Synthesis and Properties of Soluble and Light-Colored Poly(amide-imide-imide)s Based on Tetraimide-Dicarboxylic Acid Condensed from 4,4'-Oxydiphthalic Anhydride, 2,2-Bis[4-(4-aminophenoxy)phenyl]sulfone, and m-Aminobenzoic Acid, and Various Aromatic Diamines

A new-type of tetraimide-dicarboxylic acid (I) was synthesized starting from the ring-opening addition of m-aminobenzoic acid (m-ABA), 4,4'-oxydiphthalic anhydride (ODPA), and 2,2-bis[4-(4-aminophenoxy)phenyl]sulfone (BAPS) at a 2:2:1 molar ratio in N-methyl-2-pyrrolidone (NMP), followed by cyclodehydration to the diacid I. A series of soluble and light-colored poly(amide-imide-imide)s (III _a-j) was prepared by triphenyl phosphite-activated polycondensation from the tetraimide-diacid I with various aromatic diamines (II _a-j). All films cast from DMAc had cutoff wavelengths shorter than 390 nm (379–390 nm) and had b ^* values between 24.17–35.50; these polymers were much lighter in color than those of the alternating trimellitimide series. All of the polymers were readily soluble in a variety of organic solvents such as NMP, N,N-dimethyl acetamide, N,N-dimethylformamide, dimethyl sulfoxide, and even in less polar m-cresol and pyridine. Polymers III _a-j afforded tough, transparent, and flexible films, which had a strength at break ranging from 93 to 118 MPa, elongation at break from 8 to 11%, and initial modulus from 2.2 to 2.8 GPa, and some films showed yield points in the range of 95–111 MPa at stress–strain curves. The glass transition temperature of the polymers was recorded at 240–268°C. They had 10% weight loss at a temperature above 540°C and left more than 55% residue even at 800°C in nitrogen.     

Novel and Ideal Zirconium-Based Dense Membrane Reactors for Partial Oxidation of Methane to Syngas

A novel and ideal dense catalytic membrane reactor for the reaction of partial oxidation of methane to syngas (POM) was constructed from the stable mixed conducting perovskite material of BaCo_0.4Fe_0.4Zr_0.2O_3– and the catalyst of LiLaNiO/-Al₂O₃. The POM reaction was performed successfully. Not only was a short induction period of 2 h obtained, but also a high catalytic performance of 96–98% CH₄ conversion, 98–99% CO selectivity and an oxygen permeation flux of 5.4–5.8 mlcm^–2min^–1 (1.9–2.0 molm^–2S^–1Pa^–1) at 850°C were achieved. Moreover, the reaction has been steadily carried out for more than 2200 h, and no interaction between the membrane material and the catalyst took place.     

Alkylation of benzene with ethane over platinum-loaded zeolite catalyst

Alkylation of benzene with ethane was carried out using various zeolite catalysts at temperature ranges of 400–550°C. Loading of platinum onto zeolite greatly enhanced the yield of ethylbenzene. Among the zeolites tested, H-ZSM5 and H-MCM22 showed catalytic activities. By contrast, mordenite did not yield ethylbenzene. Moderate acid strength distribution is the key factor of zeolite catalysts. Optimum catalyst and conditions for this reaction are as follows. The platinum-loaded H-ZSM5 catalyst containing 6.8 wt% Pt, at a reaction temperature of 500°C, afforded ethylbenzene and styrene formation rates of 14.2 and 0.8 mmolh^–1g-cat^–1, respectively (benzene-based yields 7.3 and 0.4%). In the alkylation of benzene with ethane over platinum-loaded H-ZSM5, ethene was initially formed from ethane over the metallic platinum. Then the alkylation proceeded over the acid sites of H-ZSM5.     

Deactivation of ferrierite during the skeletal isomerization of linear butenes

Deactivation of ferrierite during the skeletal isomerization of 1-butene at atmospheric pressure and 0.15 atm 1-butene partial pressure was studied. At 300°C, the carbon content shows a sharp increase during the first 30 min-on-stream, with a slower growth thereafter. Temperature-programmed oxidation profiles corresponding to different times-on-stream are similar, showing two well-defined combustion peaks centered at about 325 and 640°C, respectively. When starting the 1-butene feed with the catalytic bed at 100 or 200°C and then increasing the temperature up to 300°C, no significant difference is observed, neither in carbon content nor in oxidation profiles. Important differences in the profiles are observed by comparing at the same time at each temperature. The lower the temperature, the higher the reactivity toward oxidation at low temperature. The carbonaceous deposit formed at 100°C shows the main combustion peak at the lowest temperature (135°C) and a more olefinic character; it could be related to a strong adsorption of reactant molecules. At 200°C, the proportion of saturated species associated to oligomers increases; while at 300°C, coke shows both aromatic and olefinic species.     

Thermally stable alumina–gallia aerogel as a catalyst for NO reduction with C3H6 in the presence of excess oxygen

In order to improve thermal stability, an alumina–gallia aerogel was prepared and the catalyst performance for NO reduction with C₃H₆ was compared with that of an alumina–gallia xerogel. Basically, both were prepared by a sol–gel method with supercritical drying for the former, while with oven drying for the latter. Upon heating at 800, 900, and 1000°C, the aerogel exhibited higher NO conversion than the xerogel at reaction temperature <400°C, while NO conversion was lower on the former than on the latter at >500°C. At 450°C, NO conversion was almost the same for these two catalysts. A marked difference was observed upon heating them at 1100°C: the aerogel still maintained quite a high activity, while the xerogel greatly lost it. After heating the aerogel at 1100°C, -phase alumina remained untransformed with its surface area of 80 m²/g, while the xerogel was completely transformed to -alumina with its surface area of 6 m²/g. The high activity remaining on the aerogel heated at 1100°C was ascribed to its large surface area.     

Synthesis and Characterization of New Polyimides Based on 3,6-Bis(4-aminophenoxy)benzonorbornane

A novel benzonorbornane-based dietheramine monomer, 3,6-bis(4-aminophenoxy)benzonorbornane (BAPBN), was prepared in two steps from aromatic nucleophilic chloro-displacement reaction of p-chloronitrobenzene with the potassium phenolate of 3,6-dihydroxybenzonorbornane, followed by hydrazine catalytic reduction of the intermediate dinitro compound. A series of benzonorbornane-based polyimides were prepared from the diamine BAPBN with various aromatic dianhydrides via a conventional two-stage synthesis in which the poly(amic acid)s obtained in the first stage were heated stage-by-stage at 150300°C to give the polyimides. The intermediate poly(amic acid)s had inherent viscosities between 0.58 and 2.03 dL/g. Almost all the solution-cast poly(amic acid) films could be thermally converted into flexible and tough polyimide films with good tensile properties. Some polyimides with more flexible backbones exhibited good solubility in polar organic solvents. Depending on the structures of the dianhydrides, the glass-transition temperatures (T _g) of these polyimides were recorded between 209 and 327°C by differential scanning calorimetry (DSC) or dynamic mechanical analysis (DMA), and the softening temperatures (T _s) determined by thermomechanical analysis (TMA) stayed in the 197320°C range. Decomposition temperatures for 10% weight loss all occurred above 480°C in both air and nitrogen atmospheres. The polyimides also showed low dielectric constants (2.62–3.53 at 1 MHz). For the comparative purpose, a series of corresponding polyimides based on l,4-bis(4-aminophenoxy)benzene (BAPB) was also prepared and characterized.     

Heterogeneous asymmetric reactions. 23. Enantioselective hydrogenation of ethyl pyruvate over cinchonine- and α-isocinchonine-modified platinum catalysts

The enantioselective hydrogenation of ethyl pyruvate to (S)-ethyl lactate over cinchonine- and -isocinchonine-modified Pt/Al₂O₃ catalysts was studied as a function of modifier concentration and reaction temperature. The maximum enantioselectivities obtained under the applied mild conditions were 89% ee using cinchonine (0.014 mmoldm^–3, 1 bar H₂, 23°C, 6% AcOH in toluene), and 76% ee in the case of -isocinchonine (0.14 mmoldm^–3, 1 bar H₂, –10°C, 6% AcOH in toluene). Since -isocinchonine of rigid structure exists only in anti-open conformation these data provide additional experimental evidence to support the former suggestion concerning the dominating role of anti-open conformation in these cinchona-modified enantioselective hydrogenations.     

Synthesis of ternary Li–Mn–O phase at a temperature of 260 ∘C and electrochemical lithium insertion into the oxide

A lithium–manganese oxide, Li _x MnO₂ (x=0.30.6), has been synthesized by heating a mixture (Li/Mn ratio=0.30.8) of electrolytic manganese dioxide (EMD) and LiNO₃ in air at moderate temperature, 260 C. The formation of the Li–Mn–O phase was confirmed by X-ray diffraction, atomic absorption and electrochemical measurements. Electrochemical properties of the Li–Mn–O were examined in LiClO₄-propylene carbonate electrolyte solution. About 0.3 Li in Li _x MnO₂ (x=0.30.6) was removed on initial charging, resulting in characteristic two discharge plateaus around 3.5V and 2.8V vs Li/Li⁺. The Li _x MnO₂ synthesized by heating at Li/Mn ratio=0.5 demonstrated higher discharge capacity, about 250mAh (g of oxide)^–1 initially, and better cyclability as a positive electrode for lithium secondary battery use as compared to EMD.     

Synthesis, Characterization and Anti-microbial Activity of Oligo-N-2-aminopyridinylsalicylaldimine and Some Oligomer-metal Complexes

The oxidative polycondensation and optimum reaction conditions of N-2-aminopyridinylsalicylaldimine using air oxygen, H₂O₂ and NaOCl were determined in an aqueous alkaline solution between 40–90°C. Oligo-N-2-aminopyridinylsalicylaldimine (OAPSA) was characterized by using ¹H-NMR, FT-IR, UV-vis and elemental analysis. N-2-aminopyridinylsalicylaldimine was converted to oligomer by oxidizing in an aqueous alkaline medium. The number average molecular weight (M _n), weight average molecular weight (M _w) and polydispersity index (PDI) values were found to be 7487 gmol^–1, 7901 gmol^–1 and 1.06, respectively. According to these values, 70% of N-2-aminopyridinylsalicylaldimine turned into oligo-N-2-aminopyridinylsalicylaldimine. During the polycondensation reaction, a part of the azomethine (–CH=N–) groups oxidized to carboxylic (–COOH) group. Besides, the structure and properties of oligomer-metal complexes of oligo-N-2-aminopyridinyl salicylaldimine (OAPSA) with Cu (II), Ni (II), and Co (II) were studied by FT-IR, UV-vis DTA, TG and elemental analysis. Anti-microbial activities of the oligomer and its oligomer-metal complexes have been tested against C. albicans, L. monocytogenes, B. megaterium, E. coli, M. smegmatis, E. aeroginesa, P. fluorescen and B. jeoreseens. Also, according to the TG and DTA analyses, oligo-N-2-aminopyridinylsalicylaldimine and its oligomer-metal complexes were found to be stable thermo-oxidative decomposition. The weight loss of OAPSA found to be 20%, 50% and 98% at 350°C, 535°C and 1000°C, respectively.     

Origin of rate bistability in Mn–O/Al2O3 catalysts for carbon monoxide oxidation: role of the Jahn–Teller effect

Peculiarities in catalytic activity in carbon monoxide oxidation as well as some structure, electronic and magnetic properties of the three oxide catalysts, Mn³⁺–O/Al₂O₃ (1), Mn³⁺–O–Fe/Al₂O₃ (Mn-substituted spinel, 2) and -Fe₂O₃/Al₂O₃ (3), were studied by kinetic measurements and by Mössbauer spectroscopy. The catalysts 1 and 2 showed a kinetic bistability with a sharp transition towards more reactive state at 200°C (ignition point). In contrast, for catalyst 3, at 200–250°C, the behavior of reaction rate against temperature did not display noticeable hysteresis. On cooling the catalysts 1 and 2, extinction was observed at about 170 and 120°C, respectively, i.e., at 30–80°C lower than the corresponding ignition points. Proximity of activation energy for the high and low activity (15–19 kJ/mol) for both Mn-containing catalysts suggests an increase in the number of active sites at high temperature with no changes in the reaction mechanism. The considerable difference between Mn-containing catalysts 1, 2 and Fe-containing catalyst 3 may be caused by Jahn–Teller (JT) type distortions of the oxygen polyhedron around Mn³⁺. A significant spontaneous axial bond stretching within the local polyhedron seems to diminish Mn–O binding energy, facilitate the participation of surface oxygen species, O_S, in the oxidation of CO by a redox mechanism and promote oxygen vacancies at the surface that would cause considerable effect on the activity. An increase in the width of the counterclockwise hysteresis loop for the catalyst 2 compared to the catalyst 1 indicates that clusters of mixed spinel provide more active sites and more labile O_S species than clusters of the binary Mn oxide.     

Characterization of phosphorus availability in selected New Zealand grassland soils

Appropriate evaluation of phosphorus (P) availability in soil is aprerequisite for ensuring the productivity and long-term sustainable managementof agroecosystems. Fifteen soils presently under grassland were collected fromdifferent areas of New Zealand and soil P availability was assessed by isotopicexchange kinetics (IEK) and related to P forms obtained by chemicalfractionation (sequential extraction). Concentrations of total P determined inthe 15 soils ranged from 375 to 2607 mg kg^–1(mean1104 mg kg^–1). Mean concentrations of inorganic P(Pi) extracted by sequential extraction with ammonium chloride, sodiumbicarbonate, sodium hydroxide (first), hydrochloric acid and sodium hydroxide(second) were 1.2, 41, 205, 113 and 23 mg kg^–1,respectively. Mean concentrations of organic P (Po) extracted by sodiumbicarbonate, sodium hydroxide (first) and sodium hydroxide (second) were 133,417 and 105 mg kg^–1, respectively. Similarly,results from IEK analysis showed that the intensity (water soluble Pi (Cp)),capacity (R/r₁ and n), and quantity (E value,isotopically exchangeable P pools (E_{1 min},E_{1 min–24 h},E_{24 h–3 m},E_{>3 m})) factors varied markedlyamongst soils. Thus Cp concentrations ranged from 0.02–1.90 mgL^–1, while concentrations of Pi determined in theE_{1 min}, E_{1 min–24},E_{24 h–3 m},E_{>3 m} pools were 2–29 (mean 10), 10–321(76), 11–745 (152), and 8–498 (177) mgkg^–1, respectively. The corresponding values forR/r₁ and n were 1.0–17.7 (mean 4.5) and0.10–0.50 (mean 0.37), respectively. Regression analysis revealed that Cpconcentrations were exponentially and inversely proportional toR/r₁,n and P sorption index (PSI)(R²=0.806(P<0.01), 0.852 (P<0.01) and 0.660(P<0.01), respectively). Cluster analysis identified twobroad groups of soils, namely those with low P availability (mean Cp0.11 mg L^–1, E_{1 min} Pi 5mg kg^–1, R/r₁ 3.9,n 0.44), and those with high P availability (mean Cp 1.33mg L^–1, E_{1 min} Pi 20mg kg^–1, R/r₁ 1.21,n 0.16). Correlation analysis indicated thatE_{1 min} P i was significantly correlated with bicarbonateextractable Pi (BPi, R²=0.37,P<0.05) and thesum of ammonium chloride extractable Pi (APi) and BPi(R²=0.38,P<0.05). However, the concentration of Pi in theE_{1 min} pool was generally lower than the sum of APi andBPi. Sodium hydroxide extractable Pi (N₁Pi) was significantlycorrelated with the sum of the E_{1 min},E_{1 min–24 h},E_{24 h–3 m} Pi pools(R₂=0.974, P<0.01),indicating that N₁Pi fractioncould be considered as representing potentially available soil P for pasturespecies over a growing season.     

Impedance spectroscopy study of electrochromism in sputtered iridium oxide films

The a.c. impedance response of sputtered iridium oxide films (SIROFs) was studied at room temperature in 1M H₂SO₄ between 1mHz and 50mHz. The spectra were recorded as a function of applied potential in the range of electrochromic properties from 0.0 to 1.0V vs SCE and before and after an electrochemical treatment consisting of alternatively colouring and bleaching the electrode. The spectra were analysed with help of an equivalent circuit. Between 0.4 and 1.0V, the spectra can be interpreted as due to electrochemical proton insertion in a single phased compound. From the data, hydrogen chemical diffusion coefficients with values ranging from 2 × 10^–8 to 1.1 × 10^–7cm²s^–1 are found. It is shown that this parameter increases fourfold after the cycling treatment and significantly decreases with the amount of inserted hydrogen. Below 0.4V spectrum changes are observed over the intermediate frequency range studied, indicating some changes of the interfacial reactivity which remain to be clarified.     

Molybdenum nitride for the direct decomposition of NO

The physico-chemical properties of passivated -Mo₂N have been investigated. The material showed high activities for NO direct decomposition: nearly 100% NO conversion and 95% N₂ selectivity were achieved at 450C. The amount of O₂ taken up by -Mo₂N increased with temperature rise and reached 3133.9 molg^–1 at 450C; we conclude that there formation of Mo₂O_xN_y occurred. This oxygen-saturated -Mo₂N material was catalytically active: NO conversion and N₂ selectivity were 89 and 92% at 450C. We found that by means of H₂ reduction at 450C, Mo₂O_xN_y could be reduced back to -Mo₂N and the oxidation/reduction cycle is repeatable; such a behaviour and the high oxygen capacity (3133.9 molg^–1) of -Mo₂N suggest that -Mo₂N is a promising catalytic material for automobile exhaust purification.     

A Sol–Gel Derived CuOx/Al2O3–ZrO2 Catalyst for the Selective Reduction of NO by Propane in the Presence of Excess Oxygen

Copper catalysts supported on alumina-doped zirconia were prepared by sol–gel processing followed by supercritical drying or aging in the mother solution at 100°C. After drying and calcination, the catalyst supports were impregnated with a copper(II) nitrate aqueous solution by the incipient wetness method to achieve a Cu loading of about 2%. The samples showed 90% NO conversion at 350–400°C. The catalytic performance of these systems appears to be determined by the degree of clustering of copper cations as probed by FTIR spectroscopy of adsorbed CO.     

Synthesis, Characterization and Optimum Reaction Conditions of Oligo-N, N′-bis (2-hydroxy-1-naphthalidene) Thiosemicarbazone

The oxidative polycondenzation reaction conditions of N, N-bis (2-hydroxy-1-naphthalidene) thiosemicarbazone (HNTSC) using air oxygen, H₂O₂ and NaOCl were studied in an aqueous alkaline medium between 50–90°C. Oligo-N, N-bis (2-hydroxy-1-naphthalidene) thiosemicarbazone was characterized by ¹H-NMR, FT-IR, UV-Vis, size exclusion chromatography (SEC) and elemental analysis techniques. Solubility testing of oligomer was investigated using organic solvents such as DMF, THF, DMSO, methanol, ethanol, CHCl₃, CCl₄, toluene acetonitrile, ethyl acetate, concentrated H₂SO₄ and an aqueous alkaline solution. Using NaOCl, H₂O₂ and air O₂ oxidants, conversion to oligo-N, N-bis (2-hydroxy-1-naphthalidene) thiosemicarbazone (OHNTSC) of N, N-bis (2-hydroxy-1-naphthalidene) thiosemicarbazone was found to be 85, 80 and 76%, respectively, in an aqueous alkaline medium. According to the SEC analyses, the number-average molecular weight, weight-average molecular weight and polydispersity index values of OHNTSC synthesized were found to be 1050 gmol^–1 1715 gmol^–1 and 1.63, using NaOCl, and 2137, 2957 gmol^–1 and 1.38, using air O₂ and 2155 gmol^–1 4164 gmol^–1 and 1.93, using air H₂O₂, respectively. Also, TG analysis was shown to be unstable of oligo-N, N-bis (2-hydroxy-1-naphthalidene) thiosemicarbazone against thermo-oxidative decomposition. The weight loss of OHNTSC was found to be 97.29% at 900°C.     

Effects of sulfide and lead nitrate addition to a gold cyanidation circuit using potentiodynamic measurements

Corrosion potentiodynamic polarization experiments on a gold electrode in a cyanide solution with 0–30ppm lead addition and 0–20ppm sulfide were carried out. Solutions containing 300ppm NaCN, adjusted to a pH 11.1 by NaOH and bubbled with air were used at atmospheric pressure and room temperature. If the concentration of lead ions was equal or larger than the sulfide ions a change of potential towards the more negative potential (a potential drop) was observed and this was accompanied by a significant increase in the corrosion rate (up to 10mmy^-1 in certain circumstances). If lead nitrate was added to a solution with a gold electrode that had been previously passivated by sulfides, the corrosion rate typically rose from about 0.3 to 0.95mmy^-1. The addition of lead nitrate to sulfides in cyanide solution can create a synergetic effect which results in an increase in dissolution rates of gold in cyanide solutions and this is accompanied by a drop in the corrosion potential of gold and a dramatic decline in thiocyanate and free sulfide concentrations.     

Water Solubility of Carbon Dioxide under Supercritical and Subcritical Conditions

The solubility of carbon dioxide in water at t = 25, 50, 100, and 150°C and p = 10–80 MPa is studied experimentally by a static method in a constant-volume cell. The results are described by the entropy method of similarity theory. The calculated and experimental data are in satisfactory agreement.     

Active-oxygen species on non-reducible rare-earth-oxide-based catalysts in oxidative coupling of methane

From supplementary in situ Raman spectroscopic studies of active-oxygen species on non-reducible rare-earth-oxide-based catalysts in the oxidative coupling of methane (OCM) and structural adaptability considerations, further support has been obtained for our proposal that there may be an active and elusive precursor (of O₂ ^– and O₂ ^2– adspecies), most probably O₃ ^2– formed from reversible redox coupling of an O₂ adspecies at an anionic vacancy with a neighboring O^2– in the surface lattice. This active precursor may initiate H abstraction from CH₄ and be itself converted to OH^–+O₂ ^–, or it may abstract an electron from the oxide lattice and be converted to O₂ ^2–+O^–. The prospect of developing this type of OCM catalysts is discussed.     

Terpolymerization: A Review

The terpolymer, poly (styrene-acrylonitrile-linalool) has been synthesized by free radical solution polymerization of the electron-donating monomers, linalool (optically active) (LIN) and styrene (STY) with the electron-accepting monomer, acrylonitrile (AN) using benzoyl peroxide (BPO) as an initiator and xylene as diluent at 75°C for 40 minutes. The system follows ideal kinetics. Rp [BPO]^0.5 [LIN]^1.0 [STY]^1.0 [AN]^1.0. ¹H-NMR spectrum of terpolymer has peaks at 7.8–8.0 due to –OH group of LIN and at 7.0–7.7 due to phenyl group of styrene. ¹³C-NMR spectrum of terpolymer has peaks at ppm = 119–120 of –CN, ppm = 129–136 of C₆H₅ and ppm = 75–77 of –C–OH. Bands at 3075 cm^–1, 2240 cm^–1 and at 3500 cm^–1 are observed in the FTIR spectrum of terpolymer, indicates the presence of phenyl, cyanide and hydroxy group respectively. The reactivity ratios, determined by the Kelen–Tüdös method [r ₁ for AN and r ₂ for (LIN + STY)] are 0.11 and 0.005 respectively. It is concluded that the system agrees with theoretical treatment and gives the relative reactivity ratio k ₁₂/k ₁₃=0.748 by treatment of the free radical propagating mechanism. The overall activation energy is 38 kJ/mol. The molecular weight of terpolymer is determined by gel permeation chromatography technique. The value of _w/ > _n is 1.36.     

Pulse electrodeposition of titanium on carbon steel in the LiF–NaF–KF eutectic melt

Electrodeposition of titanium was carried out in the K₃TiF₆–LiF–NaF–KF melt using both direct (DC) and unipolar pulse current (PC) techniques. Dense and smooth titanium coatings were obtained by PC plating at 750 °C whereas DC plating led to rough and dendritic deposits. The best results were obtained using a 100C cm^–2 pulse charge and a cathodic current density of 50 and 75mA cm^–2. The cathodic current efficiency was in the range 60–65%. The titanium deposits obtained under such conditions behaved similarly to CP-titanium in NaCl and HNO₃ solutions at room temperature.