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Herein we present a Ca[EDTA]-based synthesis and comparative study of perfectly shaped plate-like, rod–like, and prism-like carbonated apatites.

The influence of the structure of the polymer matrix on the main photoluminescence characteristics of composites based on core (CdSe) and core–shell type (CdSe/ZnS) quantum dots embedded in liquid-crystalline and amorphous polymers of similar chemical structure is studied. The photoluminescence spectra consist of two bands (2.15 and 1.70 eV), the first of which corresponds to the radiative recombination of excitons, and the second one corresponds to carriers captured by traps at the quantum dot boundary. The second band is absent in the case of CdSe/ZnS quantum dots embedded in the liquid-crystalline polymer matrix. The kinetics of photoluminescence is well described by the sum of two decaying exponentials for CdSe quantum dots in matrices of both types and CdSe/ZnS quantum dots in the amorphous matrix. To determine the photoluminescence kinetics in the case of CdSe/ZnS quantum dots in the liquid-crystalline matrix, one exponential is sufficient. These effects are explained by the appearance of regions with closely spaced quantum dots, in which, in particular, the resonance transmission of excitation is possible.

The process of film formation including the initial treatment of thin layers of cellulose solutions in N-methylmorpholine N-oxide with isobutanol followed by washing with water is investigated in detail, and the structural and morphological features of the obtained films are examined. The phase state of the N-methylmorpholine N-oxide–isobutyl alcohol system is studied by differential scanning calorimetry and optical interferometry, and a diagram describing the crystalline equilibrium and allowing determination of the temperature–concentration “window” of compatibility of components is constructed. The dependence of viscosity of N-methylmorpholine N-oxide solutions in isobutanol on temperature confirms the phase composition of the system. The process of film formation is modeled by analyzing the diffusion zone of the cellulose solution–isobutyl alcohol system. The IR study of the interaction of N-methylmorpholine N-oxide containing 13.3% water with isobutanol shows that the affinity of isobutanol for water is much higher than that for N-methylmorpholine N-oxide. For this reason, when the spinning solution is brought in contact with isobutanol, the redistribution of water between the interacting components occurs and the structure of the heterogeneous gel-like complex cellulose–N-methylmorpholine N-oxide–isobutanol “is frozen,” as proved by the X-ray diffraction study of the films. Complete removal of the solvent and isolation of cellulose from this film proceed only upon subsequent washing with water. The X-ray diffraction and optical interferometry study of the effect of temperature on the interaction of a hot cellulose solution with cold isobutanol suggests that at room temperature the film obtained from solution contains inclusions of the vitrified N-methylmorpholine N-oxide. Under isothermal conditions (at a temperature of 90°С), the rate of interdiffusion grows appreciably and the solution preserves the homogeneous structure. Thus, the precipitation of cellulose from the bicomponent solvent N-methylmorpholine N-oxide–water upon contact first with isobutanol and then with water proceeds via two stages: initially the system undergoes phase separation and a concentrated solution is formed in the isobutanol-N-methylmorpholine N-oxide blend, from which cellulose precipitates upon interaction with water. When the process of primary interaction of the solution with alcohol is conducted under the conditions of compatibility of isobutanol with N-methylmorpholine N-oxide, a more homogeneous morphology of the films can be obtained.

The macromolecular reaction of interchain cross-metathesis between polynorbornene and poly(5,6-epoxy-1-octenamer) in the presence of the first-generation Grubbs catalyst is studied. Chemically stable poly(5,6-epoxy-1-octenamer) is obtained through metathesis polymerization of 5,6-epoxycyclooct-1-ene with the second-generation Grubbs ruthenium catalyst. New random multiblock copolymers of norbornene and 5,6-epoxycyclooct-1-ene with different average block lengths determined by the reaction time, solvent type, and concentrations of the catalyst and initial homopolymers are synthesized and characterized by NMR, GPC, and DSC. Despite a distance between the epoxy substituent and the reaction center (double bond), poly(5,6-epoxy-1-octenamer) shows a lower activity in the cross-metathesis reaction with polynorbornene compared to unsubstituted polyoctenamer. The influence of epoxy groups present in the backbones of homopolymer and norbornene–cyclooctene multiblock copolymers on their thermal characteristics is studied. It is shown that the glass transition and melting temperatures increase with the concentration of epoxy groups upon the incorporation of an oxirane fragment into both homopolymers and copolymers. The crystallinity of poly(5,6-epoxy-1-octenamer) increases with the content of trans-С=С bonds in the polymer.

Using recently constructed experimental phase diagram isotactic polypropylene–1,2,4,5-tetrachlorobenzene (TeCB), we formulate a physically consistent scenario of the mixture evolution under thermally induced phase separation and predict the morphology of capillary-porous bodies that are formed after cooling down the binary system and removal of the low molecular mass component. This approach allows us to interpret the experimental data obtained by optical microscopy, scanning electron microscopy, and differential scanning calorimetry on the system with two crystallizable components. At any composition, TeCB forms needle-like crystals of nearly square section. Increasing polymer content affects crystal growth by limiting their length and by generating another population of small TeCB crystals of irregular shape and close to log-normal size distribution, located in the amorphous polymer regions. Finite rate of cooling the system leads to a hysteresis, when the values of characteristic temperatures and compositions in the phase diagram appear to be considerably shifted to lower temperatures and higher polymer contents. Combination of structural and calorimetric data provides an opportunity to characterize polymer–solvent systems from both thermodynamic and technological standpoints.

Embedding quantum dots (QDs) into an organic matrix of controllable order requires the identification of their structural characteristics. This analysis is necessary for the creation of anisotropic composites that are sensitive to external stimuli. We have studied the QD structures formed during the single-step synthesis of CdSe/ZnS QDs and their transformations after the initial ligand's substitution for another ligand. This single-step process leads to the formation of the core/shell structure. We detect the presence of two oleic acid residues ionically connected to Zn and Cd. At the same time, the amount of Cd oleate at the surface is very small. We observe the ligand exchange process at the surface of the core/shell QDs. The oleic acid residues are substituted by terphenyl-containing (TERPh-COOH) aromatic acid residues. The reaction between CdSe/ZnS carrying TOP and oleic acid residues ionically bound with QDs and terphenyl-containing acid leads to the coexistence of multiple ligands on the QD surface at a ratio of 11:6:33 for TOP/OA/TERPh-COOH.

Low-temperature properties of high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and their blends were studied. The analyzed low-temperature mechanical properties involve the deformation resistance and impact strength characteristics. HDPE is a bimodal ethylene/1-hexene copolymer, LDPE is a branched ethylene homopolymer containing short-chain branches of different length, LLDPE is a binary ethylene/1-butene copolymer and an ethylene/1-butene/1-hexene terpolymer. The samples of copolymers and their blends were studied by gel permeation chromatography (GPC), differential scanning calorimetry (DSC), 13С NMR spectroscopy, and dynamic mechanical analysis (DMA) using testing machines equipped with a cryochamber. It is proposed that such parameters as “relative elongation at break at −45 °C” and “Izod impact strength at −40 °C” are used instead of the ductile-to-brittle transition temperature to assess frost resistance properties because these parameters are more sensitive to deformation and impact at subzero temperatures for HDPE. LLDPE is shown to exhibit higher relative elongation at break at −45 °C and Izod impact strength at −20 ÷ 60 °C compared to those of LDPE. LLDPE terpolymer added to HDPE (at a content ≥ 25 wt.%) simultaneously increases flow properties and improves tensile properties of the blend at −45 °C. Changes in low-temperature properties as a function of molecular weight, MWD, crystallinity, and branch content were determined for HDPE, LLDPE, and their blends. The DMA data prove the resulting dependences. The reported findings allow one to understand and predict mechanical properties in the HDPE–LLDPE systems at subzero temperatures.

We investigate the structure–property relations of the multiblock copolymers of norbornene with cyclododecene synthesized via the macromolecular cross-metathesis reaction between amorphous polynorbornene and semicrystalline polydodecenamer in the presence of the first-generation Grubbs catalyst. By adjusting the reaction time, catalyst amount, and composition of the initial system, we obtain a set of statistical multiblock copolymers that differ in the composition and average length of norbornene and dodecenylene unit sequences. Structural, thermal, and mechanical characterization of the copolymers with NMR, XRD, DSC (including thermal fractionation by successive self-nucleation and annealing), and rotational rheology allows us to relate the reaction conditions to the average length of crystallizable unit sequences, thicknesses of corresponding lamellas, and temperatures of their melting. We demonstrate that isolated dodecenylene units can be incorporated into crystalline lamellas so that even nearly random copolymers should retain crystallinity. Weak high-temperature endotherms observed in the multiblock copolymers of norbornene with cyclododecene and other cycloolefins could indicate that the corresponding systems are microphase-separated in the melt state.

Replacing the aqueous coagulation bath with an alcoholic one during spinning cellulose fibers (films) from solutions in N-methylmorpholine-N-oxide leads to a radical restructuring of the hydrogen bonds net of cellulose and, as a result, to a change in the structure and properties of the resulting material. By the method of optical interferometry, it was possible to identify the intrinsic features of the interaction of the solvent and isomeric alcohols and to construct phase diagrams of binary systems describing the crystalline equilibrium. Knowledge of the phase states of the system at different temperatures renders it possible to exclude the process of solvent crystallization and conduct the spinning in pseudo-homogeneous conditions. The structure and morphology of samples were studied using X-ray diffraction and scanning electron microscopy methods for a specific coagulant. When the solution under certain conditions is coagulated at contact with alcohol, the solvent may be in a glassy state, whereas, when at coagulation in water, an amorphous-crystalline structure is formed. The structural features of cellulose films obtained by coagulation of solutions with water and alcohols help to select potential engineering or functional materials (textile, packaging, membranes, etc.), in which their qualities will manifest to the best extent.

Measurements of the photoluminescent spectra and kinetics, and of the excitation spectra of photoluminescence of CdSe nanoparticles embedded in various polymer matrices, show that using a liquid crystalline polymer as a matrix makes it possible to increase the lifetime of photoluminescence and the quantum yield of this process.

An effect of several polymeric stabilizers on the composites based on a diblock copolymer of styrene and 2-vinyl pyridine and spherical Au nanoparticles has been studied. Among the tested substances were thiol-terminated polystyrene, thiol-terminated poly(2-vinyl pyridine), diblock copolymers of styrene with 2- and 4-vinyl pyridine, and decanethiol as a typical low molecular mass stabilizer. Thin composite films with a microphase-separated cylindrical morphology have been prepared and characterized by atomic force and scanning electron microscopy to describe the surface morphology and nanoparticle distribution in the block copolymer matrix. In all the cases, the nanoparticles were selectively positioned either within vinyl pyridine domains or at the domain boundaries. The most effective stabilization of Au nanoparticles, both regarding their location and prevention of aggregation, was provided by the diblock copolymers.

An original optical method and differential scanning calorimetry were used to construct an experimental phase diagram for the binary composition low-density polyethylene – highly refined mineral oil. This diagram includes the polymer full amorphization curve and the oil solubility curve that describes the osmotic equilibrium between the swollen polymer and pure mineral oil. Within the domain between these curves, the system can be identified with a single-phase microheterogeneous gel with polymer crystallites as physical crosslinks. Two critical compositions containing 17 and 36 wt% of polyethylene were found. The first one corresponds to the least amount of polymer needed to form a capillary-porous body upon cooling down the pre-homogenized mixture. The second composition contains the fraction of oil above which the polymer full amorphization temperature is no longer decreased. Comparing with the optical method, calorimetry is much faster and able to catch weak mineral oil crystallinity, but less accurate and unable to supply any data for the solubility curve. An empirical analysis of the parameters describing the polymer full amorphization curve allowed us to conclude that mineral oil is less miscible with low-density polyethylene than decane and tridecane. The results obtained can be useful for the optimization of the properties of rubber-based vibration-damping compositions filled with polyethylene and mineral oil.

An exchange reaction of cross-metathesis between polynorbornene and poly(5-hydroxyoctenamer) in a chloroform–methanol mixture (10: 1 vol/vol) in the presence of Ru–carbene Grubbs’ complexes Gr-1 and Gr-2 has been studied. Gr-2 catalyst has a much higher activity and allows one to obtain multiblock copolymers, which cannot be synthesized directly from norbornene and 5-hydroxy-1-cyclooctene. The average length of the copolymer blocks varies in a wide range depending on the reaction conditions. The individual stages of the process have been studied with the use of in situ monitoring of transformations of Ru–carbene complexes by 1Н NMR spectroscopy and ex situ analysis of heterodyad evolution in copolymers via 13C NMR spectroscopy. As has been shown, poly(5-hydroxyoctenamer) forms Ru–carbene complexes with the catalyst more easily than polynorbornene; in this case, the incorporation of a substituent in the monomer unit of octenamer retards the polymer cross-metathesis. It has been found that, in systems containing Gr-2 and hydroxyoctenamer blocks, the formed ruthenium hydride complexes initiated hydrogenation process. The hydrogenation results in the appearance of crystallinity in the initially amorphous polymers, which opens up the possibilities for the targeted control of the multiblock copolymers properties.

The epoxidation of double bonds in random multiblock copolymers of norbornene and cyclooctene is studied for the first time. The initial copolymers with different composition and average block length are synthesized via the cross-metathesis reaction between polynorbornene and polycyclooctene in the presence of the first-generation Grubbs catalyst. New multiblock copolymers containing oxirane fragments in the backbone are obtained with a yield of 85–92% through epoxidation conducted under the action of m-chloroperbenzoic acid in toluene. The kinetics of epoxidation of polynorbornene, polycyclooctene, and their multiblock copolymers in deuterochloroform and deuterobenzene is investigated via the in situ monitoring of transformation of double bonds using 1Н NMR spectroscopy. It is shown that on the whole the modification of cyclooctene units occurs more easily in copolymers than that in the homopolymer. The thermal properties of epoxidized homo- and copolymers are examined. It is found that upon epoxidation the glass-transition temperature and the melting temperature of multiblock copolymers increase by 40–50 and 20–30°С, respectively, wherein the degree of crystallinity and the temperature of melting grow with the length of the cyclooctene block.

Novel membrane materials—three-dimensional polydimethylsiloxane networks with nonaggregated metal atoms (Fe, Zr)—have been synthesized using commercial siloxane rubber SKTN and polyfunctional metallosiloxane as a crosslinking agent. For the resulting composites, the permeability, diffusion, and solubility coefficients for a wide range of gases have been determined. It has been found that the permeability coefficients for most of the gases are close to values previously obtained for linear siloxanes; however, the permeability and Р(С4Н10)/Р(СН4) selectivity for n-butane are significantly higher. It has been shown that the differences in the permeability coefficients are attributed to higher solubility coefficients of gases in the synthesized composites.

A fast route to transfer Au nanoparticles from aqueous to organic media is proposed based on the use of a high molecular mass diblock copolymer of styrene and 2-vinylpyridine for ligand exchange at the nanoparticle surface. The method enables the preparation of stable sols of Au nanorods with sizes of up to tens of nanometers or Au nanospheres in various organic solvents. By comparing the optical absorbance spectra of Au hydro- and organosols with the data of numerical simulations of the surface plasmon resonance, we find that nanoparticles do not aggregate and confirm the transmission electron microscopy data regarding their shape and size. The proposed approach can be effective in preparing hybrid composites without the use of strong thiol and amine surfactants.

The paper describes the synthesis and physical-chemical properties of anisotropic derivatives of (-)-L-lactic acid and their nanocomposites. Anisotropic optically active aryl (S)-2-(ω-halogenalkoxy...

We report on effects of the matrix on photoluminescence spectra and lifetime and efficiency of up-conversion of core-type CdSe and core/shell CdSe/ZnS quantum dots embedded into smectic and amorphous polymers.

Crystallinity of statistical multiblock copolymers of norbornene and cyclooctene with nearly equimolar composition and different degrees of blockiness is studied by differential scanning calorimetry including thermal fractionation by successive self-nucleation and annealing and by X-ray diffraction. The copolymers are synthesized via recently invented reaction of polymer cross-metathesis, as a result of interchain exchange between polynorbornene and polyoctenamer in the presence of Grubbs’ catalyst of the first generation. This catalyst raises the fraction of trans-octenylene units up to more than 80% promoting formation of triclinic crystals. The copolymer degree of crystallinity and melting peak temperature decrease with the cross-metathesis conversion. At the same time the equilibrium melting temperature predicted by the Flory theory of copolymer crystallization is not much affected by the interchange reaction. Compared with the pure polyoctenamer or its equimolar blend with polynorbornene, the norborene-cyclooctene copolymers form considerably smaller crystallites. Thermal fractionation makes it possible to find their size distribution, which correlates with the average length of trans-octenylene blocks. Short annealing the multiblock copolymers above their melting points gives rise to a small but persistent endotherm 5–10 degrees above the annealing temperature, which is absent in polyoctenamer and, therefore, may indicate mixing of segregated norbornene and cyclooctene blocks.

The state diagram of the low-density polyethylene–p-xylene system that contains the solubility curve of p-xylene in the polymer is first built using the optical method with the involvement of the DSC data. It has been shown that, at 72°C, in a blend with a polymer mass fraction of 0.28, the full amorphization of the polymer proceeds simultaneously with the dissolution of p-xylene in it. Blends with a lower polymer content are also homogenized at the same temperature, although the duration of this process can take several days. In blends with a high polymer content, homogenization occurs at a higher temperature. This process is preceded by the formation of microheterogeneous single-phase gel with network junctions as polymer crystallites and amorphous regions saturated by p-xylene. Cooling of the homogeneous blends to–20°С is not accompanied by the full separation of low- and high-molecular-mass phases; in this case p-xylene not only forms an individual crystalline phase, but also partially crystallizes in amorphous regions of the polymer.

A method of controlled radical polymerization via the reversible addition fragmentation chain transfer mechanism is used to synthesize LC polymers with functional terminal thiol groups. These polymers are used to create composites containing gold nanoparticles at a concentration of up to 40 wt % and capable of LC ordering. The structural, thermodynamic, and optical properties of the composites are studied. It is shown that the spatial separation of mesogenic groups and groups responsible for the binding of a macromolecule with nanoparticles makes it possible to considerably widen the concentration range of nanoparticles while preserving the LC state of the composites.

The phase behavior of low-density polyethylene mixtures with 1,2,4,5 – tetrachlorobenzene and camphor is investigated by optical methods and differential scanning calorimetry. The use of a photoconductive cell integrated into an optical microscope equipped with a heating stage, allows us, for the first time, to combine turbidimetry with visual observations to detect crystallization of a low-molar-mass substance from the amorphous regions of a semicrystalline polymer. Crystallization in the restrained conditions of an apparently solid polymer matrix leads to crystals much smaller than the low-molar-mass crystals formed in a mixture with the melted polymer. We discuss the details of reversible structural changes taking place to the binary mixtures of crystallizable components in the course of their heating and cooling. Constructed phase diagrams provide important information for developing technologies based on thermally induced phase separation in such systems.

This research examines the possibilities of regulating the structure of cellulose precursor fibers spun from solutions in N-methylmorpholine-N-oxide when replacing aqueous coagulation baths with thermodynamically softer alcohol baths at different temperatures. The fibers were spun by the dry jet&ndash, wet method in isobutanol coagulation baths with a temperature of 25 &deg, C and 70 &deg, C. The study of the phase state of the solvent&ndash, coagulant system using viscometry and point cloud methods revealed the temperature-concentration regions of the single-phase and two-phase states of the system. Using elemental analysis, DSC (differential scanning calorimetry) and XRD (X-ray diffraction) methods, it was shown that just spun fibers, due to the presence of a residual amount of solvent and coagulant in them, regardless of the temperature of the precipitator, have an amorphous structure. Additional washing with water completely washed away the solvent and coagulant as well, however, the structure of cellulose changes slightly, turning into a defective amorphous-crystalline one. A relationship was found between the phase composition, structure, and properties of just spun fibers and precursors washed with water. Thus, the loss of structural ordering of both just spun and washed cellulose fibers leads to a decrease in strength characteristics and an increase in deformation. The thermal behavior of the fibers is determined by their phase composition. Fibers just spun into hot alcohol containing a coagulant and traces of solvent acquire thermal stability up to 330 &deg, C. During the pyrolysis of the obtained precursors up to 1000 &deg, C, the value of the carbon yield doubles. The amorphized structure of the obtained fibers allows us to consider it as a model when analyzing the transformation of the structure of precursors during thermolysis.

A new type of phase diagram semicrystalline polymer – low molecular mass substance is found for the low-density polyethylene – dimethyl terephthalate mixture. Exploiting an original optical method and differential scanning calorimetry, we demonstrate that the studied system combines the features of polymer – poor solvent and polymer – high-melting substance mixtures. Its diagram also contains a curve describing the solubility of the low molecular mass component in the polymer, which is often missing in the literature. An experimental phase diagram enables us to perform a detailed analysis of the differential scanning calorimetry, optical and scanning electron microscopy data on the cooling of homogenized mixtures of different compositions, which leads to the formation of capillary-porous polyethylene bodies via thermally induced phase separation and following removal of dimethyl terephthalate crystals.

Composites based on microphase-separated diblock copolymers of styrene with vinylpyridine and gold nanoparticles, in which the block copolymers play simultaneously both the role of a stabilizer preventing the aggregation of nanoparticles and a matrix providing their selective arrangement within domains of the predefined type, are obtained for the first time. The suggested approach implies no use of additional stabilizers and is efficient for both initially organic dispersed small (~5 nm) spheres and hydrasols of larger (9 × 30 nm) rodlike nanoparticles. Nanospheres are introduced into the composites via replacement of a labile stabilizer used in synthesis with the diblock copolymer, while nanorods synthesized in aqueous media by the two-stage method are incorporated via phase transfer mediated by the diblock copolymer. Films capable of microphase separation leading to the formation of vinylpyridine cylindrical domains with a diameter of tens nanometers are spin-coated from the obtained composites. The content of nanoparticles in the composites is up to 5 wt %; they are dispersed and arranged predominantly within vinylpyridine domains, with nanospheres being localized near domain boundaries, while nanorods being mainly oriented perpendicularly to the axis of cylinders.

Copolymers of norbornene and cyclooctene were synthesized for the first time by the cross-metathesis of polynorbornene with polyoctenamer. This strategy made it possible to use the 1st generation Grubbs catalyst, which exhibits low activity toward copolymerization of those monomers. Statistical multiblock copolymers with average block lengths varying from 200 to 2 units were obtained.

The role of specific interactions between a polymer matrix and incorporated quantum dots is one of the critical problems for understanding the effect of the polymer matrix on the optical properties of quantum dots in a nanocomposite material and for creating new photonic materials and related instruments. In this study, cadmium selenide quantum dots have been incorporated into a liquid-crystalline polymer via the interaction of carboxyl groups of the polymer with the quantum-dot surfaces through ionic bonds. From the data of transmission electron microscopy, it has been shown that this interaction provides the localization of quantum dots in the environment of the liquid-crystalline phase of the polymer. Various features of photoluminescent properties have been observed and interpreted in terms of the emission recombination of excitons in CdSe quantum dots, light reabsorption by quantum dots, the effect of the electronic states on the surface CdSe-liquid crystal, and the energy transfer from quantum dots to the polymer liquid-crystalline matrix.

Bulk and solution studies revealed a strongly pronounced effect of chain structure on the rheological and relaxation behavior of well-characterized vinyl acetate–vinyl alcohol copolymers of similar composition and polymerization degree. The frequency–temperature superposition principle is fully applicable to the random copolymers, which demonstrate all expected relaxation states, whereas a divergence of the reduced dynamic moduli–frequency dependences is observed for the multiblock copolymers. In the latter case, the terminal zone is sensitive to the self-assembling of vinyl alcohol blocks into (depending on the copolymer composition) crystalline or amorphous microstructures. The monomer unit distribution particularly affects properties of the copolymer solutions in N,N-dimethylformamide (DMF). 5% solutions behave as simple viscoelastic liquids at 20 °C and show viscoplastic behavior at −20 °C, where more blocky chains are characterized by up to 4 orders of magnitude higher yield stress values. The multib...

On the basis of copolymers of 4-methoxyphenyl-4-(6-(acryloyloxyhexyloxy)benzoate with 4-(6-acryloyloxyhexyloxy)benzoic acid, nonequilibrium composites containing nanoparticles (quantum dots) of cadmium selenide at concentrations many times higher than their solubility limit in the liquid-crystalline phase are synthesized. In the resulting material, the polymer matrix undergoes the transition to the liquidcrystalline state before separation into phases with concentrations of nanoparticles corresponding to thermodynamically equilibrium values. Under common conditions, the composites are stable for at least several months.

A comparative study of the viscoelastic properties of melts of vinyl acetate-vinyl alcohol copolymers with equimolar compositions characterized by different statistical distributions of chain units has been performed. It has been shown that the principle of temperature-frequency superposition is obeyed by copolymers close to a random copolymer, but is violated by copolymers with the block distribution of units. Unlike amorphous random copolymers, a multiblock copolymer is characterized by weak crystallinity, the absence of the relaxation flow state, and a more pronounced tendency to form interchain hydrogen bonds both between two hydroxyl groups and between hydroxyl and ester groups.

By means of in situ melt polycondensation of polyethylenterephathalate accompanied with simultaneous reduction of introduced graphene oxide, the composite of polyethylenterephathalate filled with reduced graphene oxide was prepared. Melting and crystallization of the reduced graphene oxide – polyethyleneterephthalate composite was studied by the differential scanning calorimetry method, and the rheological test was carried out by rotational rheometry and compared to the pristine polyethylenterephathalate. The morphology of the reduced graphene oxide – polyethyleneterephthalate composite was studied using optical microscopy. The reduced graphene oxide was isolated from the reduced graphene oxide – polyethyleneterephthalate composite and characterized by thermogravimetry, X-ray photoelectron spectroscopy and X-Ray diffraction methods. Since a part of polymer could not be removed from reduced graphene oxide particles by trifluoroacetic acid, the hypothesis about probable grafting of polyethyleneterephthalate on reduced graphene oxide sheets was suggested. Rheological behaviour of the reduced graphene oxide – polyethyleneterephthalate composite melt confirms this suggestion. According to the calculations based on thermogravimetry, the reduced graphene oxide, isolated from the reduced graphene oxide – polyethyleneterephthalate composite, consists of about 80% polyethyleneterephthalate.

The effect of solvent on the photoluminescence of cadmium selenide quantum dots stabilized by oleic acid is examined with the example of two organic solvents: toluene and THF. It is found that THF favors desorption of ligands and formation of surface defects to a greater extent than toluene; as a result, the maximum of the photoluminescence band shifts to the red spectral region and its intensity decreases. The addition of polymers to the solution of quantum dots causes changes in the efficiency of photoluminescence and in the kinetics of its quenching. In the range of low concentrations (≤2 wt %) of quantum dots in polymer solutions, the intensity of luminescence first grows and then passes through a maximum and decreases. This effect may be explained both by the increasing number of surface defects and by quenching via energy transfer to polymers, especially in the case of polymers containing aromatic groups.

The phase state of polyelectrolyte blends based on acrylic copolymers was investigated with differential scanning calorimetry, transmission electron microscopy (TEM), and wedge microinterferometry as a function of the blend composition and ionization of polymer functional groups. A copolymer of N,N-dimethylaminoethyl methacrylate with methyl methacrylate and butyl methacrylate was used as a polybase, a copolymer of methacrylic acid and ethyl acrylate was employed as a polyacid, and the optional plasticizer was triethyl citrate. A correlation was established between an earlier described mechanism of molecular interaction and the behavior of the glass-transition temperature (Tg) of the polymer blends. The Tg values of the polyelectrolyte complexes in the gel phase were always higher than Tg in the sol phase. This fact implies that intermolecular cohesion dominated the free volume in the stoichiometric polyelectrolyte complexes formed in the gel phase, whereas nonstoichiometric complexes formed in the sol phase were characterized with the predominant contribution of free volume. TEM and interferograms of polyelectrolyte blends showed the signs of anisotropic ordered supramolecular structure formation. A phase-state diagram of the polyelectrolyte blends was constructed. The stoichiometric polyelectrolyte complex was immiscible with parent polymers, forming a separate phase that became melted at elevation of temperature because of complex dissociation. Polyelectrolyte miscibility was supposed to result rather from the chemical reaction of the complex formation than from interdiffusion of the polymer components along the gradient of their concentration. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

A new luminescent composite based on quantum dots of CdSe immobilized on the polymer LC matrix prepared through the graft polymerization of the monomer of 4-(ω-acryloyloxyhexyloxy)benzoic acid on a fluorocarbon support after its preliminary irradiation with vacuum ultraviolet light is elaborated. The structure, composition, and optical characteristics of the prepared composite are studied via the methods of the FTIR spectroscopy, energy-dispersive and wave-dispersive analyses, and luminescence spectroscopy. The CdSe particles are shown to interact with the carboxyl groups of mesogenic fragments of the LC polymer, and this interaction leads to the integration of quantum dots into the ordered LC structure of the composite. As a result of immobilization, the luminescence peak of the quantum dots is shifted toward lower wavelengths owing to the interaction between the nanoparticles and the polymer LC matrix.

This paper briefly summarizes the state of the art in the field of designing composites containing semiconductor nanoparticles distributed in a polymer matrix. Special attention is focused on (i) nanocomposites based on block copolymers and (ii) LC polymer matrices capable of controlling the localization and alignment of nanoparticles.

The photoluminescence properties of cadmium-selenide (CdSe) quantum dots with an average size of ∼3 nm, embedded in a liquid-crystal polymer matrix are studied. It was found that an increase in the quantum-dot concentration results in modification of the intrinsic (exciton) photoluminescence spectrum in the range 500–600 nm and a nonmonotonic change in its intensity. Time-resolved measurements show the biexponential decay of the photoluminescence intensity with various ratios of fast and slow components depending on the quantum-dot concentration. In this case, the characteristic lifetimes of exciton photoluminescence are 5–10 and 35–50 ns for the fast and slow components, respectively, which is much shorter than the times for colloidal CdSe quantum dots of the same size. The observed features of the photoluminescence spectra and kinetics are explained by the effects of light reabsorption, energy transfer from quantum dots to the liquid-crystal polymer matrix, and the effect of the electronic states at the CdSe/(liquid crystal) interface.

Preparation of hybrid composite materials consisting of a polymeric matrix and inorganic nanoparticles (NPs) is considered as an approach for creating new materials for photonics. The major focus of this review is on the applications of anisotropic matrices that can control the spatial arrangement of NPs. The fundamental aspects related to hybrid organic-inorganic composites with photonic properties provided by LC polymers are of great practical interest. Several approaches are considered as efficient tools for tuning the photoluminescence by means of chemical coupling (covalent or non-covalent) of polymers with NPs, mesophase structure type and NPs morphology.

The photoluminescence (PL) of CdSe quantum dots (QDs) that form stable nanocomposites with polymer liquid crystals (LCs) as smectic C hydrogen-bonded homopolymers from a family of poly[4-(n-acryloyloxyalkyloxy)benzoic acids] is reported. The matrix that results from the combination of these units with methoxyphenyl benzoate and cholesterol-containing units has a cholesteric structure. The exciton PL band of QDs in the smectic matrix is redshifted with respect to QDs in solution, whereas a blueshift is observed with the cholesteric matrix. The PL lifetimes and quantum yield in cholesteric nanocomposites are higher than those in smectic ones. This is interpreted in terms of a higher order of the smectic matrix in comparison to the cholesteric one. CdSe QDs in the ordered smectic matrix demonstrate a splitting of the exciton PL band and an enhancement of the photoinduced differential transmission. These results reveal the effects of the structure of polymer LC matrices on the optical properties of embedded QDs, which offer new possibilities for photonic applications of QD-LC polymer nanocomposites.

The state of sorbed water in hydrogels based on hydrogen-bonded complexes between poly(N-vinyl pyrrolidone) (PVP) and short-chain poly(ethylene glycol) (PEG) has been examined by considering water vaporisation endotherms in d.s.c. heating traces and relating them to characteristics of the amorphous and crystalline phases, i.e. the thermodynamic parameters of glass transition and excess PEG melting. In compatible PVP–PEG blends water behaves as a third component in the PVP–PEG complex and is sorbed mainly by PVP, whereas PEG increases the mobility of sorbed water molecules evaluated in the terms of the entropy of water thermodesorption. Water sorption affects dramatically the state of crystalline (excess) PEG in blends, while the state of the amorphous phase, constituted by the PVP–PEG hydrogen-bonded complex, is practically unaffected by hydration.

The phase behaviour of blends of high-molecular weight poly(N-vinyl pyrrolidone) (PVP) with short-chain poly(ethylene glycol) (PEG) of M w =400, prepared by drying their solutions in a common solvent (ethyl alcohol), was studied using DSC. Upon heating of cool-quenched samples a single glass transition was observed, followed by an exotherm corresponding to cold crystallization of excess PEG, a melting endotherm, and an endotherm corresponding to vaporization of absorbed water. The temperatures of glass transition (Tg), PEG cold crystallization (Tc), and melting (Tm), along with the change in heat capacity (ΔCp) between the polymer's glassy and rubbery states at Tg, vary with blend composition and hydration. As a result the Tg/Tm, Tc/Tm and Tc/Tg ratios for PVP–PEG blends are functions of composition. PVP–PEG compatibility is due to H-bonding of PEG terminal hydroxyls to the carbonyls in the PVP repeating units. Large negative deviations of Tg values from the calculated weight averages, found mainly for PVP-overloaded blends, signify strong PVP–PEG interaction and free volume formation.

Properties of the nematic–isotropic phase transition in polymer and low molecular weight liquid crystals doped with nanoparticles have been studied both experimentally and theoretically in terms of molecular mean-field theory. The variation of the transition temperature and the transition heat with the increasing volume fraction of CdSe quantum dot nanoparticles in copolymer and low molecular weight nematics has been investigated experimentally and the data are interpreted using the results of the molecular theory which accounts for a possibility of phase separation when the system undergoes the nematic–isotropic transition. The theory predicts that the nematic and isotropic phases with different concentrations of nanoparticles may coexist over a broad temperature range, but only if the nanoparticle volume fraction exceeds a certain threshold value which depends on the material parameters. Such unusual phase separation effects are determined by the strong interaction between nanoparticles and mesogenic groups and between nanoparticles themselves.