Chlorinated polyethylene nanocomposites using PCL/clay nanohybrid masterbatches

Exfoliated nanocomposites were prepared by dispersion of poly(ε-caprolactone) (PCL) grafted montmorillonite nanohybrids used as masterbatches in chlorinated polyethylene (CPE). The PCL-grafted clay nanohybrids with high inorganic content were synthesized by in situ intercalative polymerization of ε-caprolactone between silicate layers organo-modified by alkylammonium cations bearing two hydroxyl functions. The polymerization was initiated by tin alcoholate species derived from the exchange reaction of tin(II) bis(2-ethylhexanoate) with the hydroxyl groups borne by the ammonium cations that organomodified the clay. These highly filled PCL nanocomposites (25 wt% in inorganics) were dispersed as masterbatches in commercial chlorinated polyethylene by melt blending. CPE-based nanocomposites containing 3-5 wt% of inorganics have been prepared. The formation of exfoliated nanocomposites was assessed both by wide-angle X-ray diffraction and transmission electron microscopy. The thermal and thermo-mechanical properties were studied as a function of the filler content, by differential scanning calorimetry and dynamic mechanical analysis, respectively. The mechanical properties were also assessed by tensile tests. The Young’s modulus of CPE is increased by a decade when a PCL-grafted clay masterbatch is exfoliated to reach 5 wt% of clay in the resulting nanocomposite. The influence of PCL-grafting on the properties of these nanocomposites was investigated by comparison with materials obtained with ungrafted-PCL.     

Application of Differential Scanning Calorimetry to the Reduction of Several Manganese Oxides

The aim of this work was to study the thermal transitions of several manganese oxides (MnO, MnOOH, Mn₂O₃, Mn₃O₄ and MnO₂) under reducing conditions. Differential scanning calorimetry (DSC) was used to analyse the transitions of some oxides into others. A comparison of the behavior of the synthetic samples with that of a natural manganese dioxide demonstrated that DSC is a quick tool for the distinction of natural manganese dioxide from synthetic γ-MnO₂ from other manganese oxides. This revised version was published online in July 2006 with corrections to the Cover Date.     

Annealing effects on the structure, photoluminescence, and magnetic properties of GaN/Mn3O4 core-shell nanowires

Nanowires consisting of GaN/Mn₃O₄ were prepared using a two-step approach that involved dipping the as-synthesized GaN nanowires into an aqueous manganese acetate solution. To examine the effects of annealing, GaN/Mn₃O₄ core-shell nanowires were heated thermally to 700 °C in N₂ ambient. Transmission electron microscopy showed that the continuous Mn₃O₄ shell layer had agglomerated to expose a bare GaN core surface after thermal annealing. The magnetic measurements showed that the ferromagnetic behavior of the GaN nanowires had been suppressed by coating with the Mn₃O₄ shell, without significant change by the subsequent thermal annealing. The GaN/Mn₃O₄ core-shell nanowires exhibited blue, green, and red photoluminescence (PL) emission. The red emission was enhanced by thermal annealing. This paper discusses the associated mechanism for the variations in PL and magnetic properties of GaN/Mn₃O₄ core-shell nanowires.     

Compatibilisation effect of PP-g-MA copolymer on iPP/SiO2 nanocomposites prepared by melt mixing

In the present study, a series of iPP/SiO₂ nanocomposites, containing 1, 2.5, 5, 7.5, 10 and 15 wt% SiO₂ nanoparticles, were prepared by melt mixing in a twin screw co-rotating extruder. Poly(propylene-g-maleic anhydride) copolymer (PP-g-MA) containing 0.6 wt% maleic anhydride content was added to all nanocomposites at three different concentrations, 1, 2.5 and 5 wt%, based on silica content. Mechanical properties such as tensile strength at break and Young’s modulus were found to increase and to be mainly affected by the content of silica nanoparticles as well as by the copolymer content. For the tensile strength at break as well as for yield point, a maximum was observed, corresponding to the samples containing 2.5-5 wt% SiO₂. At higher concentrations, large nanosilica agglomerates are formed that have as a result a decrease in tensile strength. Young’s modulus increases almost linearly on the addition of SiO₂, and takes values up to 60% higher than that of neat iPP. Higher concentrations of PP-g-MA resulted in a further enhancement of mechanical properties due to silica agglomerate reduction. This finding was verified from SEM and TEM micrographs. Evidently the surface silica hydroxyl groups of SiO₂ nanoparticles react with maleic anhydride groups of PP-g-MA and lead to a finer dispersion of individual SiO₂ nanoparticles in the iPP matrix. The enhanced adhesion in the interface of the two materials, as a result of the mentioned reaction, has been studied and proved by using several equations. The increased Vicat point of all nanocomposites, by increasing the PP-g-MA content, can also be mentioned as a positive effect.     

Thermal properties and combustion characterization of nylon 6/MgAl-LDH nanocomposites via organic modification and melt intercalation

The nylon 6/MgAl layered double hydroxide (MgAl-LDH) nanocomposites have been prepared by melt intercalation of nylon 6 into the part organic dodecyl sulfate (DS) anion-modified MgAl(H-DS) interlayers. The structures and properties of MgAl(H-DS) and corresponding nanocomposites were characterized by ion chromotography, X-ray diffraction (XRD), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), and cone calorimeter test (CCT). The nanoscale dispersion of MgAl(H-DS) layers in the nylon 6 matrix has been verified by the disappearance of d₀₀₁ XRD diffraction peak of MgAl(H-DS) and the observation of TEM image. DSC tests evince that these exfoliated MgAl(H-DS) layers play the role of nucleating agents with strong heterogeneous nucleation effect on the crystallization of nylon 6 and increase its crystallization temperature over 12 °C with only 5 wt% MgAl(H-DS). TGA tests show that the effect of alkaline catalysis degradation from LDH on nylon 6 decreases the thermal stability of nylon 6/MgAl-LDH nanocomposites. The data from the cone calorimeter tests show that the HRR and MLR values of the sample with 5 wt% MgAl(H-DS) decrease considerably to 664 kW/m² and 0.161 g/m² s from 1064 kW/m² and 0.252 g/m² s of pure nylon 6, respectively. This kind of exfoliated nanocomposite is promising for the application of flame-retardant polymeric materials.     

The formation and physicochemical characterization of Al2O3-doped manganese ferrites

Mn/Fe mixed oxide solids doped with Al₂O₃ (0.32-1.27 wt.%) were prepared by impregnation of manganese nitrate with finely powdered ferric oxide, then treated with different amounts of aluminum nitrate. The obtained samples were calcined in air at 700-1000 °C for 6 h. The specific surface area (S_BET) and the catalytic activity of pure and doped precalcined at 700-1000 °C have been measured by using N₂ adsorption isotherms and CO oxidation by O₂. The structure and the phase changes were characterized by DTA and XRD techniques. The obtained results revealed that Mn₂O₃ interacted readily with Fe₂O₃ to produce well-crystallized manganese ferrite (MnFe₂O₄) at temperatures of 800 °C and above. The degree of propagation of this reaction increased by Al₂O₃-doping and also by increasing the heating temperature. The treatment with 1.27 wt.% Al₂O₃ followed by heating at 1000 °C resulted in complete conversion of Mn/Fe oxides into the corresponding ferrite phase. The catalytic activity and S_BET of pure and doped solids were found to decrease, by increasing both the calcination temperature and the amount of Al₂O₃ added, due to the enhanced formation of MnFe₂O₄ phase which is less reactive than the free oxides (Mn₂O₃ and Fe₂O₃). The activation energy of formation (ΔE) of MnFe₂O₄ was determined for pure and doped solids. The promotion effect of aluminum in formation of MnFe₂O₄ was attributed to an effective increase in the mobility of reacting cations.     

Thermochemistry of Li1+xMn2−xO4 (0?x?1/3) spinel

Lithium substituted Li_1+xMn_2−xO₄ spinel samples in the entire solid solution range (0?x?1/3) were synthesized by solid-state reaction. The samples with x<0.25 are stoichiometric and those with x?0.25 are oxygen deficient. High-temperature oxide melt solution calorimetry in molten 3Na₂O·4MoO₃ at 974 K was performed to determine their enthalpies of formation from constituent binary oxides at 298 K. The cubic lattice parameter was determined from least-squares fitting of powder XRD data. The variations of the enthalpy of formation from oxides and the lattice parameter with x follow similar trends. The enthalpy of formation from oxides becomes more exothermic with x for stoichiometric compounds (x<0.25) and deviates endothermically from this trend for oxygen-deficient samples (x?0.25). This energetic trend is related to two competing substitution mechanisms of lithium for manganese (oxidation of Mn³⁺ to Mn⁴⁺ versus formation of oxygen vacancies). For stoichiometric spinels, the oxidation of Mn³⁺ to Mn⁴⁺ is dominant, whereas for oxygen-deficient compounds both mechanisms are operative. The endothermic deviation is ascribed to the large endothermic enthalpy of reduction.     

Synthesis of Mn3O4 nanoparticles by thermal decomposition of a [bis(salicylidiminato)manganese(II)] complex

The present investigation reports on the novel synthesis of Mn₃O₄ nanoparticles using thermal decomposition and their physicochemical characterization. The Mn₃O₄ nanoparticle powder has been prepared using [bis(salicylidiminato)manganese(II)] as a precursor. The effect of oleyl amine and triphenylphosphine on the particle morphology has been investigated. Transmission electron microscopy (TEM) analysis demonstrated Mn₃O₄ nanoparticles with an average diameter of about 25 nm. The structural study by X-ray diffraction (XRD) indicates that these nanoparticles have a pure tetragonal phase. The phase pure samples were characterized using X-ray photoelectron spectroscopy (XPS) for both Mn 2p and Mn 3s levels. The values of binding energies are consistent with related values reported in the literature.     

Effect of the high pressure on the structure and intercalation properties of lithium-nickel-manganese oxides

Lithium-nickel-manganese oxides (Li_1+x(Ni_1/2Mn_1/2)_1−xO₂, x=0 and 0.2), having different cationic distributions and an oxidation state of Ni varying from 2+ to 3+, were formed under a high-pressure (3 GPa). The structure and cationic distribution in these oxides were examined by powder X-ray diffraction, infrared (IR) and electron paramagnetic resonance (EPR) in X-band (9.23 GHz) and at higher frequencies (95 and 285 GHz). Under a high pressure, a solid-state reaction between NiMnO₃ and Li₂O yields LiNi_0.5Mn_0.5O₂ with a disordered rock-salt type structure. The paramagnetic ions stabilized in this oxide are mainly Ni²⁺ and Mn⁴⁺ together with Mn³⁺ (about 10%). The replacement of Li₂O by Li₂O₂ permits increasing the oxidation state of Ni ions in lithium-nickel-manganese oxides. The higher oxidation state of Ni ions favours the stabilization of the layered modification, where the Ni-to-Mn ratio is preserved: Li(Li_0.2Ni_0.4Mn_0.4)O₂. The paramagnetic ions stabilized in the layered oxide are mainly Ni³⁺ and Mn⁴⁺ ions. The disordered and ordered phases display different intercalation properties in respect of lithium. The changes in local Ni,Mn-environment during the electrochemical reaction are discussed on the basis of EPR and IR spectroscopy.     

Effect of the oxidation state of manganese in the manganese oxides used in the synthesis of Mn-substituted cordierite on the properties of the product

Catalysts based on Mn-substituted cordierite 2MnO · 2Al₂O₃ · 5SiO₂ have been synthesized using different manganese oxides (MnO, Mn₂O₃, and MnO₂) at a calcination temperature of 1100°C. The catalysts differ in their physicochemical properties, namely, phase composition (cordierite content and crystallinity), manganese oxide distribution and dispersion, texture, and activity in high-temperature ammonia oxidation. The synthesis involving MnO yields Mn-substituted cordierite with a defective structure, because greater part of the manganese cations is not incorporated in this structure and is encapsulated and the surface contains a small amount of manganese oxides. This catalyst shows the lowest ammonia oxidation activity. The catalysts prepared using Mn₂O₃ or MnO₂ are well-crystallized Mn-substituted cordierite whose surface contains different amounts of manganese oxides differing in their particle size. They ensure a high nitrogen oxides yield in a wide temperature range. The product yield increases with an increasing surface concentration of Mn³⁺ cations. The highest NO_x yield (about 76% at 800–850°C) is observed for the MnO₂-based catalyst, whose surface contains the largest amount of manganese oxides.     

Tentative links between thermal diffusivity and fire-retardant properties in poly(methyl methacrylate)-metal oxide nanocomposites

Possible relationships between fire-retardant properties and thermal diffusivity for poly(methyl methacrylate) (PMMA) filled by melt blending with titanium dioxide (TiO₂), alumina (Al₂O₃) and boehmite (AlOOH) were investigated for a better understanding of the mode of action of metal oxides as fire-retardants (FR) in PMMA. Fire-retardancy was measured with a cone calorimeter and thermal diffusivity (α) by Laser Flash Analysis (LFA). LFA measurements have shown that heat dispersion is higher with titanium dioxide and boehmite than with alumina despite a larger surface area. For thermal diffusivity, discrepancies between the different nanofillers were only visible from 10 wt% onwards. Thermal degradation of PMMA-oxide nanocomposites and their thermal diffusivity could be linked. Moreover, a bi-linear relationship between the peak of heat release rate (pHRR) and the average of heat release rate (AHRR) showed the occurrence of a barrier effect.     

Preparation and characterization of poly(propylene carbonate)/montmorillonite nanocomposites by solution intercalation

Poly(propylene carbonate) (PPC) is a new biodegradable aliphatic polycarbonate. However, the poor thermal stability and low glass transition temperatures (T_g) have limited its applications. To improve the thermal properties of PPC, organophilic montmorillonite (OMMT) was mixed with PPC by a solution intercalation method to produce nanocomposites. An intercalated-and-flocculated structure of PPC/OMMT nanocomposites was confirmed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The thermal and mechanical properties of PPC/OMMT nanocomposites were investigated by thermal gravimetric analysis (TGA), differential scanning calorimetric (DSC), and electronic tensile tester. Due to the nanometer-sized dispersion of layered silicate in polymer matrix, PPC/OMMT nanocomposites exhibit improved thermal and mechanical properties than pure PPC. When the OMMT content is 4 wt%, the PPC/OMMT nanocomposite shows the best thermal and mechanical properties. These results indicate that nanocomposition is an efficient and convenient method to improve the properties of PPC.     

Thermochemistry of iron manganese oxide spinels

Oxide melt solution calorimetry has been performed on iron manganese oxide spinels prepared at high temperature. The enthalpy of formation of (Mn_xFe_1−x)₃O₄ at 298 K from the oxides, tetragonal Mn₃O₄ (hausmannite) and cubic Fe₃O₄ (magnetite), is negative from x=0 to x=0.67 and becomes slightly positive for 0.67<x<1.0. Relative to cubic Mn₃O₄ (stable at high temperature) and cubic Fe₃O₄ (magnetite), the enthalpy of formation is negative for all compositions. The enthalpy of formation is most negative near x=0.2. There is no significant difference in the trend of enthalpy of formation versus composition for cubic (x<0.6) and tetragonal (x>0.6) spinels of intermediate compositions. The enthalpies of formation are discussed in terms of three factors: oxidation-reduction relative to the end-members, cation distribution, and tetragonality. A combination of measured enthalpies and Gibbs free energies of formation in the literature provides entropies of mixing. ΔS_mix, consistent with a cation distribution in which all trivalent manganese is octahedral and all other ions are randomly distributed for x>0.5, but the entropy of mixing appears to be smaller than these predicted values for x<0.4.     

催化苯甲醇液相氧化反应的高效无定形氧化锰催化剂

研究了焙烧温度对无定形氧化锰的织构及其催化苯甲醇液相氧化反应性能的影响.结果表明,在焙烧温度不高于400℃的条件下,MnOx均保持无定形结构,进一步提高焙烧温度会促使无定形MnOx转变为晶相的OMS-2和Mn2O3.不同氧化锰催化剂的质量比活性随焙烧温度的升高而逐渐降低,无定形MnOx比晶相氧化锰(OMS-2,γ-MnO2和Mn2O3)具有更高的质量比活性,而110℃干燥的无定形氧化锰具有最高的活性.H2-程序升温还原研究表明,氧化锰的起始还原温度与其质量比活性之间存在线性逆变关系,表明氧化锰的还原性能是决定其催化活性的关键因素.     

CTAB-Mn3O4 nanocomposites: Synthesis,NMR and low temperature EPR studies

We are reporting on the synthesis of Mn₃O₄ nanoparticles and CTAB-Mn₃O₄ nanocomposites via a sonochemical route using MnCl₂, ethanol, NaOH and CTAB. The crystalline phase was identified as Mn₃O₄. The crystallite size of the CTAB-Mn₃O₄ nanocomposite was identified as 13 ± 5 nm from X-ray line profile fitting and the particle size from TEM was 107.5 ± 1.4 nm. The interaction between CTAB and the Mn₃O₄ nanoparticles was investigated by FTIR and ¹H NMR spectroscopies. Two different magnetic phase transitions were observed for both samples below the Curie temperature (43 °C) by using a low temperature Electron Paramagnetic Resonance (EPR) technique. Also we determined the effect of the capping with CTAB on the reduction in absorbed power.     

Photodegradation of 2,4-D over PdO/Al2O3-Nd2O3 photocatalysts prepared by the sol-gel method

The photocatalytic activity of 1.0 wt% PdO supported on Al₂O₃-Nd₂O₃ binary oxides prepared by the sol-gel method was studied in the photodegradation of 2,4-dichlorophenoxyacetic acid (2,4-D). The photocatalysts were characterized by N₂ physisorption, XRD and UV-vis spectroscopy. PdO supported on γ-Al₂O₃ photo-degrades the 2,4-D, however the addition of Nd₂O₃ to γ-Al₂O₃ notably improves the photocatalytic activity. As the concentration of Nd₂O₃ in the binary oxide increases from 2 to 10 wt%, the photodegradation of 2,4-D is highly enhanced. The catalytic test for PdO supported on pure Nd₂O₃ showed scarce photocatalytic activity. Total organic carbon (TOC) analysis showed that the 2,4-D has been completely destroyed on the PdO/Al₂O₃-Nd₂O₃ photocatalysts after 6 h under irradiation.     

Preparation and characterization of poly(imide siloxane) (PIS)/titania(TiO2) hybrid nanocomposites by sol-gel processes

Poly(imide siloxane)(PIS)/titania(TiO₂) hybrid nanocomposites with organic-inorganic covalent bonding have been successfully synthesized by sol-gel processes. The PIS copolymer synthesized in this study was characterized by the observed coexisting two segments: the polyimide (PI) segment and polydimethyldiphenylsiloxane segment, and the latter were specially featured with the introduction of a diphenyl group for improved homogeneity.The obtained TiO₂ networks in PIS matrix were well dispersed and their average diameter was less than 50 nm. Meanwhile, the PIS/TiO₂ hybrid nanocomposite films exhibited good optical transparency at 20 wt% of TiO₂ content. The thermal stability, tensile strength and elongation of the nanocomposites decreased with increasing TiO₂ content. The glass transition temperature (T_g) and Young’s modulus increased with increasing TiO₂ content. The chemical structure and morphologies of PIS/TiO₂ hybrid nanocomposites was characterized by Fourier transform infrared spectroscope (FT-IR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscope (TEM). The T_g and thermal stability were measured by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA), respectively. The mechanical properties were examined by dynamic mechanical analysis (DMA) under controlled force mode.     

Nanorods of manganese oxides: Synthesis, characterization and catalytic application

Single-crystalline nanorods of β-MnO₂, α-Mn₂O₃ and Mn₃O₄ were successfully synthesized via the heat-treatment of γ-MnOOH nanorods, which were prepared through a hydrothermal method in advance. The calcination process of γ-MnOOH nanorods was studied with the help of Thermogravimetric analysis and X-ray powder diffraction. When the calcinations were conducted in air from 250 to 1050 °C, the precursor γ-MnOOH was first changed to β-MnO₂, then to α-Mn₂O₃ and finally to Mn₃O₄. When calcined in N₂ atmosphere, γ-MnOOH was directly converted into Mn₃O₄ at as low as 500 °C. Transmission electron microscopy (TEM) and high-resolution TEM were also used to characterize the products. The obtained manganese oxides maintain the one-dimensional morphology similar to the precursor γ-MnOOH nanorods. Further experiments show that the as-prepared manganese oxide nanorods have catalytic effect on the oxidation and decomposition of the methylene blue (MB) dye with H₂O₂.     

Thermal Decompositions of Pure and Mixed Manganese Carbonate and Ammonium Molybdate Tetrahydrate

The thermal decompositions of pure and mixed manganese carbonate and ammonium molybdate tetrahydrate in molar ratios of 3:1, 1:1 and1:3 were studied by DTA and TG techniques. The prepared mixed solid samples were calcined in air at 500, 750 or 1000°C and then investigated by means of an XRD technique. The results revealed that manganese carbonate decomposed in the range 300–1000°C, within termediate formation of MnO₂, Mn₂O₃ andMn₃O₄. Ammonium molybdate tetrahydrate first lost its water of crystallization on heating, and then decomposed, yielding water and ammonia. At 340°C,MoO₃ was the final product, which melts at 790°C. The thermal treatment of the mixed solids at 500, 750 or 1000°C led to solid-solid interactions between the produced oxides, with the formation of manganese molybdate. At 1000°C, Mn₂O₃ and MoO₃ were detected, due to the mutual stabilization effect of these oxides at this temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structural characterization and electrochemical intercalation of Li+ in layered Na0.65Ni0.5Mn0.5O2 obtained by freeze-drying method

New data on the structure and reversible lithium intercalation properties of sodium-deficient nickel–manganese oxides are provided. Novel properties of oxides determine their potential for direct use as cathode materials in lithium-ion batteries. The studies are focused on Na _x Ni_0.5Mn_0.5O₂ with x?=?2/3. Between 500 and 700 °C, new layered oxides Na_0.65Ni_0.5Mn_0.5O₂ with P3-type structure are obtained by a simple precursor method that consists in thermal decomposition of mixed sodium–nickel–manganese acetate salts obtained by freeze-drying. The structure, morphology, and oxidation state of nickel and manganese ions of Na_0.65Ni_0.5Mn_0.5O₂ are determined by powder X-ray diffraction, SEM and TEM analysis, and X-ray photoelectron spectroscopy (XPS). The lithium intercalation in Na_0.65Ni_0.5Mn_0.5O₂ is carried out in model two-electrode lithium cells of the type Li|LiPF₆(EC:DMC)|Na_0.65Ni_0.5Mn_0.5O₂. A new structural feature of Na_0.65Ni_0.5Mn_0.5O₂ as compared with well-known O3–NaNi_0.5Mn_0.5O₂ and P2–Na_2/3Ni_1/3Mn_2/3O₂ is the development of layer stacking ensuring prismatic site occupancy for Na⁺ ions with shared face on one side and shared edges on the other side with surrounding Ni/MnO₆ octahedra. The reversible lithium intercalation in Na_0.65Ni_0.5Mn_0.5O₂ is demonstrated and discussed.