Synthesis and Characterization of PE-g-MA／MgAI-LDH Exfoliation Nanocomposite via Solution Intercalation

An organo‐modified MgAl‐layered double hydroxide (OMgAl‐LDH) was successfully exfoliated in the xylene solution of polyethylene‐grafted‐maleic anhydride (PE‐g‐MA) under re‐fluxing condition. A PE‐g‐MA/MgAl‐LDH exfoliation nanocomposite was formed after the precipitation of PE‐g‐MA from the dispersion system. The structure and thermal property of the PE‐g‐MA/MgAl‐LDH exfoliation nanocomposite were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetry analysis (TGA). The disappearance of d₀₀₁ XRD peak of OMgAl‐LDH at 20 = 3.2° suggests that the MgAl hydroxide sheets are exfoliated in the nanocomposite. The TEM image shows that the MgAl hydroxide sheets of less than 70 nm in length or width are exfoliated and dispersed disorderly in PE‐g‐MA matrix. TGA profiles indicate that the PE‐g‐MA/MgAl‐LDH nanocomposite with 5 wt% OMgAl‐LDH loading shows a faster charring process in temperature range from 210 to 390 °C and a greater thermal stability beyond 390 °C than PE‐g‐MA does. The decomposition temperature of the nanocomposite is 25 °C higher than that of PE‐g‐MA as measured at 50% weight loss. The PE‐g‐MA/MgAl‐LDH nanocomposite is promising for application of flame‐retardant polymeric materials.     

熔融插层法制备LLDPE/MgAl-LDH 剥离型纳米复合材料及其热性能研究

The interlayer surface of MgAl layered double hydroxide （MgAl-LDH） was modified by exchanging about half of the interlayer nitrate anions by dodecyl sulfate anions （DS） to get MgAl（H-DS） LDH, and then the MgAl（H-DS） was melt intercalated by LLDPE to get the LLDPE/MgAl-LDH exfoliation nanocomposites. The samples were characterized by Fourier transform infrared （PTIR） spectroscopy, X-ray diffraction （XRD）, ion chromatography, transmission electron microscopy （TEM）, and thermogravimetry analysis （TGA）. The nanoscale dispersion of MgAl-LDH layers in the LLDPE matrix was verified by the disappearance of （001） XRD reflection of the modified MgAl-LDH and by the TEM observation. The TGA profiles of LLDPE/MgAl-LDH nanocomposites show a faster charring process between 210 and 370 ℃ and a higher thermal stability above 370 ℃than LLDPE. The decomposition temperature of the nanocomposites with 10 wt% MgAl（H-DS） can be 42 ℃ higher than that of LLDPE at 40% weight loss.     

Synthesis of heptamolybdate‐intercalated MgAl LDHs and its application in polyurethane elastomer

Heptamolybdate (Mo₇O₂₄^6?) was intercalated in the interlayer space between MgAl‐layered double hydroxides (Mo‐MgAl LDHs) by the hydrothermal and ion exchange method, and then polyurethane elastomer (PUE) based composites were prepared by the prepolymerization method with different amounts of Mo‐MgAl LDHs. X‐ray diffraction (XRD), Fourier transform infrared (FTIR) spectra, laser Raman spectroscopy (LRS), and scanning electron microscopy (SEM) were employed to characterize the obtained LDHs. The performance of the PUE/LDHs were evaluated by measuring their thermal gravimetric, heat release rate (HRR), and smoke density (Ds). The results show that PUE/LDH composites exhibit a lower peak heat release rate (pk‐HRR), Ds, and a prolonged combustion time, in comparison with neat PUE. Comparison between NO₃‐MgAl LDHs and Mo‐MgAl LDHs containing composites show that the introduction of Mo⁶⁺ is able to facilitate flame retardance and smoke suppression efficiency, which results mainly from the presence of MoO₃ derived from the decomposition of Mo₇O₂₄^6? intercalated LDHs. Mo‐MgAl LDHs reduce the pk‐HRR of composites by 39% with only 1 wt.% content, and the maximum Ds of composites is reduced to a minimal value of 274 with 10 wt.% Mo‐MgAl LDHs. More importantly, LDHs would improve the mechanical properties at a low content. The experimental results reveal the potential of Mo₇O₂₄^6? intercalated LDHs to improve both the flame retardancy and smoke suppression of PUE. Copyright © 2015 John Wiley & Sons, Ltd.     

Polytype Transformations in the SO42– Containing Layered Double Hydroxides of Zinc with Aluminum and Chromium: The Metal Hydroxide Layer as a Structural Synthon

Solid–solid inter‐polytype transformations are observed during the thermal dehydration of sulfate‐containing layered double hydroxides (LDHs). The metal hydroxide layer behaves as a “structural synthon” and the interconversion of polytypes of rhombohedral and hexagonal symmetries takes place by rigid translations of successive layers by (± 1/3, ± 2/3) relative to one another in the ab plane. These translations are selected among the many possible, as they preserve the coincidence of the symmetry elements of the individual layers and thereby conserve the threefold symmetry of the crystal across the inter‐polytype conversions. As a result, these transformations are enthalpically not expensive. These translations are facilitated at near ambient temperatures (30–60 °C) by the reversible dehydration of the LDH, which involves the deinsertion/insertion of water molecules within the restricted space of the interlayer region.     

A composite of layered double hydroxides obtained through random costacking of layers from Mg–Al and Co–Al LDHs by delamination–restacking: Thermal decomposition and reconstruction behavior

A composite of dodecylsulfate intercalated Mg–Al and Co–Al LDHs in which the layers of the two LDHs are randomly costacked was prepared starting from the monolayer colloidal dispersions of the individual surfactant intercalated LDHs obtained through delamination in 1-butanol. The surfactant ion of the composite could be exchanged for acetate ions. The thermal decomposition and reconstruction behavior of the acetate-intercalated composite was found to be different from those of an LDH in which each layer contains Mg, Co and Al and a physical mixture of Mg–Al and Co–Al LDHs. While the composite shows partial reconstruction to LDH phase even after heating up to 1000 °C the other samples do not show reconstruction beyond 800 °C.     

Synthesis and Characterization of Poly(ethylene terephthalate)/Modified Lithium‐Aluminum‐Layered Double Hydroxide Nanocomposites Prepared Using In‐situ Polymerization

Layered double hydroxides are a type of layered stacked compound, which can be intercalated with organic‐molecule modifiers. An ion‐exchange process for layered double hydroxide (LDH) was used to intercalate water‐soluble sulfanilic acid salt (SAS) and dimethyl 5‐sulfoisopthalate (DMSI) into lithium aluminum layered double hydroxides (LiAl LDHs). In this work, a hydrothermal process was used to modify LiAl LDHs, and the modified LiAl LDHs were treated with either SAS or DMSI through an ion‐exchange process and were then intercalated using bis‐hydroxyethylene terephthalate (BHET). The results indicate that the modified LiAl LDHs improved the interlayer compatibility between the PET and LiAl LDH layers; thus, enabling the oligomer molecules to more easily enter the gallery of the LiAl LDH layers so that polymer chains could be included between the LDH layers during polymerization of the matrix. The better barrier, mechanical properties, and thermal stability of these new types of PET nanocomposites are discussed.     

Characterization of layered double hydroxide Mg-Al-CO<Subscript>3</Subscript> prepared by re-hydration of Mg-Al mixed oxide

Emanation thermal analysis, differential thermal analysis, thermogravimetry, X-ray diffraction, scanning electron microscopy (SEM) and surface area and porosity determination from nitrogen adsorption/desorption measurements were used to characterize the Mg-Al-CO₃ LDH compound with the Mg:Al ratio 3:1 prepared by re-hydration of the Mg-Al mixed oxide. The mixed oxide was obtained after heating of the intial Mg-Al-CO₃ LDH compound in air at 500°C for 2 h. The samples were re-hydrated by two ways namely in a distilled water at 20°C for 5 days or by moistening at 60°C in air with RH 80% during 10 days, respectively. The characteristics of the re-hydrated LDH samples were compared with the initial Mg-Al-CO₃ compound. The influence of the re-hydration conditions on the microstructure, surface morphology and thermal stability of the regenerated Mg-Al-CO₃ LDHs samples is discussed. It was demonstrated that the re-generation of the layered structure by the hydration of the mixed oxide in water or in air, respectively, took place via the dissolution-crystallization mechanism and that the layered double hydroxide with different surface area and thermal behavior were formed after re-hydration in water or humid air, respectively. The emanation thermal analysis revealed differences in the microstructure changes of the re-hydrated sample during heating. XRD patterns and results of the methods used supported the ETA results.     

Thermal transformations of Cu–Mg (Zn)–Al(Fe) hydrotalcite-like materials into metal oxide systems and their catalytic activity in selective oxidation of ammonia to dinitrogen

Layered double hydroxides (LDHs) containing Mg²⁺, Cu²⁺ or Zn²⁺ cations in the Me^II positions and Al³⁺ and Fe³⁺ in the Me^III positions were synthesized by co-precipitation method. Detailed studies of thermal transformation of obtained LDHs into metal oxide systems were performed using high temperature X-ray diffraction in oxidising and reducing atmosphere, thermogravimetry coupled with mass spectrometry and temperature-programmed reduction. The LDH samples calcined at 600 and 900 °C were tested in the role of catalysts for selective oxidation of ammonia into nitrogen and water vapour. It was shown that all copper congaing samples presented high catalytic activity and additionally, for the Cu–Mg–Al and Cu–Mg–Fe hydrotalcite samples calcined at 600 °C relatively high stability and selectivity to dinitrogen was obtained. An increase in calcination temperature to 900 °C resulted in a decrease of their catalytic activity, possibly due to formation of well-crystallised metal oxide phases which are less catalytically active in the process of selective oxidation of ammonia.     

Evaluation of Organically Modified Layered Double Hydroxides as Fillers for the Preparation of Polymer Nanocomposites in Miniemulsion Polymerization

Latexes of poly(n‐butyl acrylate‐co‐methyl methacrylate) [P(BA‐co‐MMA)] filled with magnesium–aluminum layered double hydroxides (MgAl‐LDHs) are synthesized using miniemulsion polymerization. Three commercial LDHs organically modified with different types of anions are used as fillers (Perkalite F100S, Perkalite A100, and Perkalite AF50) and three different types of surfactants are tested to stabilize the miniemulsions including a cationic, an anionic, and a nonionic one. Stable LDH‐containing miniemulsions are prepared with a mixture of sodium dodecyl sulfate and Triton X‐405 and the polymerizable co‐stabilizer octadecyl acrylate. They are then polymerized to yield nanocomposite latexes. Depending on the type of LDH used, the presence of the inorganic material in the reaction medium affects the polymerization kinetics. X‐ray diffraction analysis of the resulting nanocomposite films suggests exfoliation of the inorganic material. The glass transition temperature of the nanocomposites is not affected by the LDHs and the decomposition temperature of the nanocomposites determined by thermogravimetric analysis is greater than that of the pure polymer.     

The effect of OCoAl‐LDH and OCoFe‐LDH on the combustion behaviors of polyvinyl chloride

The effects of the modified layered double hydroxide (LDH) of Co/Al (OCoAl‐LDH) and the modified LDH of Co/Fe (OCoFe‐LDH) on the combustion behaviors of polyvinyl chloride (PVC) during pyrolysis processes were compared and investigated. The thermal degradation and combustion behavior of the PVC composites were investigated by thermogravimetric analysis (TGA), microscale combustion calorimetry (MCC), and cone calorimetry (CONE). The results indicate that the incorporation of LDHs brought about the improved thermal stability and reduced heat release of PVC composites at a high temperature. The smoke‐suppression properties of the composites are investigated by steady‐state tube furnace (SSTF), and the results indicated that the toxic gases such as CH₄, CO, and N_xO were inhibited by both of the two LDHs, but the OCoFe‐LDH has a better effect on the smoke suppression. Subsequently, the char layer was investigated by scanning electron microscopy–energy‐dispersive spectrometry (SEM‐EDS) and Raman analysis. The results indicate that the LDHs can promote the dechlorination of PVC during the thermal oxidation process and can inhibit the production of HCl in inert gas. Generally, OCoAl‐LDH and OCoFe‐LDH can be potential catalysts for waste disposal and can improve the fire safety of PVC.     

The Role of Organomodified Different LDHs on Recycled Poly(ethylene terephthalate) Nanocomposites

Recycled poly(ethylene terephthalate)/organomodified‐layered double hydroxide (PET /organo‐LDH ) nanocomposites were successfully synthesized via a melt‐extrusion method. In an attempt to improve the compatibility with PET , LiAl , MgAl , and ZnAl LDH surfaces were modified with sulfanilic acid (SAS ) via electrostatic interaction with LDH cationic layers. In PET nanocomposites containing SAS ‐modified LDH , the (00l ) X‐ray diffraction (XRD ) peaks originating from organo‐LDH were not observed, indicating that the organomodified LDH layers were fully exfoliated and homogeneously dispersed within the PET matrix, which was also confirmed by transmission electron microscopy analysis. However, PET nanocomposites containing SAS ‐modified LiAl , MgAl , and ZnAl LDH showed broad (00l ) XRD peaks, indicating that the organo‐LDH was partially exfoliated. Thermogravimetric analysis confirmed that the thermal stability of PET/SAS‐modified LDH was significantly improved, depending on the type and loading content of SAS‐modified LDH compared to that of pristine PET . PET nanocomposites containing well‐dispersed SAS‐modified LDH showed substantial enhancement of the storage modulus.     

Synthesis of Nordstrandite and Nordstrandite-Derived Layered Double Hydroxides of Li and Al: A Comparative Study with the Bayerite Counterpart

The layered double hydroxides (LDHs) of Li and Al can be synthesized from the four polymorphs of Al(OH)₃, namely gibbsite, bayerite, nordstrandite, and doyleite. The crystal structure of this class of compounds depends on the type of the precursor used due to their topotactic reaction mechanism. While the LDHs derived from gibbsite and bayerite yield different crystal structures, the incorporation of Li into nordstrandite was expected to yield new LDH structures different from those derived from gibbsite and bayerite. The structure of nordstrandite derived LDHs were however identical to that derived from the bayerite counterpart. The absence of symmetry in the interlayer of nordstrandite (C₁) makes it unsuitable to accommodate the intercalating anions with different molecular symmetries. To make the interlayer gallery suitable for the anions, the metal hydroxide layers of the nordstrandite translate, transforming nordstrandite to bayerite. The bayerite with site symmetries O_h and C₂ stabilizes the anions in the interlayer by hydrogen bonding. The transformation of nordstrandite to bayerite, when soaked in lithium salt solution is, therefore, a manifestation of the intercalating anions.     

Structural Analysis of Defects in Layered Double Hydroxides and Related Mixed Oxides

Russian Journal of General Chemistry - Results of studying the structural defects in MgAl and NiAl layered double hydroxides and in the products of their thermal decomposition to 1000°C,...     

Crystallization Behavior and Thermal Properties of PP/MgAl LDH Nanocomposites Prepared in Non-polar Solution

Polypropylene(PP)/MgAl layered double hydroxide(MgAl LDH) nanocomposites were synthesized by refluxing PP and dodecyl sulfate-intercalated MgAl LDH[MgAl(DS)] in non-polar xylene. Their structure, thermal and crystallization properties were studied via X-ray diffraction(XRD), transmission electron microscopy(TEM), thermogravimetric analysis(TGA), differential scanning calorimetry(DSC), and polarized light microscopy(PLM). The nanoscaled dispersion of MgAl(DS) nanolayeres in the PP matrix was verified by the disappearance of the d(003) XRD diffraction peak of MgAl(DS) and observation of TEM image. The DSC data show that the SDS/LDH inorganic components negatively affect the crystallization properties of PP and decrease the size of PP spherulites because the inorganic components act as additional nuclei. The PP/MgAl LDH nanocomposites have a faster charring progress in a temperature range of 250―430 °C and a better thermal stability above 320 °C than pure PP.     

Thermal stability of flexible polyurethane foams containing modified layered double hydroxides and zinc borate

Abstract

Flexible polyurethane foams (FPUFs) have been modified to contain layered double hydroxides (LDHs) by dihydrogen phosphate (H₂PO₄ ^?). The thermal stability of the prepared foams has been characterized using thermogravimetric analysis (TGA) at 5, 10, 20, 30, and 40?°C/min heating rates. The experimental data indicate that the temperature range for the two pyrolysis stages of FPUF is about 212–350?°C and 350–565?°C, respectively. Integral programmed decomposition temperature (IPDT) has been calculated according to the measured data, which was found that the IPDT of the modified FPUF was increased to 526?°C. Additionally, the thermal stability of FPUF composite has been also evaluated by the activation energy (E) on the basis of the pyrolysis kinetics of FPUF composites during thermal decomposition using Coats–Redfern integral method. These results manifest that the presence of intercalated LDHs enhances the thermal stability of FPUF.     

The Effect of Hydrotalcite and Zinc Oxide on Smoke Suppression of Commercial Rigid PVC

To reduce the smoke release of poly(vinyl chloride) (PVC) during burning, layered double hydroxides (LDHs) and zinc oxide (ZnO) powders were used to modify the polymer. The results indicated that the addition of LDHs‐ZnO had a significant effect on smoke suppression. The limiting oxygen index (LOI) reached a maximum value and the smoke density rank (SDR) exhibited a minimum value when the weight percentages of LDHs and ZnO in PVC were 3% and 2%, respectively. Thermal stabilities of the modified PVC and degradation products were investigated by means of thermogravimetry and pyrolysis‐gas chromatography‐mass spectra (Py‐GC‐MS). The LDHs‐ZnO obviously accelerated the decomposition of PVC to release hydrogen chloride, and the decomposed PVC consequently produced the trans‐conjugated polyene sequences, which easily formed crosslinked structures. However, a cyclization reaction in PVC chain without the additives produced aromatic compounds such as benzene, toluene, and naphthalene at 350°C. Even though, an amount of aromatic compounds was released from the PVC modified with LDHs‐ZnO at the temperature of 600°C, the content of the decomposed products is relatively lower compared to unmodified PVC.     

Effect of hydrothermal treatment on properties of Ni-Al layered double hydroxides and related mixed oxides

The Ni-Al layered double hydroxides (LDHs) with Ni/Al molar ratio of 2, 3, and 4 were prepared by coprecipitation and treated under hydrothermal conditions at 180 °C for times up to 20 h. Thermal decomposition of the prepared samples was studied using thermal analysis and high-temperature X-ray diffraction. Hydrothermal treatment increased significantly the crystallite size of coprecipitated samples. The characteristic LDH diffraction lines disappeared completely at ca. 350 °C and a gradual crystallization of NiO-like mixed oxide was observed at higher temperatures. Hydrothermal treatment improved thermal stability of the Ni2Al and Ni3Al LDHs but only a slight effect of hydrothermal treatment was observed with the Ni4Al sample. The Rietveld refinement of powder XRD patterns of calcination products obtained at 450 °C showed a formation of Al-containing NiO-like oxide and a presence of a considerable amount of Al-rich amorphous component. Hydrothermal aging of the LDHs resulted in decreasing content of the amorphous component and enhanced substitution of Al cations into NiO-like structure. The hydrothermally treated samples also exhibited a worse reducibility of Ni²⁺ components. The NiAl₂O₄ spinel and NiO still containing a marked part of Al in the cationic sublattice were detected in the samples calcined at 900 °C. The Ni2Al LDHs hydrothermally treated for various times and related mixed oxides obtained at 450 °C showed an increase in pore size with increasing time of hydrothermal aging. The hydrothermal treatment of LDH precursor considerably improved the catalytic activity of Ni2Al mixed oxides in N₂O decomposition, which can be explained by suppressing internal diffusion effect in catalysts grains.     

In situ synthesis of polyethylene terephthalate nanocomposites using bis (2‐hydroxyethyl) phthalate monomer

In this article, we address in situ synthesis of polyethylene terephthalate (PET) nanocomposites using the bis (2‐hydroxyethyl) phthalate monomer and inorganic layered materials (sulfanilic acid salt‐modified magnesium aluminum‐layered double hydroxides [MgAl LDH‐SAS] and Dimethyloctadecyl [3‐(trimethoxysilyl) propyl] ammonium chloride [DTSACl] and tetraethyl orthosilicate [TEOS]‐ modified clay [CL120‐DT]). The dispersion morphology of the synthesized nanocomposites was evaluated using XRD and TEM, from these results, it was confirmed that 0.5 wt% loaded PET/MgAl LDH‐SAS and PET/CL120‐DT nanocomposites have flocculated and intercalated morphologies, respectively. Thermomechanical analyses were performed by thermogravimetric analysis, dynamic mechanical analysis, and differential scanning calorimetry, respectively. Moreover, the water vapor transmission rate (WVTR) values of a pure PET, PET/CL120‐DT 0.5 wt%, and PET/MgAl LDH‐SAS 0.5 wt% nanocomposites were found to be 49, 45, and 46 g·m^?2·day^?1, respectively. Furthermore, the gas barrier properties of PET composite films containing various amounts of inorganic nanoparticles were investigated using Gas permeability analysis (GPA).     

Embedded high density metal nanoparticles with extraordinary thermal stability derived from guest-host mediated layered double hydroxides

A chemical precursor mediated process was used to form catalyst nanoparticles (NPs) with an extremely high density (10(14) to 10(16) m(-2)), controllable size distribution (3-20 nm), and good thermal stability at high temperature (900 °C). This used metal cations deposited in layered double hydroxides (LDHs) to give metal catalyst NPs by reduction. The key was that the LDHs had their intercalated anions selected and exchanged by guest-host chemistry to prevent sintering of the metal NPs, and there was minimal sintering even at 900 °C. Metal NPs on MoO(4)(2-) intercalated Fe/Mg/Al LDH flakes were successfully used as the catalyst for the double helix growth of single-walled carbon nanotube arrays. The process provides a general method to fabricate thermally stable metal NPs catalysts with the desired size and density for catalysis and materials science.     

Effect of the Composition of Initial Components and the Conditions of Activation on the Mechanochemical Synthesis of Magnesium–Aluminum Layered Double Hydroxides

The MgAl layered double hydroxides (LDHs) were prepared by two-stage synthesis, which included mechanochemical activation at the first stage and the interaction of the resulting sample with distilled water at the second stage. The influence of the material of grinding bodies (steel and ceramics), the conditions of activation (activation time and the centripetal acceleration of balls), and the nature of initial compounds on the phase composition of the resulting products was investigated. It was established that the formation of a single-phase MgAl LDH was observed upon mechanochemical activation with the use of steel grinding bodies at an acceleration of 1000 m/s² for 30 min. The samples prepared by a traditional coprecipitation method and a method that included a stage of mechanochemical activation possessed identical structural parameters. However, the mixed oxides formed upon the calcination of LDHs synthesized by mechanochemical activation were characterized by a more uniform pore space with a pore diameter of 4–5 nm with a developed specific surface.