Magnetic glass in shape memory alloy: Ni(45)Co(5)Mn(38)Sn(12)

The first order martensitic transition in the ferromagnetic shape memory alloy Ni(45)Co(5)Mn(38)Sn(12) is also a magnetic transition and has a large field induced effect. While cooling in the presence of a field this first order magnetic martensite transition is kinetically arrested. Depending on the cooling field, a fraction of the arrested ferromagnetic austenite phase persists down to the lowest temperature as a magnetic glassy state, similar to the one observed in various intermetallic alloys and in half doped manganites. A detailed investigation of this first order ferromagnetic austenite (FM-A) to low magnetization martensite (LM-M) state transition as a function of temperature and field has been carried out by magnetization measurements. Extensive cooling and heating in unequal field (CHUF) measurements and a novel field cooled protocol for isothermal MH measurements (FC-MH) are utilized to investigate the glass like arrested states and show a reverse martensite transition. Finally, we determine a field-temperature (HT) phase diagram of Ni(45)Co(5)Mn(38)Sn(12) from various magnetization measurements which brings out the regions where thermodynamic and metastable states coexist in the HT space, clearly depicting this system as a 'magnetic glass'.     

Issues with characterizing transport properties of graphene field effect transistors

The transport properties of graphene field effect transistors are typically characterized using a conventional test structure consisting of graphene on silicon dioxide with deposited metal contacts. Two of the primary parameters affecting the total resistance of this structure are the channel mobility and contact resistance. A simple model is used to describe the impact of these parameters on total device resistance and experimentally extract them. Important issues related to characterizing the transport properties of graphene field effect transistors are presented and discussed.     

Recovery of actinides extracted by Truex solvent from high level waste using complexing agents

The sorption and migration of radiostrontium in a calcareous soil from Yu Zhong county of Gansu province (China) was studied using batch and column experiments. Sorption isotherms, breakthrough curves and concentration profiles for the untreated soil and the soil treated to remove CaCO₃ were determined, respectively. It was found that radiostrontium is a relatively mobile nuclide in calcareous soil and removal of CaCO₃ from the soil slightly increases the retention ability for radiostrontium. The breakthrough curves were fitted to the analytical solution of a one-dimensional convection-dispersion transport model that assumes a reversible linear isotherm. Good agreement was obtained between the measured and predicted concentration profiles.     

Kinetic Study of the Al-Schiff's Base Initiated Polymerization of ε-caprolactone and Synthesis of Graft Poly(methylmethacrylate-g-caprolactone)

Graft copolymers of polycaprolactone (PCL) on polymethacrylate (PMMA) backbone have been successfully synthesized and characterized by SEC, ¹H and ¹³C NMR spectroscopy. The strategy used consisted of polymerizing ε-CL, followed by end-functionalization of the resulting PCL using methacryloyl chloride. Free radical polymerization of the methacryl double bond lead to the C-C polymer backbone and an overall graft copolymer. The polymerization of ε-caprolactone was achieved using Al-Schiff's base isopropoxide (HAPENAlOⁱPr) in DCM at ambient temperature. SEC and MALDI analysis of the polymers confirmed that mostly linear chains were obtained with the Al initiator, up until high monomer conversion. The low molar mass PCL was then end-capped with a methacryloyl group, in a quantitative manner, as evidenced by ¹H NMR. The macromonomer thus obtained was copolymerized in small proportions with methyl methacrylate by conventional free radical polymerization and atom transfer radical polymerization (ATRP). Analysis of the products by NMR and SEC showed the presence of true graft copolymers and the absence of homopolymers.     

Polymerization of ε-Caprolactone and its Copolymerization with γ-Butyrolactone using Metal Complexes

Solution polymerization of ε-caprolactone (ε-CL) was performed using four different initiators namely: tin(II) octanoate (Sn(Oct)₂)/ethanolamine, aluminium Schiff's base complex-HAPENAlOⁱPr, lithium diisopropyl amide (LDA) and aluminium isopropoxide. The reaction conditions varied with the initiator used. LDA gave rise to the most rapid polymerization with the highest amount of cyclic species as detected by ¹³C NMR. However, no cyclic species were detected when HAPENAlOⁱPr was used as initiator. The tin(II) octanoate/ethanolamine system lead to an α,ω-dihydroxy-polycaprolactone (PCL). The copolymerization of ε-CL was then performed with the hard to oligomerize γ-butyrolactone using the four initiators. GPC (Gel Permeation Chromatography) analyses showed the formation of copolymers. The highest incorporation of polybutyrolactone (PBL) in the copolymer was obtained using HAPENAlOⁱPr as evidenced by ¹H NMR. ¹³C NMR indicated the presence of pseudoperiodic random copolymers with short blocks of PCL whose block length varied with initiator used. The longest and shortest block length were obtained using Sn(Oct)₂ and HAPENAlOⁱPr respectively as calculated from ¹³C NMR. The reactivity ratios were determined using the Finemann-Ross method at low conversion with HAPENAlOⁱPr as initiator. The values obtained, r_CL = 19.4 and r_BL = 0.11, confirmed the presence of long blocks of CL units in the copolymer.     

Synthesis of polylactides by new aluminium Schoff's base complexes

The kinetics of DL‐lactide polymerization was studied in CH₂Cl₂ and dioxane at 25°C and in toluene at 70°C with different aluminium Schiff's base initiators namely HAPENAlOMe, HAPENAlOⁱPr, 5‐ClSALENAlOⁱPr and 5‐ClSALOPHENAlOⁱPr. It was observed that HAPEN‐type complexes derived from 2‐hydroxyacetophenone lead to much faster polymerization as compared to SALEN‐ or 5‐ClSALEN‐type initiators derived from salicylaldehyde. Moreover, substitution of the methoxide group coordinated to the central aluminium by an isopropoxide group brings about an increase in the polymerization rate but leads to transesterification reactions at much lower percentage conversion. On the other hand, replacement of the flexible ethylene diamino group by the more rigid phenylenediamino substituent slows down considerably the polymerization reaction. Analysis of the microstructure of all poly(DL‐lactides) obtained revealed the presence of isotactic sequences in agreement with a first order Markovian statistics.