摘要
凹凸棒黏土(APT)是一种层链状含水富镁铝硅酸盐黏土矿物，特殊的棒晶结构使其具有吸附和胶体载体等功能。因此，被广泛的应用于石油、化工、建材、医药、农业和环保等领域。然而，天然APT由于范德华力和氢键作用，凹凸棒石棒晶通常以聚集体或棒晶束的形式存在， APT没有充分发挥自身的胶体性能。因此，如何解离APT的棒晶束，提高其附加值成为目前APT研究的热点之一。本论文以提高APT的黏度，扩大其在复合材料中的应用为目的，通过高压均质处理方法对APT进行盐处理和有机改性，研究了不同改性剂及改性条件对APT黏度的影响，同时将改性的APT应用于聚乙烯醇复合膜的制备，其主要研究内容如下：
1.采用不同浓度的乙酸镁对APT进行改性处理，考察了悬浮液浓度、pH值、温度和搅拌时间以及放置时间等因素对APT在蒸馏水和饱和氯化钠水溶液中黏度的影响，并通过FTIR、XRD、SEM、BET、Zeta电位、XRF等手段对其进行表征和分析。结果表明，在乙酸镁浓度10%、悬浮液浓度7.5%、pH=8、温度20℃、搅拌时间14h和放置时间24h的条件下，改性APT有最高的黏度。与APT原土相比，改性后其黏度在蒸馏水和饱和氯化钠水溶液中分别提高了63.4%和31.6%。
2.采用不同浓度的焦磷酸钠对APT进行改性处理，考察了焦磷酸钠浓度及高压均质压力对APT黏度的影响，同时采用FTIR、XRD、SEM、BET、Zeta电位、XRF等手段对其进行表征和分析。研究结果表明，焦磷酸钠和高压均质过程可明显影响改性APT的理化性能。在焦磷酸钠质量百分浓度0.5%，均质压力20MPa的条件下，改性APT有最高的黏度，与未高压均质相比，均质过程使APT的黏度增加了38.0%。
3.在APT焦磷酸钠改性的基础上，采用高压均质和不同类型表面活性剂对其进行有机化改性，考察了表面活性剂种类和浓度对APT黏度的影响。结果表明，高压均质过程、表面活性剂种类和浓度对APT黏度有显著影响。在十八烷基三甲基溴化铵质量百分浓度0.5%和均质压力20MPa的条件下，改性APT有最高黏度。与质量百分浓度0.5%焦磷酸钠改性、未经过高压均质处理的APT相比，经十八烷基三甲基溴化铵进一步改性黏度提高了95.5%。
4.采用溶液－流延成膜法，将改性的APT与聚乙烯醇(PVA)复合制备PVA/APT纳米复合膜，考察了APT质量百分浓度、均质处理APT和改性APT种类对复合膜力学性能和耐水性能的影响。结果表明，相比于纯PVA膜，当添加20MPa均质处理APT量为3%时，复合膜具有最优的性能，断裂伸长率和拉伸强度分别提高了126.01%和69.26%，吸水率降低了31.20%。不同表面活性剂种类改性APT对纳米复合膜性能的影响顺序为阳离子型>阴离子型>非离子型。相比于纯PVA膜，添加经过20MPa高压均质十八烷基三甲基溴化铵改性的APT所制备的复合膜断裂伸长率和拉伸强度分别增加了178.95%和156.09%，吸水率降低了56.01%。
Attapulgite clay (APT) is a hydrous layer-ribbon Al–Mg silicate mineral withspecial nanometer fibrous crystal structure, its unique crystal structure give it hassome functions such as adsorption and colloid carrier, etc. So it is widely used inpetroleum, chemical industry, building materials, medicine, agriculture andenvironmental protection, etc. However, the fibrous crystals of natural APT prefer toexist as aggregates or crystal bundles because of van der Waals' force and thehydrogen bonding interaction, APT does not give full play to its colloidal properties.So it becomes one of the study hotspots of APT that how to disaggregate APT crystalbundles and improve its added value. In this paper, in order to improve the viscosityof APT and enlarge its application in the composite materials for the purpose,through the methed of salt treatment, organic modification and high pressurehomogeneous to deal with APT, discussed different modifier and modificationconditions effect on the viscosity of APT, at the same time, applied the modifiedAPT to prepare PVA composite flims, The main research results are as follows:
1. APT was modified by different concentration of magnesium acetate solution,the effects on the viscosity of the APT in distilled water and saturated sodiumchloride solution were investigated, such as the suspension concentration, pH value,reaction temperature, stirring time and ageing time, and the modified microstructuresof the APT were characterized and analysed by FTIR, XRD, SEM, BET, Zeta andXRF. Results obtained from this study show that the APT under optimal modifiedconditions with magnesium acetate concentration of10%, suspension concentrationof7.5%, pH value of8, reaction temperature of20℃, stirring time of14h and ageingtime of24h exhibit the highest viscosity. Compared with natural APT, the viscosityof modified APT in distilled wate and saturated sodium chloride solution increasedby63.4%and31.6%respectively.
2. APT was modified by different concentration of sodium pyrophosphate, theeffects of sodium pyrophosphate concentration and high-pressure homogeneouspressure on the viscosity of the APT were investigated, the modified microstructuresof the attapulgite clay were characterized by FTIR, XRD, SEM, BET, Zeta and XRF.Results obtained from this study show that sodium pyrophosphate and high pressurehomogeneous process can significantly modified the physical and chemicalproperties of APT. The APT under optimal modified conditions with sodiumpyrophosphate concentration of0.5%and high-pressure homogeneous pressure at 20MPa exhibit the highest viscosity. Compared with the APT of not through highpressure homogeneous, high pressure homogeneous process maked the viscosity ofAPT increase by38.0%.
3. On the basis of the APT modification by sodium pyrophosphate, it was dealtwith through high pressure homogeneous method and organic modified by differenttypes of surfactant, the effects of surfactant types and concentration on the viscosityof APT were investigated. Results obtained from this study show that high pressurehomogeneous process, the types and concentration of the surfactant had a significanteffect on the viscosity of APT. The APT under optimal modified conditions withOTAB concentration of0.5%and high-pressure homogeneous pressure of20MPaexhibit the highest viscosity. Compared with the APT of not througu high pressurehomogeneous and modified by0.5%sodium pyrophosphate, the viscosity of APTmodified by OTAB increased by95.5%.
4. Appliedd the modified APT to PVA film to prepare PVA/APT nanocompositefilms by film-casting method, investigated the effects of the concentration of APT,the APT at high pressure homogeneous and the types of modified APT on themechanical property and water resistance of the PVA/APT nanocomposite films.Results obtained from this study show that compared with the pure PVA film, whenthe concentrations of APT at20MPa high pressure homogeneous was3%,nanocomposite films had optimal property, elongation at break and tensile strengthincreased by126.01%and69.26%respectively, water absorption reduced by31.20%.The order of different types surfactants modified APT effect on the property ofnanocomposite films was cationicsurfactant> anionicsurfactant> nonionic surfactant.Compared with the pure PVA film, add the APT modified by OTAB and at20MPahigh pressure homogeneous, the elongation at break and tensile strength ofnanocomposite films increased by178.95%and156.09%respectively, waterabsorption reduced by56.01%.
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