In situ FTIR spectroscopic study on crystallization process of isotactic polystyrene

The melt crystallization process of isotactic polystyrene (i-PS) was studied by means of in situ Fourier transform infrared (FTIR) spectroscopy, with a focus on the conformational changes during the induction period. The spectra obtained during the induction period suggested the occurrence of some ordered structure that is characterized by higher regularity and packing of the helical moieties than observed in the melt. This ordered structure was clearly different from the amorphous structure, and close to the crystal structure. The Avrami analysis indicated that the formation process of the ordered structure at the late stage of the induction period is similar to the growth process of the crystallites after the induction period. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1227–1233, 1998     

In situ crystallization of low-melting ionic liquids

Single crystals of five very low-melting ionic liquids, [emim]BF4 (mp -1.3 degrees C), [bmim]PF6 (+1.9 degrees C), [bmim]OTf (+6.7 degrees C), [hexpy]NTf2 (-3.6 degrees C), and [bmpyr]NTf2 (-10.8 degrees C), have been grown using a combined calorimetric and zone-melting approach and their crystal structures determined by X-ray diffraction.     

In situ FTIR study of the adsorption geometry of bisulfate accepted ions on a platinum electrode

It is shown that a better understanding of the geometry of adsorbed bisulfate species on the surface is gained by monitoring simultaneously more than one vibrational mode of the molecule. We propose that in the double layer region the bisulfate ions are adsorbed via an oxygen atom of its SO₃ unit with the Pt-O-S linkage along the surface normal. In the oxide region the bisulfate ions are adsorbed on the oxygen covered surface of the platinum electrode via the hydrogen atom by hydrogen bonding with the hydrogen bond showing a significant tilt (approximately 60° ).     

In situ SAXS investigations of isothermal crystallization in poly(TMPS) fractions

The isothermal crystallization kinetics of poly(TMPS) has been measured by ISSAXS and results obtained for a molecular weight fraction (21,000) below the critical entanglement molecular weight (25,000) and another one above it (371,000). The SAXS intensity vs. time curves suggest that a single transformation mechanism exists. The SAXS long period is independent of crystallization time for both poly(TMPS) fractions. However the interlamellar thickness contribution to the long period is dependent upon molecular weight and crystallization temperature, increasing with temperature and molecular weight. The crystallite contribution also increases over the range studied. Both fractions exhibit a significant, but reversible decrease in thickness on cooling the sample from the crystallization temperature to room temperature and recyling again. The change is more pronounced for 371,000 specimen in keeping with its lower crystallinity. The path dependence of lamellar dimensions has significant implications in the morphological characterization of polymers annealed or crystallized at one temperature and then measured at another one.Paper presented at the American Physical Society March 25–29, Baltimore, MD (1985).     

Ethylene-styrene copolymerization with constrained geometry catalysts: a density functional study

A density functional theory (DFT) study of the ethylene-styrene copolymerization process with titanium-based constrained geometry catalyst (CGC) is presented. To establish the difference between simplified CGC or real CGC models, i.e., considering all ligands of the catalyst, we have performed calculations for ethylene and styrene insertions in both models. Thus, we have used two different DFT functional, BP86 and B3L YP along with two basis set, LANL 2DZ (without polarization functions) and DZVP (including polarization functions). We have noted certain differences between theoretical results published by other authors and our theoretical and experimental data.     

Facile resolution of constrained geometry indenyl-phenoxide ligation

The 2-(inden-3-yl)phenoxide ligand can be resolved at both tetrahedral and octahedral Group 4 metal centers using chiral binaphthoxide ligands.     

Colloidal crystallization and banding in a cylindrical geometry

Colloidal crystallization takes advantage of the strong interfacial forces and tunable interactions that organize particles into regular structures at small scales. Thus, colloidal crystallization and patterning provide a powerful and simple method to functionalize planar surfaces with applications to optical, catalytic, sensing, and cleansing materials. Nevertheless, the ability to pattern topologically more complex surfaces such as curved, confined, or soft substrates can open new avenues for novel, "intelligent", and responsive materials. We present one step in this direction by characterizing colloidal crystallization inside circular capillaries: a nearly periodic banding is observed, and the colloidal packing is dictated by confinement produced by the wedge-like region formed by a capillary confined meniscus. The packing consists of a succession of hexagonally close-packed regions, which are separated by narrow regions of "buckled phase crystals".     

In situ crystallization of 2,2-dimethoxypropane and dimethyldimethoxysilane: hunting for Group 14 isomorphism

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In situ FT‐Raman spectroscopic study of the conformational changes occurring in isotactic polypropylene during its melting and crystallization processes

The conformational changes occurring in isotactic polypropylene during the melting and crystallization processes have been carefully investigated using FT‐Raman spectroscopy at temperatures below, at, and above the polymer melting point. Results confirmed the retention of some crystallinity up to +210 °C, which is 50 °C above the melting point. It was found that, at temperatures just above the melting point (1–10 °C), there is still some short range order of at least 12 monomer units long in certain regions of the melt. At 10 °C above the melting point, the short range order drops below 12 monomer units resulting in the disappearance of the Raman band at 841 cm^–1. Vice versa, the experimental measurements show that the iPP melt system is stable when the persistence length of helical sequences is less than 12 monomer units. As soon as the helix length exceeds 12 units, the 3₁ helix conformation extends quickly and then crystallization occurs. These results are discussed in terms of Imai's microphase separation theory and it agreed very well with it. Also, from our observations for correlation splitting, Raman bands related to conformational states were identified. This analysis indicates the existence of three different conformational states at 808, 830, and 841 cm^–1. The 808 cm^–1 band was assigned to helical chains within crystals (representing crystalline phase). The 841 cm^–1 band was shown to be composed of a band at 841 cm^–1, assigned to shorter chains in helical conformation with isomeric defects (representing the isomeric defect phase), and a broader band at 830 cm^–1 assigned to chains in nonhelical conformation (representing the melt‐like amorphous phase). This indicates the detection of a three‐phase structure in iPP, where a third phase could be due to the presence of defect regions within the crystalline region, or due to the presence of an amorphous–crystal interphase. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2173–2182, 2006     

In situ static and dynamic light scattering and scanning electron microscopy study on the crystallization of the dense zinc imidazolate framework ZIF-zni

The kinetics and mechanism of crystallization of the dense zinc imidazolate framework with zni topology, from comparatively dilute methanol solutions containing Zn(NO(3))·6H(2)O and imidazole with variation of the zinc-to-imidazole ratio, were followed in situ by time-resolved static and dynamic light scattering. The light scattering data revealed that metastable primary particles of about 100 nm in diameter form rapidly upon mixing the component solutions. After a lag time that is dependent on the imidazole concentration, the primary particles aggregate into secondary particles by a monomer addition mechanism with the primary particles as the monomers. Complementary scanning electron microscopy revealed that further evolution of the secondary particles is a complex process involving polycrystalline intermediates, the non-spherical morphologies of which depend on the initial zinc-to-imidazole ratio. Time and location of the first appearance of crystalline order could so far not be established. The pure-phase ZIF-zni crystals obtained after 240 min are twins. The aspect ratio of the tetragonal crystals can be controlled via the zinc-to-imidazole ratio.     

In situ XRD study of nanocrystalline cobalt oxide reduction

The reduction of nanocrystalline cobalt oxide samples (single-phase and supported on γ-Al₂O₃) was studied using in situ X-ray diffraction (XRD) analysis. The atomic structures of single-phase and supported Co₃O₄ samples were refined, and the occurrence of cationic vacancies was demonstrated. A set of methods (XRD, temperature-programmed reduction, and differential dissolution) was used to find that the reduction of supported and unsupported model cobalt oxide was considerably different. The single-phase sample was reduced in undiluted hydrogen to cobalt metal with a hexagonal closely packed structure. The reduction of the supported sample (unlike the single-phase sample) occurred through the formation of a crystalline CoO phase to the formation of cobalt metal with a face-centered cubic structure. Interaction of cobalt oxide with the γ-Al₂O₃ support, which hinders the reduction to cobalt metal, was detected.     

In situ DRIFTS study on the synthesis of N-alkylmorpholines

In situ diffuse reflectance Fourier-transform infrared spectroscopy was used to perform mechanistic investigation on the synthesis of N-alkylmorpholines from diethylene glycol (DEG), alcohol and ammonia. The results showed that the synthesis of N-alkylmorpholines on a heterogeneous catalyst proceeded along the reaction path between DEG and alkylamine when choosing CuO–NiO/γ-Al₂O₃ as a suitable catalyst. In addition, the yield of methylmorpholine and ethylmorpholine was 86.4 and 76.6 %, respectively.     

Synthesis and structure of boron-bridged constrained geometry complexes of titanium

The boron-bridged constrained geometry titanium complexes [Ti[eta5:eta1-(C5H4)B(NR2)NPh](NMe2)2][R = iPr (3), SiMe3(4)] and [Ti[eta5:eta1-(C9H6)B(NiPr2)NPh](NMe2)2](12) have been prepared in good yields by amine elimination reaction from [Ti(NMe2)4]. Subsequent deamination-chlorination with excess Me3SiCl yielded the corresponding dichloro-complexes (5, 6, 13). Reaction of the analogous ligand precursors (C5H5)B(NiPr2)N(H)R (R = Cy, tBu) with [Ti(NMe2)4] did not result in the expected bridged compounds, but rather in the half-sandwich complexes [Ti[(eta5-C5H4)B(NiPr2)N(H)R](NMe2)3][R = Cy (9), tBu (10)]. All compounds were fully characterised by means of multinuclear NMR spectroscopy. Thorough investigation of substituent effects was achieved by comparative X-ray diffraction studies on complexes 3, 5, 6 and 12.     

In situ characterisation of the aqueous gold colloid interface using CO as a surface probe: IR spectroscopic studies

Fourier transform infrared (FTIR) spectra are presented of CO gas-treated protected gold colloids prepared from hydrazinium hydrate reduction of an Au(III) precursor which reproducibly feature a weak, shortlived peak at ca. 2169 cm(-1). When the gold colloid was treated with 99% isotopically enriched (13)CO gas, the IR peak shifted to a frequency of 2114 cm(-1) which indicated that it represented a simple gold monocarbonyl species. The value of 2169 cm(-1) for the CO stretching frequency suggests the peak represents CO physisorbed on oxidised gold atoms on the colloid surface. The peak is not observed when the concentration of the colloidally dispersed gold is reduced either by use of lower starting salt concentrations or by aggregation. It is also not observed when solutions of the protecting agent or reducing agent or the dispersion medium (water) or even the starting Au(III) salts are CO-treated individually. This confirms that the spectral feature is uniquely associated with colloidally dispersed gold. In general, the work has shown that the surfaces of Au colloids in situ have partially oxidised Au character which is of interest in systems where supported nanoparticulate gold derived from colloid preparations are considered for low temperature oxidation catalysts for CO.     

In situ XANES study of Mn in promoted sulfated zirconia catalysts

Mn-promoted sulfated zirconia catalysts (2 wt% Mn) were investigated in situ, during the catalyst activation, isomerization of n-butane, and subsequent re-activation, using X-ray absorption spectroscopy of the Mn K-edge. The average valence of Mn in the catalysts, as determined from the edge position, was found to change from either 2.65 or 2.77 in the calcined samples to about 2.5 during activation in He (703 K for 30 min). During the isomerization of n-butane (1% in He, 80 ml min-1, 0.5 g catalyst at 333 K), the average Mn valence did not change further. When the catalyst was activated in 50% O2 the average valence only decreased from about 2.78 to 2.72. In this case, the average valence during the isomerization reaction decreased at a nearly constant rate both during the induction of activity and deactivation of the catalyst. The data do not support a stoichiometric redox reaction involving the promoter as initiator of the isomerization. However, a higher Mn valence after activation was indicative of a higher maximum conversion. It is concluded that the promoter cations function through modification of the structure of the zirconia.     

In situ X-ray diffraction study of cesium exchange in synthetic umbite

The exchange of Cs(+) into H(1.22)K(0.84)ZrSi(3)O(9)·2.16H(2)O (umbite-(HK)) was followed in situ using time-resolved X-ray diffraction at the National Synchrotron Light Source. The umbite framework (space group P2(1)/c with cell dimensions of a = 7.2814(3) ?, b = 10.4201(4) ?, c = 13.4529(7) ?, and β = 90.53(1)°) consists of wollastonite-like silicate chains linked by isolated zirconia octahedra. Within umbite-(HK) there are two unique ion exchange sites in the tunnels running parallel to the a-axis. Exchange Site 1 is marked by 8 member-ring (MR) windows in the bc-plane and contains K(+) cations. Exchange Site 2 is marked by a larger 8-MR channel parallel to [100], and contains H(2)O molecules. The occupancy of the Cs(+) cations through these channels was modeled by Rietveld structure refinements of the diffraction data and demonstrated that there is a two-step exchange process. The incoming Cs(+) ions populated the larger 8-MR channel (Exchange Site 2) first and then migrated into the smaller 8-MR channel. During the exchange process a structural change occurs, transforming the exchanger from monoclinic P2(1)/c to orthorhombic P2(1)2(1)2(1). This structural change occurs when Cs(+) occupancy in the small cavity becomes greater than 0.50. The final in situ ion exchange diffraction pattern was refined to yield umbite-(CsK) with the molecular formula H(0.18)K(0.45)Cs(1.37)ZrSi(3)O(9)·0.98H(2)O and possessing an orthorhombic unit cell with dimensions a = 10.6668(8) ?, b = 13.5821(11) ?, c = 7.3946(6) ?. Solid state (133)Cs MAS NMR showed there is only a slight difference between the two cavities electronically. Valence bond sums for the completely occupied Exchange Site 1 demonstrate that Cs-O bonds of up to 3.8 ? contribute to the coordination of the Cs(+) cation.     

In situ synthesis of mixed-valent manganese oxide nanocrystals: an in situ synchrotron X-ray diffraction study

Phase transformations of materials can be studied by in situ synchrotron X-ray diffraction. However, most reported in situ synchrotron XRD studies focus on solid state/gel systems by measuring phase/structure changes during application of pressure or heat. Phase transformations during material synthesis and their applications, especially in wet chemistry processes with different media, have not drawn much attention. Here, using manganese oxides as examples, we report the successful characterization of phase transformations in in situ hydrothermal synthesis conditions by the in situ synchrotron XRD method using a quartz/sapphire capillary tube as the synthesis reactor. The results were used for better design of materials with controlled structures and properties. This method can be generally used for synthesis of manganese oxides as well as for in situ characterization of other material syntheses using hydrothermal, sol-gel, and other methods. In addition, catalytic processes in liquid-solid, gas-solid, and solid-solid systems can also be studied in such an in situ way so that catalytic mechanisms can be better understood and catalyst synthesis and catalytic processes can be optimized.     

Screw dislocation-induced pyramidal crystallization of dendron-like macromolecules featuring asymmetric geometry

We report herein that dendron-shaped macromolecules AB_n crystallize into well-ordered pyramid-like structures from mixed solvents, instead of spherical motifs with curved structures, as found in the bulk. The design of the asymmetric molecular architecture and the choice of mixed solvents are applied as strategies to manipulate the crystallization process. In mixed solvents, the solvent selection for the Janus macromolecule and the existence of dominant crystalline clusters contribute to the formation of flat nanosheets. Whereas during solvent evaporation, the bulkiness of the asymmetric macromolecules easily creates defects within 2D nanosheets which lead to their spiral growth through screw dislocation. The size of the nanosheets and the growth into 2D nanosheets or 3D pyramidal structures can be regulated by the solvent ratio and solvent compositions. Moreover, macromolecules of higher asymmetry generate polycrystals of lower orderliness, probably due to higher localized stress.

The dendron-shaped macromolecules AB_n crystallize into well-ordered pyramid-like structures from mixed solvents, which is on the contrary to spherical motifs with curved structures in bulk.     

In situ STM evidence for the adsorption geometry of three N-heteroaromatic thiols on Au(111)

The electrochemical behavior of three heteroaromatic thiols (MBs) (2-mercaptobenzimidazole (MBI), 2-mercaptobenzothiazole (MBT), and 2-mercaptobenzoxazole (MBO)) on a Au(111) surface has been investigated by electrochemical scanning tunneling microscopy (ECSTM) and cyclic voltammetry (CV) in 0.1 M HClO(4) solution. All three thiols form oriented molecular cluster lines along the reconstruction line direction at 0.55 V. With the electrode potential shifting negatively, the molecules undergo a disordered-ordered structural transition. Molecularly resolved STM images show that all three molecules form striped adlayers in the desorption region on the Au(111) surface. The different heteroatoms in the heteroaromatic rings result in different electrochemical behavior of the MB self-assembled monolayers (SAMs). MBI, MBT, and MBO are proposed to interact with the substrate via the S-Au bonds from thiol group and the coordination interaction of N, S, and O with the substrate from the heteroaromatic ring, respectively. These results provide direct evidence of the electrochemical behavior and the adlayer structures of MB SAMs on the Au electrode.