Fully Aromatic Thermotropic Copolyesters Based on Vanillic, Hydroxybenzoic, and Hydroxybiphenylcarboxylic Acids.

Several series of new polymers were synthesized in this study: binary copolyesters of vanillic (VA) and 4'-hydroxybiphenyl-4-carboxylic (HBCA) acids, as well as ternary copolyesters additionally containing 4-hydroxybenzoic acid (HBA) and obtained via three different ways (in solution, in melt, and in solid state). The high values of logarithmic intrinsic viscosities and the insolubility of several samples proved their high molecular weights. It was found that the use of vanillic acid leads to the production of copolyesters with a relatively high glass transition temperature (~130 °C). Thermogravimetric analysis revealed that the onset of weight loss temperatures of ternary copolyesters occurred at 330-350 °C, and the temperature of 5% mass loss was in the range of 390-410 °C. Two-stage thermal destruction was observed for all aromatic copolyesters of vanillic acid: decomposition began with VA units at 420-480 °C, and then the decomposition of more heat-resistant units took place above 520 °C. The copolyesters were thermotropic and exhibited a typical nematic type of liquid crystalline order. The mechanical characteristics of the copolyesters were similar to those of semi-aromatic copolyesters, but they were much lower than the typical values for fully aromatic thermotropic polymers. Thus, vanillic acid is a mesogenic monomer suitable for the synthesis of thermotropic fully aromatic and semi-aromatic copolyesters, but the processing temperature must not exceed 280 °C.

Non-Coagulant Spinning of High-Strength Fibers from Homopolymer Polyacrylonitrile Synthesized via Anionic Polymerisation.

The rheological properties, spinnability, and thermal-oxidative stabilization of high-molecular-weight linear polyacrylonitrile (PAN) homopolymers (molecular weights Mη = 90-500 kg/mol), synthesized via a novel metal-free anionic polymerization method, were investigated to reduce coagulant use, enable solvent recycling, and increase the carbon yield of the resulting carbon fibers. This approach enabled the application of the mechanotropic (non-coagulating) spinning method for homopolymer PAN solutions in a wide range of molecular weights and demonstrated the possibility of achieving a high degree of fiber orientation and reasonable mechanical properties. Rheological analysis revealed a significant increase in solution elasticity (G') with increasing molecular weight, facilitating the choice of optimal deformation rates for effective chain stretching prior to strain-induced phase separation during the eco-friendly spinning of concentrated solutions without using coagulation baths. The possibility of collecting ~80 wt% of the solvent at the first stage of spinning from the as-spun fibers was shown. Transparent, defect-free fibers with a tensile strength of up to 800 MPa and elongation at break of about 20% were spun. Thermal treatment up to 1500 °C yielded carbon fibers with a carbon residue of ~50 wt%, in contrast to ~35 wt% for industrial radically polymerized PAN carbonized under the same conditions.

Rheology of Highly Filled Polymer Compositions-Limits of Filling, Structure, and Transport Phenomena.

The current state of the rheology of various polymeric and other materials containing a high concentration of spherical solid filler is considered. The physics of the critical points on the concentration scale are discussed in detail. These points determine the features of the rheological behavior of the highly filled materials corresponding to transitions from a liquid to a yielding medium, elastic-plastic state, and finally to an elastic solid-like state of suspensions. Theoretical and experimental data are summarized, showing the limits of the most dense packing of solid particles, which is of key importance for applications and obtaining high-quality products. The results of model and fine structural studies of physical phenomena that occur when approaching the point of filling the volume, including the occurrence of instabilities, are considered. The occurrence of heterogeneity in the form of individual clusters is also described. These heterogeneous objects begin to move as a whole that leads to the appearance of discontinuities in the suspension volume or wall slip. Understanding these phenomena is a key for particle technology and multiphase processing.

Transformation of Specific Dispersion Interactions between Cellulose and Polyacrylonitrile in Solutions into Covalent Interactions in Fibers.

Morphological transformations in emulsions of cellulose and polyacrylonitrile (PAN) ternary copolymers containing acrylonitrile, methyl acrylate, and methylsulfonate comonomers in N-methylmorpholine-N-oxide were studied over the entire range of concentrations depending on temperature and intensity of the deformation action. Based on the morphological and rheological features of the system, the temperature-concentration range of spinnability of mixed solutions was determined, and composite fibers were spun. The fibers are characterized by a heterogeneous fibrillar texture. Studies of the structure of the fibers, carried out using X-ray diffraction analysis, revealed a decrease in cellulose crystallinity with an increase in the content of PAN. The study of the thermal properties of the obtained fibers, carried out using DSC, and chemical transformations in them in a wide temperature range by high-temperature diffuse reflection IR spectroscopy made it possible to reveal a new intense exothermic peak on the thermograms at 360 °C, which according to the IR spectra corresponds to the transformation of intermacromolecular physical interactions of the PAN and cellulose into covalent bonds between polymers. In addition, the ester groups found during the thermal treatment of the PAN part of the composite fibers in the pyrolysis zone can have a key effect on the process of their further carbonization.

Rheology of Gels and Yielding Liquids.

In this review, today's state of the art in the rheology of gels and transition through the yield stress of yielding liquids is discussed. Gels are understood as soft viscoelastic multicomponent solids that are in the incomplete phase separation state, which, under the action of external mechanical forces, do not transit into a fluid state but rupture like any solid material. Gels can "melt" (again, like any solids) due to a change in temperature or variation in the environment. In contrast to this type of rheology, yielding liquids (sometimes not rigorously referred to as "gels", especially in relation to colloids) can exist in a solid-like (gel-like) state and become fluid above some defined stress and time conditions (yield stress). At low stresses, their behavior is quite similar to that of permanent solid gels, including the frequency-independent storage modulus. The gel-to-sol transition considered in colloid chemistry is treated as a case of yielding. However, in many cases, the yield stress cannot be assumed to be a physical parameter since the solid-to-liquid transition happens in time and is associated with thixotropic effects. In this review, special attention is paid to various time effects. It is also stressed that plasticity is not equivalent to flow since (irreversible) plastic deformations are determined by stress but do not continue over time. We also discuss some typical errors, difficulties, and wrong interpretations of experimental data in studies of yielding liquids.

Polyacrylonitrile Fibers with a Gradient Silica Distribution as Precursors of Carbon-Silicon-Carbide Fibers.

This study presents preparing and characterization of polyacrylonitrile (PAN) fibers containing various content of tetraethoxysilane (TEOS) incorporated via mutual spinning solution or emulsion using wet and mechanotropic spinning methods. It was shown that the presence of TEOS in dopes does not affect their rheological properties. The coagulation kinetics of complex PAN solution was investigated by optical methods on the solution drop. It was shown that during the interdiffusion process phase separation occurs and TEOS droplets form and move in the middle of the dope's drop. Mechanotropic spinning induces the TEOS droplets to move to the fiber periphery. The morphology and structure of the fibers obtained were investigated by scanning and transmission electron microscopy, as well as X-ray diffraction methods. It was shown that during fiber spinning stages the transformation of the TEOS drops into solid silica particles takes place as a result of hydrolytic polycondensation. This process can be characterized as the sol-gel synthesis. The formation of nano-sized (3-30 nm) silica particles proceeds without particles aggregation, but in a mode of the distribution gradient along the fiber cross-section leading to the accumulation of the silica particles either in the fiber center (wet spinning) or in the fiber periphery (mechanotropic spinning). The prepared composite fibers were carbonized and according to XRD analysis of carbon fibers, the clear peaks corresponding to SiC were observed. These findings indicate the useful role of TEOS as a precursor agent for both, silica in PAN fibers and silicon carbide in carbon fibers that has potential applications in some advanced materials with high thermal properties.

Synthesis and Characterization of Novel Wholly Aromatic Copolyesters Based on 4'-Hydroxybiphenyl-3-Carboxylic and 3-Hydroxybenzoic Acids.

A series of new wholly aromatic (co)polyesters based on m-substituted bifunctional comonomers-4'-hydroxybiphenyl-3-carboxylic (3HBCA) and 3-hydroxybenzoic (3HBA) acids with molar ratios of 3HBCA:3HBA from 0:100 to 60:40, respectively-was synthesized. NMR and FTIR spectroscopy methods proved the full compliance of the copolymer composition with the target ratio of comonomers, as well as high compositional homogeneity (absence of block sequences). The resulting copolyesters have a sufficiently high molecular weight and their intrinsic viscosity values are in the range of 0.6-0.8 dL/g. Thermal analysis showed that all 3HBCA-3HBA copolyesters are amorphous, and with an increase in the content of biphenyl units (3HBCA), the glass transition temperature increases significantly (up to 190 °C). The onset of the intense thermal decomposition of the synthesized polyesters occurs above 450 °C. Thus, this indicates a sufficiently high thermal stability of these polyesters. Rheological measurements have shown that melts of copolyesters with a high content of 3HBCA units exhibit anisotropic properties. At the same time, the method of polarization optical microscopy did not confirm the transition to the liquid crystal state for these polyesters. These results confirm that it is possible to obtain high-performance polyesters based on 3HBCA, but not a mesogenic comonomer. Thus, 3HBCA is a promising comonomer for the synthesis of new thermotropic copolyesters with controlled anisotropic properties.

The Elasticity of Polymer Melts and Solutions in Shear and Extension Flows.

This review is devoted to understanding the role of elasticity in the main flow modes of polymeric viscoelastic liquids-shearing and extension. The flow through short capillaries is the central topic for discussing the input of elasticity to the effects, which are especially interesting for shear. An analysis of the experimental data made it possible to show that the energy losses in such flows are determined by the Deborah and Weissenberg numbers. These criteria are responsible for abnormally high entrance effects, as well as for mechanical losses in short capillaries. In addition, the Weissenberg number determines the threshold of the flow instability due to the liquid-to-solid transition. In extension, this criterion shows whether deformation takes place as flow or as elastic strain. However, the stability of a free jet in extension depends not only on the viscoelastic properties of a polymeric substance but also on the driving forces: gravity, surface tension, etc. An analysis of the influence of different force combinations on the shape of the stretched jet is presented. The concept of the role of elasticity in the deformation of polymeric liquids is crucial for any kind of polymer processing.

Experimental Study on the Manufacturing of Functional Paper with Modified by N-Methylmorpholine-N-oxide Surfaces.

The manufacturing of paper with new functional properties is a current problem today. A method of modifying the surface layer of paper by the partial dissolution of cellulose on its surface is proposed. N-Methylmorpholine-N-oxide (NMMO) is proposed for use as a solvent, the regeneration of which provides an environmentally friendly process. It was shown that among the possible hydrate forms of the solvent, the monohydrate and higher-melting forms are optimal for modifying the paper surface. The temperature-time modes of processing were revealed and the weight gain and density increase in the course of modification were estimated. The structural and morphological features of the original and modified paper were studied by X-ray imaging and scanning microscopy. The NMMO surface treatment makes it possible to vary the air permeability of the paper, making it practically non-permeable. The capillary and pore system were radically transformed after the partial dissolution of cellulose and its coagulation, as the formed cellulose film isolates them, which leads to a decrease in surface absorbency. The processing conditions allowing for the optimization of the optical and strength properties of the modified paper samples are revealed. The resulting paper with a modified N-methylmorpholine-N-oxide surface layer can be used for printing valuable documents.

Melt-Spinnable Polyacrylonitrile-An Alternative Carbon Fiber Precursor.

The review summarizes recent advances in the production of carbon fiber precursors based on melt-spun acrylonitrile copolymers. Approaches to decrease the melting point of polyacrylonitrile and acrylonitrile copolymers are analyzed, including copolymerization with inert comonomers, plasticization by various solvents and additives, among them the eco-friendly ways to use the carbon dioxide and ionic liquids. The methods for preliminary modification of precursors that provides the thermal oxidative stabilization of the fibers without their melting and the reduction in the stabilization duration without the loss of the mechanical characteristics of the fibers are discussed. Special attention is paid to different ways of crosslinking by irradiation with different sources. Examples of the carbon fibers preparation from melt-processable acrylonitrile copolymers are considered in detail. A patent search was carried out and the information on the methods for producing carbon fibers from precursors based on melt-spun acrylonitrile copolymers are summarized.

Silica-Filled Polyacrylonitrile Solutions: Rheology, Morphology, Coagulation, and Fiber Spinning.

The fumed silica influence on the morphology, coagulation processes, and rheological properties of suspensions in dimethyl sulfoxide (DMSO) and polyacrylonitrile (PAN)-DMSO solutions has been studied for the production of composite films and fibers. It has been shown that silica-DMSO concentrated suspensions (24 wt%) form a weak gel with a yield point of about 200 Pa. At concentrations of ~5 wt% and above the dispersions, depending on the shear stress, are pseudoplastic or dilatant liquids. It has been found that the silica addition method into a PAN solution has a significant impact on the aggregates dispersibility and the rheological behavior of the obtained systems. A thixotropy appearance and a sharp increase in the relaxation time were observed for PAN solutions at a SiO2 content of more than 3-5 wt%, which indicates the formation of structures with a gel-like rheological behavior. Upon reaching the critical stress their destruction takes place and the system starts to behave like a viscoelastic liquid. Two spinning methods have been used for preparing fibers: standard wet and mechanotropic. By the mechanotropic method it is possible to achieve a higher draw ratio at spinning and to obtain fibers with better mechanical properties. It is possible to spin fibers from PAN solutions containing up to 15 wt% of silica per polymer with a tensile strength up to 600 MPa.

High Molecular Weight AB-Polybenzimidazole and Its Solutions in a Complex Organic Solvent: Dissolution Kinetics and Rheology.

AB-polybenzimidazole (ABPBI) dissolution kinetics in an eco-friendly complex acid-free solvent based on dimethyl sulfoxide (DMSO), methanol and KOH, and the rheological behavior of their solutions are investigated. The optimal component ratio of solvent providing the complete ABPBI dissolution is determined. Methanol containing dissolved KOH contributes to the creation of a single-phase superbasic medium, which accelerates and improves the polymer solubility in a mixture with DMSO, significantly reducing the viscoelasticity of the resulting solution. The optimum methanol content is up to 60 wt.% related to DMSO. The polymer dissolution rate increases by 5 times in this composition. It found the polymer concentration of 9% is close to the dissolution limit due to the strong solution structuring, which is probably associated with an increase in the amount of water released during the KOH-methanol-DMSO interactions. As a result, the conditions for obtaining high concentrated solutions in a complex, mainly organic solvent for fiber spinning are developed. The viscoelastic properties of solutions are measured in the concentration range of 1-9% at temperatures of 20-50 °C. The flow activation energy for 7 and 9% solutions decreases by 1.5 and 2.3 times, respectively, as the content of methanol in the complex solvent increases from 10 to 60%.

The Role of Structure in Polymer Rheology: Review.

The review is devoted to the analysis of the current state of understanding relationships among the deformation-induced structure transformations, observed rheological properties, and the occurrence of non-linear effects for polymer liquids (melts, solutions, and composites). Three levels of non-linearity are the base for consideration. The first one concerns changes in the relaxation spectra of viscoelastic liquids, which are responsible for weak non-linear phenomena. The second one refers to the strong non-linearity corresponding to such changes in the structure of a medium that leads to the emergence of a new relaxation state of a matter. Finally, the third one describes the deformation-induced changes in the phase state and/or the occurring of bifurcations and instability in flow and reflects the thermodynamic non-linear behavior. From a structure point of view, a common cause of the non-linear effects is the orientation of macromolecules and changes in intermolecular interaction, while a dominant factor in describing fluid dynamics of polymer liquids is their elasticity. The modern understanding of thixotropic effects, yielding viscoplastic materials, deformation-induced phase transition, and the experimental observations, demonstrating direct correlations between the structure and rheology of polymer liquids, are the main objects for discussion. All these topics are reviewed and discussed mainly on the basis of the latest five-year publications.

Some Specifics of Defect-Free Poly-(o-aminophenylene)naphthoylenimide Fibers Preparation by Wet Spinning.

A series of model experiments were carried out on drops of poly-(o-aminophenylene)naphthoylenimide (PANI-O) solutions in N-methyl-2-pyrrolidone (NMP) surrounded by a coagulant of different compositions as starting points of defect-free fibers spinning by the wet method. An influence of compositions of dopes and multicomponent coagulants on the diffusion kinetics and drop morphology during coagulation has been investigated. It is shown that the defining parameters of the coagulation process are viscoelastic properties of the polymer solution and the diffusion activity of the coagulant, meaning not only the rate of coagulation but also the presence/absence of macro defects in the resulting fiber. The optimal morphology of as-spun fibers is obtained by coagulation of solution in a three-component mixture containing solvent and two precipitants of different activity (water and ethanol). The chosen coagulating mixture was used for the fiber spinning of PANI-O with different molecular weights dopes, and fibers with sufficiently high strength (~250 MPa), moduli (~2.1 MPa), and elongation at break (50%) were obtained.

Influence of Alkyl Acrylate Nature on Rheological Properties of Polyacrylonitrile Terpolymers Solutions, Spinnability and Mechanical Characteristics of Fibers.

The influence of alkyl acrylate comonomers in the rank of methyl- (MA), butyl- (BA), ethylhexyl- (EGA), and lauryl- (LA) in ternary copolymers based on acrylonitrile, alkyl acrylate and acrylamide (PAN-alkyl acrylate) on their solutions rheological behavior in dimethyl sulfoxide (DMSO), and mechanical properties of the spun fibers have been investigated. To reveal the role of molecular weight, two series of copolymers with molecular weights of ~50 and 150 kg/mol have been studied. It was shown that the nature of the alkyl acrylate does not significantly affect the rheological behavior of their solutions regardless of the length of the alkyl substituent and the content of the alkyl acrylate in copolymers. An exception is the high-molecular PAN-LA, which is characterized by a non-Newtonian behavior at lower concentrations. Two series of fibers were spun from the characterized ranks of low and high-molecular-weight copolymer solutions. For all copolymers, a 2.5-5-fold increase in the strength and elastic modulus of the fiber was found with an increase in Mw. It has been shown that PAN-MA and PAN-LA fibers have a tensile strength of 800 MPa that is 1.5-3 times higher than that of other copolymers spun in the same conditions.

Rheology of Highly Concentrated Suspensions with a Bimodal Size Distribution of Solid Particles for Powder Injection Molding.

Powder injection molding (PIM) is one of the modern and prospective technologies in processing different materials. We proposed to use bimodal compositions of particles for increasing their content in the final products. A set of model suspension of Al with low-molecular-weight poly (ethylene glycol) as a binder based on theoretical arguments concerning the filling capacity of bimodal suspensions was prepared. Studying the rheological properties of these compositions showed that they demonstrate elasto-viscous behavior with significant plasticity that is favorable for the technological process. Using compositions with bimodal distributions allows for increasing the content of the solid phase up to 75 vol. % for PIM technology, which is significantly higher than the standard practical limit. This rheological approach developed for model formulations was applied to processing compositions containing aluminum oxide as typical ceramics and polyolefines as a binder widely used in technological practice. The obtained sintered ceramic samples have quite acceptable mechanical properties of the usual corundum articles.

Synthesis and Properties of Thermotropic Copolyesters Based on Poly(ethylene terephthalate) and 4'-Acetoxy-4-biphenyl-carboxylic Acid.

A series of novel copolyesters based on polyethylene terephthalate (PET) and 4'-hydroxy-biphenyl-4-carboxylic acid (HBCA) was obtained by melt polycondensation of bis(2-hydroxyethyl) terephthalate and 4'-acetoxybiphenyl-4-carboxylic acid (ABCA) as co-monomers with Sb2O3 as a catalyst. Using this synthetic procedure, a set of copolymers containing 20-80 mol% of HBCA units was prepared. According to NMR spectroscopy, the copolymers were of random composition. Copolyesters comprising 60-80 mol% of HBCA possessed increased heat resistance and formed nematic melts at 270 °C and higher. The liquid crystal (LC) phase formation was accompanied by transition to non-Newtonian characteristics of the melt flow, as well as an equalization of storage and loss moduli values. According to XRD and polarizing microscopy, the LC glassy phase of the copolyesters coexists with crystalline regions of poly-(4'-hydroxy-4-biphenylcarboxylate), non-melting up to 400 °C and above. The mechanical characteristics of these LC copolyesters showed similar or better values than those of well-known LC polymers. These novel copolyesters can be useful in obtaining heat-resistant materials with an ordered structure and, as a consequence, improved performance.

Solubility, Rheology, and Coagulation Kinetics of Poly-(O-Aminophenylene)Naphthoylenimide Solutions.

The effect of temperature and storage time at a constant temperature on the stability of poly-(o-aminophenylene)naphthoylenimide solutions in N-methylpyrrolidone has been analyzed using rotational rheometry. A temperature-time window beyond which an irreversible change in the viscoelastic properties of solutions due to cumulative reactions of continuous polymerization and possible intramolecular cyclization has been detected. The influence of polymer concentration and its molecular weight on the rheological properties of solutions determining the choice of methods for their processing into fibers and films has been investigated. The effect of non-solvents (water and ethanol) additives on the rheological properties of solutions and the kinetics of their coagulation has been studied. Dosed addition of non-solvent into the solution promotes a significant increase in the viscoelasticity up to gelation and phase separation. Non-solvent presence in the polymer solutions reduces the activity of the solvent, accelerates the movement of the diffusion front at coagulation, and minimizes the number of macro defects. The combination of parameters under investigation renders it possible for the first time to develop new principles modifying dopes for wet spinning into aqueous or ethanol coagulation bath and finally to obtain a heat- and fire-resistant polynaphthoylenebenzimidazole fibers.

The Effect of the Synthetic Procedure of Acrylonitrile-Acrylic Acid Copolymers on Rheological Properties of Solutions and Features of Fiber Spinning.

The influence of introducing acrylic acid (AA) into the reaction mixture with acrylonitrile at the synthesis of copolymers by free-radical polymerization (FRP) and radical polymerization with reversible addition-fragmentation chain transfer (RAFT) on the rheological properties of their solutions in dimethyl sulfoxide, as well as on the capability to spin fibers by the mechanotropic method, is analyzed. The influence of AA dosing conditions on the rheological properties of the solutions in the concentration range above the crossover point was not revealed. In the case of RAFT synthesis, the rheological properties differ distinctively in the high concentration region that is expressed by unusual viscoelastic characteristics. Dilute solution viscometry revealed the influence of the comonomer loading order on the interaction intensity of the copolymer macromolecules with a solvent, which is more pronounced for samples synthesized by FRP and can be associated with the copolymers' molecular structure. Fiber spinning from solutions of polyacrylonitrile and its copolymers (PAN) synthesized by the RAFT method was not able to achieve a high degree of orientation drawing, while for polymers with a wider molecular weight distribution synthesized by FRP, it was possible to realize large stretches, which led to high-quality fibers with strength values up to 640 MPa and elongation at a break of 20%.

Effect of Composition and Interfacial Tension on the Rheology and Morphology of Heavy Oil-In-Water Emulsions.

Rheological and morphological properties of heavy crude oil-in-water (O/W) emulsions have been studied. Two series of emulsions were considered: first, the surfactant type remained constant, while the continuous phase content was varied and second, the surfactant type was varied while the continuous phase content remained constant. Under stress-controlled shearing, all samples exhibit viscoplastic behavior. The rheological properties are directly related to the morphology of the emulsions which vary in size of dispersed phase droplets and their inherent structure. Adding a surfactant characterized by a high value of interfacial oil-water tension results in a decrease in the yield stress (which is a measure of the interparticulate structure strength). The same effect is attained by increasing the water content. Meanwhile, these two factors determine the viscosity which can be much lower than that of the basic heavy crude oil if the O/W type of emulsions has been created. Special attention was paid to the viscoelastic properties which have been scarcely reported. Correlations were found between the surfactant properties, composition of the emulsion, and rheological characteristics of emulsions (yield stress, apparent viscosity, and viscoelastic properties), which allows for reduction in the crude oil viscosity down to a low enough level acceptable for pipe transportation.