CN101659518A - Microcrystalline glass with high transparency and high heat resistance and preparation method thereof - Google Patents

Microcrystalline glass with high transparency and high heat resistance and preparation method thereof Download PDF

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Publication number
CN101659518A
CN101659518A CN200910086649A CN200910086649A CN101659518A CN 101659518 A CN101659518 A CN 101659518A CN 200910086649 A CN200910086649 A CN 200910086649A CN 200910086649 A CN200910086649 A CN 200910086649A CN 101659518 A CN101659518 A CN 101659518A
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glass
raw material
sio
microcrystalline glass
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李要辉
梁开明
曹建尉
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Beijing Shengkangning Science & Technology Development Co Ltd
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Beijing Shengkangning Science & Technology Development Co Ltd
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Abstract

The invention relates to a microcrystalline glass with high transparency, ultralow-thermal expansion and high heat resistance, which is characterized by comprising the components by weight percent: 3.0-5.0 percent of Li2, 20-24 percent of Al2O3, 58-65 percent of SiO2, 0.5-1.0 percent of Na2, 0.5-1.0 percent of K2O, 0.5-1.0 percent of MgO, 1.0-2.0 percent of BaO, 1.0-2.0 percent of ZnO, 2-4 percentof Ta2O5, 0-2 percent of TiO2, 0-2 percent of ZrO2, 0.5-1 percent of P2O5 and 1-2 percent of Sb2O3. The expansion coefficient of the microcrystalline glass is -2.0 to 5.0 multiplied by 10<-7>/DEG C,the visible range average transmittance achieves above 93 percent, the bending strength exceeds 150 Mpa, and the impact toughness achieves 2.0 MPa.m<1/2>. The microcrystalline glass can be widely usedin the fields of fireproof glasses, bulletproof glasses, heat resistance furnace window glasses, high temperature elements and the like, and a product of the microcrystalline glass has the advantagesof high transparency, high heat resistance, strong strength, high toughness, long service life and the like.

Description

A kind of microcrystalline glass with high transparency and high heat resistance and preparation method
Technical field
The invention belongs to glass production manufacturing technology field, relate generally to the heat-resisting serial devitrified glass that a kind of thermal expansivity is extremely low, transmittance is high.
Background technology
High transparent, high heat-resisting devitrified glass is a kind of novel glass system of rising recently, wherein Li 2O-Al 2O 3-SiO 2(LAS) devitrified glass relies on its good resistance to sudden heating, higher intensity and lower even approach zero or negative thermal expansivity, is all obtaining very big achievement aspect theory research and the suitability for industrialized production.Recently, the LAS devitrified glass has become the another novel high-performance fire safety glass after common sodium calcium silicon steel glass, borosilicate series fire-proofing glass.
All there are some defectives in essence in conventional tempering type soda-lime-silica glass and low-expansion boron silicate fire-resisting glass, under the fiery state of chance, can lose the tempering effect by physical toughened glass, and bursting and being out of shape also appears in their flame resistant glass compound, hollow type easily, be difficult to reach the requirement of opticglass simultaneously, and have very big technical matters difficulty requirement.Because the drawbacks limit on above-mentioned parent glass and the reinforcing process can't reach multifunctional and composite type shatter proof glass truly.
LAS crystallite flame resistant glass is to add TiO in chemical constitution 2, ZrO 2Deng the nucleus agent, heat-treat again behind the glass melting, make to separate out crystallite and evenly grow to form polycrystal, this glass has good chemical stability and mechanical property, the physical strength height, the softening temperature height, thermal expansivity is little.The lithium aluminium silicon transparent glass-ceramics of Chu Xianing is mainly used in fields such as heat-resisting kitchen tools and panel in the market, mostly is black, reddish-brown, and the material many places are in translucent (or milkiness) state.Fact proved, work as TiO 2Addition greater than 3% o'clock, glass is faint yellow, is pale brown look after the crystallization.Report all with TiO about the patent and the product of lithium silicon aluminum micro-crystal glass at present 2Or TiO 2, ZrO 2Compound is main nucleating agent, and so-called transparent LAS devitrified glass also inevitably presents faint yellow, and the next use tinting material of more susceptible condition makes product present black or reddish-brown.
If the lithium silicon aluminum micro-crystal glass with excellent low bulk and high light transmittance energy is applied to fire safety glass and other precision optics (as laser navigation, astronomical telescope eyeglass etc.) high-tech area, prepares colourless high transparency and high heat resistance LAS devitrified glass and be significant.
Summary of the invention
The purpose of this invention is to provide a kind of high transparent, high heat-resisting Li 2O-Al 2O 3-SiO 2Microcrystalline glass in series makes it have extremely low even thermal expansivity zero and higher visible light transmittance rate, and can use glass ware forming technology at present commonly used to carry out large-scale industrial production.
For achieving the above object, the present invention takes following technical scheme:
A kind of colourless high transparency and high heat resistance Li 2O-Al 2O 3-SiO 2Microcrystalline glass in series, this devitrified glass composition is expressed as with weight percent: Li 2O:3.0～5.0%; Al 2O 3: 20～24%; SiO 2: 58～65%; Na 2O:0.5～1.0%; K 2O:0.5～1.0%; MgO:0.5～1.0%; BaO:1.0～2.0%; ZnO:1.0～2.0%; Ta 2O 5: 2～4%; TiO 2: 0～2%; ZrO 2: 0～2%; P 2O 5: 0.5～1%; Sb 2O 3: 1～2%.
High transparency and high heat resistance Li of the present invention 2O-Al 2O 3-SiO 2The microcrystalline glass in series composition is convenient to melt, the needs of clarification and moulding processability, has suitably increased alkaline earth metal oxide, and alkali metal oxide content is introduced tantalum oxide simultaneously and replaced part or all of titanium dioxide as the part nucleating agent.Selected raw material is a technical pure level industrial chemicals, requires various trace metal impurities weight contents to satisfy: (Fe 2O 3+ Cr 2O 3+ MnO 2) %＜0.05%.
A kind of colourless high transparency and high heat resistance Li 2O-Al 2O 3-SiO 2The preparation method of microcrystalline glass in series, its technical process comprises:
(1) take by weighing corresponding raw material according to each composition weight percent in the above-mentioned devitrified glass, wherein, the Li in the devitrified glass 2O is raw material with the Quilonum Retard; Na 2O is raw material with soda ash; K 2O is raw material with salt of wormwood; P 2O 5With the ammonium di-hydrogen phosphate is raw material; BaO is raw material with the barium carbonate, converts and takes by weighing above-mentioned raw materials weight by the mentioned component weight percent; In addition, press Al 2O 3, SiO 2, MgO, ZnO, Ta 2O 5, TiO 2, ZrO 2And Sb 2O 3Weight percent take by weighing with the weight of mentioned component as raw material; (2) raw material mixes; (3) melting furnaces are founded, and temperature of fusion is 1580～1650 ℃; (4) moulding; (5) 750～900 ℃ of crystallization are handled; (6) cooling; (7) cutting, grinding, polishing; (8) deburring, check, stamp, packing.
Moulding process wherein can be selected calendering formation, compression moulding or floating process moulding for use.
Devitrified glass of the present invention is selected Ta for use 2O 5And TiO 2, ZrO 2Three kinds of nucleating agents also carry out optimization design, and compound nucleating agent has higher forming core efficient, and the crystallization temperature wide ranges reaches 50 ℃, can obtain evenly tiny nanometer crystal microstructure after the crystallization, have guaranteed the physicochemical property of material excellence.
Devitrified glass thermal expansivity of the present invention extremely low (even approaching zero), its resistance toheat and thermal shock resistance are higher than existing sheet glass and congruent glasswork far away.This lithium aluminium silicon transparent glass is after micritization is handled, can not burst and softening transform after being heated 850 ℃ of following long periods of high temperature, the result is presented at insulation 10h under 850 ℃ of high temperature, material structure is stable, thermal expansivity, bending strength do not have tangible change, and transmittance remains unchanged substantially, sample under effect under the gravity deflection less than 0.1 ‰, therefore can prolong fire resistance period effectively, stop spreading of the intensity of a fire.
The devitrified glass product grains that the present invention obtained is tiny, because part or all of TiO has been replaced in the adding of tantalum oxide 2As nucleating agent, avoided Ti 4+The royal purple of the added light part that the ultraviolet strong absorption of ion pair causes absorbs, the ultraviolet cut-on absorption limit of glass and devitrified glass all remains on about 300nm before and after the crystallization, therefore the transparent glass-ceramics that obtains has higher transmittance in whole visible-range, the visible-range average transmittances reaches more than 93%, and visual inspection simultaneously shows as water white transparency.Rely on its excellent structural stability, its optical property has good stability in bigger temperature range and heated time, getting confused and the devitrification phenomenon after can not occurring being heated.
At high transparency and high heat resistance Li of the present invention 2O-Al 2O 3-SiO 2In the microcrystalline glass in series, by adding the tinting material such as the Cr of certainweight ratio 2O 3, MnO 2, V 2O 5, CoO, can prepare colored or translucent devitrified glass.
Architectural window glass and glass partitions such as fire prevention devitrified glass application widely that the present invention manufactures and high-end residential, hotel, office building also can be used as various heat-resisting class baking trays, panel and table top etc. simultaneously.The monolithic glass that is obtained simultaneously can with organic materials, the compound acquisition composite type safety of inorganic materials glass.
Its key technical indexes of the present invention is:
Density: 2.58g/cm 3
Thermal expansivity (25～800 ℃) :-2.0～5.0 * 10 -7/ K
Heat shock resistance temperature :≤850 ℃
Visible light transmissivity: 〉=93%
Bending strength: 150Mpa
Impelling strength: 2.0MPam 1/2
Young's modulus: 85Gpa.
Embodiment
Embodiment 1
Glass formula is expressed as Li with weight percent 2O:4.0%; Al 2O 3: 21%; SiO 2: 62%; Na 2O:0.5%; K 2O:0.5%; MgO:1.0%; BaO:2.0%; ZnO:1%; Ta 2O 5: 4%; ZrO 2: 2%; P 2O 5: 1%; Sb 2O 3: 1%.
Take by weighing corresponding raw material weight umber, Quilonum Retard 9.9 according to each composition weight percent in the above-mentioned devitrified glass; Aluminum oxide 21.0; Quartz sand 63.2; Soda ash 0.86; Salt of wormwood 0.73; Ammonium di-hydrogen phosphate 1.62; Barium carbonate 2.58; Zinc oxide 1.0; Magnesium oxide 1.0; Tantalum pentoxide 4.0; Zirconium white 2.0; Weisspiessglanz 1.0.After above-mentioned raw materials mixed, through 1650 ℃ of fusings down, clarification back calendering formation, 500 ℃～600 ℃ annealing obtain transparent lithium silicon aluminum micro-crystal glass (analyzing glass ingredient through X-ray fluorescence spectra requires for prescription) at 750 ℃～900 ℃ thermal treatment 2h.The thermal expansivity of gained print is-2.5～5.0 * 10 -7/ ℃, the visible-range average transmittances reaches 93%, and ultraviolet cut-on absorbs and is limited to 300nm, and bending strength reaches 150Mpa, and impelling strength is 2.0MPam 1/2, about 900 ℃ of softening temperature.
Embodiment 2
Glass formula is expressed as Li with weight percent 2O:5.0%; Al 2O 3: 24%; SiO 2: 58%; Na 2O:0.5%; K 2O:0.5%; MgO:1.0%; BaO:2.0%; ZnO:1%; Ta 2O 5: 4%; TiO 2: 2%; P 2O 5: 1%; Sb 2O 3: 1%.
Take by weighing the raw material of corresponding parts by weight by above-mentioned prescription, after mixing, through 1600 ℃ of fusings down, clarification back calendering formation, 500～600 ℃ of annealing obtain transparent lithium silicon aluminum micro-crystal glass at 750 ℃～850 ℃ thermal treatment 2h.The thermal expansivity of gained print is 5.0～10.0 * 10 -7/ ℃, the visible-range average transmittances reaches 90%, and it is 325nm that ultraviolet cut-on absorbs line, and bending strength reaches 150Mpa, and impelling strength is 2.0MPam 1/2, softening temperature is higher than 850 ℃.
Embodiment 3
Glass formula is expressed as Li with weight percent 2O:3.0%; Al 2O 3: 20%; SiO 2: 65%; Na 2O:0.5%; K 2O:0.5%; MgO:1.0%; BaO:2.0%; ZnO:1%; Ta 2O 5: 2%; TiO 2: 2%; ZrO 2: 1%; P 2O 5: 1%; Sb 2O 3: 1%.
Take by weighing the raw material of corresponding parts by weight by above-mentioned prescription, after mixing, through 1650 ℃ of fusings down, the floating process moulding of clarification back, 500～600 ℃ of annealing obtain transparent lithium silicon aluminum micro-crystal glass at 750 ℃～900 ℃ thermal treatment 2h.The thermal expansivity of gained print is 0～5.0 * 10 -7/ ℃, the visible-range average transmittances reaches 90%, and it is 350nm that ultraviolet cut-on absorbs line, and bending strength reaches 180Mpa, and impelling strength is 2.0MPam 1/2, softening temperature is higher than 900 ℃.

Claims (3)

1, a kind of high transparency and heat-proof Li 2O-Al 2O 3-SiO 2Microcrystalline glass in series is characterized in that its composition is by weight percentage:
Li 2O：3.0～5.0％；Al 2O 3：20～24％；SiO 2：58～65％；Na 2O：0.5～1.0％；K 2O：0.5～1.0％；MgO：0.5～1.0％；BaO：1.0～2.0％；ZnO：1.0～2.0％；Ta 2O 5：2～4％；TiO 2：0～2％；ZrO 2：0～2％；P 2O 5：0.5～1％；Sb 2O 3：1～2％。
2, the described high transparency and high heat resistance Li of claim 1 2O-Al 2O 3-SiO 2The preparation method of microcrystalline glass in series, its technical process comprises:
(1) take by weighing corresponding raw material according to each composition weight percent in the described devitrified glass of claim 1, wherein, the Li in the devitrified glass 2O is raw material with the Quilonum Retard; Na 2O is raw material with soda ash; K 2O is raw material with salt of wormwood; P 2O 5With the ammonium di-hydrogen phosphate is raw material; BaO is raw material with the barium carbonate, converts and takes by weighing above-mentioned raw materials weight by the mentioned component weight percent; In addition, press Al 2O 3, SiO 2, MgO, ZnO, Ta 2O 5, TiO 2, ZrO 2And Sb 2O 3Weight percent take by weighing with the weight of mentioned component as raw material; (2) above-mentioned raw materials is mixed; (3) mixed raw material is founded, temperature of fusion is 1580～1650 ℃; (4) carry out moulding process after founding; (5) glass after the moulding being carried out 750～900 ℃ of crystallization handles; (6) glass after the crystallization is cooled off; (7) cut then, grind and polish; (8) carry out deburring, check, stamp and packing at last.
3, high transparency and heat-proof Li according to claim 5 2O-Al 2O 3-SiO 2The preparation method of microcrystalline glass in series is characterized in that, the moulding process in the described step (4) is calendering formation, compression moulding or floating process moulding.
CN200910086649A 2009-06-16 2009-06-16 Microcrystalline glass with high transparency and high heat resistance and preparation method thereof Pending CN101659518A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102775070A (en) * 2012-08-21 2012-11-14 何德开 Microcrystalline glass plate manufactured by using copper-tin metallic tailings and manufacturing method thereof
CN106495494A (en) * 2016-10-20 2017-03-15 广西大学 A kind of mobile phone screen and preparation method thereof
CN106854038A (en) * 2016-11-29 2017-06-16 枞阳县铭瑞电子科技有限公司 A kind of mobile phone wear and shock-resistant cover-plate glass
CN110372216A (en) * 2018-04-12 2019-10-25 深圳市东丽华科技有限公司 Flat glass, tempered glass, 3D curved surface devitrified glass and its preparation process
CN111348833A (en) * 2017-12-01 2020-06-30 成都光明光电股份有限公司 Glass ceramics and substrate thereof
CN111943514A (en) * 2020-06-29 2020-11-17 成都光明光电股份有限公司 Glass-ceramic and glass-ceramic article
CN112047633A (en) * 2020-08-21 2020-12-08 江苏悦丰晶瓷科技有限公司 Glass ceramic ware and preparation method thereof
CN115531605A (en) * 2022-10-28 2022-12-30 深圳玉汝成口腔材料有限公司 Dental glass ceramic restoration and preparation method thereof
CN116553833A (en) * 2023-03-23 2023-08-08 成都光明光电有限责任公司 Low-expansion glass ceramic and preparation method thereof

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102775070A (en) * 2012-08-21 2012-11-14 何德开 Microcrystalline glass plate manufactured by using copper-tin metallic tailings and manufacturing method thereof
CN102775070B (en) * 2012-08-21 2015-09-02 何德开 Crystallizing glass sheet material and preparation method thereof is manufactured with copper tin metal mine tailing
CN106495494A (en) * 2016-10-20 2017-03-15 广西大学 A kind of mobile phone screen and preparation method thereof
CN106854038A (en) * 2016-11-29 2017-06-16 枞阳县铭瑞电子科技有限公司 A kind of mobile phone wear and shock-resistant cover-plate glass
CN111348833A (en) * 2017-12-01 2020-06-30 成都光明光电股份有限公司 Glass ceramics and substrate thereof
CN111348833B (en) * 2017-12-01 2022-04-08 成都光明光电股份有限公司 Glass ceramics and substrate thereof
CN110372216A (en) * 2018-04-12 2019-10-25 深圳市东丽华科技有限公司 Flat glass, tempered glass, 3D curved surface devitrified glass and its preparation process
CN111943514A (en) * 2020-06-29 2020-11-17 成都光明光电股份有限公司 Glass-ceramic and glass-ceramic article
CN112047633A (en) * 2020-08-21 2020-12-08 江苏悦丰晶瓷科技有限公司 Glass ceramic ware and preparation method thereof
CN115531605A (en) * 2022-10-28 2022-12-30 深圳玉汝成口腔材料有限公司 Dental glass ceramic restoration and preparation method thereof
CN115531605B (en) * 2022-10-28 2023-09-12 深圳玉汝成口腔材料有限公司 Dental glass ceramic prosthesis and preparation method thereof
CN116553833A (en) * 2023-03-23 2023-08-08 成都光明光电有限责任公司 Low-expansion glass ceramic and preparation method thereof

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Open date: 20100303