Effect of rare‐earth ion size on elasticity and crack initiation in rare‐earth aluminate glasses

In oxide glasses, “hardness” and “damage‐tolerance” are usually competing attributes. The main reason for this is that hard glasses usually have closely packed structures compared to those of damage‐resistant glasses. Recent progress on the mechanical properties of alumina‐rich glasses has thrown some light on how to obtain hard and damage‐tolerant glasses. In this work, the elastic properties and indentation behavior of a glass system based on (R = La, Sm, Gd, Er, Tm, Y), prepared by an aerodynamic levitation technique, was investigated. It was found that the rare‐earth ions exhibited a strong size effect on the mechanical properties of the glasses. The elastic moduli and hardness increased with the packing density and as the ionic radii of the rare‐earth ions decreased. In addition, the resistance to surface damage by indentation increased with larger rare‐earth cations. Our results show that the elastic properties and damage tolerance of rare‐earth aluminate glasses can be tuned depending on the ionic radii of rare‐earth ions.     

Investigation of rare earth ions adsorption properties of PP‐g‐AA

Acrylic acid (AA) was grafted onto the powdered isotactic polypropylene (i‐PP) with the electron‐beam‐induced preirradiation method (Chen, D.‐T.; Shi, N.; Xu, D.‐F. J Appl Polym Sci 1999, 73, 1357–1362). Some rare earth ions, including Sm³⁺, Nd³⁺, Eu³⁺, Gd³⁺, and Er³⁺, were adsorbed onto the grafting product PP‐g‐AA. The properties of Sm³⁺ adsorbed were investigated in detail. These properties include the influences of the adsorption time, acidity, ion concentration of the solution, grafting yield of AA onto i‐PP, and temperature on the quantity and efficiency of the ion adsorption. Some kinetic and thermodynamic equilibrium constants of the adsorption were obtained in the experiments. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1549–1553, 2000     

Copolymerization of butadiene with styrene using a rare‐earth metal compound – dialkylmagnesium – halohydrocarbon catalytic system

Copolymerizations of butadiene (Bd) with styrene (St) were carried out with catalytic systems composed of a rare‐earth compound, Mg(n‐Bu)₂ (di‐n‐butyl magnesium) and halohydrocarbon. Of all the rare earth catalysts examined, Nd(P₅₀₇)₃–Mg(n‐Bu)₂–CHCl₃ showed a high activity in the copolymerization under certain conditions: [Bd] = [St] = 1.8 mol l^?1, [Nd] = 6.0 × 10^?3 mol l^?1, Mg/Nd = 10, Cl/Nd = 10 (molar ratio), ageing for 2 h, copolymerization at 50 °C for 6–20 h. The copolymer of butadiene and styrene obtained has a relatively high styrene content (10–30 mol%), cis‐1,4 content in butadiene unit (85–90%), and molecular weight ([η] = 0.8–1 dL g^?1). Monomer reactivity ratios were estimated to be r_Bd = 36 and r_St = 0.36 in the copolymerization. © 2002 Society of Chemical Industry     

The influence of Sb on glass‐forming ability of Ga‐containing As2Se3 glasses

Effect of As to Sb substitution on glass‐forming ability of As₂Se₃ glass under Ga additions was comprehensively studied using optical spectroscopy in visible and IR regions, differential scanning calorimetry, X‐ray diffraction as well as Raman scattering techniques. The crystallization processes enhanced by Ga additions to As₂Se₃ glass were significantly suppressed under such As to Sb substitution. Following conventional synthesis, it was possible to substitute up to 50% of As by Sb within Ga_y(As_0.40?xSb_xSe_0.60)_100?y cut‐section without essential impact on glassy state, thus improving optical properties in the IR region by lowering the phonon energy. In the case of Ga_y(As_0.28Sb_0.12Se_0.60)_100?y cut‐section, up to 8 at.% of Ga can be introduced without crystallization, whereas in case of Ga_y(As_0.40Se_0.60)_100?y system, glass‐forming ability is limited just up to 3 at.% of Ga. The prepared Ga₅(As_0.28Sb_0.12Se_0.60)₉₅ glass composition was shown to be the richest in Ga keeping its vitreous state, good optical and thermodynamic properties allowing further rare‐earth doping and fiber drawing.     

High‐efficiency recovery of rare earth ions by hydrolyzed poly(styrene‐co‐maleic anhydride)

Hydrolyzed poly(styrene‐co‐maleic anhydride) (PSMA) as a high‐efficiency adsorbent is used for recovering La³⁺, Eu³⁺, Tb³⁺, and Yb³⁺ from the simulate wastewater of bastnaesite leach liquor. The pseudo‐first‐order and pseudo‐second‐order models are used to fit adsorption data in the kinetic studies and the results show good correlation with the pseudo‐second‐order model. The Langmuir model is found to fit for the isotherm data of all the rare earth ions (RE³⁺) and the maximum adsorption capacity of hydrolyzed PSMA is 285.79, 301.92, 305.46, and 336.65 mg g^?1 at 298 K for La³⁺, Eu³⁺, Tb³⁺, and Yb³⁺, respectively. The adsorption could be conducted in at pH 6.0 and the equilibrium is fast established in 30 min. Competition from coexisting ions (Ca²⁺, Mg²⁺) was proved to be insignificant. Moreover, the spent adsorbent could be well regenerated and kept above 80% of adsorption efficiency at the end of the fifth cycle. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43676.     

Random copolymerization of 2,2‐dimethyltri methylene carbonate and ε‐caprolactone using a rare‐earth tris(4‐tert‐butylphenolate)s as a single‐component initiator

Highly random copolymers of 2,2‐dimethyltrimethylene carbonate (DTC) and ε‐caprolactone (CL) were synthesized by single component rare‐earth tris(4‐tert‐butylphenolate)s [Ln(OTBP)₃] for the first time. The influences of reaction conditions on the copolymerization initiated by La(OTBP)₃ have been examined in detail. The monomer reactivity ratios of DTC and CL determined by the Fineman–Ross method are 4.0 for r_DTC and 0.27 for r_CL. The microstructure of the copolymer was determined by the analyses of the diads DTC–DTC, DTC–CL, CL–DTC and CL–CL of the ¹H NMR spectra. The high degree of randomness of the chain structure was further confirmed by the ¹³C NMR spectra and differential scanning calorimetry. The thermal properties of the copolymers as a function of composition are reported. The mechanism investigated by ¹H NMR data indicates that the rare‐earth tris(4‐tert‐butylphenolate)s initiate the ring‐opening copolymerization of DTC and CL with acyl‐oxygen bond cleavages of the monomers. Copyright © 2004 Society of Chemical Industry     

Polymerization of N‐phenylmaleimide with a rare‐earth coordination catalyst

The polymerization of N‐phenylmaleimide was carried out with the binary rare‐earth coordination catalyst lanthanum phosphonate [La(P₅₀₇)]–trisobutyl aluminum [Al(i‐Bu)₃] in toluene at 60°C. The dependence of the polymerization on the polymerization time, the molar ratio of Al(i‐Bu)₃ to La(P₅₀₇), and the concentration of the catalyst were studied. The structures of the resultant polymer were characterized with ¹H‐NMR, ¹³C‐NMR, and Fourier transform infrared spectrophotometry, and the thermal properties of the polymer were measured with thermogravimetric analysis. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 979–982, 2005     

Dy3+‐Doped Selenide Chalcogenide Glasses: Influence of Dy3+ Dopant‐Additive and Containment

This work reports on process‐induced impurities in rare‐earth ion: Dy³⁺‐doped selenide chalcogenide glasses, which are significant materials for active photonic devices in the mid‐infrared region. In particular, the effect of contamination from the silica glass ampoule containment used in chalcogenide glass synthesis is studied. Heat‐treating Dy‐foil‐only, and DyCl₃‐only, separately, within evacuated silica glass ampoules gives direct evidence of silica ampoule corrosion by the rare‐earth additives. The presence of [Ga₂Se₃] associated with [Dy] on the silica glass ampoule that has been contact with the chalcogenide glass during glass melting, is reported for the first time. Studies of 0–3000 ppmw Dy³⁺‐doped Ge_16.5As₉Ga₁₀Se_64.5 glasses show that Dy‐foil is better than DyCl₃ as the Dy³⁺ additive in Ge‐As‐Ga‐Se glass in aspects of avoiding bulk crystallization, improving glass surface quality and lowering optical loss. However, some limited Dy/Si/O related contamination is observed on the surfaces of Dy‐foil‐doped chalcogenide glasses, as found for DyCl₃‐doped chalcogenide glasses, reported in our previous work. The surface contamination indicates the production of Dy₂O₃ and/or [≡Si‐O‐Dy=]‐containing particles during chalcogenide glass melting, which are potential light‐scattering centers in chalcogenide bulk glass and heterogeneous nucleation agents for α‐Ga₂Se₃ crystals.     

Erbium(III)‐doped polyurethaneureas: Novel broadband ultraviolet‐to‐visible converters

Novel, polymeric UV‐to‐visible converters were prepared by doping elastomeric poly(ether‐urethaneurea) copolymers with 5–25% by weight of ErCl₃ 6H₂O, corresponding to Er³⁺ concentrations of 2.19 to 10.86% by weight. When excited in the UV at 355 nm, the doped films generated a very broad, continuous visible luminescence between 400 and 750 nm. Preparation and spectroscopic characterization of the samples are discussed in detail. The color coordinates, color temperature, color rendering index of the samples, and the degree of overlap of their emission bands with the spectral response of the eye were determined. The color rendering index of samples is in the 57–70 range. The sample containing 2.19% by weight of Er³⁺ was found to give the color coordinates closest to the white‐source region and the highest color rendering index. The color temperatures of the samples were in the 5093–5540 K range. Overlap between the emission bands and the spectral response of the eye improved with increasing erbium concentration. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Pr3+/Yb3+:PLZT ferroelectric ceramics for near‐infrared radiation at 1340 nm

The near‐infrared luminescence properties of Pr³⁺/Yb³⁺:PLZT ferroelectric ceramics have been examined for the first time. Independently, upon either 450 nm (Pr³⁺) or 980 nm (Yb³⁺) excitation, luminescence centered at 1340 nm was observed, which corresponds to the ¹G₄→³H₅ transition of Pr³⁺. Several spectroscopic parameters for the ¹G₄→³H₅ transition of Pr³⁺ ions were determined. The average product of emission cross section and radiative lifetime were relatively large for all x/65/35 PLZT samples (x=6‐10) studied, with values close to 105±2 (×10^?26 cm²·s). These spectroscopic investigations indicate that Pr³⁺/Yb³⁺:PLZT ferroelectric ceramics are promising candidate for efficient sources emitting near‐infrared radiation at 1340 nm.     

Ring‐opening polymerization of D,L‐lactide by rare earth 2,6‐dimethylaryloxide

Ring‐opening polymerization of D,L ‐lactide (LA) has been successfully carried out by using rare earth 2,6‐dimethylaryloxide (Ln(ODMP)₃) as single component catalyst or initiator for the first time. The effects of different rare earth elements, solvents, monomers and catalyst concentration as well as polymerization temperature and time on the polymerization were investigated. The results show that La(ODMP)₃ exhibits higher activity to prepare poly(D,L ‐lactide) (PLA) with a viscosity molecular weight of 4.5 × 10⁴ g mol^?1 and the conversion of 97 % at 100 °C in 45 min. The catalytic activity of Ln(ODMP)₃ has following sequence: La > Nd > Sm > Gd > Er > Y. A kinetic study has indicated that the polymerization is first order with respect to both monomer and catalyst concentration. The apparent activation energy of the polymerization of LA with La(ODMP)₃ is 69.6 kJ mol^?1. The analyses of polymer ends indicate that the LA polymerization proceeds according to ‘coordination–insertion’ mechanism with selective cleavage of the acyl–oxygen bond of the monomer. Copyright © 2004 Society of Chemical Industry     

Polymerization of lactides and lactones. II. Ring‐opening polymerization of ε‐caprolactone and DL‐lactide by organoacid rare earth compounds

Ring‐opening polymerization of lactone and lactide have been initiated with rare earth organoacid compounds, such as lanthanum acetate in bulk. The polymerization mechanism is in agreement with the “nonionic–coordination–insertion” mechanism, which involves the selective cleavage of the acyl–oxygen bond of the monomer. These organoacid rare earth initiators can give high yield of medium to high molecular weight products. An interesting aspect of this investigation is the good agreement between the performance of the initiator and the solubility of the initiator in the monomer. However, the relatively slow initiation step makes it difficult to control the molecular weight and results in a broad molecular weight distributions. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1941–1948, 1999     

Synthesis and fluorescence properties of novel 1,10‐phenanthroline‐functionalized polyaryletherketone and its rare earth complexes

1,10‐Phenanthroline‐functionalized polyaryletherketone (PPEK) was synthesized by the amidation reaction of 5‐amino‐1,10‐phenanthroline with polyaryletherketone containing pendant acyl chloride groups. Subsequently, a series of novel rare earth coordination polymers (with rare earths Eu³⁺, Tb³⁺, Sm³⁺ and Dy³⁺) were prepared, using PPEK as macromolecular ligand and the small 1,10‐phenanthroline (Phen) molecule as synergistic ligand. Their structures were characterized using Fourier transform infrared spectroscopy, elemental analysis and X‐ray diffraction, which confirmed that both PPEK and Phen participated in the coordination reaction with the rare earth ions, and that the rare earth ions could disperse homogeneously in the polymer matrix. The rare earth coordination polymers were soluble in polar solvents such as N,N‐dimethylformamide, N,N‐dimethylacetamide and N‐methylpyrrolidone, and could be easily cast into transparent tough thin films. Fluorescence measurements indicated that all the coordination polymers exhibited the intense characteristic fluorescence of the corresponding rare earth ions under ultraviolet excitation, showing their application potential in optical display devices. Copyright © 2010 Society of Chemical Industry     

High activity of rare earth tetrahydroborates for ring‐opening polymerization of ω‐pentadecalactone

Ring‐opening polymerization of ω‐pentadecalactone (PDL) by tetrahydroborate complexes of rare earth metals, Ln(BH₄)₃(THF)₃ (Ln = La ( 1 ), Nd ( 2 ), Y ( 3 )), was studied. These complexes showed high activity for PDL polymerization in THF at 60°C. Among the complexes 1 – 3 , the neodymium complex 2 was most active. The obtained poly(PDL) was demonstrated to be hydroxy‐telechelic by ¹H‐NMR and MALDI‐TOF MS spectroscopy. Biodegradation of the poly(PDL) in compost at 60°C was investigated, where 18% weight loss of the samples was observed after 280 days. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synergistic extraction and separation study of rare earth elements from nitrate medium by mixtures of sec‐nonylphenoxy acetic acid and 2,2′‐bipyridyl

BACKGROUND: Synergistic extraction has been proven to enhance extractability and selectivity. Numerous types of synergistic extraction systems have been applied to rare earth elements, among which sec‐nonylphenoxyacetic acid (CA100) has proved to be an excellent synergistic extractant. In this study, the synergistic enhancement of the extraction of holmium(III) from nitrate medium by mixtures of CA100 (H₂A₂) with 2,2′‐bipyridyl (bipy, B) in n‐heptane has been investigated. The extraction of all other lanthanides (except polonium) and yttrium by the mixtures in n‐heptane has also been studied. RESULTS: Mixtures of CA100 and bipy have significant synergistic effects on all rare earth elements, for example holmium(III) is extracted as Ho(NO₃)₂HA₂B with the mixture instead of HoH₂A₅, which is extracted by CA100 alone. The thermodynamic functions, ΔH^o, ΔG^o, and ΔS^o have been calculated as 2.96 kJ mol^?1, ? 6.23 kJ mol^?1, and 31.34 J mol^?1 K^?1, respectively. CONCLUSION: Methods of slope analysis and constant molar ratio have been successfully applied to study the synergistic extraction stoichiometries of holmium(III) by mixtures of CA100 and bipy. Mixtures of these extractants have also shown various synergistic effects with other rare earth elements, making it possible to separate them. Thus CA100 + bipy may be used to separate yttrium from other lanthanides at appropriate ratios of the extractants. Copyright © 2011 Society of Chemical Industry     

Preparation and properties of fluorine‐containing polysiloxanes obtained via ring‐opening copolymerization of trifluoropropyltrimethylcyclotrisiloxane with cyclotetrasiloxane catalyzed by rare earth solid superacid SO$_{4}^{2-}$/TiO2/Ln3+

Traditional catalysts such as (CH₃)₄NOH, NaOH, KOH, n‐BuLi and CF₃SO₃H can catalyze the copolymerization of trifluoropropyltrimethylcyclotrisiloxane with cyclotetrasiloxane to afford fluorine‐containing polysiloxanes. However, use of these catalysts poses significant difficulties in handling and separation. In this work, fluorine‐containing polysiloxanes were synthesized through a novel and environmentally friendly method: ring‐opening copolymerization of trifluoropropyltrimethylcyclotrisiloxane with cyclotetrasiloxane catalyzed by rare earth solid superacid SO /TiO₂/Ln³⁺. The effects of reaction conditions were examined in detail. The yield sequence of various rare earth catalysts is Nd ～ La ～ Y ～ Sm > Gd, while the number‐average molecular weight sequence is Nd > La > Y > Sm > Gd. The optimum conditions for the ring‐opening copolymerization of trifluoropropyltrimethylcyclotrisiloxane with cyclotetrasiloxane are as follows: [Nd³⁺] = 0.05 mol L^?1 and mol L^?1 in the immersing solution, SO /TiO₂/Nd³⁺ calcined at 500 °C and the copolymerization conducted at 80 °C for 40 min. Structures of resulting copolymers were characterized using size exclusion chromatography, ¹H NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis and contact angle measurements. According to the copolymerization features, a cationic equilibrium reaction mechanism is proposed. Copyright © 2012 Society of Chemical Industry     

Synthesis of vinyl end‐capped polydimethylsiloxane by ring opening polymerization of octamethylcyclotetrasiloxane (D4) catalyzed by rare earth solid super acid SO42‐/TiO2/Ln3+

Rare earth solid super acids SO₄^2?/TiO₂/Ln³⁺ have been successfully developed to synthesize vinyl end‐capped polydimethylsiloxane by ring opening polymerization of octamethylcyclotetrasiloxane (D4) end‐capped with 1,1,3,3‐tetramethyl‐1,3‐divinyldisiloxane. The features of ring opening polymerization reactions have been investigated in detail. The preferable conditions for the ring opening polymerization of D4 are as follows: [Nd³⁺] = 0.07 mol L^?1 and [SO₄^2?] = 1.85 mol L^?1 in the immersing solution; the amount of SO₄^2?/TiO₂/Nd³⁺ calcined at 500 °C was 5 wt% of the amount of D4; polymerization at 80 °C for 1 h. The average molecular weights of the products obtained using various rare earth catalysts were in order Nd > La > Sm > Gd, which shows that the light rare earths were more favorable for higher molecular weight products than the heavy ones. According to the polymerization features, a cationic equilibrium reaction mechanism is proposed. © 2013 Society of Chemical Industry     

Synthesis of N‐polyethereal polypyrroles and their application for the preconcentration of rare earth ions

Conducting polymers containing polyether pseudocages (P I , P II , P III ) have been synthesized via chemical oxidation of 1,5‐bis(1,1‐pyrrole)‐3‐oxabutane (M I ), 1,8‐bis(1,1‐pyrrole)‐3,6‐dioxahexane (M II ), and 1,11‐bis(1,1‐pyrrole)‐3,6,9‐trioxaundecane (M III ) using anhydrous FeCl₃ in CHCl₃. Because as obtained polymer resins did not give any response toward any cations, they were reduced (undoped) using chemical reducing agents. Tetrabutylammonium hydroxide was found to be more effective in undoping to obtain more reproducible and reusable polymer resins. The undoped polymer resins were tried in the extraction of rare earth metal ions from the aqueous medium. Among them, only P III resin removes La(III), Eu(III) and Yb(III) and can be employed for the preconcentration of these metal ions. For batch extraction of La(III), Eu(III) and Yb(III) at neutral pH values, percent recoveries of 98.0 ± 1.0, 90.7 ± 1.4, 87.3 ± 4.0, respectively, has been obtained. The sorption capacity is found as 1.3 mg of La(III) per gram of P III resin. The P III resin could be reused at least five times without significant change in its sorption capacity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Regioselective Synthesis of β‐Aryl Enaminones and 1,4,5‐ Trisubstituted 1,2,3‐Triazoles from Chalcones and Benzyl Azides

A highly regioselective synthesis of β‐aryl enaminones and 1,4,5‐trisubstituted 1,2,3‐triazoles from chalcones and benzyl azides based on reaction solvent selection is reported. In the presence of a catalytic amount of Ce(OTf)₃, reactions of chalcones with benzyl azides in DMF at 100 °C afforded densely substituted Z‐β‐aryl enaminones in good to excellent yields, whereas treatment of chalcones with benzyl azides in toluene at 100 °C selectively produced 1,4,5‐trisubstituted 1,2,3‐triazoles in excellent yields.

     

Tetrahydrosalen‐stabilized,chloride‐containing rare‐earth complexes: Facile initiator precursors for the preparation of hydroxytelechelic poly(ε‐caprolactone)s

End‐capped poly(ε‐caprolactone)s (PCLs) have been prepared elsewhere by various initiators. However, hydroxytelechelic PCLs have been reported less frequently, although there are two hydroxyl end groups in one polymer chain, which allows diversified functionalization. Two tetrahydrosalen‐backboned chlorides containing rare‐earth complexes, YbLCl(DME)₂ and ErLCl(DME) {where L is 6,6′‐[ethane‐1,2‐diylbis(methylazanediyl)]bis (methylene)bis(2,4‐di‐tert‐butylphenol) and DME is dimethoxyethane}, were first synthesized in this study, and they were used as initiator precursors for a ring‐opening polymerization in the presence of NaBH₄ to afford hydroxytelechelic PCLs. The polymerization under different conditions was investigated, and a possible mechanism is proposed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009