The effects of morphology on 1H NMR spectra and relaxation in semicrystalline polyolefins

A brief résumé is given of the role of structural heterogeneity, magnetic dipolar couplings, molecular structure, and molecular motion in determining the ¹H NMR spectra and relaxation properties of heterogeneous solids such as semicrystalline polymers. Measurements of ¹H spin-lattice relaxation in laboratory (T₁) and rotating frames (T) are reported for a number of solid polyolefin samples. These include solution-crystallized and melt-crystallized polyethylene, annealed and quenched isotactic polypropene, and isotactic polybut-1-ene. In addition, broad-line ¹H spectra, both normal and partially (T) relaxed, are reported for these materials as well as a number of pulsed NMR experiments having the philosophy of the so-called Goldman–Shen experiment. Spin-lattice relaxation (T₁) for all samples is a single exponential process, whereas rotating-frame relaxation comprises three exponential processes both on-resonance (θ = 90°) and off-resonance at the magic angle (θ = 54.7°), with the latter generally being much slower. The spectra show clearly the existence of components having differing degrees of mobility and, with the exception of the solution-crystallized polyethylene, the partially (T) relaxed spectra indicate a correlation between breadth of resonance line and magnitude of T_1ρ. The Goldman–Shen-type experiments indicate a spin-diffusional transport of magnetization between the different spectral and (T) components. A computer program has been used to simulate the NMR behavior of a three-region system comprising repeating units of infinite lamellae of different widths, each region having different intrinsic relaxation times and spin diffusion coefficients. The results demonstrate that the observed ¹H NMR behavior of these samples can be interpreted in terms of this model and that, inter alia, the long-time T behavior reflects, qualitatively, the time taken for magnetization to diffuse a distance of the order of the dimensions of the region to which it corresponds.     

Cross-condensation and particle growth in aqueous silane mixtures at low concentration

We have observed the condensation of a mixture of gamma-glycidoxypropylmethyldiethoxysilane and 3-aminopropyltriethoxysilane in dilute aqueous solutions. NMR and IR spectroscopy have allowed to follow the condensation process in the mixture, which is noticeably enhanced and proceeds faster than for each silane on its own. Cross-condensation between the two silanes was evidenced. When the hydrophilic aminosilane is in excess, the condensation, as evidenced by dynamic light scattering, proceeds toward gel formation because the oligomers formed are essentially hydrophilic. When the more hydrophobic epoxysilane is in excess, oligomer growth proceeds slowly and results in a destabilization of the solution: due to their hydrophobic character, the oligomers formed coalesce suddenly into 200-nm-diameter aggregates. Coatings deposited from such solutions with high epoxysilane content can be used to strengthen glass. We show that the progress of condensation in solution results in a wetting transition during deposition of the silane film on glass by dip coating. The production of increasingly hydrophobic oligomers as the reaction time increases results in adsorption of more hydrophobic aggregates at the surface, which eventually leads to dewetting of the film: in the absence of film, glass strengthening disappears.     

Theory of DNA electrophoresis: a look at some current challenges

Although electrophoresis is one of the basic methods of the modern molecular biology laboratory, new ideas are being suggested at an accelerated rate, in large part because of the pressing demands of the biomedical community. Although we now have, at least for some methods, a fairly good theoretical understanding of the physical mechanisms that lead to the observed peak spacings, widths and shapes, this knowledge is often too qualitative to be used to guide further technical developments and improvements. In this article, we review some selected elements of the current state of our theoretical ignorance, focusing mostly on DNA electrophoresis, and we offer several suggestions for further theoretical investigations.     

Molecular interactions at the interface in blends of ester groups-functionalized polyolefins

Due to the apolarity of the aliphatic backbones, unmodified polyolefins are scarcely miscible with most of other polymers. The functionalization of preformed polyolefins is a way which has been successfully followed to improve the polymer miscibility. The functionalization of linear low density polyethylene (LLDPE) and ethylene-propylene copolymers (EP), with diethyl maleate (DEM) and dicumyl peroxide (DCP) as radical initiator, gives products containing up to 2–5 mol % of well defined functional groups (2-diethyl succinate). Intermolecular interactions of these functional groups are characterized by comparison with suitable low-molecular-weight structural models in the presence of different solvents containing acidic hydrogen atoms. On the basis of these indication evidences of interface molecular interactions in blends with halogenated polymers are described between the functionalized polyolefins and poly(vinyl chloride) (PVC), poly(vinylidene fluoride) (PVDF) or vinylidene fluoride-hexafluoropropene copolymer obtained in semiindustrial Brabender mixers. It is shown that a smooth functionalization of the polyolefins can modify the phase behaviour and structure of these systems. The FT-IR microanalysis supports the occurrence of partial miscibility phenomena which can be accounted for by specific intermolecular interactions involving the inserted functional groups and occurring mainly at the interfaces between domains of polyolefins and of the halogen-containing polymers.     

Modifying zeolite particle morphology and size using water/oil/surfactant mixtures as confined domains for zeolite growth

Here we report the synthesis of silicalite-1 particles using microemulsions wherein the particle size and morphology can be varied.     

New routes to high solid content latexes: a process for in situ particle nucleation and growth

A means of generating latices with solid contents well over 70% (v/v) without the use of intermediate seeds is proposed. It is demonstrated that the use of an electrically neutral initiation system (hydrogen peroxide) in the initial stages of the process, followed by an initiator yielding negatively charged free radicals (ammonium persulphate) changes the way in which the system generates stable particles. The reason for this change is the need to avoid stabilising small, homogeneously nucleated particles during the first portion of the process, and the desire to generate controlled quantities of them during the second portion. The processes are highly reproducible, as are the particle size distributions and rheological properties of the final latices.     

Photothermal oxidation of squalane: A model compound for polyolefins

Photothermal oxidation of squalane has been studied by oxygen uptake measurements in a quartz glass reaction cell. The activation energy for oxidation has been found to be ∼ 12·7 kcal/mole which supports the intramolecular hydrogen abstraction at the tertiary CH bond site. Hydroperoxy groups are formed during the induction period, which on decomposition (OO bond scission) leads to accelerated degradation and results in the formation of carbonyl and unsaturated groups.     

Modelling particle formation and growth in a plasma synthesis reactor

A model for particle nucleation and growth in a thermal plasma reactor is discussed. A nondimensional form of the aerosol general dynamic equation is derived under a set of simplifying assumptions which are appropriate to plasma powder synthesis, and the resulting set of equations is solved numerically. The results are converted to dimensional form for the case of iron powder, for which experimental data are available, and for silicon carbide. Calculated particle sizes increase significantly with increasing reactant concentrations and with decreasing cooling rate, although the influence of cooling rate is mainly a residence time effect.     

Interplay between fluorescence and morphology in composite MEH-PPV/PCBM nanoparticles studied at the single particle level

We report the study of the photoluminescence properties of composite conjugated polymer (MEH-PPV)/fullerene (PCBM) nanoparticles as a function of PCBM doping level. The emission properties of individual nanoparticles were studied by Single Particle Spectroscopy (SPS), and distinct changes in vibronic structure with nanoparticle composition were observed. These changes are found to be due to the presence of domains in the nanoparticles with two distinct types of optical signatures, one with molecular and one with aggregate character, for which the abundance and morphology is found to change with PCBM doping levels. Interestingly, highly delocalized structures with a large extent of exciton migration are formed at low PCBM doping levels, while at high PCBM doping levels the exciton collapses into highly localized structures. Furthermore, at very high doping levels phase separation within the MEH-PPV/PCBM nanoparticles is found, even though the reported nanoparticles are only a few tens of nanometers in diameter.     

A particle growth theory for heterogeneous Ziegler polymerization

Samples of “as produced” polypropylene particles at progressively higher yield levels (grams polymer/gram catalyst) were sliced and examined by electron microscopy. In the polymerization of propylene with the TiCl₃–(C₂H₅)₂AlCl catalyst system the catalyst breaks up immediately into basic 100–1000 Å particles. As the yield increases, the catalyst particles gradually disappear and finally become completely dispersed in the polymer particle. These results are compatible with a theory which views the catalyst as a porous crystal containing a single species of active sites uniformly distributed. As polymerization progresses, all sites should eventually initiate a polymer chain whose length should be inversely proportional to the depth of the site below the surface of the particle. Two apparently equivalent statistical models were developed on the basis of this concept. Both models predict a slow increase in the X?_w/X?_n ration (Q) with increasing molecular weight, after an initial rapid increase. The most useful of these models states that Q is equal to the sum of X?_w terms of the simple harmonic series, and that a complete spectrum of x-mers should be present in the product. This agrees satisfactorily with analytically determined values.     

A model for describing the thermodynamics of multivalent host-guest interactions at interfaces

A model has been described for interpreting the binding of multivalent molecules to interface-immobilized monovalent receptors through multiple, independent interactions. It is based on the concept of effective concentration, C(eff), which has been developed before for multivalent binding in solution and which incorporates effects of lengths and flexibilities of linkers between interacting sites. The model assumes: (i). the interactions are independent, (ii). the maximum number of interactions, p(max), is known, (iii). C(eff) is estimated from (simple) molecular models. Simulations of the thermodynamics and kinetics of multivalent host-guest binding to interfaces have been discussed, and competition with a monovalent competitor in solution has been incorporated as well. The model was successfully used to describe the binding of a divalent guest to self-assembled monolayers of a cyclodextrin host. The adsorption data of more complex guest-functionalized dendrimers, for which p(max) was not known beforehand, was interpreted as well. Finally, it has been shown that the model can aid to deconvolute contributions of multivalency and cooperativity to stability enhancements observed for the adsorption of multivalent molecules to interfaces.     

A new look at bonding in trialuminides: reinvestigation of TaAl3

Single crystals of TaAl3 were grown at high temperatures from an Al-rich, binary solution. TaAl3 adopts the D0(22) structure type, space group I4/mmm with a=3.8412(5) A, c=8.5402(17) A, and Z=2. The structure type, which is the preferred structure for all group 5 trialuminides and TiAl3 as well as the high-temperature form of HfAl3, is a binary coloring of the face-centered-cubic (fcc) arrangement. The distribution of Ta atoms creates a three-dimensional network of vertex and edge-sharing square pyramids of Al atoms. Temperature-dependent electrical resistivity and magnetic susceptibility measurements are consistent with TaAl3 being a metallic compound with a relatively low density of states at the Fermi surface. Furthermore, tight-binding electronic structure calculations are utilized to describe the bonding in these compounds and to compare their stability with respect to the alternative fcc-related, e.g., the D0(23) (ZrAl3-type) and the L1(2) (AuCu3-type), structures. A modified Wade's rule argument provides insights into the structural preferences.     

Progress in electrohydrodynamics of soft microbial particle interphases

Electrokinetic phenomena, such as electrophoresis, are valuable tools for determining the interfacial (double layer) properties of colloidal particles. The theoretical formalisms employed to interpret electrokinetic data (electrophoretic mobility) were initially derived for the restrictive case of hard (non-permeable) particles with the electrokinetic potential as unavoidable primary variable. In this paper, we underline the inadequacy of such models for addressing the electrostatic and hydrodynamic characteristics of microbes like bacteria, viruses or yeast cells. These bioparticles are characterized by heterogeneous, soft, permeable interphases formed with the outer electrolytic medium, which requires advanced electrokinetic analyses where the concept of zeta-potential must be abandoned. We review the progresses made in the measurement and analysis of interphasial properties of bioparticles under electrokinetic conditions. In particular, emphasis is given on the necessity to couple appropriately interpreted electrokinetics with other physico-chemical measurements (e.g. issued from AFM imaging/force spectroscopy) and microbiological techniques (genetic manipulation of microbes). Using such a combination, a clear connection between complex interphase properties of microbes and e.g. their propensity to adhere onto charged surfaces should be achieved.     

Progress in manipulating zeolite morphology and related applications

The control of zeolite morphology is of interest because it will permit the rational design of products that have a wide array of applications, from catalysis to thin films for electronic devices. Over the past couple of years, some progress has been made in manipulating zeolite crystal shape, though much more mechanistic understanding has to be gained for targeted design of zeolite morphology. There have also been important studies that have linked zeolite morphology and the presence of hierarchical porosity with improved functionality like catalytic activity and selectivity.