锡氟磷酸盐玻璃—聚合物杂化材料的流变行为研究

发布时间：2018-05-20 05:48

本文选题：锡氟磷酸盐玻璃 + 杂化材料　；参考：《湘潭大学》2015年硕士论文

【摘要】：锡氟磷酸盐玻璃(TFP)因具有较低的玻璃化转变温度(Tg)及优异的加工性能而引起了人们的广泛兴趣,近年来关于锡氟磷酸盐玻璃(TFP)的研究热点集中在其等温、非等温结晶动力学、结晶态、相容性、熔融行为等,关于其流变行为的研究较少。本论文从探究TFP-聚合物杂化材料流变行为出发,对比三种不同填料TFP、碳酸钙(CaCO3)、硅灰石(CaSiO3)对PA6流变行为影响的异同;进一步探究TFP加入对低流动树脂PC流变行为的影响,了解其构-效关系;最后将TFP引入至GF-PA6复合材料中,观察TFP对该材料的流变行为的影响。不同填料对PA6流变行为研究结果显示,少量TFP能使材料的模量和复数粘度(η*)降低,并且TFP填充体系出现较为显著的剪切变稀。CaSiO3、CaCO3填充体系则表现不同的流变行为,在整个测试范围内材料的模量及η*均增加,CaCO3体系表现轻微的剪切变稀。CaSiO3、CaCO3呈无规则状分布在基体中,TFP以细小玻璃微珠嵌在基体中。CaSiO3、CaCO3和基体PA6并不存在分子间化学相互作用,而TFP和PA6存在一定氢键相互作用。TFP降低PA6的熔点(Tm)和结晶温度(Tc),而CaSiO3、CaCO3填充体系的Tm和Tc基本不变。TFP-PC杂化材料研究结果表明,在低频区TFP-PC材料的储能模量(G′)表现增大趋势,但当TFP低于30%时杂化材料的损耗模量(G″)都低于纯PC;TFP的加入使PC的η*下降,并且出现剪切变稀行为,当TFP含量超过30%时η*剧增,同时剪切变稀更加明显,表明TFP很大程度上改善了PC的成型加工性能。TFP以细小颗粒均匀分散在PC基体中,且二者有明显的过渡相,界面层模糊;在成型加工过程中TFP发生形变,当TFP含量较高时出现团聚现象。因此推测TFP与PC基体间存在相互作用,红外谱图表明这种相互作用可能是氢键作用;DSC测试发现加入TFP降低了PC的Tg,TFP在PC基体中表现出一定的塑化作用。通过研究TFP-GF-PA6三元复合材料流变行为,得出以下结论:在低频区,TFP加入使得GF-PA6复合体系的η*、G′以及G″均出现增加,高频区则减小,材料各流变参数均表现较强的频率依赖性。材料出现一定程度的剪切变稀,加工性能得到较为显著的改善。含量较少的TFP在体系中以细小玻璃微珠分布,当TFP含量达到50%时发生团聚现象。在基体中引入GF并未影响PA6和TFP间的氢键作用;TFP降低了复合体系的Tm和Tc,同时结晶速率也有一定的下降。
[Abstract]:Tin fluorophosphate glass (TFP) has attracted wide interest due to its low glass transition temperature (TG) and excellent processability. In recent years, the research focus on TFPs has focused on its isothermal and non-isothermal crystallization kinetics. There are few studies on the rheological behavior of crystalline state, compatibility, melting behavior and so on. Based on the study of rheological behavior of TFP-polymer hybrid materials, the effects of three different fillers, calcium carbonate, calcium carbonate and wollastonite on the rheological behavior of PA6 were compared, and the effects of TFP addition on the rheological behavior of low flow resin PC were further investigated. Finally, TFP was introduced into the GF-PA6 composite to observe the effect of TFP on the rheological behavior of the composite. The experimental results of rheological behavior of PA6 with different fillers show that a small amount of TFP can decrease the modulus and complex viscosity (畏 _ (n) of the material, and that the shearing thinning of TFP filled system. CaSiO _ 3 / CaCO _ 3 filled system shows different rheological behavior. In the whole testing range, the modulus and 畏 * of Caco _ 3 system showed slight shear thinning. CaSiO _ 3 / CaCO _ 3 distributed irregularly in the matrix. There was no intermolecular chemical interaction between the matrix and the matrix PA6, which was embedded in the matrix with fine glass beads. However, there exists a certain hydrogen bond interaction between TFP and PA6. TFP decreases the melting point (Tm) and crystallization temperature (Tc) of PA6, while the Tm and TC of CaSiO3 / CaCO3 filled system are almost unchanged. The results show that the storage modulus of TFP-PC material increases in low frequency region. However, the loss modulus (G ") of the hybrid material is lower than that of pure PC-TFP when TFP is lower than 30%. The 畏 * of PC decreases and the shear thinning behavior occurs. When the content of TFP exceeds 30%, 畏 * increases dramatically, and the shear thinning becomes more obvious. The results show that TFP greatly improves the processing performance of PC. TFP is dispersed uniformly in the PC matrix with fine particles, and the interfacial layer is blurred and the TFP is deformed during the molding process. When the content of TFP is high, the agglomeration occurs. Therefore, the interaction between TFP and PC matrix was speculated, and the IR spectra showed that the interaction was probably due to hydrogen bonding. It was found that the addition of TFP reduced the plasticization of TFP in PC matrix to a certain extent. By studying the rheological behavior of TFP-GF-PA6 ternary composites, the following conclusions can be drawn: the addition of TFP-GF-PA6 in low frequency region can increase the 畏, G 'and G "of GF-PA6 composite system, but decrease in the high frequency region. The rheological parameters of the composites show a strong frequency dependence. The material is shearing thinning to a certain extent, and the processing property is obviously improved. The TFP with less content was distributed as fine glass beads in the system, and agglomeration occurred when the content of TFP reached 50%. The addition of GF into the matrix did not affect the hydrogen bond interaction between PA6 and TFP. The Tm and Tc of the composite system were decreased, and the crystallization rate was also decreased to a certain extent.
【学位授予单位】：湘潭大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB332

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