Influence of surface texture and acid–base properties on ozone decomposition catalyzed by aluminum (hydroxyl) oxides

The decomposition of aqueous ozone in the presence of three aluminum (hydroxyl) oxides was studied, respectively. It was hypothesized that surface hydroxyl groups and acid–base properties of aluminum (hydroxyl) oxides play an important role in catalyzed ozone decomposition. The variables investigated were oxide dose, aqueous pH, presence of inorganic anions (sulfate and nitrate), the effect of tert-butyl alcohol (TBA) and surface hydroxyl groups density of the three aluminum (hydroxyl) oxides. All three aluminum (hydroxyl) oxides tested, i.e. γ-AlOOH (HAO), γ-Al₂O₃ (RAO) and α-Al₂O₃ (AAO), enhanced the rate of ozone decomposition. The net surface charge of the aluminum (hydroxyl) oxides favored in catalyzed ozone decomposition. The greatest effect on catalyzed ozone decomposition was observed when the solution pH was close to the point of zero charge of the aluminum (hydroxyl) oxide. Sulfate and nitrate were substituted for the surface hydroxyl groups of the aluminum (hydroxyl) oxides, which then complexed with Al³⁺ in a ligand exchange reaction. Therefore, inorganic anions may be able to inhibit catalyzed ozone decomposition. It was confirmed that surface hydroxyl groups were important for ozone decomposition with aluminum (hydroxyl) oxides as catalysts. TBA inhibited ozone decomposition in the presence of HAO, RAO and AAO. It was also tested whether aluminum (hydroxyl) oxides catalyzed ozone-transformed hydroxyl radicals. The relationship between surface hydroxyl groups and the ratio of hydroxyl radical concentration to ozone concentration (R_ct) was investigated quantitatively. Higher density of surface hydroxyl groups of the aluminum oxide tested was favorable for the decay of ozone into hydroxyl radicals.     

Hydroisomerization of model FCC naphtha over sulfided Co(Ni)–Mo(W)/MCM-41 catalysts

Deep hydrodesulfurization (HDS) of gasoline generally brings about the saturation of olefins and leads to the serious octane number losses. Conversion of linear olefins to branched ones followed by hydrogenation to isoalkanes would minimize such octane number losses. In this work, MCM-41-supported Co–Mo, Ni–Mo and Ni–W catalysts were prepared by the incipient wetness impregnation method, and compared with an industrial Co–Mo/γ-Al₂O₃ catalyst. The surface acidities were measured by the techniques of microcalorimetry and infrared spectroscopy for the adsorption of ammonia, and probed by the reaction of conversion of isopropanol. The isomerization and hydrogenation of 1-hexene as well as the HDS of thiophene were studied by using model FCC naphtha. It was found that the sulfidation enhanced significantly the surface Brønsted acidity that favored the skeletal isomerization of 1-hexene under the HDS conditions. Since the isomerization and hydrogenation of 1-hexene are the two competition reactions, the catalysts with relatively lower hydrogenation activity may have higher selectivity to the isomerization reactions. The Co–Mo/MCM-41 showed the high selectivity to the skeletal isomerization reactions due to its strong surface Brønsted acidity and the relatively low hydrogenation activity. On the other hand, the Ni–Mo/MCM-41 exhibited high hydrogenation activity and therefore low selectivity to the isomerization reactions although it possessed quite strong surface Brønsted acidity. The Ni–W/MCM-41 exhibited the low activity for the HDS of thiophene and isomerization of 1-hexene due to the poor dispersion of active metals.     

Studies on structural properties, surface acidity and benzene isopropylation activity of sulphated ZrO2–TiO2 mixed oxide catalysts

A series of sulphated ZrO₂–TiO₂ mixed oxide with different nominal sulphate loadings in the range of 2–15 wt.% was prepared and characterized for their structural properties, surface acidity and benzene isopropylation activity. The catalyst with 10 wt.% nominal sulphate loading showed highest surface area and uniform pore size distributions. Surface acidity, measured by NH₃–TPD method, showed increase in acidity with sulphate loading and the 10 wt.% sulphate loaded catalyst showed highest acidity. The activities of these catalysts were tested for isopropylation of benzene to cumene using 2-propanol as the alkylating agent. The 10 wt.% sulphate-loaded catalyst also showed highest activity for this reaction with 97% cumene selectivity. The higher activity of this catalyst was attributed to its higher acidity.     

The effect of the Rh–Al, Pt–Al and Pt–Rh–Al surface alloys on NO conversion to N2 on alumina supported Rh, Pt and Pt–Rh catalysts

NO conversion to N₂ in the presence of methane and oxygen over 0.03 at.%Rh/Al₂O₃, 0.51 at.%Pt/Al₂O₃ and 0.34 at.%Pt–0.03 at.%Rh/Al₂O₃ catalysts was investigated.

δ-Alumina and precious metal–aluminum alloy phases were revealed by XRD and HRTEM in the catalysts.

The results of the catalytic activity investigations, with temperature-programmed as well as steady-state methods, showed that NO decomposition occurs at a reasonable rate on the alloy surfaces at temperatures up to 623 K whereas some CH₄ deNO_x takes place on δ-alumina above this temperature. A mechanism for the NO decomposition is proposed herein. It is based on NO adsorption on the precious metal atoms followed by the transfer of electrons from alloy to antibonding π orbitals of NO_(ads.) molecules. The CH₄ deNO_x was shown to occur according to an earlier proposed mechanism, via methane oxidation by NO_2(ads.) to oxygenates and then NO reduction by oxygenates to N₂.     

Synthesis of and photodegradation in a series of poly(ethylene terephthalate)–co–4,4′-sulfonyldibenzoate yarns

Phototendering studies of poly(ethylene terephthalate) homopolymer yarn and a series of poly(ethylene terephthalate–co–4, 4′-sulfonyldibenzoate) copolymer yarns have shown that photosensitized degradation occurs more readily in the copolymers than in the homopolymer. A photo-oxidative mechanism involving the second monomer, dibutyl 4, 4′-sulfonyldibenzoate, has been proposed to account for the photosensitization. The photophysical processes in the second monomer, dibutyl 4, 4′-sulfonyldibenzoate, were studied by absorption and luminescence techniques. The lowest excited singlet and triplet in this compound were identified as the ¹(π, π^*) and ₃(π, π^*) states, respectively. The energy levels in the second monomer have been assigned as follows: ¹S₁ ～ 33,000 cm^?1, ¹S₂ ～ 42,000 cm^?1, and ³T₁ ～ 26,000 cm^?1.     

Thermal shock acoustic emission and microstructure of refractories I. High Alumina refractories (60–90% Al2O3)

Acoustic emission generated on thermal shocks makes it possible to investigate the processes of cracking that take place in high alumina refractories separately at heating and cooling stages, as well as on successive thermal shocks. It is dependent on the raw material type, technological process and the microstructure of products (i.e. number, size and shape of pores and cracks). The damage present after 20 thermal shocks in the material tested was illustrated by the microstructure examinations.     

Synthesis,photodegradation, and energy transfer in a series of poly(ethylene terephthalate–co–4,4′-biphenyldicarboxylate) copolymers

Poly(ethylene terephthalate) (PET) filament yarns were photostabilized by addition of 0.5–4.0 mole % dimethyl 4,4′-biphenyldicarboxylate (4,4′-BPDC) to the polymerization feed. The mechanism of photostabilization is proposed to be a triplet–triplet energy transfer from excited terephthalate units to ground-state biphenyldicarboxylate units. The mechanism of transfer is reported to be via an electron exchange mechanism, with the “quenching sphere” calculated to be 14.9 Å. Kinetic studies show the “pseudo” zero-order rate constant of initial photodegradation to decrease from 3.4 × 10^?19 for the PET homopolymer to 2.0 × 10^?19% breaking strength loss/quantum exposure/cm² for the copolyester containing 4.0 mole % of the 4,4′-biphenyldicarboxyl moieties. The photophysical processes available to the dimethyl 4,4′-biphenyldicarboxylate monomer were characterized by absorption and luminescence studies. In solution, dimethyl 4,4′-biphenyldicarboxylate was shown to emit an intense fluorescence from a ²(π,π*) state and a weaker (～10^?2×) phosphorescence from a ¹(π,π*) state derived from the ¹A→supn1L_b absorption. The copolymer yarns were shown to exhibit both fluorescence and phosphorescence from the biphenyldicarboxylate units: the fluorescence from direct excitation, the phosphorescence by sensitized transfer.     

Copper-exchanged mordenites as active catalysts for NO selective catalytic reduction by propene under oxidising conditions: Effect of Si/Al ratio, copper content and Brönsted acidity

CuMOR catalysts with different Si/Al ratios and copper contents, prepared from the acid and sodium forms, were studied in NO reduction with propene in the presence of excess oxygen. It was observed that the influence of zeolite Si/Al ratio on CuMOR catalytic activity for NO SCR by propene depends on the catalyst copper content, the reverse being also true. For mordenites prepared from the acid form, it was shown that the most active catalyst must have 60% of copper exchange, whereas for those prepared from the sodium form, the maximum catalytic activity is obtained for catalysts with 20% of copper exchange. Moreover, it was observed that at low copper-exchange levels, the catalyst prepared from the sodium form exhibits much higher activity than those prepared from the acid form. Although, when the copper-exchange level increases, the effect of zeolite form is less pronounced. Thus, it was indicated that Brönsted acidity does not promote the NO selective reduction by propene.     

Morphological,infrared, and ionic conductivity studies of poly(ethylene oxide)–49% poly(methyl methacrylate) grafted natural rubber–lithium perchlorate salt based solid polymer electrolytes

The potential of poly(ethylene oxide) (PEO) and 49% poly(methyl methacrylate) grafted natural rubber (MG49) as a polymer host in solid polymer electrolytes (SPE) was explored for electrochemical applications. PEO–MG49 SPEs with various weight percentages of lithium perchlorate salt (LiClO₄) was prepared with the solution casting technique. Characterization by scanning electron microscopy, Fourier transform infrared spectroscopy, and impedance spectroscopy was done to investigate the effect of LiClO₄ on the morphological properties, chemical interaction, and ionic conductivity behavior of PEO–MG49. Scanning electron microscopy analysis showed that the surface morphology of the sample underwent a change from rough to smooth with the addition of lithium salts. Infrared analysis showed that the interaction occurred in the polymer host between the oxygen atom from the ether group (C? O? C) and the Li⁺ cation from doping salts. The ionic conductivity value increased with the addition of salts because of the increase in charge carrier up to the optimum value. The highest ionic conductivity obtained was 8.0 × 10^?6 S/cm at 15 wt % LiClO₄. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Flame retardancy mechanisms of triphenyl phosphate,resorcinol bis(diphenyl phosphate) and bisphenol A bis(diphenyl phosphate) in polycarbonate/acrylonitrile–butadiene–styrene blends

The flame retardancy mechanisms of three aryl phosphates, triphenyl phosphate (TPP), resorcinol bis(diphenyl phosphate) (RDP) and bisphenol A bis(diphenyl phosphate) (BDP), in a polycarbonate/acrylonitrile–butadiene–styrene (PC/ABS) blend are investigated and compared. Further, the influence of polytetrafluorethylene (PTFE) on viscosity and thermal decomposition is discussed in the systems PC/ABS and PC/ABS + BDP. Mechanisms are proposed based on the results of various methods. Thermogravimetric analysis, Fourier transform infrared spectroscopy and kinetics are used to study the pyrolysis. The fire behaviour is studied by means of cone calorimeter measurements at different heat fluxes and the flammability is specified by limiting oxygen index (LOI) and UL 94. Rheology measurements are used to illuminate the changed dripping behaviour due to PTFE. TPP shows only a gas phase action. RDP shows mainly a gas phase action and some condensed phase action. BDP shows a crucial condensed phase action in addition to a gas phase action. TPP and RDP are somewhat superior in terms of flammability (LOI), whereas BDP shows superior performance in forced flaming combustion (cone calorimeter). Synergistic effects between PTFE and BDP are found. Copyright © 2007 Society of Chemical Industry     

Analysis of pulverized coal particles (10–100 μm) for Fe, S, Ca, Si and Al on a particle-by-particle basis

A computer controlled scanning electron microscope fitted with soft X-ray fluorescence analysed thousands of pulverized coal particles in the size range 10 to 100 μm for amounts of Al, Si, Ca, S and Fe in each of the particles. Two coals were used, namely, subbituminous C, Comanche-Wyoming and subbituminous B, Rosebud-Montana. In pulverized coal combustion Rosebud coal has a bad slagging record not predictable from conventional slagging indices based on the elemental analyses of the total coal ash. The coal particles were placed into one of four groups: little mineral matter; low melting point inorganic composition; high melting point compositions; and large amounts of iron or pyrite. On this basis, Rosebud coal had 47% of its mineral matter in groups likely to cause slagging compared with 12% for Comanche coal, in agreement with the slagging record. It is concluded that although the particle-by-particle analysis technique used here is in a crude state of development, it can give a correct indication of the possible slagging behaviour of a pulverized coal in cases where conventional slagging indices based on the analysis of the total mean coal ash fail to give the correct indication.     

Synthesis,characterization and surface properties of poly(lactic acid)–perfluoropolyether block copolymers

Laboratory‐scale synthesis and morphological and surface energy characterization of triblock A–B–A copolymers based on poly(lactic acid) (PLA; A segment) containing various block lengths of perfluoropolyether (PFPE; B segment) at 5 wt% PFPE content are reported. Incorporation of PFPE segments in PLA lowers significantly both the polar and dispersive components of total surface energy. Total surface energy is lowered from ca 35 to ca 17 mN m^?1 on copolymerization of PLA with 5 wt% PFPE. Thermal analysis data reveal that lower molecular weight PFPE segments lower significantly the glass transition, crystallization and melting temperatures of the PLA matrix. Although block length variation of the PFPE segment does not affect surface energies of copolymer films, smaller PFPE segments increase significantly the low‐temperature modulus as observed from dynamic mechanical analysis. Copyright © 2010 Society of Chemical Industry     

Synthesis,photodegradation, and energy transfer in a series of poly(ethylene terephthalate–co–2,6-naphthalenedicarboxylate) copolymers

Triplet–triplet energy transfer has been shown to occur from poly(ethylene terephthalate) (PET) units to the 2,6-naphthalenedicarboxylate (2,6-ND) monomer units in a series of poly(ethylene terephthalate–co–2,6-naphthalenedicarboxylate) (PET–2,6-ND) copolymers, as filament yarns, by an exchange mechanism at 77°K. The radius of the “quenching sphere” has been calculated to be 19.7 Å, indicating the presence of triplet energy migration. Photostabilization was observed in the copolymer yarns with the concentration of the monomer dimethyl 2,6-naphthalenedicarboxylate (2,6-DMN) at or above 2 mol %; the rate of phototendering in an air atmosphere was shown to decrease from 2.0 × 10^?19% breaking strength loss/quantum absorbed/cm² in the homopolymer PET to 0.7 × 10^?19% breaking strength loss/quantum absorbed/cm² in the copolymer yarns. The photophysical processes in the monomers, dimethyl terephthalate and 2,6-DMN, were examined by absorption and luminescence studies. The lowest excited singlet and triplet in both monomers were identified to be the ¹(π, π^*) and ³(π, π^*) states, respectively. The phosphorescence of PET was shown to originate from a ³(π, π^*) state, while the complex fluorescence spectrum may arise from some oriented aggregates in the polymer matrix. In copolymer yarns, only the fluorescence emission from the 2,6-ND monomer units at 380 nm was observed. The phosphorescence spectra of the copolymer yarns showed phosphorescence emissions from the PET and 2,6-ND monomer units; in addition, delayed fluorescence from the 2,6-ND monomer was also observed.     

Structure and properties of poly(o‐methoxyaniline)–clay nanocomposite materials

In this study, we prepared a series of polymer–clay nanocomposite (PCN) materials that consisted of an emeraldine base of poly(o‐methoxyaniline) and layered montmorillonite. Organic o‐methoxyaniline monomers were first intercalated into the interlayer regions of organophilic clay hosts followed by a one‐step in situ oxidative polymerization. The as‐synthesized PCN materials were subsequently characterized by FTIR spectroscopy, wide‐angle powder X‐ray diffraction, and transmission electron microscopy. The molecular weights of PMA extracted from PCN materials and bulk PMA were determined by GPC with THF as eluant. Effects of the material composition on the thermal stability, flame resistance, electrical conductivity, and corrosion inhibition performance of PMA, along with a series of PCN materials in the form of fine powder and coating, were also studied by TGA, limiting oxygen index measurements, four‐point probe technique, and electrochemical corrosion measurements, respectively. Morphological images of as‐synthesized materials were also investigated by SEM. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1072–1080, 2003     

Synthesis and luminescence studies of poly(vinyl acetate)–Eu (III) coordination compound

In this research, the polymeric coordination compound of PVAc–Eu (III) was synthesized, and the formation of coordination bonding between Eu (III) and the carbonyl oxygen in PVAc was investigated by Fourier transform infrared (FT‐IR) spectroscopy, Raman spectroscopy (RS), and X‐ray photoelectron spectroscopy (XPS). The luminescent characteristics/properties of the prepared PVAc–Eu (III) were studied using fluorescence spectroscopy (FS). The results indicated that (1) the interaction/association between PVAc and Eu (III) in the prepared PVAc–Eu (III) was coordination bonding instead of weak physical adsorption, and (2) the photoluminescence intensity of PVAc–Eu (III) was approximately three times that of EuCl₃. This research provided a theoretical foundation for the potential use of PVAc–Eu (III) as an innovative polymeric luminescent material, particularly for the applications in areas such as adhesives, coatings, textiles and others, the areas in which PVAc is an important raw material. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3617–3622, 2007     

Synthesis,characterization, and catalytic activity of 4 mol % N,N′‐methylene bisacrylamide crosslinked poly(acrylic acid)–metal complexes

The metal‐ion complexation behavior and catalytic activity of 4 mol % N,N′‐methylene bisacrylamide crosslinked poly(acrylic acid) were investigated. The polymeric ligand was prepared by solution polymerization. The metal‐ion complexation was studied with Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) ions. The metal uptake followed the order: Cu(II) > Cr(III) > Mn(II) > Co(II) > Fe(III) > Zn(II) > Ni(II). The polymeric ligand and the metal complexes were characterized by various spectral methods. The catalytic activity of the metal complexes were investigated toward the hydrolysis of p‐nitrophenyl acetate (NPA). The Co(II) complexes exhibited high catalytic activity. The kinetics of catalysis was first order. The hydrolysis was controlled by pH, time, amount of catalyst, and temperature. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 272–279, 2004     

Microscopic surface and bulk morphology of semicrystalline poly(dimethylsiloxane)–polyester copolymers

In this study, two series of semicrystalline poly(dimethylsiloxane) (PDMS)–polyester segmented copolymers with various PDMS contents were synthesized. One series was based on polybutylene adipate (PBA) as the polyester segment and the other was based on a polybutylene cyclohexanedicarboxylate ester (PBCH) segment. The copolymers were characterized using ¹H‐nuclear magnetic resonance, size exclusion chromatography, dynamic mechanical analyses, differential scanning calorimetry (DSC), and wide‐angle X‐ray diffraction (WAXD). The microscopic surface morphology and the microscopic bulk morphology were investigated using atomic force microscopy (AFM) and transmission electron microscopy, respectively. The effects of the polyester type and the PDMS content on the crystallinity degree as well as the copolymer surface and bulk morphology at room temperature were investigated for each series. DSC and WAXD results showed the ability of the copolymers to crystallize, to various degrees, depending on the polyester type and the PDMS content. The results showed that the PDMS content had a greater influence on the crystallinity degree in the PDMS‐s‐PBCH (cycloaliphatic) copolymer series than in the PDMS‐s‐PBA (aliphatic) copolymer series. In the copolymers with a low PDMS content, the AFM images showed spherulitic crystal morphology and evidence of PDMS nanodomains in between the crystal lamellae of the ester phase on the copolymer surface. A heterogeneous distribution of the PDMS domains was also observed for these copolymers in the bulk morphology as a result of this segregation between the polyester lamellae. All the copolymers, in both series, showed microphase separation as a result of the incompatibility between the PDMS segment and the polyester segment. Three types of surfaces and bulk morphologies were observed: spherical microdomains of PDMS in a matrix of polyester, bicontinuous double‐diamond type morphology, and spherical microdomains of polyester in a matrix of PDMS as the PDMS content increases. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Surface Properties of CaO (or BaO)–La2O3–MgO Catalysts and Their Performance in Oxidative Coupling of Methane

CaO–La₂O₃–MgO and BaO–La₂O₃–MgO catalysts with different compositions have been studied for their bulk and surface properties (viz. crystal phases, surface area, acidity/acid strength distribution, basicity/base strength distribution, etc.) and catalytic activity/selectivity in the oxidative coupling of methane (OCM) at different processing conditions (reaction temperature, 700–850°C; CH₄/O₂ ratio in feed, 3·0, 4·0 and 8·0 and GHSV, 102000 and 204000 cm³ g⁻¹ h⁻¹). The surface acidity and strong basicity of La₂O₃–MgO are found to be increased due to the addition of a third component (CaO or BaO), depending upon its concentration in the catalyst. The addition of CaO or BaO to La₂O₃–MgO OCM catalyst causes a significant improvement in its performance. Both the CaO- and BaO-containing catalysts show a high activity and selectivity at 800°C, whereas, the activity and selectivity of BaO-containing catalysts at 700°C is lower than that of CaO-containing catalysts. © 1997 SCI.     

Preparation,Microstructure, and Mechanical Properties of Nb4AlC3–Nb5(Si,Al)3 Composites

Niobium aluminum carbide (Nb₄AlC₃), as a member of the MAX phases, can retain its stiffness and strength up to over 1400°C, however, the strength at room temperature is relatively low. In this work, Nb₅(Si, Al)₃ was used to strengthen Nb₄AlC₃. Nb₄AlC₃–Nb₅(Si, Al)₃ composites with different amount of Nb₅(Si, Al)₃ were synthesized from the elemental powders by in situ hot‐pressing/solid–liquid reaction synthesis process. The RT flexural strength was significantly improved from 370 MPa of monolithic Nb₄AlC₃ to 432 MPa of Nb₄AlC₃‐15 vol% Nb₅(Si, Al)₃ composite without the degradation of its high‐temperature mechanical properties. While a slightly decrease in fracture toughness occurs with the increment of Nb₅(Si, Al)₃ content. Meanwhile, Transmission electron microscopy (TEM) observations reveal that the interfaces between Nb₄AlC₃/Nb₄AlC₃, Nb₄AlC₃/Nb₅(Si, Al)₃, and Nb₅(Si, Al)₃/Nb₅(Si, Al)₃ are free of amorphous layers, which is also beneficial to its high‐temperature mechanical properties.