Continuous hydrothermal synthesis of nanometric BaZrO3 in supercritical water

Nanocrystalline barium zirconate (BaZrO₃) was synthesized using a hydrothermal synthesis process working in supercritical conditions and in a continuous way. By this method, we succeeded in the continuous and rapid production of nanopowders. As a preliminary work three barium precursors have been investigated: barium hydroxide (Ba(OH)₂), barium acetate (Ba(CH₃COO)₂) and barium nitrate (Ba(NO₃)₂). Two of them (Ba(CH₃COO)₂ and Ba(NO₃)₂) led to the pure perovskite phase. Then an experimental design has been conducted in order to determine the influence of the experimental parameters on the crystallinity and the grain size of the final product.     

Controlled Anionic Synthesis of Poly[2‐(3‐nitrocarbazolyl)ethyl methacrylate]

Poly[2‐(3‐nitrocarbazolyl)ethyl methacrylate] (poly(NCzMA)) with controlled molecular weight and narrow molecular weight distribution was successfully synthesized using (methyl methacryloyl)potassium (MMA) as a weak initiator in the presence of diethylzinc (Et₂Zn) in THF at –78°C. Et₂Zn acted both as an additive for the coordination with enolate anion and nitro group and as a scavenger to remove impurities. Block copolymers PMMA‐block‐poly(NCzMA)‐block‐PMMA and poly(NCzMA)‐block‐PS‐block‐poly(NCz‐MA), were also synthesized quantitatively (PMMA: poly(methyl methacrylate), PS: polystyrene). The results indicate that Et₂Zn can be used to synthesize the polymers of solid, nitro group‐containing methacrylate monomers by anionic polymerization in THF.     

Properties of Systems Ba(HCOO)2-M(HCOO)2-H2O (M = Ca or Mg) at 25°C

The systems Ba(HCOO)₂-Ca(HCOO)₂-H₂O and Ba(HCOO)₂-Mg(HCOO)₂-H₂O were studied at 25°C by the solubility method. The effect of the ionic radii of doubly charged metals on the formation of double salts containing barium formate was considered.     

Determination calorimetrique de l'enthalpie de formation des alliages (Al,Ba) riches en aluminum

The heats of formation of some aluminium-barium alloys have been determined by drop calorimetry at high temperature. The heats of mixing of pure liquid Al and Ba to give the liquid alloy are Δ_mH(x_Ba=O.056, 1215 K)=?6.6 kJ mole^?1 and Δ_mH(x_Ba=O.333, 1215 K)=?31.0 kJ mole^-1. To measure its heat of formation, the solid compound Al₄Ba was precipitated by addition of pure barium from a liquid (Al, Ba) bath. It was found that Δ_fH(Al_0.8Ba_O.2, solid, 1215 K)=-(37.1 ? 1.5) kJ mole^?1 with reference to the pure metals in the solid state.     

AN XPS study of the interaction of model Ba/TiO2 AND Ba/ZrO2 NSR catalysts with NO2

X-ray photoelectron spectroscopy is used to study the interaction of model NO₂ storage-reduction catalysts (NSR catalysts) Ba/TiO₂ and Ba/ZrO₂ with NO₂. The catalysts are prepared on the surface of ultrathin Al₂O₃ film substrates obtained by the FeCrAl alloy oxidation. It is shown that at room temperature the model catalysts react with NO₂ with the successive formation of surface barium nitrite and nitrate. The NO₂ reduction with the formation of barium nitrite at the initial step of the interaction is assumed to be accompanied by the oxidation of residual metallic barium and amorphous carbon impurity. It is found that the formation of barium nitrate proceeds more efficiently on Ba/ZrO₂ rather than on Ba/TiO₂.     

Synthesis and Characterization of Polymers Containing Rare Earth Metals

Europium and terbium salts of methacrylic acid (MA) and octanoic acid (OCA) were prepared by a method similar to that described in the literature. Either Eu(MA)₃ or Tb(MA)₃ with three double bonds (C?C) was used as a crosslinker containing rare earth metal ions, but the octanoic acid salts were used as additives. The salts were dissolved in methacrylic acid (<20%) and then copolymerized with methyl methacrylate (>80%) using AIBN (0.2 wt%) as initiator. The two types of polymers, one containing Eu(MA)₃ or Tb(MA)₃ and the other with Eu(OCA)₃ or Tb(OCA)₃, were synthesized by bulk copolymerization in molds made of two glass plates and characterized. The fluorescence spectroscopy of these polymers under ultraviolet/visible excitation light was investigated. The fluorescence excitation and emission spectra of the polymers showed the characteristic spectra of the free Eu³⁺ or Tb³⁺. The fluorescence intensity of the rare earth metal ions increased with increasing rare earth metal content. Fluorescence measurements for Eu(MA)₃, Tb(MA)₃, and Eu(OCA)₃ polymers do not display fluorescence quenching behavior within the range of the rare earth metal content used in our experiments. But for Tb(OCA)₃ polymers, this phenomenon was observed, illustrating that ionic aggregates exist in Tb(OCA)₃ polymeric systems.     

Influence of barium source on the characteristics of sol-precipitated BaTiO<Subscript>3</Subscript> powders and related ceramics

In order to obtain pure and fine BaTiO₃ powders with controlled morphology, sol-precipitation methods involving the use of titanium iso-propoxide and of two different barium sources, i.e. barium nitrate and barium acetate, were proposed in this work. The thermal behaviour of the synthesized gels and the X-ray diffraction data obtained for the oxide powders pointed out that, by using Ba(NO₃)₂ as barium source, the decomposition process was completed at lower temperature (750°C) and was accompanied by a more pronounced tendency to obtain a single phase BaTiO₃ composition, by comparison with the synthesis where barium acetate was used as raw material (1100°C). Scanning electron microscopy investigations emphasized the effect of the nature of barium source and synthesis conditions on the morphology of the oxide powders, as well as on the microstructure of the related ceramics.     

Fabrication and characterization of cerium doped barium titanate/PMMA nanocomposites

The cerium doped barium titanate (BaTiO₃:Ce)/poly methyl methacrylate(PMMA) polymer nano-composites (PNC) were successfully fabricated via solvent evaporation method with microwaves (2.4 GHz) heating. The X-ray diffraction measurements confirm the formation of barium titanate (BT) with crystallite size ranges from 55 to 62 nm. Differential scanning calorimetry study shows that the glass transition temperature (T_g) directly affected by microwaves heat treatment and particle size of filler. The broadband dielectric spectroscopy was employed to investigate the frequency and temperature dependence of the dielectric properties of the nanocomposites in a frequency range from 75 kHz to 5 MHz and temperature range 80–400 K. The introduction of different BT fillers in PMMA enhance the dielectric constant of PNCs drastically and give a smooth response in frequency range mentioned above. The loss factor of the composite can be suppressed by using cerium doped barium titanate filler rather than pure barium titanate filler.     

Synthesis,thermal, and photophysical properties of polymethylmethacryalte (PMMA) doped with ternary deuterated Eu(III) complexes

Two Eu(III) ternary luminescent complexes, Eu(tpb-H)₃(Tppo)₂ and Eu(tpb-H)₃(Topo)₂ (Tppo: triphenylphosphine oxide, Topo: trioctylphosphine oxide, tpb: 4,4,4-trifluoro-1-phenyl-1,3-butanedione) were synthesized using β-diketonates and phosphine oxides as ligands. Luminescent polymers were fabricated by incorporating the deuterated Eu(III) complexes in a PMMA matrix. Luminescent PMMA containing Eu(tpb-D)₃(Tppo)₂ exhibited relatively higher quantum yield, faster radiation rate, sharper red emission and larger stimulated emission cross-section and the results indicated prepared luminescent polymers including Eu(tpb-D)₃(Tppo)₂ showed promising results for applications in novel organic Eu(III) devices. Additionally, the Eu(III) complexes and luminescent PMMA showed good thermostabilization.     

Hybrid polymeric latexes containing magnetite

The work describes a study for preparing polystyrene (PSt) and polymethyl methacrylate (PMMA) latex, containing magnetite (Fe₃O₄), covalently bounded to the polymeric chains. The magnetite was functionalized with various alkoxysilanes containing double bonds: vinyltriethoxysilane (VTES), methacryloyl propyl trimethoxysilane (MPTS) and vinyldimethylethoxysilane (VMe₂TES). The ferrite-silane composite forms higher average size particles with MPTS than with VTES. Ferrite functionalized with VMe₂TES forms stable latexes with both PSt and PMMA polymers. PSt forms also stable latexes with ferrite functionalized with VTES but unstable with ferrite functionalized with MPTS.     

Structure and real composition of undoped and Cr- and Ni-doped Sr<Subscript>0.61</Subscript>Ba<Subscript>0.39</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> single crystals

Strontium barium niobate crystals with congruent melting composition Sr_0.61Ba_0.39Nb₂O₆ (SBN-61), both nominally pure and doped with Cr³⁺ и Ni³⁺ ions, have been investigated by neutron diffraction. Different strontium and barium contents as well as their different distribution over the Sr1, of Sr2 and Ba2 crystallographic sites of SBN-61 structure, caused by introduction of dopants, have been revealed. Coordination polyhedra of cations have been established based on the analysis of cation–anion internuclear distances together with the calculation of bond-valence sums for cations, which are equal to their formal charge. It was found that the Nb1 and Nb2 atoms are located in distorted octahedra with quadfurcated (the Nb1O₆ polyhedron) or bifurcated (the Nb2O₆ polyhedron) vertices, and the Sr1 atoms are located in a cuboctahedron with bifurcated vertices in the base plane. Different polyhedra have been revealed for the Sr2 and Ba2 atoms: Sr2 atoms are coordinated by 15 oxygen atoms to form a highly distorted five-capped pentagonal prism, whereas Ba2 atoms are located in a highly distorted three-capped trigonal prism with a coordination number 9. Comparison of interatomic and internuclear distances, determined by X-ray and neutron diffraction analyses, respectively, allowed to reveal a highly pronounced shift of electron density in Nb1 and Sr2 polyhedra, responsible for the covalent bond and properties of crystals. Location of Cr³⁺ и Ni³⁺ dopant ions in the SBN-61 structure as well as their formal charges has been discussed.     

Evaluation of Spectroscopic and Morphological Properties of PMMA Modified with ILs

Summary: In recent years, an important class of new compounds, ionic liquids (ILs), has been investigated as additives for polymers. In this work, we carried out the synthesis of 4 different ILs: 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM.BF₄), 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM.PF₆), and the chiral ILs acetyl-(−)menthol-1-buthylimidazole tetrafluoroborate ([amebim]BF₄) and acetyl-(−)menthol-1-buthylimidazole hexafluorophosphate ([amebim]PF₆). These ILs were added to poly(methyl methacrylate) (PMMA) in 10, 20 and 30% ratios by weight and the ILs, PMMA and the obtained materials (PMMA:ILs) were characterized by infrared, visible spectroscopy and atomic force microscope. The ILs added to PMMA did not provide significant changes in the infrared spectra, compared to pure PMMA. However, the absorption spectra in the visible region of the PMMA:ILs materials showed differences, compared to the spectrum of pure PMMA.     

Substituted propenyl end groups as reactive intermediates in radical polymerization

The addition of propagating radicals of methyl acrylate (MA) and styrene (St) to CH₂?C(CO₂CH₃)CH₂? and CH₂?C(C₆H₅)CH₂? ω‐end groups of poly(methyl methacrylate) (PMMA) and polystyrene (PSt) was investigated. The end groups were as reactive as MA and St toward the poly(methyl acrylate) (PMA) and PSt radicals, respectively. The adduct radical derived from the two types of PMMA end groups and PMA radicals underwent β fragmentation exclusively to yield PMMA radicals and end groups bound to PMA chains. The addition of PSt radicals to PMMA with CH₂?C(CO₂Me)CH₂? end groups resulted in adduct radicals that underwent β fragmentation and addition to St or coupling with PSt radicals. Adduct radicals formed by the addition of PMA radicals to both types of end groups of PSt exclusively formed C? C bond by coupling with PMA radicals to form branched structures or by addition to MA monomer to give a copolymer. The fate of the adduct radicals was highly dependent on the type of polymer chain and the substituent bound to the end group. Steric congestion of the adduct radical arising from the α‐methyl group of the PMMA chain was considered to be crucial for fragmentation to expel the PMMA radical. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 645–654, 2003     

Studies of ESR Nitroxide probe mobility in polymer blends

We report studies of the temperature-dependence of the ESR spectrum of the nitroxide spin radical 4-(2-bromoacetamide)-2,2,6,6 tetramethyl-1-oxyl piperidine (BRAMO) dispersed in poly(vinylidene fluoride) (PVDF), poly(methyl methacrylate) (PMMA), poly(vinyl acetate) (PVAc), and PVDF/PMMA and PVAC/PMMA blends of varying composition. In PVDF/PMMA blends which show a single composition-dependent T_g, the mobility of BRAMO is identical to that in pure PMMA. On the other hand, in PVAC/PMMA blends, the mobility of BRAMO corresponds to that in pure PVAC. The results suggest that (1) BRAMO selectively binds to polymers based on hydrogen bonding affinity, (2) the spin probe is sensitive to segmental motions on a length scale shorter than those which give rise to the glass transition, and (3) compatible polymer blends are heterogeneous on the length scale of the BRAMO probe (ca. 8.3 Å).     

A Molecular Barium Hydrido Complex Stabilized by a Super‐Bulky Hydrotris(pyrazolyl)borate Ligand

Hydrogenolysis of the scorpionate‐supported barium alkyl complex (Tp^Ad,iPr)Ba[CH(SiMe₃)₂](THF) (Tp^Ad,iPr=hydrotris(3‐adamantyl‐5‐isopropyl‐pyrazolyl)borate) afforded the dinuclear barium hydrido complex [(Tp^Ad,iPr)Ba(μ‐H)]₂ ( 2 ), which was characterized by NMR spectroscopy and single‐crystal X‐ray analysis. Exposure of 2 with 1 atm of CO resulted in a reductive coupling process to form the cis‐ethendiolate dianion ( 3 ). Reaction of 2 with one equivalent of PhC≡C−C≡CPh gave barium 1,4‐diphenyl‐2‐butyne‐1,4‐diyl complex {[(Tp^Ad,iPr)Ba]₂(PhCH−C≡C−CHPh) ( 4 ).     

catena‐Poly[[(acetato‐κ2O,O′)triaquabarium(II)]‐μ3‐acetato‐κ4O:O,O′:O′]

The present form of barium acetate, formulated as [Ba(C₂H₃O₂)₂(H₂O)₃]_n, is the largest reported hydrate of the salt and this leads to a distinct structural behaviour setting it apart from the rest of the family. The compound is a linear polymer with a nine‐coordinate Ba(O_aqua)₃(O_acetate)₆ monomer unit. The non‐H part of the structure is ordered according to C2/m symmetry, while the disordered water H atoms only abide by this symmetry in a statistical sense. Each molecule is halved by a mirror plane bisecting the Ba centre, one water molecule and one acetate ligand, while containing the other acetate ligand. The chains are interconnected by a disordered water–water/acetate O—H...O hydrogen‐bonding network involving all water H atoms. The structure and stability of this phase are compared with the other known acetates of barium which differ in the degree of hydration.     

Investigation of structural,rheological and thermal properties of PMMA/ONi-Al LDH nanocomposites synthesized <Emphasis Type="Italic">via</Emphasis> solvent blending method: Effect of LDH loading

This article addresses the synthesis of organically tailored Ni-Al layered double hydroxide (ONi-Al LDH) and its use in the fabrication of exfoliated poly(methyl methacrylate) (PMMA) nanocomposites. The pristine Ni-Al LDH was initially synthesized by co-precipitation method and subsequently modified using sodium dodecyl sulfate to obtain ONi-Al LDH. Nanocomposites of PMMA containing various amounts of modified Ni-Al LDH (3 wt%-7 wt%) were synthesized via solvent blending method to investigate the influence of LDH content on the properties of PMMA matrix. Several characterization methods such as X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), rheological analysis, differential scanning calorimetry (DSC) and thermo gravimetric analysis (TGA), were employed to examine the structural, viscoelastic and thermal properties of PMMA/OLDH nanocomposites. The results of XRD and TEM examination confirm the formation of partially exfoliated PMMA/OLDH nanocomposites. The FTIR results elucidate that the characteristic bands for both pure PMMA and modified LDH are present in the spectra of PMMA/OLDH nanocomposites. Rheological analyses were carried out to examine the adhesion between polymer matrix and fillers present in the nanocomposite sample. The TGA data indicate that the PMMA nanocomposites exhibit higher thermal stability when compared to pure PMMA. The thermal decomposition temperature of PMMA/OLDH nanocomposites increases by 28 K compared to that of pure PMMA at 15% weight loss as a point of reference. In comparison with pure PMMA, the PMMA nanocomposite containing 7 wt% LDH demonstrates improved glass transition temperature (T _g) of around 3 K. The activation energy (E _a), reaction orders (n) and reaction mechanism of thermal degradation of PMMA/OLDH nanocomposites were evaluated using different kinetic models. Water uptake capacity of the PMMA/OLDH nanocomposites is less than that of the pure PMMA.     

Photoreduction of 9,10-Phenanthrenequinone in the Presence of Dimethacrylate Oligomers and Their Polymers

The effective rate constants for the photoreduction (k_H) of 9,10-phenanthrenequinone (PQ) in the presence of dimethacrylate monomers (ethylene glycol dimethacrylate (DMEG), triethylene glycol dimethacrylate (TGM-3), and oligocarbonate dimethacrylate (OKM-2)) and porous polymers based on them have been spectrophotometrically determined. The values of k_H in the presence of DMEG and TGM-3 in benzene solutions and in the monomer media are two times greater than in the presence of OKM-2. The values of k_H for PQ in pores of polyDMEG, polyTGM-3, and polyOKM-2 are approximately identical and do not depend on the pore size (up to hundreds of nanometers) and the specific surface area.     

Synthesis of AB3‐type miktoarm star polymers with steroid core via a combination of “Click” chemistry and ring opening polymerization techniques

Well‐defined AB₃‐type miktoarm star‐shaped polymers with cholic acid (CA) core were fabricated with a combination of “click” chemistry and ring opening polymerization (ROP) methods. Firstly, azide end‐functional poly(ethylene glycol) (mPEG), poly(methyl methacrylate) (PMMA), polystyrene (PS), and poly(ε‐caprolactone) (PCL) polymers were prepared via controlled polymerization and chemical modification methods. Then, CA moieties containing three OH groups were introduced to these polymers as the end groups via Cu(I)‐catalyzed click reaction between azide end‐functional groups of the polymers ( mPEG‐N₃ , PMMA‐N₃ , PS‐N₃ , and PCL‐N₃ ) and ethynyl‐functional CA under ambient conditions, yielding CA end‐functional polymers ( mPEG‐Cholic , PMMA‐Cholic , PS‐Cholic , and PCL‐Cholic ). Finally, the obtained CA end‐capped polymers were employed as the macroinitiators in the ROP of ε‐caprolactone (ε‐CL) yielding AB₃‐type miktoarm star polymers ( mPEG‐Cholic‐PCL₃ , PMMA‐Cholic‐PCL₃ , and PS‐Cholic‐PCL₃ ) and asymmetric star polymer [ Cholic‐(PCL)₄ ]. The chemical structures of the obtained intermediates and polymers were confirmed via Fourier transform infrared and ¹H nuclear magnetic resonance spectroscopic techniques. Thermal decomposition behaviors and phase transitions were studied in detail using thermogravimetric analysis and differential scanning calorimetry experiments. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3390–3399     

Swelling behaviour of thermo-sensitive hydrogels based on oligo(ethylene glycol) methacrylates

The thermo-sensitive swelling behaviour of hydrogels based on 2-(2-methoxyethoxy)ethyl methacrylate (MEO₂MA) and synthesized by free radical polymerization has been investigated. The homopolymer hydrogel presents a low critical solution temperature (LCST) close to room temperature, which can be modulated by copolymerization with longer oligo(ethylene glycol) side chain methacrylates (OEG_xMA). Then, three series of copolymeric hydrogels synthesized with MEO₂MA and several low ratios of OEG_xMA with M_n = 475 g mol⁻¹ (OEG₈MA), M_n = 1100 g mol⁻¹ (OEG₂₃MA) and M_n = 2080 g mol⁻¹ (OEG₄₅MA) were studied. In addition to conventional tetra(ethylene glycol) dimethacrylate (TEGDMA) crosslinker, the use of biodegradable oligo(caprolactone) dimethacrylate (OCLDMA) was also tested. The hydrophilic/hydrophobic balance, function of the short and the long OEG side chains, establishes a swelling behaviour depending on monomer composition, side chain length and temperature. The swelling at equilibrium increases with increasing the amount of OEG_xMA in the copolymer and, at the same time, the collapsing moves progressively to higher temperature. The temperature dependent volumetric response of some of these hydrogels can be compare with the most extended thermo-sensitive hydrogel, which is based on poly(N-isopropylacrylamide) (P(N-iPAAm)). Therefore, they are potential candidates to replace it in applications where biocompatibility is required.