SOLVENT EXTRACTION OF SOME TERVALENT LANTHAN01DS WITH 5-BR0M0-, 3,5-DIBROMO- AND 5-NITROSALICYLALDEHYDE ACETOHYDRAZONES

ABSTRACT

5-Bromo-, 3,5-dibromo- and 5-nitrosalicylaldehyde acetohydrazones (BSAH, DBSAH and NSAH, respectively, or H₂L) were synthesized. The extraction of lanthanoid ions (Ln3+) including praseodymium, europium and ytterbium ions into 1,2-dichloroethane with the synthesized hydrazones in the presence of both tri-n-butylphos-phate (TBP) and perchlorate has been investigated. The extracted species were (Ln³⁺)(HLP^?)₂(TBP)₃(CI₄ ^?) for all the hydrazones. The acid dissociation constants, Ka, and the partition coefficients, K_o, of the hydrazones and the extraction constants, K_ex, of the lanthanoid complexes were determined. The introduction of electron-withdrawing bromo or nitro groups to the 3- and/or 5-position of the benzene ring in salicylaldehyde acetohydrazone (SAH), the mother compound of the synthesized hydrazones, was very effective for increasing not only the K_ex value of SAH but also its K_D value and the K_ex values of its lanthanoid complexes. Taking into consideration the above-mentioned three constants, of the synthesized hydrazones DBSAH was the most balanced and recommend-able extractant for the lanthanoids.     

SOLVENT EXTRACTION OF SOME TERVALENT LANTHANOIDS WITH SALICYLALDEHYDE n-ALKANOHYDRAZONES

Sal icylaldehyde n-alkanohydrazones (SAAH or H₂L) having 1 to 13 carbon atoms in their alkyl chains were synthesized and used for the extraction of some lanthanoid ions (Ln³⁺) including praseodymium, europium and ytterbium ions from aqueous solutions containing both tri-n-butyIphosphate (TBP) and perchlorate into I,2-dichloroethane The extracted species were (Ln³⁺) (HL-)₂(TBP)₃(C10₁,-) for all SAAH. The partition coefficients, Kd, of SAAH increased with an increase in the carbon number of the alkyl chain, the increment of log Kb being 0.64 per a carbon atom. The acid dissociation constants of SAAH also increased slightly with an increase in the carbon number, but the extraction constants of their lanthanoid complexes were almost independent of the length of the alkyl chain.     

Extraction and separation of rare earths from chloride medium with mixtures of 2‐ethylhexylphosphonic acid mono‐(2‐ethylhexyl) ester and sec‐nonylphenoxy acetic acid

BACKGROUND: 2‐ethylhexylphosphonic acid mono‐(2‐ethylhexyl) ester (HEHEHP, H₂A₂) has been applied extensively to the extraction of rare earths. However, there are some limitations to its further utilization and the synergistic extraction of rare earths with mixtures of HEHEHP and another extractant has attracted much attention. Organic carboxylic acids are also a type of extractant employed for the extraction of rare earths, e.g. naphthenic acid has been widely used to separate yttrium from rare earths. Compared with naphthenic acid, sec‐nonylphenoxy acetic acid (CA100, H₂B₂) has many advantages such as stable composition, low solubility, and strong acidity in the aqueous phase. In the present study, the extraction of rare earths with mixtures of HEHEHP and CA100 has been investigated. The separation of the rare earth elements is also studied. RESULTS: The synergistic enhancement coefficient decreases with increasing atomic number of the lanthanoid. A significant synergistic effect is found for the extraction of La³⁺ as the complex LaH₂ClA₂B₂ with mixtures of HEHEHP and CA100. The equilibrium constant and thermodynamic functions obtained from the experimental results are 10^?0.92 (K_AB), 13.23 kJ mol^?1 (ΔH), 5.25 kJ mol^?1 (ΔG), and 26.75 J mol^?1 K^?1 (ΔS), respectively. CONCLUSION: Graphical and numerical methods have been successfully employed to determine the stoichiometries for the extraction of La³⁺ with mixtures of HEHEHP and CA100. The mixtures have different extraction effects on different rare earths, which provides the possibility for the separation of yttrium from heavy rare earths at an appropriate ratio of HEHEHP and CA100. Copyright © 2009 Society of Chemical Industry     

SOLVENT EXTRACTION OF SOME TERVALENT LANTHANOIDS WITH 4-ACYL-3-PHENYL-5-ISOXAZOLONES

ABSTRACT

The solvent extraction of some tervalent lanthanoid ions (Ln³⁺) with five 4-acyl-3-phenyl-5-isoxazolones (AcyPI or HL),i.e. 4-acetyl-, 4-benzoyl-, 4- (4-toluoyl)-, 4- (4-fluorobenzoyl) - and 4-(4-nitrobenzoyl)-3-phenyl-5-isoxazolones (API,BPI, TPI, FBPI and NBPI respectively) into benzene was studied in the presence of tri-n-butylphosphate (TBP). The extracted species were (Ln³⁺) (L^-)₃ (TBP)₂ for AcyPI.     

Effect of diantimony trioxide on direct esterification between terephthalic acid and ethylene glycol

Experiments at various Sb₂O₃ concentrations were made in a pilot plant and the effect of Sb₂O₃ on continuous esterification between terephthalic acid (TPA) and ethylene glycol (EG) was obtained. Reaction rate constants of the previously reported reaction scheme were determined to fit with the experimental data obtained. It was found that the effect of Sb₂O₃ on reaction rate constant (k_i) can be expressed as follows.

• k₁ = (3.75 × 10^?4Sb + 1.0) × 1.5657 × 10⁹exp(?19,640/RT)
• k₂ = (4.75 × 10^?4Sb + 1.0) × 1.5515 × 10⁸exp(?18,140/RT)
• k₃ = (6.25 × 10^?4Sb + 1.0) × 3.5165 × 10⁹exp(?22,310/RT)
• k₄ = (4.50 × 10^?4Sb + 1.0) × 6.7640 × 10⁷exp(?18,380/RT)
• k₅ = (3.50 × 10^?4Sb + 1.0) × 7.7069 × exp(?2810/RT)
• k₆ = (1.75 × 10^?4Sb + 1.0) × 6.2595 × 10⁶exp(?14.960/RT)
• k₇ = (3.75 × 10^?4Sb + 1.0) × 2.0583 × 10¹⁵exp(?42,520/RT)

Simulation of esterification with these reaction rate constants at various Sb₂O₃ concentrations was made and the following results were obtained.

• 1 Sb₂O₃ accelerates the esterification reaction between TPA and EG.
• 2 Sb₂O₃ accelerates the main reaction and its effects on side reactions are minor. The higher the addition rate of Sb₂O₃, the lower the carboxyl end-group concentration (AV) and diethylene glycol content (DEG).
• 3 The comparison between simulation with potassium titanium oxyoxalate (PTO) in the previous report and with Sb₂O₃ in the present report shows that the acceleration of polycondensation reaction by Sb₂O₃ is higher. DEG formation rate is lower with PTO than Sb₂O₃.

     

Synthesis and surface properties of amphiphilic fluorine-containing diblock copolymers

Amphiphilic diblock copolymers (DCs) of 2,3,4,5,6-pentafluorostyrene (PFS) and 2-hydroxyethyl methacrylate (HEMA) of different composition and molecular weights were prepared by two-step reversible addition–fragmentation chain transfer (RAFT) polymerization and first used for preparation of superhydrophobic coatings for cotton/polyester fabrics. The transition from hydrophobic to superhydrophobic coatings is controlled by the ratio between poly(2,3,4,5,6-pentafluorostyrene) (PPFS) block and poly(2-hydroxyethyl methacrylate) (PHEMA) block lengths (P_n^PFS/P_n^HEMA). The increase in P_n^PFS/P_n^HEMA is accompanied by a significant increase in water (θ^Н₂^О) and diiodomethane (θ^CH₂^I₂) contact angles, which reach the plateau at P_n^PFS/P_n^HEMA = 3.5 and remains almost constant up to P_n^PFS/P_n^HEMA = 6.2. Surface modification of the cotton/polyester fabric with the DC having P_n^PFS/P_n^HEMA = 6.2 produced superhydrophobic surface with θ^Н₂^О = 158 ± 4° and contact angle hysteresis CAH = 5 ± 2°, and θ^CH₂^I₂ = 107 ± 3°.     

Development of a Green Process for the Preparation of Antioxidant and Pigment-Enriched Extracts from Winery Solid Wastes Using Response Surface Methodology and Kinetics

Red grape pomace (RGP), an abundant wine industry solid waste, was used for the recovery of polyphenols and anthocyanin pigments, using ultrasound-assisted extraction and water/glycerol mixtures as the solvent. Glycerol concentration (C_gl) and liquid-to-solid ratio (R_L/S) were first optimized by implementing Box?Behnken experimental design and the process was further studied through kinetics. The optimal conditions were found to be C_gl = 90% (w/v) and R_L/S = 90 mL g^?1, and under these conditions the extraction of total polyphenols (TP) and total pigments (TPm) obeyed first-order kinetics. Maximum diffusivity (D_e) values were 4.22 × 10^?12 and 12.59 × 10^?12 m² s^?1, for TP and TPm, respectively, and the corresponding activation energies were (E_a) 13.94 and 8.22 kJ mol^?1.     

Properties of aqueous salt solutions of poly(vinylpyrrolidone). II. Polymer dimensions and thermodynamic quantities

The unperturbed dimensions and thermodynamic parameters of poly(vinylpyrrolidone) (PVP) have been studied in aqueous salt solutions, e.g. phosphates, mono- and dihydrogen phosphates, carbonates, sulphates of sodium and potassium. Values of K₀ ( = [η]_ΘM^-1/2, where [η]_Θ is intrinsic viscosity at the theta temperature and M is molecular weight) with M_w = 78 000 g mol^-1 were found to range from 4·63×10^-4 to 5·56×10^-4 dl g^-1, and root-mean-square end-to-end distances, 〈r²〉₀^1/2, ranging from 1·61×10^-6 to 1·68×10^-6cm were evaluated. Values of the characteristic ratio, C_n, the steric parameter, σ, and the enthalpy and the entropy of dilution parameters, χ_H and χ_S, have also been calculated, and the interaction parameter was found to be χ-0·5<-0·001 for aqueous salt solutions of PVP. ©1997 SCI     

Graft copolymerization of acrylamide onto cellulose in presence of comonomer using ceric ammonium nitrate as initiator

The graft copolymerization of acrylamide (AAm) and ethylmethacrylate (EMA) monomers onto cellulose has been carried out using ceric ammonium nitrate (CAN) as initiator in presence of nitric acid at (25 ± 1)°C and varying feed molarity from 7.5 × 10^?2 mol dm^?3 to 60.0 × 10^?2 mol dm^?3 at fixed feed composition (f_AAm = 0.6). The graft yield (%G_Y) has shown a linear increasing trend upto a feed molarity of 37.5 × 10^?2 mol dm^?3. The composition of grafted copolymer chains was found to be constant (F_AAm = 0.56) during feed molarity variation but shown variations with feed composition (f_AAm) and reaction temperature. The grafting parameters have shown increasing trends up to 7.5 × 10^?3 mol dm^?3 concentration of ceric (IV) ions and decreased on further increasing the concentration of ceric (IV) ions beyond 7.5 × 10^?3 mol dm^?3. The IR and elemental analysis data were used to determine the composition of grafted chains (F_AAm) and reactivity ratio of acrylamide (r₁) and ethylmethacrylate (r₂) comonomers. The reactivity ratio for acrylamide (r₁) and ethylmethacrylate (r₂) has been found to be 0.7 and 1.0 respectively, which suggested for an alternate arrangement of average sequence length of acrylamide (mM?₁) and ethylmethacrylate (mM?₂) in grafted chains. The rate of graft copolymerization of comonomers onto cellulose was found to be proportional to square concentration of comonomers and square root to the concentration of ceric (IV) ions. The energy of activation (ΔEa) of graft copolymerization was found to be 9.57 kJ mol^?1 within the temperature range of 20–50°C. On the basis of experimental findings, suitable reaction steps have been proposed for graft copolymerization of selected comonomers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2546–2558, 2006     

Molecular weight and chain conformation of amylopectin from rice starch

By using laser light scattering (LS) and size exclusion chromatography combined LS, we have investigated the molecular weight and chain conformation of amylopectin from rice of India (II‐b), japonica (IJ‐b), and glutinous (IG‐b) in dimethyl sulfoxide (DMSO) solution. The weight‐average molecular weight (M_w) and radius of gyration (〈S²〉^½) of amylopectin were determined to be 4.06 × 10⁷ and 128.5 nm for India rice, 7.41 × 10⁷ and 169.6 nm for japonica rice, 2.72 × 10⁸ and 252.3 nm for glutinous rice, respectively. The 〈S²〉^½ values were much lower than that of normal polymers, indicating a small molecular volume of amylopectin, as a result of highly branched structure. Ignoring the difference of degree of branching, approximated dependences of 〈S²〉^½ and intrinsic viscosity ([η]) on M_w for amylopectin in DMSO at 25°C were estimated to be 〈S²〉^½ = 0.30M_w^0.35 (nm) and [η] = 0.331M_w^0.41 (mL g^?1) in the M_w range studied. Moreover, from the 〈S²〉^½ values of numberless fractions obtained from many experimental points in the SEC chromatogram detected with LS, the dependence of 〈S²〉^½ on M_w for the II‐b sample was estimated also to be 〈S²〉^½ = 0.34 M_w^0.347, coinciding with the above results. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Interaction of polystyryl radical with Cu(DMF)2Br2

The kinetics of 2,2′-azobisisobutyronitrile (AIBN) initiated polymerization of styrene in N,N-dimethylformamide (DMF) at 60°C were investigated in the presence of dibromo(N,N-dimethylformamide)copper(II) complex. The complex was prepared in situ by mixing tetrakis (N,N-dimethylformamide)copper(II) perchlorate with LiBr in the molar ratio of 1 : 2. The equilibrium constant for [Cu(DMF)₄]²⁺ + 2Br^? ? Cu(DMF)₂Br₂ + 2DMF was calculated by the limiting logarithmic method as 1.80 × 10³ L² mol^?2. The velocity constant at 60°C for the interaction of polystyryl radical with Cu(DMF)₂Br₂ is 7.46 × 10⁴ L mol^?1 s^?1.     

Gas permeability of polyacetylenes carrying substituents

The gas permeabilities of three polyacetylene films, prepared from poly[1-(trimethylsilyl)-1-propyne], poly(tert-butylacetylene), and poly(1-chloro-2-phenylacetylene), were studied. Although depending on conditions of polymerization and membrane preparation, typical permeability coefficients P of the polymers to oxygen and nitrogen at 25°C were as follows: poly[1-(trimethylsilyl)-1-propyne], P_O2 = 40 × 10^?8, P_Nr2 = 20 × 10^?8; poly(tert-butylacetylene), P_O2 = 3.0 × 10^?8, P_N2 = 1.0 × 10^?8; poly(1-chloro-2-phenylacetylene), P_O2 = 9.4 × 10^?10, P_N2 = 2.0 × 10^?10 cm³(STP) · cm/(cm² · s · cm Hg). Thus P_O2 of a poly[1-(trimethylsilyl)-1-propyne] film is the largest among those ever known, and the values of poly(tert-butylacetylene) and poly(1-chloro-2-phenylacetylene) films are also fairly large. Influences of polymer structure, measuring temperature, and so forth on the P_O2 and P_N2 of these polyacetylene films were studied. The possibility of applying these films to oxygen enrichment of air are being discussed.     

Thermophysical properties of laboratory-prepared corn/wheat dried distillers grains and dried distillers solubles dehydrated with superheated steam and hot air

The objective of this study was to dry–wet distillers grains and centrifuged solubles and to examine the effect of two different drying media, superheated steam and hot air, at different drying temperatures (110, 130, and 160°C), moisture contents (5–30% wb), and percentages of solubles’ presence (0 or 100%) on some thermophysical properties of laboratory-prepared corn/wheat dried distillers co-products, including geometric mean diameter (d_g), particle density (ρ_p), bulk density (ρ_b), bulk porosity (?_b), specific heat (C), effective thermal diffusivity (α_eff), and bulk thermal conductivity (λ_b). The values of d_g of corn/wheat dried distillers co-products ranged from 0.358 ± 0.001 to 0.449 ± 0.001 mm. Experimental values of ρ_p, ρ_b, and ?_b varied from 1171 ± 6 to 1269 ± 3 kg m^?3, from 359 ± 7 to 605 ± 5 kg m^?3, and from 0.54 ± 0.01 to 0.71 ± 0.01 kg m^?3, respectively. The values of α_eff were between 0.58 × 10^?7 and 0.93 × 10^?7 m² s^?1. The calculated values of C ranged from 1887 ± 11 to 2599 ± 19 J kg^?1 K^?1, and the values of λ_b of corn/wheat dried distillers co-products ranged from 0.06 ± 0.01 to 0.09 ± 0.01 W m^?1 K^?1. Multiple linear regression prediction models were developed to predict the changes in d_g, ρ_p, ρ_b, ?_b, C, α_eff, and λ_b of laboratory-prepared corn/wheat dried distillers co-products with different operational factors.     

Reaction Kinetics of Hydroxyl Radicals with Model Compounds of Fuel Cell Polymer Membranes

The chemical stability of perfluorinated and non‐perfluorinated low temperature fuel cell model compounds (MCs) against attack by hydroxyl radicals, HO^•, is compared using a competition kinetics approach in aqueous solutions at ambient temperature. HO^• radicals were generated in situ by UV photolysis of hydrogen peroxide in the electron spin resonance (ESR) resonator. Acetic acid (AA), trifluoroacetic acid (TFAA), methanesulfonic acid (MSA), trifluorosulfonic acid (TFSA), and perfluoro(2‐ethoxyethane)sulfonic acid (PFEESA) were chosen as MCs, while the rate constants of 5,5‐dimethyl‐1‐pyrroline‐N‐oxide (DMPO) and methanol (CH₃OH) served as reference for the determination of relative rate constants by means of steady state ESR signal amplitudes. In decreasing order the rate constants are: k_MSA = (4.8 ± 0.2) × 10⁷ M^–1 s^–1, k_AA = (4.2 ± 0.3) × 10⁷ M^–1 s^–1, k_PFEESA = (3.7 ± 0.1) × 10⁶ M^–1 s^–1, k_TFAA = (7.9 ± 0.2) × 10⁵ M^–1 s^–1, and k_TFSA < 1.0 × 10⁵ M^–1 s^–1. Applying these results to perfluorinated fuel cell membranes like Nafion®, the main points of attack by HO^• are concluded to be the ether groups of the side chains, followed by the remaining carboxyl groups from the manufacturing process of the polymers.     

Synthesis and characterization of functional copolymers of citronellol with butylmethacrylate initiated by benzoyl peroxide

Benzoyl peroxide (BPO)‐initiated free radical copolymerization of citronellol with butylmethacrylate (BMA) in xylene at 80°C ± 0.1°C under the inert atmosphere of nitrogen has been studied. The kinetics expression is R_p α [I]^0.5±0.27 [citronellol]^1.0±0.13 [BMA]^1.0±0.18. The overall activation energy has been calculated as 65 kJ/mol. Bands at 3436 and 1732 cm^?1 in the FTIR spectrum of the copolymer(s) have indicated the presence of hydroxy, ester group of citronellol and butylmethacrylate, respectively. The ¹H‐NMR spectrum shows peaks at 7.0–7.7 δ due to ? OH proton of citronellol and at 3.2–4.0 δ due to ? OCH₂ proton of butylmethacrylate. The molecular weight M_v and η_int of the copolymers have been measured with the help of gel permeation chromatography in tetrahydrofuran at 25°C to calculate Mark‐Houwink constants as K = 2.68 × 10^?4 and α = 0.34 ± 0.40. The alternating nature of the copolymer is confirmed by reactivity ratios r₁ (BMA) = 0.023 ± 0.004 and r₂ (Citronellol) = 0.0025 ± 0.22. The Alfrey‐Price Q‐e parameters for citronellol have been calculated as Q₂ = 0.13 and e₂ = –1.28. Thermal decompositions of copolymer are evaluated with the help of thermal gravimetric analysis technique. The mechanism of copolymerization has been elucidated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of polyaniline/NiO nanocomposite

Spherical nickel oxide (NiO) nanoparticles were prepared by using nickel chloride as precursor in the ethylene glycol as solvent and urea as precipitant. The X‐ray diffraction study showed that NiO has single‐phase cubic structure with average crystallite size of 35 nm. The prepared NiO nanoparticles were incorporated into polyaniline (PANI) matrix during in situ chemical oxidative polymerization of aniline with different molar ratios of aniline: NiO (12 : 1, 6 : 1, and 3 : 1) at 5°C using (NH₄)₂S₂O₈ as oxidant in aqueous solution of sodium dodecylbenzene sulfonic acid, as surfactant and dopant under N₂ atmosphere. The synthesized composites have been characterized by means of X‐ray diffraction (XRD), thermogravimetric analysis, Fourier transform infrared (FTIR), scanning electron microscopy, TEM, and vibrating sample magnetometer for its structural, thermal, morphological, and magnetic investigation. The XRD and FTIR studies show that the NiO particles are in the composite. The room temperature conductivities of the synthesized PANI, PANI/NiO (12 : 1), (6 : 1), and (3 : 1) composites were found to be 3.26 × 10^?4, 1.88 × 10^?4, 1.5 × 10^?4, and 4.61 × 10^?4 S/cm, respectively. The coercivity (H_c) and remnant magnetization (M_r) of NiO, PANI/NiO NCs (12 : 1), (6 : 1), and (3 : 1) at 5 K was found to be 8.22 × 10^?2, 6.31 × 10^?2, 6.42 × 10^?2, 6.27 × 10^?2 T, and 6.64 × 10^?3, 1.83 × 10^?4, 3.07 × 10^?4, and 3.98 × 10^?4 emu/g, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Extraction relationship of Li+ and H+ using tributyl phosphate in the presence of Fe(III)

ABSTRACT

During the extraction of lithium from high Mg-containing salt lake brines by tributyl phosphate (TBP) in the presence of Fe(III), H⁺ is used to stabilize Fe(III). However, the distribution ratio of H⁺ (D_H) is 4–6 times higher than that of Li⁺ (D_Li), which affects the extraction of Li⁺ significantly. In this study, the competition mechanism between H⁺ and Li⁺ was investigated by spectral analysis and thermodynamic equilibrium. The extracted species are determined as HFeCl₄ · 2TBP and LiFeCl₄ · 2TBP for H⁺ and Li⁺, respectively. The apparent equilibrium constants are K_H = 799.8 and K_Li = 120.6, respectively. Both equilibrium constants and the distribution ratios for H⁺ and Li⁺ extraction show that extraction of H⁺ is stronger than Li⁺.     

Radical polymerization behavior of dimethyl vinylphosphonate: Homopolymerization and copolymerization with trimethoxyvinylsilane

Dialkyl vinylphosphonates such as dimethyl vinylphosphonate (DMVP) and diethyl vinylphosphonate were quantitatively polymerized with dicumyl peroxide (DCPO) at 130°C in bulk. The polymerization of DMVP with DCPO was kinetically studied in bulk by fourier transform near‐infrared spectroscopy (FTNIR) and electron spin resonance (ESR) spectroscopy. The initial polymerization rate (R_p) was given by R_p = k[DCPO]^0.5[DMVP]^1.0 at 110°C, being the same as that of the conventional radical polymerization involving bimolecular termination. The overall activation energy of the polymerization was estimated to be 26.2 kcal/mol. The polymerization system involved ESR‐observable propagating polymer radicals under the practical polymerization conditions. ESR‐determined rate constants of propagation (k_p) and termination (k_t) were k_p = 19 L/mol s and k_t = 5.8 × 10³ L/mol s at 110°C, respectively. The molecular weight of the resultant poly(DMVP)s was low (M_n = 3.4 ? 3.5 × 10³), because of the high chain transfer constant (C_m = 3.9 × 10^?2 at 110°C) to the monomer. DMVP (M₁) showed a considerably high reactivity in the radical copolymerization with trimethoxyvinylsilane (TMVS) (M₂) at 110°C in bulk, giving an inorganic component‐containing functional copolymer with potential flame‐retardant properties; r₁ = 1.6 and r₂ = 0. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of acrylic acid neutralization on ‘livingness’ of poly[styrene‐ran‐(acrylic acid)] macro‐initiators for nitroxide‐mediated polymerization of styrene

BACKGROUND: The effect of acrylic acid neutralization on the degradation of alkoxyamine initiators for nitroxide‐mediated polymerization (NMP) was studied using styrene/acrylic acid and styrene/sodium acrylate random copolymers (20 mol% initial acrylate feed concentration) as macro‐initiators. The random copolymers were re‐initiated with fresh styrene in 1,4‐dioxane at 110 °C at SG1 mediator/BlocBuilder^® unimolecular initiator ratios of 5 and 10 mol%. RESULTS: The value of k_pK (k_p = propagation rate constant, K = equilibrium constant) was not significantly different for styrene/acrylic acid and styrene/sodium acrylate compositions at 110 °C (k_pK = 2.4 × 10^?6–4.6 × 10^?6 s^?1) and agreed closely with that for styrene homopolymerization at the same conditions (k_pK = 2.7 × 10^?6–3.0 × 10^?6 s^?1). All random copolymers had monomodal, narrow molecular weight distributions (polydispersity index M?_w/M?_n = 1.10–1.22) with similar number‐average molecular weights M?_n = 19.3–22.1 kg mol^?1. Re‐initiation of styrene/acrylic acid random copolymers with styrene resulted in block copolymers with broader molecular weight distributions (M?_w/M?_n = 1.37–2.04) compared to chains re‐initiated by styrene/sodium acrylate random copolymers (M?_w/M?_n = 1.33). CONCLUSIONS: Acrylic acid degradation of the alkoxyamines was prevented by neutralization of acrylic acid and allowed more SG1‐terminated chains to re‐initiate the polymerization of a second styrenic block by NMP. Copyright © 2008 Society of Chemical Industry     

Effects of Gd Substitution on Sintering and Optical Properties of Highly Transparent (Y0.95−xGdxEu0.05)2O3 Ceramics

Highly transparent (Y_0.95?xGd_xEu_0.05)₂O₃ (x = 0.15–0.55) ceramics have been fabricated by vacuum sintering at the relatively low temperature of 1700°C for 4 h with the in‐line transmittances of 73.6%–79.5% at the Eu³⁺ emission wavelength of 613 nm (~91.9%–99.3% of the theoretical transmittance of Y_1.34Gd_0.6Eu_0.06O₃ single crystal), whereas the x = 0.65 ceramic undergoes a phase transformation at 1650°C and has a transparency of 53.4% at the lower sintering temperature of 1625°C. The effects of Gd³⁺ substitution for Y³⁺ on the particle characteristics, sintering kinetics, and optical performances of the materials were systematically studied. The results show that (1) calcining the layered rare‐earth hydroxide precursors of the ternary Y–Gd–Eu system yielded rounded oxide particles with greatly reduced hard agglomeration and the particle/crystallite size slightly decreases along with increasing Gd³⁺ incorporation; (2) in the temperature range 1100°C–1480°C, the sintering kinetics of (Y_0.95?xGd_xEu_0.05)₂O₃ is mainly controlled by grain‐boundary diffusion with similar activation energies of ~230 kJ/mol; (3) Gd³⁺ addition promotes grain growth and densification in the temperature range 1100°C–1400°C; (4) the bandgap energies of the (Y_0.95?xGd_xEu_0.05)₂O₃ ceramics generally decrease with increasing x; however, they are much lower than those of the oxide powders; (5) both the oxide powders and the transparent ceramics exhibit the typical red emission of Eu³⁺ at ~613 nm (the ⁵D₀→⁷F₂ transition) under charge transfer (CT) excitation. Gd³⁺ incorporation enhances the photoluminescence and shortens the fluorescence lifetime of Eu³⁺.