林江珍Lin, Jiang-Jen臺灣大學:高分子科學與工程學研究所張文馨Chang, Wen-HsinWen-HsinChang2010-05-122018-06-292010-05-122018-06-292008U0001-2306200817314400http://ntur.lib.ntu.edu.tw//handle/246246/183111利用有機黏土與鐵離子以共沈澱法製備磁性有機黏土複合材料，並探討氧化鐵粒子與有機黏土的機制及其在原油吸附上的應用。、將磁性氧化鐵粒子利用逐步插層法，插層於矽酸鹽層黏土中。鈉型蒙脫土經由一系列聚醚胺鹽插層改質（稱為有機黏土），可將層間距由12 Å最高提至91 Å。利用共沈澱法結合可在低溫下分散於水中的有機黏土及磁性氧化鐵，以製備有機黏土與磁性氧化鐵之複合材料，並探討磁性氧化鐵吸附或插層於有機黏土的機制。研究發現利用層間距最大之有機黏土D4000/MMT (91 Å)，因其較大的層間距可提供氧化鐵在黏土層間生成。由TEM觀察可知，氧化鐵粒子生成於黏土層間（層間距約47 Å）。、為了使此複合材料可作為磁性有機吸附劑，具有高的有機含量是必需的。D4000-MMT/Iron oxide複合材料由TGA測量得知，其有機含量可高達51 wt %，並可分散於甲苯中（1 wt %），進而將其應用於原油吸附。相對於複合材料的重量，最大原油吸附量可高達4倍，並維持其磁性，且氧化鐵含量僅17 wt %。鍵詞：磁性有機黏土、層狀矽酸鹽黏土、氧化鐵、原油、吸附、插層。Magnetic and organic layered composite was prepared by the co-precipitation of organoclay with Fe(II)/Fe(Ⅲ) salts. Interaction mechanism of iron oxide particles into organoclay interlayer and their application for crude oil adsorption are studied. art Ⅰ: The iron oxide particles were intercalated into the layered silicate clay by stepwise intercalation. The sodium montmorillonite (Na+–MMT) was modified by a series of poly(oxyalkylene)-amine salts to yield a spatially-expanded silicates (named as Organoclay) from the original 12 Å up to 91 Å. Combining the low-temperature-dispersible Organoclay with the iron-oxide particles ultimately produced a series of organoclay/iron oxide composite by the co-precipitation method. Two different mechanisms of adsorption and intercalation were found. The use of D4000 intercalated MMT at high d spacing (91 Å) allowed the incorporation of iron-oxide in the organoclay interlayer. As a result, the composite of Fe3O4/D4000/clay at 47 Å d spacing were obtained and observed the iron-oxide particles existed in the clay gallery by TEM.art Ⅱ: In order to prepare a magnetic composite with functions for absorbing organics, high organic content in the clay layers is prepared. The TGA data of D4000-MMT/iron oxide composite showed the organic fraction up to 51 wt % and consequently dispersible in toluene (1 wt %). When applied for oil adsorption, the result of adsorption capacity at 4-fold of crude oil weight absorbed by the composites (by weight) was achieved. Due to the presence of iron-oxide particles (ca. 17 wt %), the oil-adsorbed Organoclay still retained the magnetic property and the compounds were movable by an applied magnetic field.eywords: magnetic organoclay, layered silicate, iron oxide, crude oil, adsorption, intercalation.Contents試委員會審定書 icknowledgements ii要 iiibstract ivhapter 1 Introduction 1.1 Organically Modified Layered Silicate (OLS) 1.2 Synthesis of Magnetite 3.3 The History of the Layered Silicate/Iron Oxide Composites 5.3.1 Preparation of the Layered Silicate/Iron Oxide Composites 5.3.2 Application of Magnetic Particles and Composites 7hapter 2 Experimental 9.1 Materials 9.1.1 Iron (II) Chloride Tetrahydrate (FeCl2 • 4H2O) 9.1.2 Iron (Ⅲ) Chloride Hexahydrate (FeCl3 • 6H2O) 9.1.3 Concentrated Ammonium Hydroxide (NH4OH) 9.1.4 Layered Silicates 9.1.5 Jeffamine® Poly(oxyalkylene)amines 10.2 Analytic Instruments 11.2.1 X-ray Diffractometry (XRD) 11.2.2 Thermal Gravimetric Analyzer (TGA) 12.2.3 Transmission Electron Microscopy (TEM) 12.3 Experimental Procedures 12.3.1 Intercalation of Montmorillonite by Jeffamine®amines 12.3.2 Synthesis of Pure Iron Oxide 13.3.3 Preparation of the Organoclay/Iron Oxide (Magnetite, Fe3O4) Composites 13.3.4 Mixtures of Iron Ion Added Stepwise to ED2001-MMT Dispersion 14.3.5 Oil Adsorption Application of Organoclay/Iron oxide Composites 17hapter 3 Results and Discussion 18.1 Preparation and Characterization of Poly(oxyalkylene)amines Intercalated Montmorillonite 18.2 Preparation of Organoclay/Iron Oxide Composites by Using the Property of Low Critical Dispersion Temperature 19.3 Effect of Acidification on Organic Fraction of D2000-MMT/Iron Oxide Composites 20.4 Preparation of Magnetic High-Organic-Fraction Composites by Using D4000-MMT with Spatially-Expanded Basal Spacing 23.5 Analysis of XRD Diffraction Patterns and the Crowding-Out Effect of Iron Ion on Organoclay Composites, including D2000-MMT/Iron Oxide and ED2001-MMT/Iron Oxide 24.6 The Morphologies of ED2001-MMT/Iron Oxide and D2000-MMT/Iron Oxide by Transmission Electron Microscopy 27.7 Unique Performances of D4000-MMT/Iron Oxide Composites 30.8 Dispersability and Oil Adsorption Capacity of D4000-MMT and Its Composites 35hapter 4 Conclusion 37eferences and Notes: 39ist of Tablesable 1.1 Basal Spacing and Properties of Na+–MMT Intercalated by POP– and POE–Diamines13 2able 1.2 Basal Spacing, Composition, and Solvophilicity of MMT Intercalated by Poly(oxyalkylene) Amines15 3able 1.3 The Iron Oxides16 4able 3.1 Basal Spacing and Properties of Na+－MMT Intercalated by POP－and POE－Amines 18able 3.2 Properties of D2000-MMT/Iron Oxide Composites Prepared by Method A and Method B 22able 3.3 Organic Fractions of D2000-MMT/Iron Oxide Composites Prepared by Method B and Method C 22able 3.4 Properties of D4000-MMT/Iron Oxide Composites 24able 3.5 Properties of ED2001-MMT/Iron Oxide Composites 25able 3.6 The Maximum Adsorption Capacity of Crude Oil on Organoclay and Organoclay/Iron Oxide Composites 36ist of Figuresigure 1.1 XRD Patterns of the Samples Z-Na+ (a), Z-Na+/Mag (b) and Z-Na+/CoFe (c) Including Insets Showing the Characteristic Reflection at 35.58 Due to the Presence of Magnetite and Co Ferrite Particles in the Corresponding Magnetic Composites 32 6igure 1.2 TEM Micrographs and Particle Size Distributions (% in number of particles) of Fe-Mont2 Composite (Left) and Fe-Lap2 Composite (Right) 34 7igure 2.1 Chemical Structures of Jeffamine® Poly(oxyalkylene)amines. 11igure 3.1 XRD Patterns of the Magnetite Prepared from the Conditions of (a) Room Temperature and (b) Low Temperature 20igure 3.2 X-ray Diffraction Patterns of (a) D2000-MMT/Iron Oxide and (b) ED2001-MMT/Iron Oxide Composites with a Weight Ratio of 83/17. Insets Show the Peaks at the Range of 2–10° 26igure 3.3 The Variation of d Spacing when Iron Ion Mixtures Added Stepwise to ED2001-MMT Dispersion 27igure 3.4 TEM Micrographs of (a) ED2001-MMT/Iron oxide (w/w = 50/50) and (b) D2000-MMT/Iron Oxide (w/w = 50/50) Composites. Arrow A: clay/organoclay; Arrow B: iron oxide particles 28igure 3.5 TEM Micrographs of (a) ED2001-MMT/Iron Oxide (w/w = 50/50) and (b) D2000-MMT/Iron oxide (w/w = 50/50) Composites 29igure 3.6 X-ray Diffraction Patterns of D4000-MMT/Iron Oxide Composites with a Weight Ratio: (a) 50/50, (b) 71/29, and (c) 83/17 31igure 3.7 TEM Micrographs of (a) D4000-MMT/Iron Oxide Composite (w/w = 83/17) (b) Magnified at 2.5 times 32igure 3.8 Photographs of 1 wt % Toluene Dispersions of D4000-MMT/Iron Oxide Composites with Weight Ratio: (a) 50/50, (b) 71/29, and (c) 83/17 35igure 3.9 Photographs of 4-fold the Weight of Crude Oil Adsorption of D4000-MMT/Iron Oxide Composites (w/w = 83/17). Place the Magnet Bar Next to the Complex (a) in the Begin and (b) in 15 min 36application/pdf1450067 bytesapplication/pdfen-US磁性有機黏土層狀矽酸鹽黏土氧化鐵原油吸附插層magnetic organoclaylayered silicateiron oxidecrude oiladsorptionintercalationthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/183111/1/ntu-97-R95549008-1.pdf