Novel blends from agave fibers and poly(methyl methacrylate)

Cellulose-rich fibers were isolated from Agave lechuguilla (AL) and Agave fourcroydes (AF) growing in the Mexican northeast. These fibers are a valuable feedstock for the preparation of blends with synthetic polymers like poly(methyl methacrylate), PMMA. Blends of different types of agave fibers (dewaxed, mercerized, and grafted) and PMMA were prepared and investigated by means of tension measurements and dynamic mechanical analysis. The fiber-containing blends are more stable than the plain PMMA. Surprisingly, the mechanical stability of the blends is practically independent of the pretreatment of the fibers. Methyl methacrylate (MMA) was grafted onto the biopolymer fibers initiated by the cerammonium nitrate redox initiator. Grafting yields of 26.5% were realized with fibers from AL while up to 75.8% MMA was grafted onto fibers from AF. The materials were characterized by means of FTIR spectroscopy and DSC.     

Correlation between Hammett substituent constants and directly calculated pi-conjugation strength

The results of an energy decomposition analysis of ortho-, meta-, and para-substituted benzylic cations and para-substituted benzylic anions H2C-C6H4Rq (R = H, F, CN, Me, OH, NH2, NO2, CHO, CO2H; q = +, -) are presented and discussed. The calculated values for the pi bonding between CH2(q) and C6H4R show for substituents which have pi orbitals a linear correlation with the Hammett sigma(p), sigma(+)(p), and sigma(m) constants.     

Correlation between hydrogen‐bonding interaction and mechanical properties of polyimide fibers

Novel co‐polymerization polyimide (PI) fibers based on 4,4′‐oxydianiline (ODA)‐pyromellitic dianhydride (PMDA) were prepared. 2‐(4‐Aminophenyl)‐5‐aminobenzimidazole (PABZ) containing the N? H group was introduced into the structure of the fibers as the proton donor. The results of Fourier transform infrared (FTIR) and dynamic mechanical analysis (DMA) showed that hydrogen bonding occured between the N? H group and chains, which strongly enhanced interchain interaction. This hydrogen bonding interaction increased the tensile strength and initial modulus of the PI fibers up to 2.5 times and 26 times, respectively, compared to those of homo‐PI PMDA‐ODA fibers with no hydrogen‐bonding interaction because of the absence of proton donors after the imidization process. In the mean time, glass transition temperature (T_g) of the modified PI fibers was found to be 410–440°C, which was higher than that of the homo‐PI PMDA‐ODA fibers. From the result, a novel access to molecular design and manufacture of high performance PI fibers with good properties could be provided. Copyright © 2009 John Wiley & Sons, Ltd.     

Correlation between properties of a solid sample and laser-induced plasma parameters

To investigate the influence of mechanical properties of a solid sample on the laser-induced plasma parameters (temperature and mass ablated) a number of aluminum–lithium alloys and lithium ferrites with different microstructure and composition have been studied. The specific approach to estimate excitation temperature for low-resolution emission spectra has been developed. The main limitations of this approach were discussed on the basis of comparison with the energy width of several multiplets. Overall uncertainties for temperature calculation were evaluated by taking into account the accuracy of Einstein's coefficients and errors of the proposed multiplets method. The temporal evolution of laser plasma during the evaporation of these materials was studied. Extremely high value of the Li I excitation temperature has been estimated to be T > 10⁵ K for the annealed ferrite ablation, in contrast to the temperature T  1.5 · 10⁴ K for non-annealed ferrite. Only for ablation of annealed ferrite the Li II emission line at 548.4 nm was observed. It means that this laser-induced plasma was the hottest. In the case of alloys, the temperature calculated by using Li I transitions was proportional to the microhardness of the solid samples. The negative correlation between crater volume/opto-acoustic signal and alloy microhardness was observed. At the first pulses the mechanical properties of the alloys didn't correlate with the ablated mass, while the maximal correlation coefficients were observed after ablation by 10 or 50 consequent laser pulses.     

Structural macromolecular parameters determining electroconductivity of oxidized poly-n-vinylpyrrole

The dependence of electroconductivity on conjugation length as well as the related basic mechanism was investigated by chemical (FeCl₃) oxidation of insulating polymers from N-vinylpyrrole (NVP) starting with different Fe/NVP ratios and different molecular weights. The results allow to establish that oxidation occurs mainly intrachain and that electroconductivity has a sharp increase for a conjugation length higher than ∼15 NVP-units.     

Empirical polarity parameters for various macromolecular and related materials

Empirical polarity parameters are recommended as useful characteristics for describing the internal and external surface properties of various solid materials, e. g. synthetic polymers, native polymers, inorganic oxides, sol‐gel hybrids, and composites. The polarity properties of a macromolecule have been expressed by three independent terms: the α value (the hydrogen bond donating, HBD, capacity or acidity), the β value (the hydrogen bond accepting, HBA, capacity or basicity), and the π* value (the dipolarity/polarizability). These terms can be defined using the Kamlet‐Taft solvents parameter set as the reference system. A complex property, XYZ, of a macromolecular material under study, with reference to a standard system (XYZ)₀ (i. e. gas phase or a nonpolar polymer), can then be described by a simplified Kamlet‐Taft LSE (linear solvation energy) equation: XYZ = (XYZ)₀ + sπ* + aα + bβ. a, b, and s are coefficients reflecting the susceptibility of the polarity terms upon XYZ. Empirical solvatochromic polarity parameters [α, β, π*, E_T (30)] for synthetic polymers, copolymers, native polymers, inorganic oxidic materials, functionalized silica particles, hybrids, and composite materials have been determined by means of the following solvatochromic probe dyes: 2,6‐diphenyl‐(2,4,6‐triphenyl‐1‐pyridinio)‐4‐phenolate ( 1 a ), Michler's ketone ( 2 ), dicyano‐bis(1,10‐phenanthrolin)iron II ( 3 ), and a novel aminobenzodifuranone dye ( 7 ). The solvatochromic band shifts of these indicators correlate precisely with the Kamlet‐Taft solvent parameters α, β, and π*. The results are compared with each other, with related solvent model compounds, and literature values. The relation of the well established E_T (30) solvent polarity scale to the Kamlet‐Taft parameters α and π* of solid materials is demonstrated. Hence, a general polarity scale for solid materials is suggested.     

Sisal chemically modified with lignins: Correlation between fibers and phenolic composites properties

Sisal fibers have been chemically modified by reaction with lignins, extracted from sugarcane bagasse and Pinus-type wood and then hydroxymethylated, to increase adhesion in resol-type phenolic thermoset matrices. Inverse gas chromatography (IGC) results showed that acidic sites predominate for unmodified/modified sisal fibers and for phenolic thermoset, indicating that the phenolic matrix has properties that favor the interaction with sisal fibers. The IGC results also showed that the phenolic thermoset has a dispersive component closer to those of the modified fibers suggesting that thermoset interactions with the less polar modified fibers are favored. Surface SEM images of the modified fibers showed that the fiber bundle deaggregation increased after the treatment, making the interfibrillar structure less dense in comparison with that of unmodified fibers, which increased the contact area and encouraged microbial biodegradation in simulated soil. Water diffusion was observed to be faster for composites reinforced with modified fibers, since the phenolic resin penetrated better into modified fibers, thereby blocking water passage through their channels. Overall, composites' properties showed that modified fibers promote a significant reduction in the hydrophilic character, and consequently of the reinforced composite without a major effect on impact strength and with increased storage modulus.     

Correlation strength and information entropy

The correlation present in the nondegenerate ground state of an interacting Fermi system is discussed in terms of reduced density matrices and their cumulant expansion. By generalizing a result obtained for the interacting uniform electron gas (correlation induced exchange-hole narrowing), possible measures of the correlation strength in terms of natural occupation numbers (the eigenvalues of the true one-particle density matrix) are introduced. These quantities-the v-order nonidempotency and the information entropy of the natural occupation numbers-result from the correlated many-body wave function and characterize the ground-state correlation in addition to the usual correlation energy. The uniform electron gas serves as a first illustrative example. © 1995 John Wiley & Sons, Inc.     

某些含氧酸的酸强度与量化参数的相关性

本文利用从头计算法, 采用STO-3G基集计算了某些含氧酸分子的电子结构, 它们的标准几何构型取自已知的实验数据. 将氢、氧原子上的总电荷密度以及氧原子上的亲电子超离域度与实验测得的酸性离解常数相联系, 应用多元回归法, 得到了较好的线性关系.     

Effect of size on the strength of polymeric fibers

Using a molecular model introduced previously, we study the effects of chain-end segregation on the relationship between strength (σ) and diameter (d) in polymeric fibers. For segregated structures with a monodisperse molecular weight distribution, our results show a scaling law σ ～ d^?α, with α in the range [0.4–0.5], in agreement with experimental observation. A weaker dependence is found for polydisperse systems. Further investigation also reveals that macroscopic cracks have little influence on the fiber strength/diameter relationship, unless the crack width shows a faster than linear increase with fiber diameter. Finally, our model results also indicate a very weak dependence of fiber strength on its length, in good agreement with experimental observation. ©1995 John Wiley & Sons, Inc.     

Correlation between processing conditions,microstructure and mechanical behavior in regenerated silkworm silk fibers

Regenerated silkworm fibers spun through a wet‐spinning process followed by an immersion postspinning drawing step show a work to fracture comparable with that of natural silkworm silk fibers in a wide range of spinning conditions. The mechanical behavior and microstructure of these high performance fibers have been characterized, and compared with those fibers produced through conventional spinning conditions. The comparison reveals that both sets of fibers share a common semicrystalline microstructure, but significant differences are apparent in the amorphous region. Besides, high performance fibers show a ground state and the possibility of tuning their tensile behavior. These properties are characteristic of spider silk and not of natural silkworm silk, despite both regenerated and natural silkworm silk share a common composition different from that of spider silk. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

An improved microbond test method for determination of the interfacial shear strength between carbon fibers and epoxy resin

An improved microbond method, with a corresponding testing device, was developed to measure the interfacial shear strength (IFSS) between carbon fibers and epoxy resin. Compared to other methods, this proposed approach is both highly efficient and easy to operate. As a case study for this new method, we measured the IFSS between carbon fibers and epoxy resin. Although the average IFSS obtained was only 7.08 MPa, which is much lower than values documented in several previous studies, the displacement-load curves demonstrate the strong reliability of this method. The lower IFSS could be explained by the highly inert surface of the carbon fibers, which was highly graphitized and had no sizing treatment. Therefore, this method has high potential in applications for screening the sizing agents of carbon fibers or optimizing the surface sizing processes.     

Photocrosslinking of ultra high strength polyethylene fibers

Ultra high strength polyethylene (HSPE) fibers have been successfully photocrosslinked using benzophenone as photoinitiator. The introduction of photoinitiator without disturbing the fiber structure is a difficult problem which was solved by vapor absorption at elevated temperature while keeping the fiber under constant strain. The crosslinked fiber showed no decrease in mechanical properties at room temperature as is the case when fibers are crosslinked by other reported methods such as radiation and chemical crosslinking. The crosslinked fiber showed enhanced high temperature resistance as well as much lower creep rate on prolonged stressing. Photocrosslinking of HSPE fiber is superior to other crosslinking methods reported in the literature.     

Low-angle x-ray estimation of macromolecular parameters of the scattering particles in Agave sisalana

Various macromolecular parameters of Agave sisalana (sisal) fiber were investigated by the low-angle x-ray scattering method. The well known Kratky camera of the latest design was utilized for the experimental measurements. The sample studied was a densely packed colloidal system belonging to a general micelle system, and the theories of Kratky and Kratky and Porod were utilized to estimate the parameters. Pore analysis of the substance yields a value for the specific inner surface of the dispersed phase of 0.406 × 10^?1 m²/cm³; the transversal length is the same as the length of inhomogeneity, 107.31 Å, and the length of coherence is 342.21 Å. The air fraction of the scattering particles was found to be 0.01%.     

Characterization of macromolecular orientation in κ-carrageenan fibers using polarized Fourier-transform infrared spectroscopy

In the current study, polarized infrared (IR) microspectroscopy was employed to characterize the macromolecular orientation in wet-spun and stretched κ-carrageenan fibers. The fibers were shown to be well oriented by X-ray diffraction, suggesting that the κ-carrageenan molecules were generally aligned along the fiber axis direction. Longitudinal fiber pieces of about 10 μm thick were obtained by focused ion beam (FIB) micromilling. The fiber pieces were examined by polarized IR in transmission mode. Several bands, including those characteristic of κ-carrageenan at 845 and 930 cm⁻¹, were polarization-dependent, demonstrating polarized IR as a useful tool to evaluate macromolecular orientation in carrageenan fibers. Band assignments were discussed by considering the general alignment of molecules and the polarization dependence of vibration modes, and our results agreed well with band assignments from previous reports.     

Tensile deformation of high strength and high modulus polyethylene fibers

The influence of tensile deformation on gel-spun and hor-drawn ultra-high molecular weight polyethylene fibers has been investigated. In high modulus polyethylene fibers no deformation energy is used to break chemical bonds during deformation, and flow is predominantly present next to elastic behavior. Flow is reversible after tensile deformation to small strains, but becomes irreversible when yielding occurs.Stress relaxation experiments were used to determine the elastic and flow contribution to tensile deformation. A simple quantitative relation could then be derived for the stress-strain curve that directly links yield stress to modulus. Experimental stress-strain curves could be reasonably described by this relation.Flow during tensile deformation is shown to be correlated with the introduction of the hexagonal phase in crystalline domains. A mechanism of flow is proposed in which, at first, tie molecules or intercrystalline bridges are pulled out of crystalline blocks (reversible), followed by the break-up of crystalline blocks through slip of microfibrils past each other (stress-induced melting, irreversible).     

Correlation between dielectric/organic interface properties and key electrical parameters in PPV-based OFETs

We report on the influence of the dielectric/organic interface properties on the electrical characteristics of field-effect transistors based on polyphenylenevinylene derivatives. Through a systematic investigation of the most common dielectric surface treatments, a direct correlation of their effect on the field-effect electrical parameters, such as charge carrier mobility, On/Off current ratio, threshold voltage, and current hysteresis, has been established. It is found that the presence of OH groups at the dielectric surface, already known to act as carrier traps for electrons, decreases the hole mobility whereas it does not substantially affect the other electrical characteristics. The treatment of silicon dioxide surfaces with gas phase molecules such as octadecyltrichlorosilane and hexamethyldisilazane leads to an improvement in hole mobility as well as to a decrease in current hysteresis. The effects of a dielectric polymer layer spin coated onto silicon dioxide substrates before deposition of the semiconductor polymer can be related not only to the OH groups density but also to the interaction between the dielectric and the semiconductor molecules. Specifically, the elimination of the OH groups produces the same effect observed with hexamethyldisilazane. The hole mobility values obtained with hexamethyldisilazane and polymer dielectrics are the highest reported to date for PPV-based field-effect transistors.     

Correlation between 2H NMR side-chain order parameters and sequence conservation in globular proteins

Side-chain 2H NMR relaxation data have been collected for the SH3 domain from the Fyn tyrosine kinase and analyzed with respect to sequence preference and per-residue solvent accessibility. Residues that are highly preferred at a given position show a tendency to be less mobile than average with a coefficient of correlation that is greater than that obtained when side-chain flexibility and solvent accessibility are compared. The same trend is observed for five of six additional proteins considered. This provides evidence for the existence of conserved structural features other than hydrophobic burial that govern side-chain motions. Through examination of an SH3 domain structural alignment, we identify side-chain hydrogen bonding of threonine residues and a specific secondary structural element as potential determinants of protein internal dynamics.