水羟硅钠石的制备与表征

水羟硅钠石(kenyaite)以其良好的离子交换性、吸附性和热稳定性而被广泛应用于催化和吸附等领域。本文以高纯度且价格低廉的沉淀白炭黑为硅源、以碳酸钠(分析纯)和氢氧化钠(分析纯)为碱源,水热法制备了高纯度的单一晶相的水羟硅钠石,考察了反应时间和反应温度对制备的影响。利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、红外光谱仪(IR)、X射线荧光光谱仪(XRF)和同步热分析仪等对样品进行了测试表征。实验结果表明,温度是影响kenyaite制备的主要因素,单一晶相水羟硅钠石的最佳晶化合成条件为晶化温度为180℃,晶化时间为24h,所制备的水羟硅钠石形态为玫瑰花形且其热稳定性在350℃以下。     

Synthesis of Kenyaite, Magadiite and Octosilicate Using Poly(ethylene glycol) as a Template

Three types of layered silicates, namely octosilicate, magadiite and kenyaite, were synthesized using poly(ethylene glycol) (PEG). The influence of reaction parameters, including alkali source, silica source, PEG molecular weight, reaction time and temperature, on the formation of these three phases was investigated. The results indicate that magadiite is preferred when (i) using NaOH as the alkali source and at a lower temperature (150°C), with fumed silica, tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), Ludox-AS 40 or colloidal sol acting as the silica source in the presence of PEG 200; (ii) using fumed silica as the silica source and PEG 300 as the template at 150°C; (iii) at a higher temperature (180°C), using PEG 200 as template and TEOS as the silica source; and (iv) at 180°C with a combination of PEG 300 and fumed silica. Compared to magadiite, kenyaite was favored at a higher temperature (180°C) with PEG 200 and NaOH, KOH or RbOH, while using fumed silica, silica gel, or colloidal sol as silica source; or at the lower temperature (150°C) using NaOH as alkali source, PEG 200 as template, and silica gel or silicic acid as the silica source. Octosilicate was obtained at 90°C with the combination of NaOH, PEG 200 and fumed silica.     

麦羟基硅钠石的可控合成及其阳离子交换性能研究

目前,开发绿色高效的重金属吸附材料受到人们的广泛关注。以硅藻土为原料,经水热法选择性地制备了2类硅酸盐材料即麦羟基硅钠石和方沸石。吸附测试结果表明,麦羟基硅钠石层间的钠离子能够与锂离子、镁离子、锌离子、钴离子、镍离子、铜离子等进行阳离子交换且能保持层状母体框架的稳定性。以钴离子、镍离子为例深入研究其吸附动力学和吸附机制发现,钴离子和镍离子的嵌入分别将麦羟基硅钠石的层间距由本征的1.56 nm减小到0.24、0.23 nm;室温下,对钴离子、镍离子的最大吸附量分别可达45、39 mg/g,均符合Langmuir单层吸附模型;钠离子的置换量大约是吸附的钴离子、镍离子量的两倍,证实层间离子交换主导吸附化学过程。因此,麦羟基硅钠石材料在多金属硅酸盐功能材料的合成以及环境吸附净化领域具有较大的应用潜力。     

Sodic and Acidic Crystalline Lamellar Magadiite Adsorbents for the Removal of Methylene Blue from Aqueous Solutions: Kinetic and Equilibrium Studies

The present study reports the feasibility of two synthetic crystalline lamellar nano-silicates, sodic magadiite (Na-mag) and its converted acidic form (H-mag), as alternative adsorbents for the removal of the dye methylene blue (MB) from aqueous solutions. The ability of these adsorbents for removing the dye was explored through the batch adsorption procedure. Effects such as the pH and the adsorbent dosage on the adsorption capacities were explored. Four kinetic models were applied, the adsorption being best fitted to a fractionary-order kinetic model. The kinetic data were also adjusted to an intra-particle diffusion model to give two linear regions, indicating that the kinetics of adsorption follows multiple sorption rates. The equilibrium data were fitted to Langmuir, Freundlich, Sips, and Redlich-Peterson isotherm models. The maxima adsorption capacities for MB of Na-mag and H-mag were 331 and 173 mg g^?1, respectively.     

麦羟硅钠石/聚合物纳米复合材料研究进展

麦羟硅钠石（magadiite）是一种新型的层状纳米硅酸盐材料，由于其具有制备工艺简单、比表面积大、阳离子交换性能高、吸附性能强、层间膨胀性能好等优点，成为纳米材料提升聚合物性能最具有发展潜力的材料之一。本文主要综述了麦羟硅钠石/聚合物纳米复合材料的常用制备方法及其优缺点，包括聚合物插层法、单体原位插层聚合法、锚固插层聚合法。浅谈了国内外利用3种方法制备的基于聚苯乙烯、聚丙烯、环氧树脂、尼龙6、聚己内酯和聚甲基丙烯酸甲酯等多种聚合物的麦羟硅钠石/聚合物纳米复合材料，对在纳米复合材料结构中出现界面不相容、麦羟硅钠石分布不均匀的问题提出了解决方法，并阐述了麦羟硅钠石对纳米复合材料结构和性能的影响，最后展望了麦羟硅钠石/聚合物纳米复合材料的发展前景。     

伊利石硅渣蒸汽辅助合成麦羟硅钠石及其对Cu2+的吸附研究

以伊利石硅渣为原料,采用蒸汽辅助转化法(SAC)合成了高产率、高结晶度的纯相麦羟硅钠石(Magadiite)。采用X射线衍射仪(XRD)和扫描电子显微镜(SEM)考察了钠硅比(n(Na₂O)/n(SiO₂))、晶化温度和晶化时间对合成样品结构及形貌的影响。结果表明,该体系的初步优化合成条件为钠硅比0.15,晶化温度170 ℃,晶化时间16 h,样品形貌为玫瑰花形(尺寸约12 μm)。对合成的Magadiite进行Cu²⁺吸附性能测试,探究了吸附剂用量、pH值、吸附时间和Cu²⁺初始浓度对吸附效果的影响。在吸附剂用量为2 g/L,pH值为5,吸附时间为30 min时,Magadiite对Cu²⁺的最大吸附量为25.99 mg/g。     

Mechanical reinforcement in magadiite/styrene‐butadiene rubber composites

This work investigates mechanical properties of styrene‐butadiene rubber (SBR) composites incorporating magadiite (MGD), a synthetic layered silicate (Na₂Si₁₄O₂₉·9H₂O) with surface chemistry similar to precipitated silica used in tire tread formulations. Treatment with cetyltrimethylammonium (CTA⁺) expands the MGD layers and makes the interlayer face surfaces accessible to sulfur‐functional silane TESPT (Si69) and SBR, primarily during batch mixing. DMA and tensile testing of cured CMGD/SBR composites show that CTA‐treated MGD (CMGD) provides substantially higher levels of mechanical reinforcement than equivalent amounts of silica. However, CMGD/SBR composites exhibit larger loss tangent values above T_g, probably due to lower SBR‐SBR crosslink density resulting from interlayer trapping of sulfur released by Si69 during vulcanization. DMA and tensile testing also demonstrate Si69′s critical role in forming MGD‐SBR graft sites essential to mechanical reinforcement. Replacing silica with CMGD reduces composite weight without sacrificing tensile modulus, suggesting that use of CMGD in tire rubber formulations could improve vehicle energy efficiency. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44763.     

Magadiite/styrene‐butadiene rubber composites for tire tread applications: Effects of varying layer spacing and alternate inorganic fillers

Magadiite (MGD), a synthetic layered silicate (Na₂Si₁₄O₂₉·9H₂O) with surface chemistry similar to precipitated silica, was cation‐exchanged with three different organic cations to explore the effect of varying MGD layer spacing on the mechanical properties of MGD‐based styrene‐butadiene rubber (SBR) composites. This work also compares the mechanical properties of MGD/SBR composites with those formulated with montmorillonite (MMT) and precipitated silica. Dodecylpyridinium (DP⁺) produces greater expansion of MGD layers than cetyltrimethylammonium (CTA⁺); the resulting DP‐MGD/SBR composites have greater yield strain, toughness, and rubbery storage modulus than comparable CTA‐MGD/SBR composites. MGD treated with hexadecylammonium (HDA⁺) has the greatest layer spacing, but the HDA‐MGD layers collapse upon melt‐blending with SBR. CTA‐treated MMT (CMMT) exfoliates in aqueous suspension, but the platelets re‐stack upon drying and during melt‐blending with SBR. The presence of exfoliated and/or disordered platelet stacks in CMMT/SBR probably accounts for its higher tensile and dynamic moduli compared to MGD‐ and silica‐based SBR composites. Dynamic mechanical properties are used to predict tire tread performance metrics for these composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44764.     

Recrystallization of magadiite into offretite in the presence of tetramethylammonium cations

BACKGROUND: This study was aimed at investigating the recrystallization of magadiite into offretite in the presence of tetramethylammonium cations (TMA). The offretite was characterized by X‐ray powder diffraction, scanning electron microscopy, infrared spectroscopy, N₂ adsorption analysis, thermogravimetry and differential thermal analysis. The influence of key reaction parameters on the formation of offretite, including reaction time, TMA cations, potassium cations and the SiO₂/Al₂O₃ reactant ratio, were examined. RESULTS: Well‐crystallized offretite, which was composed of agglomerated samples, was prepared from a dispersion with the molar composition: 3.6 K₂O: 3.6 Na₂O: 1.0 Al₂O₃: 6.5 SiO₂: 320 H₂O: 1.5 TMA⁺ by heating at 140 °C for 3 days. The structure of offretite collapsed when the temperature rose above 1000 °C. The organic template was removed when the sample was calcined at 550 °C for 10 h. CONCLUSION: Magadiite has been used to synthesize offretite with a high purity and well crystallized in the presence of tetramethylammonium cations. The results of the present study indicate the feasibility of a synthetic route to offretite through recrystallization of magadiite in the presence of tetramethylammonium cations. Copyright © 2009 Society of Chemical Industry     

The role of interlayer grafting on the mechanical properties of magadiite/styrene‐butadiene rubber composites

This work examines the mechanisms by which magadiite (MGD), a synthetic layered silicate, acts as an active filler to provide high levels of mechanical reinforcement in styrene‐butadiene rubber (SBR) composites. Cetyltrimethylammonium (CTA⁺) expands the MGD layer spacing and promotes intercalation of SBR and silane coupling agent (Si69); the resulting CMGD/SBR composites have greater tensile moduli than comparable silica/SBR composites. CMGD was reacted in solution with Si69 (or MPTES) to prepare “pre‐grafted” MGD with varying levels of interlayer silane functionalization (SMGD). If the silane graft density is relatively low, the resulting SMGD/SBR composite has mechanical properties comparable to CMGD composites prepared with Si69 added during batch mixing. However, SMGD with high silane graft density does not permit SBR intercalation and produces composites with inferior mechanical properties, demonstrating the necessity of silane‐mediated interlayer grafting. Omitting Si69 from the formulation dramatically reduces the level of mechanical reinforcement as measured by DMA and tensile testing. Adding extra bulk sulfur (to replace sulfur omitted with Si69) does not produce composites with mechanical properties comparable to CMGD/SBR or SMGD/SBR prepared with Si69. This work demonstrates that silane‐mediated SBR‐MGD grafts within the MGD interlayer space are essential for achieving high levels of mechanical reinforcement in MGD/SBR composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45025.