CN101857363A - White light glass and preparation method thereof - Google Patents

White light glass and preparation method thereof Download PDF

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CN101857363A
CN101857363A CN 201010205012 CN201010205012A CN101857363A CN 101857363 A CN101857363 A CN 101857363A CN 201010205012 CN201010205012 CN 201010205012 CN 201010205012 A CN201010205012 A CN 201010205012A CN 101857363 A CN101857363 A CN 101857363A
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light
white
oxide
glass
tin
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CN 201010205012
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严祁祺
杨云霞
沈策
陈国荣
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华东理工大学
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Abstract

The invention relates to a white light glass and a preparation method thereof, in particular to a white light glass with tin oxide and manganese oxide as light emitting centers and a preparation method thereof. White light illumination plays an important role in daily production and living, but the existing white light illumination has low efficiency, complicated process and difficult miniaturization. Under the condition, the research on the white light glass is taken seriously because the white light glass has the advantages of simple preparation, high luminous efficiency, easy color temperature regulation and the like. Currently, the researches focus on the white light glass doped with rare earth, but rare earth light emission can generate quenching at high concentration, and the lighting peak position can shift along with the use time so as to cause color temperature change. The white light glass with the tin oxide and the manganese oxide as the light emitting centers can make up the shortcomings. The tin oxide and the manganese oxide belong to network intermediates, can be introduced at high concentration, and have higher luminous intensity and conversion efficiency. Simultaneously, the tin oxide and the manganese oxide adopt wide spectrum lighting, and the compounded white light color temperature basically does not change along with time.

Description

一种白光玻璃及其制备方法 One kind of white glass and preparation method

技术领域 FIELD

[0001] 本发明涉及白光材料及其制备,尤其是涉及以Sn02*Mn0为发光中心的白光玻璃及其制备方法。 [0001] The present invention relates to a white light emitting material and its preparation, and more particularly to a white glass preparation method Sn02 * Mn0 as the luminescent center.

背景技术 Background technique

[0002] 近些年米,随着能源消耗的不断增加,能源危机和环境污染越来越严重。 [0002] In recent meters, with the increase of energy consumption, the energy crisis and environmental pollution is getting worse. 在寻找新型替代能源的同时,也必须在节能减排方面取得一定的突破,这就很有必要对现有的能源消耗结构进行调整,从而达到节能减排的目的。 While looking for new alternative energy sources must also be made in energy conservation definite breakthrough, which is necessary for current energy consumption structure adjustment, so as to achieve the purpose of energy saving. 照明在人类生产生活中起到了不可或缺的作用,但也因此消耗了大量的能源,所以对照明方式的改进已经迫在眉睫。 Lighting plays in the production of human life in an integral role, but also consumes a lot of energy and therefore, the improvement of lighting is imminent. 就目前而言,白炽灯和荧光灯是照明的主要方式。 For now, incandescent and fluorescent lamps are the main form of lighting. 由于白炽灯是通过加热钨丝到白炽状态而实现的发光, 很大部分能量转换成了热能损耗,其能量利用效率极低。 Since the light emitting incandescent tungsten filament is heated to incandescence achieved, most of the energy is converted into heat loss, a very low energy efficiency. 荧光灯主要是通过电致汞蒸气产生紫外线,而后激发内部的荧光粉而实现的发光,其能量利用效率较高,但其结构及制备过程较为复杂,难以小型化,应用受到一定的限制。 Fluorescent light produced by electroluminescence mainly mercury vapor ultraviolet rays excite the phosphor and then the interior of the light emission to achieve high energy efficiency, but its structure and preparation process is more complicated, difficult to downsize, the application subject to certain restrictions. 上个世纪90年代以来,国内外对开拓和制备用于生产生活等领域的照明材料的研究有了许多报道。 Lighting materials research since the 1990s, at home and abroad to open up the field of production and preparation for life there have been many other reports. 其中发光二极管(LED)受到了高度的关注,由于其发光效率高,结构紧凑,制备简单而得到了大量的研究。 Wherein the light emitting diode (LED) by a high degree of attention, because of its high luminous efficiency, compact, simple to prepare and give a great deal of research. 目前已经可以通过特定LED的组合实现白光发射,而且这些产品已经部分商业化。 At present white light emission can be achieved already by the combination of the particular LED, and these products have been commercialized portion. 但由于现有的LED基本都是利用稀土作为发光中心,其发光为线状谱,在使用过程中发光波长会产生偏移,从而使复合出的白光色温发生变化。 However, due to the basic conventional LED as a light emitting center is the use of rare earth, which is a linear light emission spectrum, light emission in the course of a wavelength shift is generated, so that the composite of the white color temperature changes. 同时,由于LED用发光基质一般为荧光粉,其封装过程中需要作为薄膜沉积在LED芯片上,厚度不易控制,从而导致发出的白光颜色不均勻。 Meanwhile, since the light emitting LED with the phosphor matrix generally, the package as required during the deposition of a film on the LED chip, a thickness difficult to control, resulting in white light emitted color unevenness. 并且,其封装过程需要用到环氧树脂,从而不可避免的产生老化问题。 And that need to use an epoxy resin packaging process, thus inevitably produce aging.

[0003] 以氧化锡(Sn02)和氧化锰(MnO)为发光中心的白光玻璃可以弥补上述白光照明的缺点。 [0003] In tin oxide (Sn02) and manganese oxide (MnO) as a white glass luminescent center would compensate for the above-described white light illumination. 氧化锡和氧化锰属于玻璃网络中间体,可以在玻璃中以较高的浓度引入,从而使玻璃具有较高的发光强度,提高了光电转换率。 Tin oxide and manganese oxide glass network belonging intermediates, can be introduced at a higher concentration in the glass so that the glass has a high emission intensity and improve the photoelectric conversion efficiency. 氧化锡和氧化锰的发光为宽谱,在使用过程中波长偏移对白光的色温几乎不会产生影响。 Tin oxide and manganese oxide emission is a broad spectrum, wavelength shift during use of the color temperature of white light hardly affect. 同时,由于直接用玻璃作为发光基质,不存在封装后发光不均勻以及老化问题。 Meanwhile, since the light-emitting glass substrate directly, after packaging, and uneven light emission is not present aging.

发明内容 SUMMARY

[0004] 本发明的目的之一,提供一种能够用于生产生活照明、显示技术等领域的白光玻璃,以部分取代目前广泛使用的白炽灯、荧光灯等,后者具有发光效率低,结构复杂,尺寸较大等缺点。 [0004] One object of the present invention, to provide a life for the production of light and a display of white areas of glass technology, widely used to partially replace incandescent, fluorescent lamp, which has a low emission efficiency, complex structure , larger size and other shortcomings.

[0005] 本发明目的之二,提供一种制备上述白光玻璃的方法。 [0005] Another object of the present invention is two, there is provided a method of preparing the above-mentioned white glass.

[0006] 发明构思: [0006] The inventive concept:

[0007] 氧化锡和氧化锰是发光效率很高的宽谱发光中心,具有发光强度大,激发和发射波长宽,能在玻璃中大量引入等优良特点,在玻璃中引入这两种氧化物之后,可以通过一般的成型技术,如模压、热压和挤压技术等直接制备发光器材。 [0007] manganese oxide, tin oxide and the light emission efficiency is very high broad spectrum emission center, light emission having intensity, excitation and emission wave length and width, can be introduced in a large number of glass and other fine features, the introduction of these two oxides in a glass after , by ordinary molding techniques, such as molding, extrusion, and pressing techniques, etc. a light emitting devices directly. 与传统的白炽灯、荧光灯以及新型的LED相比,具有发光效率高,结构简单,发光稳定,成本低廉等优势。 Compared with conventional incandescent, fluorescent, and the LED novel, high luminous efficiency, simple structure, light emission stable, low cost advantages. [0008] 本发明是一种以氧化锡和氧化锰为发光中心的白光玻璃,该系统玻璃的组成涉及兼顾了如下因素:玻璃的形成能力,近紫外及可见区域的高光学透过性,复合白光的色温, 白光的强度。 [0008] The present invention is a white glass is tin oxide and manganese as an emission center, the glass composition of the system involves the following factors into account: the optical high glass forming ability, ultraviolet and visible region near permeable composite the color temperature of white light, the intensity of white light.

[0009] 技术方案: [0009] Technical Solution:

[0010] 本发明所述的白光玻璃包括如下组分及含量(含量以摩尔百分比mol%计算): [0010] The present invention comprises white glass and the content of the following components (mol% content calculated in mole percent):

[0011] P205 :10-90 [0011] P205: 10-90

[0012] R0 :0-50 [0012] R0: 0-50

[0013] Sn02 :0-10 [0013] Sn02: 0-10

[0014] MnO :0-10 [0014] MnO: 0-10

[0015]其中 R = Ca,Sr,Ba [0015] where R = Ca, Sr, Ba

[0016] 制备上述白光玻璃的方法包括如下步骤: [0016] The method of preparing the above-mentioned white glass comprising the steps of:

[0017] a)玻璃配合料的制备 [0017] a) Preparation of glass batch

[0018] 将原料按照上述的组分及含量经充分混合后制得玻璃配合料。 [0018] According to the above raw material components and the content was sufficiently mixed to prepare glass batch. 其中P205,MnO和R0分别以NH4H2P04,MnC03和RC03形式引入。 Wherein P205, MnO and R0 are incorporated NH4H2P04, MnC03 and RC03 forms.

[0019] b)配合料的熔制: [0019] b) melting the batch:

[0020] 将由步骤(a)制得的玻璃配合料置于容器中熔化,熔化温度为1200-1300°C,熔化时间为1-3小时。 [0020] The glass obtained from step (a) in a container batch is melted, the melting temperature of 1200-1300 ° C, the melting time was 1-3 hours.

[0021] 将熔化的玻璃液倒入模具内固化成型。 [0021] The molten glass was poured into the mold Curing. 将固化成型后的玻璃移至马弗炉内,在450 °C保温半小时,冷却后得到玻璃试样。 The solidified glass forming moved muffle furnace, held at 450 ° C for half an hour, and cooled to obtain glass samples.

[0022] 其中:所用模具最好预先加热至450°C左右,马弗炉预先升温至450°C左右 [0022] wherein: the preferably pre-heated to about 450 ° C with a mold, pre-heated muffle furnace to about 450 ° C

[0023] c)热处理: [0023] c) Heat treatment:

[0024] 将由步骤(b)制得玻璃试样重新放入马弗炉,在温度为350-550°C,保温3-10个小时,冷却后即得到本发明所述的快速闪烁玻璃。 [0024] from step (b) to obtain glass samples again placed in a muffle furnace, rapid blinking of the present invention is a glass at a temperature of 350-550 ° C, 3-10 hours incubation, after cooling.

[0025] 本发明所述白光玻璃与现有的掺稀土白光材料相比,则具有荧光强度高,激发和发射波长宽,白光色温易于调节等特点;同时,本发明所述的发光玻璃又具有熔制过程简单,玻璃形成能力强,色温易于调整,发光中心离子引入浓度高的特点。 [0025] The present invention is compared with conventional white glass white rare earth doped material, having a high fluorescence intensity, excitation and emission wave length and width, easy to adjust the white color temperature characteristics; Meanwhile, the luminescent glass of the present invention also has melting process is simple, glass-forming ability, easy to adjust the color temperature, a high concentration of a luminescent center ion is introduced characteristics. 本发明所述的白光玻璃可以应用于生产生活照明、显示技术等领域。 White glass according to the present invention may be applied to the production and living lighting, display technology and other fields.

具体实施方式 detailed description

[0026] 为了更好的理解本发明的内容,下面通过实施对本发明作进一步说明,但所举实施例并不限制本发明的保护范围。 [0026] For a better understanding of the present invention, the following further illustrated by the embodiment of the present invention, but the cited examples do not limit the scope of the present invention.

[0027] 实施例1 [0027] Example 1

[0028] 配方设计: [0028] formulation:

[0029] 采用磷酸盐系统。 [0029] The phosphate system. 组分设计如下: Design of the following components:

[0030] 表1实施例1的玻璃组成(mol % ) [0030] Table 1 glass composition of Example 1 (mol%)

[0031] [0031]

4 4

[0032] 配合料配制: [0032] The batch preparation:

[0033] 分别采用高纯度(99. 9 % )磷酸二氢铵(NH4H2P04),碳酸锶(SrC03),碳酸锰(MnC03) 和氧化锡为引入p205,Sr0,Mn0和Sn02的原料,按表1所示的组成进行配方计算及配合料配制。 [0033] respectively using high purity (99.9%) ammonium dihydrogen phosphate (NH4H2P04), strontium carbonate (SrC03), manganese carbonate (MnC03) and tin oxide to introduce p205, Sr0, Mn0 and Sn02 materials according to Table 1 the composition shown in recipe calculation and batch formulation. 配合料配制方法与常规的玻璃配合料配制方法相同。 The method of the same material batch formulation and preparation method of conventional glass fitted. 配合料需充分混合。 Batch to be fully mixed.

[0034] 玻璃熔制: [0034] melting glass:

[0035] 将混合均勻的配合料放入刚玉坩埚内,在电炉内熔制玻璃。 [0035] The batch is mixed into the alumina crucible, melting the glass in an electric furnace. 熔制气氛为空气,熔化温度为1250°C,熔化时间为2小时,保温期间内对玻璃进行人工搅拌2次,以改善玻璃液的 Melting an air atmosphere, the melting temperature is 1250 ° C, the melting time was 2 hours, the incubation period the glass is stirred twice doing, to improve the molten glass

熔化与澄清质量。 Melting and refining quality.

[0036] 将熔化好的玻璃液倒入耐热不锈钢的模具内自然成型。 [0036] The molten glass was poured into a good heat-resistant stainless steel within the natural shape of the mold. 不锈钢模具预先加热至450°C,将固化后的玻璃试样移至马弗炉内。 Stainless steel molds preheated to 450 ° C, the glass samples after curing moved muffle. 马弗炉预先升温至450°C。 Muffle furnace previously heated to 450 ° C. 在马弗炉中保温半个小时候将电炉关闭,玻璃试样随炉冷却至室温。 Incubated for half an hour in a muffle furnace candidate off the electric furnace, the glass sample was cooled in the furnace to room temperature.

[0037] 热处理: [0037] Heat treatment:

[0038] 将冷却后的玻璃试样重新放入马弗炉,加热温度为450°C,保温时间为6小时。 [0038] The glass sample was re-cooled muffle furnace, the heating temperature was 450 ° C, holding time was 6 hours. 保温结束后,将马弗炉关闭,玻璃试样随炉冷却至室温。 After incubation, the muffle is closed, the glass sample was cooled in the furnace to room temperature.

[0039] 实验结果: [0039] The results:

[0040] 所得到的玻璃试样经切割、表面研磨、抛光处理后做荧光性能测试以及色坐标计算。 Glass sample [0040] The resulting calculated the cut, polished surface after the polishing process to do performance testing and fluorescent color coordinates.

[0041] 测试及计算结果见表2. [0041] and test results in Table 2.

[0042] 表2实施例1玻璃的荧光性能和色坐标计算结果 [0042] Table fluorescent properties and color coordinates of the glass of Example 1 2 The results

[0043] [0043]

[0044] 实施例2-6 [0044] Example 2-6

[0045] 在下述各实施例中,玻璃的制备方法同实施例1,所采用的不同玻璃组成的荧光性能测试及色坐标计算结果分别列于表3和表4. [0045] In the following various embodiments, the phosphor prepared with a glass performance testing and color coordinate of Example 1, the glass composition used in different embodiments of the results are shown in Table 3 and Table 4.

[0046] 表3实施例2-6的玻璃组成(mol % ) [0046] TABLE 3 Example 2-6 embodiment glass composition (mol%)

[0047] [0047]

[0048] [0048]

[0049] 表4实施例2-6玻璃的荧光性能和密度测试结果 [0049] Table fluorescent property and glass density test Example 2-6 4 embodiment results

[0050] [0050]

Claims (3)

  1. 一种白光玻璃,其特征在于,所述的玻璃包括如下组分及含量(含量以摩尔百分比计算):P2O5:10-90RO:0-50SnO2:0-10MnO:0-10其中R=Ca,Sr,Ba One kind of white glass, wherein said glass comprises the following components and content (content calculated in mole percent): P2O5: 10-90RO: 0-50SnO2: 0-10MnO: 0-10 wherein R = Ca, Sr , Ba
  2. 2.制备权利要求1所述玻璃的方法,其特征在于,所述的制备方法包括如下步骤:A)玻璃配合料的制备将原料按照权利要求1所述的组成及含量经充分混合后制得玻璃配合料;B)配合料的熔制将由步骤(a)制得的玻璃配合料置于刚玉坩埚中熔化,熔化温度为1200-1300°C,熔化时间为1-3小时,将熔化的玻璃液倒入模具内固化成型,将成型后的玻璃移到马弗炉内,在450°C左右保温半个小时,冷却后得到玻璃试样:C)热处理将由步骤(b)制得的玻璃试样重新放入马弗炉,在温度为350-550°C,保温3-10小时, 冷却后得到本发明所述的白光玻璃。 2. The method as claimed in claim 1 for preparing glass, wherein said preparation method comprises the following steps: A) Preparation of the raw material glass batch composition according to claim 1 and claim content was sufficiently mixed to obtain glass batch; B) obtained by melting glass in step (a) the batch batch was placed in a corundum crucible melting, a melt temperature of 1200-1300 ° C, the melting time of 1-3 hours, the molten glass curing was poured into the mold, after molding the glass moves muffle furnace, after about half an hour incubation at 450 ° C, cooled to obtain glass samples: C) by the heat treatment in step (b) prepared in a glass test sample in the muffle furnace, to obtain a glass of the present invention, the white light after the temperature is 350-550 ° C, incubated 10 hours, cooled.
  3. 3.如权利要求2所述的制备方法,其特征在于,其中步骤(b)中所用模具预热至450°C 左右,马弗炉预先升温至450 °C左右。 The production method as claimed in claim 2, wherein wherein step (b) in the mold preheated to about 450 ° C with a muffle furnace previously heated to about 450 ° C.
CN 201010205012 2010-06-18 2010-06-18 White light glass and preparation method thereof CN101857363A (en)

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CN104108879A (en) * 2014-07-28 2014-10-22 武汉工程大学 Preparation method of luminous glass/microcrystal glass for LED
CN105347673A (en) * 2015-11-23 2016-02-24 华东理工大学 Tin-terbium co-doped luminescent glass having excitation wavelength broadened to deep ultraviolet region

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102923947A (en) * 2012-11-06 2013-02-13 华东理工大学 Novel white light glass and preparation method thereof
CN104108879A (en) * 2014-07-28 2014-10-22 武汉工程大学 Preparation method of luminous glass/microcrystal glass for LED
CN104108879B (en) * 2014-07-28 2017-02-15 武汉工程大学 A method for preparing a light emitting diode emitting Glass / Glass Ceramics
CN105347673A (en) * 2015-11-23 2016-02-24 华东理工大学 Tin-terbium co-doped luminescent glass having excitation wavelength broadened to deep ultraviolet region

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