Two-dimensional correlation relaxometry studies of cement pastes performed using a new one-sided NMR magnet

We present preliminary results of the first NMR T₁-T₂ two-dimensional relaxation correlation experiments performed using a one-sided NMR system in cement based materials. Two-dimensional correlation relaxometry has itself only recently been demonstrated in cement paste where it proved to be a particularly sensitive probe of pore-water dynamics providing direct information on exchange of water between the gel and capillary pore networks. Further to this we have observed differences in the structural development of a selection of cement pastes throughout the early stages of hydration and verified the theoretical frequency dependence of the ratio T₁ / T₂. When coupled with instrumentation developments in one-sided NMR magnets the way is opened to detailed, spatially resolved studies of the development of hydration and porosity in the surface layers (top 50 mm) of cementitious materials. A new magnet, suitable for such applications, is discussed.     

NMR determination of crystallinity for poly(?-l-lysine)

Crystallinity of poly(?-l-lysine) (?-PL) was discussed by analyzing the differences in the ¹H spin-spin relaxation times (T₂^H), the ¹³C spin-lattice relaxation times (T₁^C), and the ¹³C NMR signal shapes between the crystalline and the non-crystalline phases. The observed ¹H relaxation curve (free induction decay followed by solid-echo method) showed the sum of Gaussian and exponential decays. Similarly, the observed ¹³C relaxation curves obtained from the Torchia method were double-exponential. The ¹³C NMR spectrum of ?-PL was divided into the narrow and the broad lines by utilizing the intrinsic differences in the ¹H spin-lattice relaxation times in the rotating-frame between them, which are attributed to the crystalline and the non-crystalline phases, respectively. Even though the crystallinity is obtained from the identical NMR measurements, the estimated values are different with each other. The crystallinity estimated from the T₂^H differences was 75.8 ± 0.1% at 333 K and 60.7 ± 0.4% at 353 K. From the T₁^C differences, the value was estimated to be 62 ± 11%. Furthermore, the value estimated from the NMR signal separation was 54 ± 5%. In this study we have explained these discrepancies by the difference in susceptibility among the experiments for the inter-phase, which exists in-between the crystalline and the amorphous phases. Furthermore, the estimated crystallinity was ascertained by the X-ray diffraction experiment.     

NMR quantification of the partition of coronal chain segments of block copolymer vesicles

In vesicles of an ABC triblock copolymer, the soluble A and C blocks can be grafted onto the outer or the inner surfaces of the wall made of the insoluble B block. Traditionally, the determination of the fractions of A and B chain segments partitioned onto these two surfaces has been difficult. We show that they can be readily determined from NMR paramagnetic relaxation experiments. In such an experiment, a paramagnetic reagent that does not readily permeate the vesicular wall is added into a solution. This greatly shortens the spin-lattice relaxation times T₁ of these chain segments on the outer surface relative to those on the inner surface. Treating such T₁ relaxation data with a double exponential function yields the coefficients for these terms with different T₁ values and thus the relative populations for chain segments on the inner and outer vesicular wall surfaces. This method is simple and straightforward.     

H NMR study of thermotropic phase transitions in D2O solutions of poly(N-isopropylmethacrylamide)/poly(vinyl methyl ether) mixtures

¹H NMR spectroscopy was used to investigate thermotropic phase transitions in D₂O solutions of poly(N-isopropylmethacrylamide) (PIPMAm)/poly(vinyl methyl ether) (PVME) mixtures. In all studied solutions (polymer concentrations c=0.1-10 wt%) two phase transitions were detected at temperatures roughly corresponding to different lower critical solution temperatures of PIPMAm and PVME. While the phase transition of PVME component (located at lower temperatures) is not affected by the presence of PIPMAm in the mixture, the phase transition temperatures of PIPMAm component (located at higher temperatures) are affected by the phase separation of the PVME component. Measurements of ¹H spin-spin relaxation of residual water (HDO) molecules revealed that above the phase transition, a certain portion of water molecules is bound to polymer globular structures. A major part of bound water is present in globular structures of predominating polymer component in the mixture.     

Quantitative analysis of partial acylglycerols and free fatty acids in palm oil by 13C nuclear magnetic resonance spectroscopy

The chemical shifts, spin-lattice relaxation times (T ₁), and one-bond C−H coupling constants of the glycerol carbons of mono-, di-, and triacylglycerols in CDCI₃ solution are presented and discussed. The glycerol carbons have low T ₁ values (<1.0 s) and full nuclear Overhauser effect and also exhibit broader linewidths than the aliphatic carbons, suggesting that the glycerol carbons are at or near the T ₁ minimum for the dipole-dipole relaxation mechanism. Therefore, for quantitative measurement of the composition of partial acylglycerols (relative to the triacylglycerols) in palm oil, the nuclear magnetic resonance (NMR) spectrum of the β-carbons, which lie exclusively in the region δ68.3–72.1 ppm, should preferably be acquired at medium or low magnetic fields and at an elevated temperature in order to ensure that the condition for extremely narrow spectral lines is satisfied. The chemical shifts and spinlattice relaxation times of the aliphatic C-2 and C-3 carbons and of the carbonyl carbons (C-1) of acyl groups present in palm oil are also presented and discussed. The presence of free fatty acid in the palm oil is easily detected and quantified in the spectrum of the aliphatic carbons. The presence of partial acylglycerols in palm oil can also be detected and/or quantified in the NMR spectra of the C-2 and the carbonyl carbons. The quantitative analysis of the glycerol carbons of a known mixture of acylglycerols obtained by using this method is presented.     

Interactions in miscible blends and complexes of poly(N-acryloylmorpholine) with poly(p-vinylphenol)

Poly(p-vinylphenol) (PVPh) and poly(N-acryloylmorpholine) (PAcM) form interpolymer complexes in ethanol/water (1:1) solution. However, only ordinary blends are obtained from dimethylformamide solution. Each of the complexes and ordinary blends shows one composition-dependent glass transition temperature, indicating its single-phase nature. Fourier transform infrared spectroscopy and ¹³C solid-state nuclear magnetic resonance spectroscopy reveal the existence of hydrogen-bonding interactions between the hydroxyl groups of PVPh and the carbonyl groups as well as the ether oxygen of PAcM in the blends and complexes. In addition, X-ray photoelectron spectroscopy shows that the nitrogen atoms in PAcM are also involved in hydrogen-bonding interactions. Measurements of proton spin-lattice relaxation time in the rotating frame, T_1ρ(H), reveal that each of the complexes and ordinary miscible blends has one composition-dependent T_1ρ(H), indicating an intimate mixing on a scale of about 1.5 nm. The blends show a higher degree of surface enrichment of PVPh than the complexes.     

Magnetic properties of fluffy Fe@α-Fe2O3 core-shell nanowires

Novel fluffy Fe@α-Fe₂O₃ core-shell nanowires have been synthesized using the chemical reaction of ferrous sulfate and sodium borohydride, as well as the post-annealing process in air. The coercivity of the as-synthesized nanowires is above 684 Oe in the temperature range of 5 to 300 K, which is significantly higher than that of the bulk Fe (approximately 0.9 Oe). Through the annealing process in air, the coercivity and the exchange field are evidently improved. Both the coercivity and the exchange field increase with increasing annealing time (T_A) and reach their maximum values of 1,042 and 78 Oe, respectively, at T_A = 4 h. The magnetic measurements show that the effective anisotropy is increased with increasing the thickness of theα-Fe₂O₃ by annealing. The large values of coercivity and exchange field, as well as the high surface area to volume ratio, may make the fluffy Fe@α-Fe₂O₃ core-shell nanowire a promising candidate for the applications of the magnetic drug delivery, electrochemical energy storage, gas sensors, photocatalysis, and so forth.     

Structural and electrochemical behaviors of metastable Li2/3[Ni1/3Mn2/3]O2 modified by metal element substitution

Layered metastable lithium manganese oxides, Li_2/3[Ni_1/3−xMn_2/3−yM_x+y]O₂ (x = y = 1/36 for M = Al, Co, and Fe and x = 2/36, y = 0 for M = Mg) were prepared by the ion exchange of Li for Na in P2-Na_2/3[Ni_1/3−xMn_2/3−yM_x+y]O₂ precursors. The Al and Co doping produced the T^#2 structure with the space group Cmca. On the other hand, the Fe and Mg doped samples had the O6 structure with space group R-3m. Electron diffraction revealed the 1:2 type ordering within the Ni_1/3−xMn_2/3−yM_x+yO₂ slab. It was found that the stacking sequence and electrochemical performance of the Li cells containing T^#2-Li_2/3[Ni_1/3Mn_2/3]O₂ were affected by the doping with small amounts of Al, Co, Fe, and Mg. The discharge capacity of the Al doped sample was around 200 mAh g⁻¹ in the voltage range between 2.0 and 4.7 V at the current density of 14.4 mA g⁻¹ along with a good capacity retention. Moreover, for the Al and Co doped and undoped oxides, the irreversible phase transition of the T^#2 into the O2 structure was observed during the initial lithium deintercalation.     

Ionic liquids in electrochromic devices

The ionic liquid (PYR₁₄TFSI) has proved to be the key material to make a Li-ion conducting element of a complete electrochromic device, when interposed between transparent film electrodes like WO₃ and Li-charged V₂O₅. The key features of this ionic liquid and its mixtures with LiTFSI are the excellent transparency in the visible and NIR optical regions, the good ionic conductivity and the electrochemical compatibility with inorganic Li-intercalation oxide thin film electrodes used in electrochromic devices. The higher optical contrast found during WO₃ colouration with PYR₁₄TFSI-LiTFSI, compared to that in a conventional non-aqueous electrolyte like PC-LiTFSI, was attributed to the larger inertness of the former one (no decomposition reaction at the lowest electrode potential). This highly conductive ionic liquid has been incorporated into a polymer matrix (P(EO)₁₀LiTFSI), in order to obtain a transparent solid electrolyte with high Li ion conductivity and good mechanical stability. Finally this solid PYR₁₄TFSI-P(EO)₁₀LiTFSI transparent ion conductor was interposed between the same electrodes as above in order to yield a fully solid-state, Li-ion electrochromic device. This new solid electrolyte was able to transfer reversibly a Li ionic charge between 5 mC cm⁻² and 10 mC cm⁻² from the lithium storage electrode Li_xV₂O₅ to the WO₃ electrochromic electrode in less than 100 s at room T, darkening the device from an initial 80% to a final 30% transmittance (at 650 nm). Such a device has been tested first under various constant current conditions, and later under potentiostatic control using ±2 V steps. The latter method allows not only for a faster response of the electrochromic system, but provides also an easier life stability test of the device, which withstood 2000 cycles with little changes in its optical contrast.     

Miscibility study of Torlon polyamide-imide with Matrimid 5218 polyimide and polybenzimidazole

We have discovered two new miscible polymer blend systems, namely, Torlon^® 4000T with Matrimid^® 5218 and Torlon 4000T with polybenzimidazole (PBI). Both Matrimid 5218 and PBI are miscible at a molecular level with Torlon 4000T over the whole composition range as confirmed by microscopy, DSC, FTIR and DMA. DSC and DMA studies show the existence of a single glass transition in each blend. The T_g-composition curve of Torlon/Matrimid blend system forms a sigmoid curve as a function of composition, while the T_g-composition curve of the Torlon/PBI blend system is double parabola-like. FTIR spectra show the existence of hydrogen-bonding interactions in these two polymer blend systems.     

Sol–gel auto combustion synthesis of CoFe2O4/1-methyl-2-pyrrolidone nanocomposite: Its magnetic characterization

A magnetic nanocomposite was generated by the sol–gel auto-combustion method in the presence of 1-methyl-2-pyrrolidone, a functional solvent. The temperature-dependent magnetic properties of the CoFe₂O₄ nanoparticles have been extensively studied in the temperature range of 10–400 K and magnetic fields up to 80 kOe. Zero field cooled (ZFC) and field cooled (FC) curves indicate that the blocking temperature (T_B) of the CoFe₂O₄ nanoparticles is above 400 K. It was found from M–H curves that the low temperature saturation magnetization values are higher than bulk value of CoFe₂O₄. The saturation magnetization (M_s), remanence magnetization (M_r), reduced remanent magnetization (M_r/M_s) and coercive field (H_c) values decrease with increasing temperature. The M_r/M_s value of 0.75 at 10 K indicates that the CoFe₂O₄ nanoparticles used in this work have, as expected, cubic magnetocrystalline anisotropy according to the Stoner–Wohlfarth model. T^1/2 dependence of the coercive field was observed in the temperature range of 10–400 K according to Kneller's law. The extrapolated T_B and the zero-temperature coercive field values calculated according to Kneller's law are almost 427 K and 13.2 kOe, respectively. The room temperature H_c value is higher than that of the previously reported room temperature bulk values. The effective magnetic anisotropy constant (K_eff) was calculated as about 0.23×10⁶ erg/cm³ which is lower than that of the bulk value obtained due to disordered surface spins.     

Textural and pseudocapacitive characteristics of sol-gel derived RuO2·xH2O: Hydrothermal annealing vs. annealing in air

Hydrous ruthenium dioxide (RuO₂·xH₂O) prepared in a modified sol-gel process was subjected to annealing in air and water at various temperatures for supercapacitor applications. The textural and pseudocapacitive characteristics of RuO₂·xH₂O annealed in air and water were systematically compared to show the benefits of annealing in water (denoted as hydrothermal annealing). An important concept that hydrothermal annealing effectively restricts condensation of hydroxyl groups within nanoparticles, inhibits crystal growth, and maintains high water content of RuO₂·xH₂O is demonstrated in this work. The unique textural characteristics of hydrothermally annealed RuO₂·xH₂O are attributable to the high-pressured, water-enriched surroundings which restrain coalescence of RuO₂·xH₂O nanocrystallites. The crystalline, hydrous nature of hydrothermally annealed RuO₂·xH₂O favors the utilization of active species in addition to a merit of minor dependence of specific capacitance on the scan rate of CV for pseudocapacitors. As a result, RuO₂·xH₂O with hydrothermal annealing at 225 °C for 24 h exhibits 16 wt.% water, an average particle size of about 7 nm, and specific capacitance of ca. 390 F g⁻¹.     

Reinforcement of model filled elastomers: characterization of the cross-linking density at the filler-elastomer interface by H NMR measurements

The cross-linking density at the filler-elastomer interface is analyzed by ¹H NMR measurements in model reinforced elastomers composed by grafted nanosilica particles and cross-linked ethylacrylate chains. We have focused our attention on the effect of introducing fillers on the relaxation of the bulk polymer matrix which is observed at long times (t>100 μs). Measurements performed at high temperature (T>T_g+120 K) have revealed that its relaxation is affected by the topological constraints existing at the particle surface. We deduce that the effect of particles in the bulk matrix can be interpreted as that of an homogeneous additional constraint density which increases proportionally to the surface area introduced in the matrix.     

Characterization of a semisolid state in milk fat through T2* resolved T1 distributions by time domain nuclear magnetic resonance

The solid-to-liquid ratio is an important parameter in the study of fats. Many methods can be used: dilatometry, differential scanning calorimetry (DSC), and nuclear magnetic resonance (NMR). However, below approximately 20°C, NMR gives much lower solid-to-liquid values than DSC. This difference can be attributed to the presence of a semisolid state, whose T₂ value would be of the order of 50–200 μs, and which should give an NMR signal of 14 to 88.5% of the total signal of this phase at a time when the signal of the liquid phase is measured. Thus, such a state is seen partially as a liquid by NMR. In a previous study using time domain NMR, we have shown that in milk fat samples an intermediate component state clearly exists between the solid and liquid phases, constituting only about 6% of an aged milk fat. The T₂* distribution of these components in this intermediate state shows two peaks at about 60 and 170 μs. We have shown from the T₂* resolved T₁ distribution of the peak, corresponding to a T₂* of approximately 60 μs, that there is in the continuity in the crystalline phase. This first intermediate component state does not exist in pure triglyceride or in cocoa butter, and is scarcely present in a tristearin crystal/soy oil suspension. We have attributed this first intermediate component to fatty acid residue extremities that protrude from the crystalline phase and/or to chain ends at the edges of holes created by short chains.     

Synthesis and characterization of ZnxMg1 − xGa2O4:Co fabricated by low-temperature burning method

A series of Zn_xMg_1 − xGa₂O₄:Co²⁺ spinels (x = 0, 0.25, 0.5, 0.75, and 1.0) was successfully produced through low-temperature burning method by using Mg(NO₃)₂·4H₂O, Zn(NO₃)₂·6H₂O, Ga(NO₃)₃·6H₂O, CO(NH₂)₂, NH₄NO₃, and Co(NO₃)₂·6H₂O as raw materials. The product was characterized by X-ray diffraction, transmission electron microscopy, and photoluminescence spectroscopy. The product was not merely a simple mixture of MgGa₂O₄ and ZnGa₂O₄; rather, it formed a solid solution. The lattice constant of Zn_xMg_1 − xGa₂O₄:Co²⁺ (0 ≤ x ≤ 1.0) crystals has a good linear relationship with the doping density, x. The synthesized products have high crystallinities with neat arrays. Based on an analysis of the form and position of the emission spectrum, the strong emission peak around the visible region (670 nm) can be attributed to the energy level transition [⁴T₁(⁴P) → ⁴A₂(⁴F)] of Co²⁺ in the tetrahedron. The weak emission peak in the near-infrared region can be attributed to the energy level transition [⁴T₁(⁴P) → ⁴T₂(⁴F)] of Co²⁺ in the tetrahedron.     

Synthesis, characterization and photocatalytic activity of β-Ga2O3 nanostructures

Nanostructured β-Ga₂O₃ samples were prepared by a combination of the solvothermal processes and subsequent heat treatments. β-Ga₂O₃ samples with various morphologies were obtained by using different kinds of solvent, including water, isopropanol and ethylene glycol. One-dimensional β-Ga₂O₃ nanorods were obtained in water medium, while β-Ga₂O₃ spheres were prepared in alcohol. The possible mechanism related to the phase formation and morphology of the as-prepared materials was discussed. Photocatalytic performance of the synthesized β-Ga₂O₃ samples was also examined. Results revealed that β-Ga₂O₃ sample prepared with ethylene glycol showed the highest photocatalytic activity for the degradation of salicylic acid. This could be ascribed to the high surface area, abundant hydroxyl groups, and wide band gap of β-Ga₂O₃ sample synthesized in ethylene glycol.     

The key factor determining the anodic deposition of vanadium oxides

This work demonstrates that anodic deposition of vanadium oxide (denoted as VO_x·nH₂O) can be considered as the chemical co-precipitation of V⁵⁺ and V⁴⁺ oxy-/hydroxyl species and the accumulation of V⁵⁺ species at the vicinity of electrode surface is the key factor for the successful anodic deposition of VO_x·nH₂O at a potential much more negative than the equilibrium potential of the oxygen evolution reaction (OER). The results of in situ UV-vis spectra show that the V⁴⁺/V⁵⁺ ratio near the electrode surface can be controlled by varying the applied potential, leading to different, three-dimensional (3D) nanostructures of VO_x·nH₂O. The accumulation of V⁵⁺ species due to V⁴⁺ oxidation at potentials ≥0.4 V (vs. Ag/AgCl) has been found to be very similar to the phenomenon by adding H₂O₂ in the deposition solution. The X-ray photoelectron spectroscopic (XPS) results show that all VO_x·nH₂O deposits can be considered as aggregates consisting of mixed V⁵⁺ and V⁴⁺ oxy-/hydroxyl species with the mean oxidation state significantly increasing with the applied electrode potential.     

Sequestration of electroactive materials in a high Tg, insulating polymer matrix for optoelectronic applications. Part 2. Photovoltaic devices

The incorporation of high levels of electroactive compounds into a high T_g matrix polymer was investigated in photovoltaic (PV) devices. The combination of electron donor-electron acceptor pairs with optionally light harvesting organics (e.g. laser dyes) in the high T_g polymer matrix yielded PV performance in the range of literature data typically reported for organic based PV devices. The advantages for using a high T_g matrix include increasing the T_g of the electroactive compounds, preventing crystallization, improving the mechanical properties of the active layer(s) and the ability to employ lower cost fabrication processes. While the basic concept has been demonstrated, further optimization would be required to achieve a useful combination of photovoltaic properties. As in the companion paper on utilization of a high T_g polymer to sequester low molecular weight electroactive species for LED devices, this paper demonstrates the same concept for PV devices. The approach to solve the issues with low molecular weight electroactive species noted in the literature to date often involves covalent bonding of these compounds to polymeric backbones. This and the companion paper well-illustrates the blend approach is equally viable and offers a much simpler methodology.     

Excess conductivity in Cu0.5Tl0.5Ba2(Ca2−yMgy)(Cu0.5Zn2.5)O10−δ superconductor

Synthesis and characterization of Cu_0.5Tl_0.5Ba₂(Ca_2−yMg_y)(Cu_0.5Zn_2.5)O_10−δ (y=0, 1.0, and 1.5) superconductor with 0%, 50%, and 75% Mg-doping at the Ca sites are reported. The samples were synthesized by solid-state reaction and characterized by X-ray diffraction (XRD), dc-resistivity (ρ) and fluctuation induced conductivity (FIC) analysis. The zero resistivity critical temperature {T_c(R=0)} was decreased with the increase of Mg-doping at Ca sites. The microscopic parameters such as the cross-over temperature (T_o), zero temperature coherence length {ξ_c(0)} and interlayer coupling (J) were deduced from FIC analysis. According to Aslamazov Larkin equations, a distinct cross-over temperature (T_o1) from three-dimensional (3D) to two-dimensional (2D) fluctuation induced conductivity regions was observed in all samples. Another cross-over temperature (T_o2) from 2D to zero-dimensional (0D) fluctuations was also witnessed. FIC analysis revealed the deterioration of superconductivity with increased Mg-content.     

Radical copolymerization of methyl 2-norbornene-2-carboxylate and 2-phenyl-2-norbornene with styrene, alkyl acrylate, and methyl methacrylate: Facile incorporation of norbornane framework into polymer main chain and its effect on glass transition temperature

Radical copolymerization behavior of methyl 2-norbornene-2-carboxylate 1 and 2-phenyl-2-norbornene 2 was investigated. Radical copolymerization of 1 and 2 with styrene, alkyl acrylate, and methyl methacrylate in a variety of monomer combinations afforded copolymers, whose main chains consisted of norbornane framework. Relative monomer reactivity ratios for the copolymerization of 1 and 2 with n-butyl acrylate (n-BA) were determined by the Fineman-Ross method. Temperature-modulated DSC analysis for poly(1 or 2-co-n-BA)s revealed remarkable T_g-raising effect of incorporation of norbornane framework into the polymer main chain, compared to that effect of styrene repeating unit.