CN102503124A - Ultra-low-sodium lead-free glass and applications thereof - Google Patents

Ultra-low-sodium lead-free glass and applications thereof Download PDF

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Publication number
CN102503124A
CN102503124A CN2011102982773A CN201110298277A CN102503124A CN 102503124 A CN102503124 A CN 102503124A CN 2011102982773 A CN2011102982773 A CN 2011102982773A CN 201110298277 A CN201110298277 A CN 201110298277A CN 102503124 A CN102503124 A CN 102503124A
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China
Prior art keywords
extremely low
crown glass
glass
low sodium
sodium
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CN2011102982773A
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Chinese (zh)
Inventor
潘佩聪
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Shanghai Yaming Lighting Co Ltd
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Shanghai Yaming Lighting Co Ltd
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Priority to CN2011102982773A priority Critical patent/CN102503124A/en
Publication of CN102503124A publication Critical patent/CN102503124A/en
Priority to PCT/CN2012/080989 priority patent/WO2013044721A1/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/102—Glass compositions containing silica with 40% to 90% silica, by weight containing lead
    • C03C3/105—Glass compositions containing silica with 40% to 90% silica, by weight containing lead containing aluminium

Abstract

The invention belongs to the technical field of the energy-saving light source material and relates to ultra-low-sodium lead-free glass and applications thereof. The sodium content of the ultra-low-sodium lead-free glass is below 0.5% and above 0.23%, thus the lumen maintenance of the lamp tube is extremely improved in the use process, the luminous decay of the lamp tube is minimized, the effect of extremely high lumen maintenance is realized without adopting protective film coating, the cost is saved and the coating difficulty of the fluorescent powder is reduced. The ultra-low-sodium lead-free glass does not contain As2O3 and Sb2O3; the content of PbO is extremely low, which is below 0.012%, thus the product belongs to lead-free glass; and the weight percent of CeO2 is not zero and the glass material meets the Rohs environmental protection standard. The ultra-low-sodium lead-free glass can be widely used to prepare various electronic luminous bodies such as fluorescent lamp tubes or energy saving lamp tubes.

Description

A kind of extremely low sodium crown glass and application thereof
Technical field
The invention belongs to electricity-saving lamp source material technical field, relate to a kind of electricity-saving lamp with extremely low sodium crown glass (meeting environmental protection requirement and glass material that prevent ultraviolet radiation output) and electronic illumination bodies such as prepared electricity-saving lamp or luminescent lamp.
Background technology
The low-pressure mercury charging source, promptly fluorescent light has been widely used in various domestic lightings and illumination occasion, has become the requisite of daily life.From nineteen ninety-five to 2010 year, low sodium crown glass is made green innoxious being achieved of fluorescent light by widespread production and use.As the cell-shell material of this light source, always include up to now and be not less than 6.0% Na 2O.The existence of sodium oxide makes that the lux maintenance of fluorescent tube bulb is high always.In order to satisfy the high lux maintenance requirement of high-end luminescent lamp, generally use at Glass tubing surfaces coated Al 2O 3Or Y 2O 3The method of protective membrane is separated the element of mercury in sodium oxide composition in the glass and the fluorescent tube.The coating of protective membrane has increased the fluorescent tube manufacturing cost on the one hand, has introduced new chemical element in fluorescent tube inside on the other hand, has increased foreign gas and has got into the chance in the fluorescent tube, causes the fluorescent tube downgrade.A luminescent lamp industry significant effort direction in decades is: on the low sodium crown glass processing characteristics basis of invariable of maintenance, increases under the limited prerequisite, sodium content forced down as much as possible in the glass manufacturing cost, even to no sodium.Realizing that it is the milestone of fluorescent tube industry that the tube glass sodium content descends significantly, also is the major action that promotes the luminescent lamp quality.
Following Chinese patent is approaching or relevant with the present invention: 200410067162.3; 200410025374.5; 99118719.9; 99102177.0; 200510023944.1; 200610076538.6.The related glass of above patent all contains and is not less than 6.0% Na 2O belongs to low sodium crown glass category.
In U.S. Pat 4666871, described a kind of extremely low effective glass of sodium vapor lamp, its sodium content is in 0-1.3% (weight ratio), but this glass contains 5% PbO, makes this glass can't use on the domestic and international market at present.
Summary of the invention
The object of the present invention is to provide a kind of luminescent lamp, electricity-saving lamp cell-shell or other electronic illumination body fluorescent tubes with extremely low sodium lead-free glass material; Its sodium content is lower than 0.5% but be higher than 0.23%; Reach the effect of high fluorescent tube lux maintenance to realize need not to use protective membrane to apply; Be convenient to select the glass manufacturing with starting material and the lower material cost of realization simultaneously; This helps guaranteeing that this material is more approaching than the glass material cost that uses at present in the industry, promotes the application on the market at home and abroad of high-quality luminescent lamp.Another characteristic of this material is CeO 2Content be not less than 0.23%, to realize glass material, guarantee to meet the ultraviolet radiation safety requirements with the light source product of this material prepn to ultraviolet absorption.The content of PbO is not higher than 0.012% in this material, and assurance meets the laws and regulations of the environment protection aspect of countries in the world.
Extremely low sodium crown glass of the present invention comprises the component of following parts by weight:
SiO 263-69 part; Be preferably 63-66.4 part;
Al 2O 34.5-5 part;
Na 2O 0.25-0.5 part; Be preferably 0.25-0.36 part;
Li 2O 3.0-3.7 part;
K 2O 11.8-12.2 part;
CaO+MgO 4.5-6.8 part;
SrO 4.5-5.6 part;
BaO 7.0-7.3 part;
PbO 0-0.012 part; Be preferably 0.011-0.012 part;
SO 30.12-0.21 part;
Fe 2O 30.015-0.03 part;
CeO 20.23-0.31 part.
Extremely low sodium of the present invention is meant that the weight percent content of the sodium oxide in the glass is lower than 0.5%, but is higher than 0.23%; The described unleaded weight percent content of the plumbous oxide in the glass that is meant is lower than 0.012%, promptly is lower than 120ppm, even reaches unleaded.
Extremely low sodium lead-free glass material of the present invention meets environmental protection requirement, and PbO＜500ppm promptly complies with the national standard requirements; Extremely low sodium lead-free glass material of the present invention has restraining effect to ultraviolet radiation, CeO 2Content non-vanishing.
Extremely low sodium crown glass of the present invention is prepared burden according to the stoicheiometry of each component in the above-mentioned extremely low sodium crown glass, on the producing apparatus of original low sodium crown glass, implements to get final product.SiO wherein 2Raw material adopt purity at the silica sand more than 99.9%, CeO 2Raw material adopt the SILVER REAGENT product, its purity reaches 99.99%, the raw material of other components adopts corresponding chemical reagent to get final product, purity is generally more than 99%.
The melting condition of extremely low sodium crown glass of the present invention is controlled to be: melt temperature is 1550-1700 ℃.
Preferable, when said electricity-saving lamp prepares with extremely low sodium crown glass, according to the stoicheiometry batch mixing of each component in the extremely low unleaded material glass of sodium evenly after; Compound is put into alumina crucible, in the electrically heated muffle furnace, earlier temperature is raised to 1700 ℃, drop to 1550-1610 ℃ again after 10 hours; Be incubated 8-12 hour; And then slowly cooling, accomplish the making of glass sample, wherein the speed of cooling is 80 ℃/hour.The too fast meeting of cooling rate causes in the vitreum grain formation, can't obtain complete vitreum piece.The Glass tubing that the system lamp uses need be accomplished through outer the drawing of tube drawing bench rotation in glass melt.The diameter of Glass tubing and thickness of pipe are by pulling rate and speed of rotation decision.The temperature distribution in temperature distribution and trombone slide exit causes very big influence to the physicochemical property of glass in the stove.Vitrea fusion is formed in the air atmosphere to be accomplished.
The present invention also provides the electronic illumination body that adopts the extremely low sodium crown glass of above-mentioned glass to be prepared from.Electronic illumination body of the present invention is meant with the various light sources of glass as outer closure material.
Preferable, said electronic illumination body is a low-pressure mercury discharge lamp, in said low-pressure mercury discharge lamp is managed when room temperature is not lighted or the air pressure＜10torr in the bubble.
Better, said low-pressure mercury discharge lamp is electricity-saving lamp or straight tube fluorescent lamp.
Said energy-saving lamp tube is straight pipe type or the various shaped bodies that processed by cast, like the fluorescent tube of straight light tube (as shown in Figure 1), helical type lamp and other shapes.
Said straight tube fluorescent lamp the inner surface of tube scribbles the fluorescent material that can the ultraviolet ray that geseous discharge produces be transformed into visible light.Above-mentioned fluorescent material adopts in the prior art can be transformed into the fluorescent material of the visible light of various degree with the ultraviolet ray that gas discharge produces, and can select based on demand of practical production.
The extremely low sodium crown glass of said preparation electronic illumination body meets national environmental protection and requires the Rohs environmental protection standard; And its ultraviolet radiation output is controlled within the scope to human body safety, meets GB/T 17263-2012 (electricity-saving lamp integrated lamp national standard) and European electricity-saving lamp EUP/ERP light source product standard.
Extremely low sodium crown glass of the present invention; Because its sodium content is extremely low, is lower than 0.5%, but greater than 0.23%; Greatly improve fluorescent tube lux maintenance during use; The light decay of fluorescent tube is minimized, so the mercury content that fluorescent tube charged into when making can be lower, for the preparation of unsaturated mercury gas discharge lamp provides necessary material foundation; The cost that guarantees glass material simultaneously is in zone of reasonableness.
Na in the glass of the present invention 2The decline of O content generally is accompanied by Li 2O and K 2The rising of the larger proportion of O content.Because Lithium Oxide 98min is unusual precious materials, the price of potassium oxide is also expensive a lot of than sodium oxide, therefore realizes the decline of sodium oxide content, can cause the cost of whole glass material to rise to some extent.
Extremely low sodium crown glass of the present invention, the quantity of its BaO and low sodium crown glass of the prior art remain basically stable, and have both guaranteed that the glass cost maintains an equal level on this project, can not change the glass physicochemistry parameter again.
Extremely low sodium crown glass of the present invention, its viscosity is basic consistent with low sodium crown glass of the prior art with the variation of temperature curve, so the application in this glass luminescent lamp or electricity-saving lamp manufacturing field in the prior art is no problem.
Do not contain As in the extremely low sodium crown glass of the present invention 2O 3And Sb 2O 3, the content of PbO is trace extremely, is lower than 0.012%, is crown glass, and this glass material meets the Rohs environmental protection standard.
Extremely low sodium crown glass of the present invention can greatly improve fluorescent tube lux maintenance during use, and the light decay of fluorescent tube is minimized.Extremely low sodium crown glass will be the indispensable material of high-end luminescent lamp of new generation, can avoid the use of glass protection film coating when adopting this glass preparation luminescent lamp or electricity-saving lamp, reach to save cost and reduce fluorescent powder coated difficulty.
Description of drawings
Fig. 1 is the luminescent lamp synoptic diagram
Wherein, 1 is glass envelope, and 2 is seal wire, and 3 is filament, and 4 is fluorescent coating, and 5 are the cathode sputtering thing.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment, should be understood that these embodiment only are used to the present invention is described and are not used in restriction protection scope of the present invention.
The glass of embodiment 1-2 is formed as shown in table 1, embodiment 1 with 2 extremely hang down in the unleaded material frit of sodium SiO 2Adopt 99.9% silica sand as raw material, CeO 2Adopt the SILVER REAGENT product, purity reaches 99.99%, and the raw material of other components adopts corresponding chemical reagent to get final product, and purity is generally more than 99%.
The preparation condition of embodiment 1 and 2 the extremely low unleaded material glass of sodium is following:
According to the stoicheiometry batch mixing of each component in the extremely low unleaded material glass of sodium evenly after; Compound is put into alumina crucible, earlier temperature is raised to 1700 ℃, drop to 1550-1610 ℃ again after 10 hours; Be incubated 10 hours; And then slowly cooling, accomplish the making of glass sample, wherein the speed of cooling is 80 ℃/hour.The too fast meeting of cooling rate causes in the vitreum grain formation, can't obtain complete vitreum piece.The Glass tubing that the system lamp uses need be accomplished through outer the drawing of tube drawing bench rotation in glass melt.The diameter of Glass tubing and thickness of pipe are by pulling rate and speed of rotation decision.The temperature distribution in temperature distribution and trombone slide exit causes very big influence to the physicochemical property of glass in the stove.Vitrea fusion is formed in the air atmosphere to be accomplished.
The light plumbous of the lime material glass of Comparative Examples 1 and Comparative Examples 2 expected glass all from " electric light source technology " (first volume) Page18-35, author: square road fat/Cai Zuquan, press of Fudan University.The low sodium crown glass composition of Comparative Examples 3 is from Chinese patent 97190817.6,01132297.7 or 01134245.5.
Glass composition and the performance of embodiment 1-2 and Comparative Examples 1-3 are as shown in table 1.Wherein, the linear expansivity in the table 1 is measured according to the SJ689 testing standard, and softening temperature is to measure by the SJ690 testing standard, and sample rate directly calculates according to the weight and volume value.
Table 1
Figure BDA0000095562540000051
Figure BDA0000095562540000061
The extremely low unleaded material glass of sodium in the table 1 and high soda glass (lime the material)/middle soda glass in the Comparative Examples (light plumbous material)/low soda glass (the low unleaded material of sodium) can be known in the extremely low unleaded material glass of sodium of embodiment 1 and 2 appropriate sodium oxide content, PbO content and CeO 2Content makes extremely low sodium crown glass of the present invention can greatly improve fluorescent tube lux maintenance during use; The light decay of fluorescent tube is minimized; Can avoid the use of glass protection film coating when adopting this glass preparation luminescent lamp or electricity-saving lamp, reach and save cost and reduce fluorescent powder coated difficulty.Each excellent property and the cost of the extremely low unleaded material glass of sodium therefore of the present invention are not expensive, meet the actual requirement of high-end luminescent lamp material of new generation.
Adopt the extremely low unleaded material glass of sodium of embodiment 1 or 2 can prepare various electronic illumination bodies such as luminescent lamp as shown in Figure 1.

Claims (9)

1. one kind is extremely hanged down the sodium crown glass, comprises the component of following parts by weight:
SiO 263-69 part;
Al 2O 34.5-5 part;
Na 2O 0.25-0.5 part;
Li 2O 3.0-3.7 part;
K 2O 11.8-12.2 part;
CaO and MgO 4.5-6.8 part;
SrO 4.5-5.6 part;
BaO 7.0-7.3 part;
PbO 0-0.012 part;
SO 30.12-0.21 part;
Fe 2O 30.015-0.03 part;
CeO 20.23-0.31 part.
2. extremely low sodium crown glass as claimed in claim 1 is characterized in that, said extremely low sodium crown glass comprises following components in weight percentage content:
SiO 263.5-66.5 part;
Al 2O 34.5-5 part;
Na 2O 0.25-0.36 part;
Li 2O 3.1-3.7 part;
K 2O 11.8-12.12 part;
CaO and MgO 4.5-6.8 part;
SrO 4.5-5.6 part;
BaO 7.1-7.3 part;
PbO 0.011-0.012 part;
SO 30.12-0.21 part;
Fe 2O 30.015-0.03 part;
CeO 20.23-0.31 part.
3. extremely low sodium crown glass according to claim 1 and 2 is characterized in that, does not contain As in the said extremely low sodium crown glass 2O 3And Sb 2O 3, the weight percentage of PbO is less than 500ppm.
4. the electronic illumination body of extremely low sodium crown glass preparation according to claim 1 and 2.
5. the electronic illumination body of extremely low sodium crown glass preparation according to claim 4 is characterized in that said electronic illumination body is a low-pressure mercury discharge lamp, in said low-pressure mercury discharge lamp manage when room temperature is not lighted or the air pressure＜10torr in steeping.
6. the electronic illumination body of extremely low sodium crown glass preparation according to claim 5 is characterized in that said low-pressure mercury discharge lamp is electricity-saving lamp or straight tube fluorescent lamp.
7. the electronic illumination body of extremely low sodium crown glass preparation according to claim 6 is characterized in that, said energy-saving lamp tube is straight pipe type or the various shaped bodies that processed by cast.
8. the electronic illumination body of extremely low sodium crown glass preparation according to claim 6 is characterized in that, said straight tube fluorescent lamp the inner surface of tube scribbles the fluorescent material that can the ultraviolet ray that geseous discharge produces be transformed into visible light.
9. the electronic illumination body for preparing according to the arbitrary described extremely low sodium crown glass of claim 4-8; It is characterized in that; The extremely low sodium crown glass of said preparation electronic illumination body meets the Rohs environmental protection standard, and its ultraviolet radiation output National standard GB/T 17263-2012 and European electricity-saving lamp EUP/ERP light source product standard.
CN2011102982773A 2011-09-28 2011-09-28 Ultra-low-sodium lead-free glass and applications thereof Pending CN102503124A (en)

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CN2011102982773A CN102503124A (en) 2011-09-28 2011-09-28 Ultra-low-sodium lead-free glass and applications thereof
PCT/CN2012/080989 WO2013044721A1 (en) 2011-09-28 2012-09-05 Lead-free glass with very low sodium, and use thereof

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013044721A1 (en) * 2011-09-28 2013-04-04 上海亚明照明有限公司 Lead-free glass with very low sodium, and use thereof
CN106277759A (en) * 2016-08-10 2017-01-04 上海罗金光电科技股份有限公司 A kind of unleaded electric light source glass tubing and preparation method thereof

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US5509841A (en) * 1994-02-18 1996-04-23 Winsor Corporation Stamped metal flourescent lamp and method for making
CN1196713A (en) * 1996-05-13 1998-10-21 菲利浦电子有限公司 Glass composition suitable for use in fluorescent lamp, lamp envelope manufactured from said glass composition and lamp envelope with said glass composition
CN101065821A (en) * 2004-11-24 2007-10-31 皇家飞利浦电子股份有限公司 Low-pressure mercury vapor discharge lamp and apparatus for treatment

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JP2002137935A (en) * 2000-10-26 2002-05-14 Nippon Electric Glass Co Ltd Glass for fluorescent lamp, glass tube for fluorescent lamp and fluorescent lamp
JP2002358925A (en) * 2001-05-30 2002-12-13 Toshiba Lighting & Technology Corp Tubular bulb product
CN1594159A (en) * 2004-06-23 2005-03-16 上海孟仕玻璃有限公司 Leadless glass fit for machining energy-saving tube
US20100240515A1 (en) * 2009-03-20 2010-09-23 L. Lighting Glass Company Limited Low-sodium-oxide glass and glass tube
CN102503124A (en) * 2011-09-28 2012-06-20 上海亚明灯泡厂有限公司 Ultra-low-sodium lead-free glass and applications thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5509841A (en) * 1994-02-18 1996-04-23 Winsor Corporation Stamped metal flourescent lamp and method for making
CN1196713A (en) * 1996-05-13 1998-10-21 菲利浦电子有限公司 Glass composition suitable for use in fluorescent lamp, lamp envelope manufactured from said glass composition and lamp envelope with said glass composition
CN101065821A (en) * 2004-11-24 2007-10-31 皇家飞利浦电子股份有限公司 Low-pressure mercury vapor discharge lamp and apparatus for treatment

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013044721A1 (en) * 2011-09-28 2013-04-04 上海亚明照明有限公司 Lead-free glass with very low sodium, and use thereof
CN106277759A (en) * 2016-08-10 2017-01-04 上海罗金光电科技股份有限公司 A kind of unleaded electric light source glass tubing and preparation method thereof
CN106277759B (en) * 2016-08-10 2018-12-04 上海罗金光电科技股份有限公司 A kind of unleaded electric light source glass tube and preparation method thereof

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Application publication date: 20120620