K. A. Prokhorov

Short-period multilayer X-ray mirrors.

Multilayer structures with short periods have been systematically investigated using a tunable soft X-ray synchrotron, BESSY II, and X-ray tube radiation. Multilayer X-ray mirrors of W/B(4)C, W/Sc, Mo/B(4)C, Mo/C, La/B(4)C, Cr/C and Cr/Sc, with periods from 0.8 nm to 3.5 nm and number of periods up to 300-400, were constructed and investigated. The high reflectivity and spectral resolution of the mirrors allow them to be used to create multimirror systems for X-ray diagnostics of high-temperature plasma, for X-ray astronomy and microscopy.

Polarized Raman study of random copolymers of propylene with olefins

The polarized Raman spectroscopy is employed in the study of structural modifications in the films of isotactic polypropylene (PP) whose chain contains ethylene, 1-butene, 1-hexene, 1-octene, and 4-metyl-pentene-1, which represents an isomer of 1-hexene. It is demonstrated that the phase and conformational compositions of copolymer molecules depend on the comonomer content and the side-chain length of the second monomer. The content of the PP molecules in the helical conformation in the crystalline and amorphous phases of the copolymers monotonically decreases with increasing content of the second monomer. The decrease in the content of helical macromolecules in the crystalline phase is faster than the decrease in the amorphous phase. At a certain content of comonomers, the total content of the helical fragments decreases with increasing length of the side chain of the second monomer. The structures and Raman spectra of the copolymers of propylene with 1-hexene and 4-methyl-1-pentene are similar.

Raman Spectroscopic Characterization of the Interlayer Structure of Na+-Montmorillonite Clay Modified by Ditetradecyl Dimethyl Ammonium Bromide

Raman spectroscopy has been applied for the rapid and nondestructive monitoring of the interlayer structure of sodium montmorillonite (MMT) clay modified by ditetradecyl dimethyl ammonium (DDA+) bromide. This work demonstrates that a detailed analysis of Raman spectra in the fingerprint region (600-1600 cm(-1)), in combination with model simulation, allows one to distinguish different conformational states of DDA+ in the interlayer space of the modified clay, namely, a liquidlike state but rich in trans conformers, disordered conformational states, and a crystallike conformation appearing at increasing modifier content. These conformations differ in the angle between their alkyl chains, the relative content of trans and gauche conformers and the relative length of trans segments. The shape and width of the Raman band at 1300 cm(-1) and the peak intensity ratio I1088/I1064 can be used for a qualitative analysis of the ratio of gauche/trans conformers. The integral intensity ratios I*1064/I*1300 and I*1300/I*705 help to determine the proportion of trans conformers and the content of the modifier in the clay, respectively, thereof providing quantitative characterization of the modified clay (conformational reorganization and modifier content). Noteworthy, the transition from a liquidlike to crystal-like conformation is further supported by the splitting of the symmetric C-C stretching Raman band of the trans segments within the alkyl chains at 1133 cm(-1) (liquidlike conformation) into two modes at 1124 and 1135 cm(-1) corresponding to two parallel trans chains of nonequivalent lengths (crystal-like conformation).

Raman study of ethylene-propylene copolymers and polyethylene-polypropylene reactor blends

The Raman spectra of the ethylene-propylene copolymers (EPC) synthesized using new metallocene catalytic systems and the polypropylene/polyethylene/diblockcopolymer of propylene and ethylene (PP/PE/DBC) blends obtained using the sequential polymerization are studied. The copolymer and reactor blend spectra are analyzed using the Raman spectra of a series of liquid n-alkanes. Significant monotonic changes are observed in the spectra of EPC and the PP/PE/DBC blends when the ethylene content increases. Substantial differences between the series of samples of blends and copolymers are revealed. In contrast to the EPC spectra, the spectra of the PP/PE/DBC reactor blends are represented as an exact superposition of the homopolymer spectra with the weight coefficients proportional to the contents of the blend components. A monotonic blue shift of the line that corresponds to the symmetric stretching mode of the CH2 groups is observed in the EPC Raman spectra when the ethylene content increases. It is demonstrated that, for this line, the peak position only depends on the relative content of comonomers and does not depend on the contents of the PP and PE crystalline phases. The intensity ratio of two fundamental vibrations of PE and PP with frequencies of 1295 and 1330 cm−1 can be used to determine the relative contents of the PE molecules in the trans-conformation and PP macromolecules in the helical conformation in the PP/PE blends. It is demonstrated that variations in the Raman spectra of n-alkanes, EPC, and PP/PE/DBC reactor blends related to variations in the relative contents of various chemical groups are reliably traced in the spectra of all of the materials under study.

Raman study of polyethylene-polypropylene blends

The Raman spectra of the blends that result from the melt mixing of polyethylene (PE) and isotactic polypropylene (PP) are studied. The contents of the blend components can be determined using the ratio of the integral intensities of the PE and PP fundamental vibrations.

Raman spectra of various polymorphs of isotactic polypropylene

The Raman spectra of the α, γ, and smectic modifications of isotactic polypropylene (PP) are studied. The most significant spectral differences are observed in the frequency range around 2960 cm−1 for the spectral doublet assigned to the asymmetric stretching vibrations of the CH3 groups and in the frequency range around 800 cm−1, which is used for analysis of the phase composition of isotactic PP. It is demonstrated that the peak positions and relative intensities of the doublet assigned to the asymmetric stretching vibrations of the CH3 groups can be used to identify the polymorph modifications of isotactic PP.

Quantitative characterization of the orientation of macromolecules in intercalated nanocomposites of polyolefins/layered silicates by Raman spectroscopy

Raman spectroscopy is used to study variations in the orientational order of macromolecules in the uniaxially drawn intercalated nanocomposites based on two polymer matrices (polyethylene (PE) and isotactic polypropylene (PP)) and a filler (modified clay (MC)). The orientation parameters of macromolecules measured using Raman spectroscopy are compared with the X-ray data. It is demonstrated that, for the uniaxially drawn PE-MC and PP-MC intercalated nanocomposites, the filler impedes the orientation along the draw direction for the macromolecules localized in the noncrystalline phase of the polymer matrix. The orientational ability of the PE and PP crystallites in nanocomposites is not affected by the filler.

Analysis of cross-correlation of interface roughness in multilayer structures with ultrashort periods

The diffusion scattering method is used for studying a series of W/B4C multilayer structures with ultrashort periods (d = 0.8–1.5 nm). A simple theoretical model is described; the model takes into account both the dynamic effects in the interaction of counter-propagating diffuse-scattered waves and the mixing of film materials at the boundaries of the layers. It is shown that multilayer structures with a number of bilayers up to N = 700 and values of periods up to 0.8 nm are multilayer structures, which are well-correlated along the boundaries and exhibit resonance diffuse scattering. For structures with a period d > 1.1 nm, the largest contribution to the imperfection of boundaries comes not from the roughness, but from mixing of the films. The range of minimal periods of multilayer structures, for which the continuity of the films is preserved, is determined. The effect of “smoothing” of the substrate surface is discovered in multilayer structures with intact continuity; this contradicts to a certain extent the assumption concerning complete longitudinal correlation of roughnesses, which forms the basis of the theory.

Symmetric C-C stretching mode splitting versus CH2-chain conformation order in sodium montmorillonite modified by cetyltrimethylammonium bromide.

Exploiting Raman spectroscopy and computational modeling, for the first time, we report and explain an interesting phenomenon in clay modified by cetyltrimethylammonium bromide. A splitting of the CH(2)-chains symmetric C-C stretching Raman mode found at ~1128 cm(-1) in cetyltrimethylammonium bromide into two bands at 1128 and 1139 cm(-1) in clay modified by cetyltrimethylammonium bromide is observed. We demonstrate that this splitting appears if two types of trans-segments with nonequivalent lengths and terminal groups coexist in the CH(2)-chain of the alkylammonium ion embedded into the clay interlayer space. We report Raman experimental evidence for a CH(2)-chain bending within the clay galleries, resulting in the symmetric C-C stretching band splitting, as was also suggested by computational modeling. Noteworthy, we postulate that this unique behavior based on CH(2)-chain bending provides a general understanding of conformation reorganization and switching within long CH(2)-chain molecules confined within modified clay interlayer galleries. For all modifier concentrations, we show that the intercalated cetyltrimethylammonium ions exist in a liquid-like state, consisting mainly of trans conformations (~86%) of two types in approximately equal proportions. Moreover, we demonstrate that the integral Raman intensity ratio I(1295)(CH(2))/I(705)(clay) provides a rapid nondestructive quantification of the relative content of alkylammonium ions in modified clays. These results demonstrate that a simple direct monitoring of specific modifier-dependent interlayer conformational states is possible, which is of great importance for a tunable fabrication of modified clays-based nanocomposites with desired properties.

Hyper-Raman scattering by 2LO-phonons in a CdS crystal

A theoretical treatment of the resonant hyper-Raman scattering (RHRS) of light by 2LO-phonons is presented for a CdS crystal. The scattering mechanisms of the RHRS by 1LO- and 2LO-phonons are considered. The corresponding efficiencies are compared.