SPS快速烧结制备含铋玻璃及其性能研究

发布时间：2018-08-27 11:38

【摘要】：铋离子掺杂玻璃自发现具有超宽带近红外发光性能以来受到了科研人员的广泛关注,它很有可能制成超宽带光纤放大器以解决现有稀土掺杂光纤放大器增益带宽不足的问题,从而实现光纤通信的超大容量传输。目前对于铋离子掺杂玻璃的研究主要集中在提高其发光性能和探讨其发光机理等问题上,而掺铋玻璃的制备方法是影响其性能的一个重要因素之一。铋离子掺杂玻璃的制备多采用高温熔融法,这种方法存在着熔融温度高、熔融时间长等缺点,这对于制备铋离子这种易挥发离子的掺杂玻璃来说十分不利。为此,我们提出采用新型的玻璃制备工艺来制备铋离子掺杂玻璃。本文采用多孔材料结合新型的放电等离子体烧结(Spark Plasma Sintering,SPS)技术制备掺铋玻璃。多孔材料因其具有大的比表面积而具有较高的烧结活性,和普通粉体材料相比它更容易烧结。放电等离子体烧结技术具有升温速度快、烧结时间短、烧结过程中可以加压等优点。我们将多孔材料和SPS技术有机的结合在一起成功的探索出了一条低温快速制备透明石英玻璃的新方法。这一低温快速的制备方法对于铋离子掺杂玻璃的制备十分有利。本工作首先通过微孔材料zsm-5烧结制备样品的透明与不透明的转变过程研究了不导电材料在sps烧结过程中的温度分布,并采用ansys热分析软件对烧结过程中的温度分布进行了模拟。二是以zsm-5和介孔材料sba-15为原料采用sps制备了石英玻璃。通过改变zsm-5粉体的烧结参数,系统地研究了沸石分子筛zsm-5由有序结构变成无序结构的过程;通过拉曼光谱、红外光谱以及同步辐射等测试技术分析了在有序无序转变过程中zsm-5沸石分子筛结构的变化,并研究了这些结构变化对于样品透过率、发光性能以及力学性能的影响。探索了sps烧结介孔材料sba-15制备石英玻璃样品的烧结过程,并对烧结样品的性能进行了研究。三是通过等体积浸渍法制备了不同浓度铋铝共掺杂的zsm-5粉体,采用sps技术对粉体进行烧结得到铋离子掺杂zsm-5玻璃。系统地研究了铋离子和铝离子浓度对于掺铋玻璃发光性能的影响,考察了不同激发波长对于样品近红外发光性能的影响,并结合实验现象和相关实验结果对铋离子的近红外发光机理进行了探讨。四是采用不同的粉体制备工艺制备出了铋离子单掺或铋铝共掺的sba-15粉体,然后采用sps技术对粉体进行烧结得到铋离子掺杂的sba-15玻璃。系统地研究了不同粉体制备工艺对于样品颜色和发光性能的影响。本文得到的主要研究成果和结论如下:(1)利用沸石分子筛zsm-5烧结制备样品的透明与不透明的转变过程研究了不导电材料在sps烧结过程中的温度分布,研究发现样品在径向和轴向上都存在温度梯度。1325℃烧结制备的样品出现了中间透明边缘不透明的现象,说明样品存在径向的温度梯度,ansys热分析软件模拟结果表明样品中心温度比边缘温度高26℃;1315℃烧结制备的样品出现了上表面透明部分大于下表面的现象,说明样品存在轴向的温度梯度,ansys热分析软件模拟结果表明样品上表面的温度比下表面高5℃。(2)采用sps技术对微孔分子筛zsm-5和介孔材料sba-15进行烧结,实验表明两种粉体都能成功制备出透明的玻璃样品。对zsm-5粉体烧结的一系列样品的研究表明:样品的透过率随烧结温度的升高是逐渐增大的,1300℃烧结制备的样品在250~1700nm范围内的透过率小于5%,当样品的烧结温度达到1350℃以上时,样品完全透明透过率达到最大值,在近红外区(780~1700nm)的透过率在80%以上,在紫外-可见光区(250~780nm)的透过率也能达到60%以上,但在300nm处出现了一个吸收峰;样品的发光则相反,随着烧结温度的升高样品的发光强度逐渐降低;采用同步辐射x射线衍射和透射电镜的测试结果都表明即使在完全透明的样品中仍存在着少量的未完全坍塌的zsm-5,从而产生了缺陷,造成了样品的吸收和发光。对sba-15粉体烧结的样品进行研究,发现在1050℃就能够获得完全透明的样品。样品在可见紫外区的透过率均能够达到近90%,这一透过率值和传统熔融法制备的石英玻璃基本相当,要好于zsm-5烧结制备的玻璃样品,也明显好于sps烧结纳米二氧化硅和无定形二氧化硅制备的玻璃样品。(3)采用sps烧结掺铋zsm-5粉体成功制备出了掺铋玻璃,制备出的铋离子掺杂玻璃具有良好的近红外发光性能。铋离子掺杂浓度对于sps烧结制备的掺铋玻璃发光性能的影响是十分复杂的,含铝量少时,采用500和700nm的光激发都能够得到较强的近红外荧光发射,但800nm的光激发无法得到近红外发射;含铝量较多时,样品采用500、700和800nm的光激发都能够得到近红外的荧光发射,但发光强度的变化规律是不同的,采用500、700nm的光激发产生的近红外光的发光强度变化是一致的,而800nm激发产生的近红外光的发光强度变化和它们不同。铝离子对于铋离子掺杂玻璃的性能具有十分大的影响,样品的颜色会随着铝离子浓度的增加而加深;铝离子含量在一定范围内的提高会增强500、700、800nm激发产生的近红外发光的发光强度,但铝离子的含量是不同的,500、700nm在铋铝比为1:3时就达到了最大值,而800nm在铋铝比为1:9时才达到最大值。有趣的是我们研究激发波长的影响时发现采用600nm的光激发掺铋玻璃能够产生荧光半高宽为273nm、发光峰位置为1207nm的近红外发光,而且其发光强度要好于800nm激发产生的近红外光。通过对实验现象和结果的分析我们认为掺铋玻璃在~1140nm处的发光是由于bi+的3p1→3p0的能级跃迁产生的,在~1240nm处的发光来自于bi0的2d3/2→4s3/2的能级跃迁,在~1440nm处的发光可以归结为(bi2)2-的→3Π2g的能级跃迁。(4)采用不同的粉体制备工艺制备了铋离子单掺杂的sba-15粉体和铋铝共掺杂的sba-15粉体,然后采用sps技术对粉体进行烧结得到了掺铋玻璃。铋离子单掺sba-15粉体制备的掺铋玻璃在500、700和800nm的光激发下并没有表现出近红外发光性能,说明铝离子等修饰剂对于掺铋玻璃的近红外发光性能是必不可少的。采用等体积浸渍法制备的铋铝共掺杂粉体烧结后样品呈现出灰黑色,且随着浓度的增加颜色逐渐加深,采用500、700nm的光激发样品可以产生近红外光,但800nm的光激发并没有发现很明显的发射现象。采用原位合成稀释球磨制备的低浓度样品的颜色和发光性能与等体积浸渍法制备样品的颜色和性能基本一致。采用水热法合成的铋铝共掺杂粉体制备的样品在掺杂浓度为0.10mol%时,样品的颜色呈现出灰黑色,XRD表明样品中出现了铋金属,而当掺杂浓度大于0.30mol%时样品呈现出红色,且随着铋离子浓度的增加颜色逐渐加深,荧光性能测试表明红色的样品在500、700或800nm的光激发下都能够产生强的荧光发射,而灰黑色样品的发光性能很差,800nm的光激发时几乎没有荧光发射。采用不同的激发波长对0.90mol%的样品进行测试发现大部分发光峰的峰值与ZSM-5制备的样品相比都有一定程度的红移,而且荧光半高宽变得更加的均匀,大多集中在230、240nm。对于低浓度SBA-15体系掺铋样品变成灰黑色的原因我们认为可能是铋氧化物的热分解作用、SBA-15表面的硅羟基或者粉体的烧结机理等因素造成的,也可能是这些因素共同作用的结果。
[Abstract]:Bismuth ion-doped glass has attracted much attention of researchers since it was found to have ultra-wideband near-infrared luminescence properties. It is possible to make ultra-wideband fiber amplifiers to solve the problem of insufficient gain bandwidth of existing rare earth-doped fiber amplifiers, so as to realize ultra-large capacity transmission of optical fiber communications. The research of glass is mainly focused on improving its luminescent properties and discussing its luminescent mechanism. The preparation method of bismuth-doped glass is one of the important factors affecting its properties. Bismuth-doped glasses are very disadvantageous for the volatile ion-doped glasses. Therefore, we propose a new glass preparation process to prepare Bismuth-doped glasses. In this paper, the porous materials combined with a new spark plasma sintering (SPS) technology are used to prepare Bismuth-doped glasses. Porous materials have a large specific surface area. The spark plasma sintering technology has the advantages of rapid heating, short sintering time and pressure during sintering process. We have successfully combined the porous materials and SPS technology to explore a rapid preparation of transparent quartz at low temperature. A new method for preparing bismuth ion-doped glass at low temperature and high speed is proposed. The temperature distribution of non-conductive materials during SPS sintering is studied by the transparent and opaque transition process of samples prepared by sintering microporous material zsm-5. The sintering process is analyzed by using ANSYS thermal analysis software. Temperature distribution in Zsm-5 was simulated. Secondly, quartz glass was prepared from ZSM-5 and mesoporous material SBA-15 by sps. By changing the sintering parameters of ZSM-5 powder, the process of zeolite zeolite ZSM-5 from ordered structure to disordered structure was systematically studied. Raman spectroscopy, infrared spectroscopy and synchrotron radiation were used to analyze the process. The structural changes of zeolite ZSM-5 during ordered disorder transformation were studied. The effects of these structural changes on the transmittance, luminescence and mechanical properties of the samples were investigated. The sintering process of mesoporous material SBA-15 was explored and the properties of the sintered samples were studied. Bismuth-doped ZSM-5 glasses were prepared by deposition impregnation method. Bismuth-doped ZSM-5 glasses were sintered by SPS technique. The effects of Bismuth ion and Al ion concentration on the luminescent properties of Bismuth-doped glasses were studied systematically. The influence of excitation wavelength on the Near-infrared Luminescent Properties of samples was investigated. The mechanism of near infrared luminescence of bismuth ion was discussed by experimental phenomena and correlative experimental results. Fourthly, different powder preparation techniques were used to prepare bismuth ion mono-doped or bismuth-aluminum co-doped SBA-15 powders. Then bismuth ion-doped SBA-15 glass was obtained by SPS technique. The main research results and conclusions are as follows: (1) the temperature distribution of non-conductive materials during SPS sintering was studied by using the transparent and opaque transition process of the samples prepared by zeolite ZSM-5 sintering, and the temperature gradients were found in both radial and axial directions. The results of ANSYS thermal analysis software simulation show that the center temperature of the sample is 26 degrees higher than the edge temperature; the transparent part of the upper surface is larger than the lower surface of the sample sintered at 1315 degrees Celsius, indicating that the sample has a radial temperature gradient. The results of ANSYS thermal analysis software simulation show that the temperature of the upper surface of the sample is higher than that of the lower surface by 5 (?) The transmittance of the sample increases gradually with the sintering temperature. The transmittance of the sample sintered at 1300 C is less than 5% in the range of 250 ~ 1700 nm. When the sintering temperature of the sample is above 1350 C, the transmittance of the sample reaches the maximum value. The transmittance in the near infrared region (780 ~ 1700 nm) is above 80%, and in the ultraviolet - visible region (25 - 1700 nm). The transmittance of 0~780 nm can reach over 60%, but an absorption peak appears at 300 nm. On the contrary, the luminescence intensity of the samples decreases with the increase of sintering temperature. The results of synchrotron radiation X-ray diffraction and transmission electron microscopy show that there are still a small amount of unfinished samples even in completely transparent samples. The samples sintered by SBA-15 powder were found to be completely transparent at 1050 C. The transmittance of the samples in the visible-ultraviolet region reached nearly 90%, which was almost the same as that of the quartz glass prepared by traditional melting method. (3) Bismuth-doped glass was successfully prepared by using sps-sintered bismuth-doped ZSM-5 powder, and the prepared bismuth-doped glass has good near-infrared luminescence properties. The influence of Al content on the luminescent properties of bismuth-doped glasses is very complex. When Al content is small, the near-infrared fluorescence can be obtained by 500 nm and 700 nm photoexcitation, but the near-infrared fluorescence can not be obtained by 800 nm photoexcitation. When Al content is high, the samples can be excited by 500,700 and 800 nm photoexcitation to obtain near-infrared fluorescence. The luminous intensity of the near infrared light excited by 500,700 nm is the same, but the luminous intensity of the near infrared light excited by 800 nm is different from them. Increasing the concentration of Al ions in a certain range will enhance the near-infrared luminescence intensity produced by 500,700,800 nm excitation, but the content of Al ions is different. 500,700 nm reaches the maximum when the ratio of Bi to Al is 1:3, and 800 nm reaches the maximum when the ratio of Bi to Al is 1:9. When the excitation wavelength is changed, it is found that the near-infrared luminescence can be produced by using 600 nm light to excite the bismuth-doped glass with a half-width of 273 nm and a peak position of 1207 nm, and the luminescence intensity is better than that of 800 nm light. The luminescence at ~1240 nm comes from the 2d_3/2 4s_3/2 energy level transition of Bi + at 3p_1 3p_0. The luminescence at ~1440 nm can be attributed to the 3 2G energy level transition of 2 of 2 of 2 of 2 of 2 of 2 of 3 2 of 2 of 2 of 2 of 2 of 2 of Bismuth-doped glass was obtained by SPS technique. Bismuth-doped glass prepared by SBA-15 powder doped with Bismuth ion did not exhibit Near-infrared Luminescent Properties under 500,700 and 800 nm light excitation, indicating that aluminum ion modifier is essential for Near-infrared Luminescent Properties of Bismuth-doped glass. Bismuth-doped glass was prepared by isovolumetric impregnation method. The samples sintered by bismuth-aluminium co-doped powders show gray-black color, and the color gradually deepens with the increase of concentration. The samples excited by 500,700 nm light can produce near-infrared light, but there is no obvious emission at 800 nm. The color and luminescent properties of low concentration samples prepared by in-situ synthesis dilution ball milling The color and properties of the samples prepared by hydrothermal method are basically the same as those prepared by isovolumetric impregnation method. When the doping concentration is 0.10mol%, the color of the samples is gray-black. XRD shows that there is bismuth metal in the samples, but when the doping concentration is more than 0.30mol%, the samples show red, and with the separation of bismuth. The fluorescence properties of the samples with different excitation wavelengths of 0.90 mol% showed that most of the samples with different excitation wavelengths produced strong fluorescence emission. The peak value of the distribution peak has a certain red shift compared with the sample prepared by ZSM-5, and the fluorescence half-width becomes more uniform, mostly concentrated at 230,240 nm. The sintering mechanism and other factors may also be the result of these factors.
【学位授予单位】：东华大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TQ171.1

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