Composition-structure-property effects of antimony in soda-lime-silica glasses
Composition-structure-property effects of antimony in soda-lime-silica glasses
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DOI：
10.1016/j.jnoncrysol.2020.120184
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发表时间：
2020-07
影响因子：
3.5
通讯作者：
T. Chen;P. Rautiyal;S. Vaishnav;Gaurav Gupta;H. Schlegl;R. J. Dawson;A. Evans;Saeed Kamali;Jacqueline A. Johnson;Charles E. Johnson;Paul A. Bingham
中科院分区：
文献类型：
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作者：
T. Chen;P. Rautiyal;S. Vaishnav;Gaurav Gupta;H. Schlegl;R. J. Dawson;A. Evans;Saeed Kamali;Jacqueline A. Johnson;Charles E. Johnson;Paul A. Bingham
采用0 ~ 10 mol% sb2o3熔制浮法玻璃型sio2 - na20 - cao玻璃，并对其组成、结构、热学和光学性能进行了表征。所有玻璃均呈x射线非晶态，随着sb2o3含量的增加，玻璃化转变温度（Tg）和膨胀软化点（Td）逐渐降低，尽管al2o3含量因坩埚腐蚀而增加。121Sb Mössbauer光谱证实Sb主要以Sb3+（Sb3+/ΣSb ~ 0.9）的形式结合，拉曼光谱表明Sb显著降低了(Si, Al)-O的平均Qnspeciation。两种方法都证实了Sb3+离子在三角锥体[:SbO3]多面体中被掺入。XRF和拉曼光谱证实，so3含量随sb2o3含量的增加而降低。TGA分析表明，随着sb2o3含量的增加，材料的质量增加从700℃开始，在1175℃达到最大值，然后在1175℃以上出现质量损失，符合氧化（Sb3+→Sb5+）→还原（Sb5+→Sb3+）的规律。在测量过程中，TGA样品已达到或接近Sb氧化还原平衡。光学吸收光谱（UV- vis - nir）显示，随着sb2o3含量的增加，紫外吸收边发生红移，这与Sb3+和Sb5+s→p跃迁的远紫外吸收带强度增加相一致。紫外-可见-近红外荧光光谱显示出以~25,000 cm−1为中心的宽发光带，这是由于Sb3+的3p1→1s1跃迁，从~40,000 cm−1的1s1→3p1吸收处Stokes位移了~15,000 cm−1。当Sb2O3含量为0.5 mol%时，发光强度最大，当Sb2O3含量较高时，发光强度随浓度猝灭而降低。因此，在浮法型钠石灰硅玻璃中添加sb2o3可以降低熔融能量和/或新的太阳能应用。
Float glass-type SiO2-Na2O-CaO glasses with 0 – 10 mol% Sb2O3were melted and their compositional, structural, thermal and optical properties characterised. All glasses were X-ray amorphous and increasing Sb2O3content progressively decreased glass transition temperature (Tg) and dilatometric softening point (Td), despite increases in Al2O3content from greater crucible corrosion.121Sb Mössbauer spectroscopy confirmed that Sb was predominantly incorporated as Sb3+(Sb3+/ΣSb ~ 0.9) and Raman spectroscopy showed that Sb substantially decreased average (Si, Al)-O Qnspeciation. Both techniques confirmed that Sb3+ions were incorporated in trigonal pyramidal [:SbO3] polyhedra. XRF and Raman spectroscopies confirmed that SO3content decreased with increasing Sb2O3content. TGA analysis showed, as a linear function of Sb2O3content, mass gain commencing at 700°C, reaching a maximum at 1175°C, then mass loss above 1175°C, consistent with oxidation (Sb3+→ Sb5+) then reduction (Sb5+→ Sb3+). The TGA samples were shown to have attained or approached Sb redox equilibrium during measurement. Optical absorption spectroscopy (UV-Vis-nIR) showed red-shifts of the UV absorption edge with increasing Sb2O3content, consistent with increasing intensity of far-UV absorption bands from Sb3+and Sb5+s→p transitions. UV-Vis-nIR fluorescence spectroscopy evidenced a broad luminescence band centred at ~25,000 cm−1, attributed to the3P1→1S0transition of Sb3+, which is Stokes shifted by ~15,000 cm−1from the1S0→3P1absorption at ~40,000 cm−1. The most intense emission occurred at 0.5 mol% Sb2O3, with concentration quenching reducing luminescence intensities at higher Sb2O3contents. Additions of Sb2O3to float-type soda-lime-silica glasses could thus enable lower melting energies and/or new solar energy applications.