.3g, magnesiumcarbonate 3.6g, barium carbonate 4.0g, titanium oxide 12.2g.The finings of selecting for use is an ammonia chloride, and its consumption is 4.5g, and the glass chemistry that makes its batching satisfy table 1 embodiment 4 is formed, and uses and embodiment 1 identical preparation technology and evaluation method, has shown the fundamental property of sample at table 1.
In general, embodiment 4 is example relatively, and glass clarifying is effective, and hectogram glass blister number has good visible light transmissivity less than 1, and good ultraviolet stops characteristic, and the moderate coefficient of expansion can adopt the sealing-in of tungsten group.The temperature-viscosity characteristic is better, and frit is longer, presses T
WdEvaluation can easily production high precision small size Glass tubing.Electric property is good simultaneously, meets the electric light source service requirements.Anti-tan by the sun performance and be better than comparative example, tan by the sun not easy to change for a long time.The harmful element that does not contain artificial adding is an environment-friendly type electric light source glass.
The chemical constitution of [table 1] embodiment and comparative example and performance
Claims (1)
1. the borosilicate glass of a suitable electric light source is characterized in that: constituted by the borosilicate glass that contains following composition, and by the quality percentage composition,
SiO
2 55～75
B
2O
3 5～22
Al
2O
3 2～6
Li
2O 0～1
Na
2O 1～5
K
2O 2～8
And Li
2O+Na
2O+K
2O 5～12
MgO 0～2
CaO 0～5
BaO 0～3
SrO 0～3
And MgO+CaO+BaO+SrO 0～8
ZrO
2 0～1
TiO
2 0.5～4
ZnO 0～2
SnO
2 0～1
Cl
2 0～0.5
And SnO
2+ Cl
20.3～1.0.
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|---|---|---|---|
| CNA2008102392280A CN101428966A (en) | 2008-12-05 | 2008-12-05 | Borosilicate glass suitable for electric light source |
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|---|---|---|---|
| CNA2008102392280A CN101428966A (en) | 2008-12-05 | 2008-12-05 | Borosilicate glass suitable for electric light source |
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Family
ID=40644643
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2008
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Application publication date: 20090513 |