Polymer Phase Research Articles

High Internal Phase Emulsion for Constructing Chiral Helical Polymer-Based Circularly Polarized Luminescent Porous Materials.

Polymerized high internal phase emulsions (polyHIPEs) with circularly polarized luminescence (CPL), as an interesting class of porous materials, are of great significance for the development of CPL porous materials but have not been reported so far. Herein, we report the construction of polyHIPE-based CPL porous materials, taking advantage of an adsorption strategy. The pristine polyHIPEs constructed by chiral helical polymers, which acted as a chiral microenvironment, were fabricated by coordination polymerization of chiral acetylene monomers (R/S-SA) using HIPEs as templates. Achiral fluorescent small molecules were dispersed in the pores of the 3D porous organic chiral polymer matrix provided by polyHIPEs through the adsorption strategy, and CPL-active porous materials with blue, cyan, and green emissions were constructed using a fluorescence-selective absorption mechanism that does not rely on chirality transfer at the molecular level. The maximum luminescence dissymmetry factor (glum) value was -2.6 × 10-2. This work establishes a new and simple way for developing CPL porous materials.

Effects of psychological stress on the emission of volatile organic compounds from the skin

Thirty-five women were included in a clinical study to characterize the volatile organic compounds (VOCs) emitted by the skin during exposure to psychological stress. An original silicon-based polymeric phase was used for VOC sampling on the forehead before and after stress induction. Cognitive stress was induced using specialized software that included a chronometer for semantic and arithmetic tasks. Assessment of stress was monitored using a State-trait anxiety inventory questionnaire, analysis of participants’ verbal expressions and clinical measurements. Identification and relative quantification of VOCs were performed by gas chromatography-mass spectrometry. Stress induction was validated by a significant increase in state-anxiety as indicated by the questionnaire, modifications in electrodermal activity measurements and the expression of stress verbatims. In parallel, a sebum production increase and a skin pH decrease were observed. A total of 198 VOCs with different potential sources were identified. They were categorized in 5 groups: probable cosmetic composition, VOCs produced by the body or its microbiota, environmental origin, and dietary intake. In our qualitative statistical approach, three VOCs were found to be correlated with stress induction and 14 compounds showed significance in the paired Wilcoxon test. Fatty-acyls derived from lipids were predominantly identified as well as ethylbenzenes.

Deformable Joule heating electrode based on hybrid layers of silver nanowires and carbon nanotubes and its application in a refreshable multi-cell Braille display.

Stretchable electrodes are an essential component in soft actuator systems. In particular, Joule heating electrodes (JHEs) are required for thermal actuation systems. A highly stretchable, patternable, and low-voltage operating JHE based on hybrid layers of silver nanowires (AgNWs) and carbon nanotubes (CNTs) is reported. The conductive layers were applied on a locally pre-strained bistable electroactive polymer (BSEP) membrane to form a wrinkled conductive surface with a low resistance of 300 Ω/sq, and subsequently patterned to a serpentine trace by laser engraving. The resistance of the resulting electrode remains nearly unchanged up to ~80-90% area strain. By applying a voltage of 7 - 9 V to the electrode, the temperature of the BSEP membrane increased to more than 60 °C, well above the polymer's phase transition temperature of 46 °C, thereby lowering its modulus by a factor of 103. An electronic Braille device based on the JHEs on a BSEP membrane was assembled with a diaphragm chamber. The electrode was patterned into 3 × 2 individually addressable pixels according to the standard U.S. Braille cell format. Through Joule heating of the pixels and local expansion of the BSEP membrane using a small pneumatic pressure, the pixels deformed out of the plane by over 0.5 mm to display specific Braille letters. The Braille content can be refreshed for 20,000 cycles at the same operating voltage.

Dynamically vulcanized CNC‐reinforced thermoplastic elastomer based on PP/EPDM: Morphology and mechanical properties control via interfacial compatibilization

AbstractIn this study, dynamically vulcanized thermoplastic elastomer nanocomposites consisting of polypropylene (PP) as the thermoplastic matrix, ethylene propylene diene monomer (EPDM) rubber as the dispersed phase, and needle‐like cellulose nanocrystals (CNC) were investigated. The two polymers were melt blended in a ratio of 70/30 (PP/EPDM) and 60/40% w/w (PP/EPDM) together with CNC (2, 3, and 5 phr) and sulfur‐curing system. The potential of EPDM‐g‐MA and PP‐g‐MA's as interfacial compatibilizers for enhancing interfacial interactions between components and partitioning of CNC between the two polymer phases was examined by measuring the decrease in the size of EPDM particles. The resulting thermoplastic vulcanizates (TPV) were characterized using a melt rheometric mechanical spectrometer (RMS), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and tensile tests. The inclusion of any type of interfacial compatibilizers led to enhanced tensile properties when compared to the samples lacking compatibilizers in both TPVs and TPEs in different ratios. EPDM‐g‐MA was found to be more effective for 60/40% w/w (PP/EPDM) TPVs, while PP‐g‐MA showed higher potential for 70/30% w/w TPVs. The CNC‐reinforced TPVs displayed higher melt elasticity than their unloaded counterparts. These nanocomposites also showed reduced EPDM particle size, enhanced Young modulus, and a higher degree of crystallinity.Highlights Nanocomposite thermoplastic vulcanizates (TPVs): polypropylene (PP)/ethylene propylene diene monomer (EPDM)/cellulose nanocrystals (CNC) with matrix‐dispersed morphology. Interfacial enhancement: Compared EPDM grafted maleic anhydride (EPDM‐g‐MA) and PP‐g‐MA potentials. Tensile properties: EPDM‐g‐MA is more effective in higher rubber content TPVs. Mechanical enhancements: Improved properties and Young's modulus in CNC‐filled TPVs. Diverse applications: PP/EPDM/CNC nanocomposites in auto, electrical, electronic, and packaging industries.

Dynamics of polylactic acid under ultrafine nanoconfinement: The collective interface effect and the spatial gradient.

Polymers under nanoconfinement can exhibit large alterations in dynamics from their bulk values due to an interface effect. However, understanding the interface effect remains a challenge, especially in the ultrafine nanoconfinement region. In this work, we prepare new geometries with ultrafine nanoconfinement ∼10nm through controlled distributions of the crystalline phases and the amorphous phases of a model semi-crystalline polymer, i.e., the polylactic acid. The broadband dielectric spectroscopy measurements show that ultrafine nanoconfinement leads to a large elevation in the glass transition temperature and a strong increment in the polymer fragility index. Moreover, new relaxation time profile analyses demonstrate a spatial gradient that can be well described by either a single-exponential decay or a double-exponential decay functional form near the middle of the film with a collective interface effect. However, the dynamics at the 1-2nm vicinity of the interface exhibit a power-law decay that is different from the single-exponential decay or double-exponential decay functional forms as predicted by theories. Thus, these results call for further investigations of the interface effect on polymer dynamics, especially for interfaces with perturbed chain packing.

Boundary Frustration in Double-Gyroid Thin Films.

Self-consistent field theory for thin films of AB diblock polymers in the double-gyroid phase reveals that in the absence of preferential wetting of monomer species at the film boundaries, films with the (211) plane oriented parallel to the boundaries are more stable than other orientations, consistent with experimental results. This preferred orientation is explained in the context of boundary frustration. Specifically, the angle of intersection between the A/B interface and the film boundary, the wetting angle, is thermodynamically restricted to a narrow range of values. Most termination planes in the double gyroid cannot accommodate this narrow range of wetting angles without significant local distortion relative to the bulk morphology; the (211)-oriented termination plane with the "double-wave" pattern produces relatively minimal distortion, making it the least frustrated boundary. The principle of boundary frustration provides a framework to understand the relative stability of termination planes for complex ordered block polymer phases confined between flat, nonpreferential boundaries.

Photo-curable bio-based comb/bottle brush epoxy resin/beeswax/copper foam phase change materials with high enthalpy value, high conductivity, and multifunctional properties

At present, the demand for green energy has reached a new height in history, and thermal energy storage technology has been widely used to reduce energy consumption. It is still a challenge to develop bio-based polymeric form-stable phase change materials (FSPCMs) with high enthalpy value and thermal conductivity (TC), short curing time, and multifunctional properties. This work not only exploited a series of adjustable and photo-curable comb/bottle brush bio-based epoxy resin/beeswax (bw) FSPCMs with the above superiorities, but also revealed the effects of cross-linking density on the energy storage capacity and encapsulation rate of the FSPCMs. As a result, the optimal system can encapsulate the maximum amount of bw (60 wt%) and obtain the highest enthalpy value (142.1 J/g) with only 0.5% enthalpy loss. Through further introducing the optimal curing system into the copper (Cu) foam, the electromagnetic interference shielding property, TC, tensile strength, and photo-thermal conversion efficiency of the final composite (modified by Cu of 95% porosity) can reach 110 dB, 2.387 W m−1K−1, 2.81 MPa, and 80%, respectively, and the enthalpy value (84.2 J/g) is still satisfactory. This study can provide theoretical guidance for the structural design of reliable fast photo-curable bio-based polymeric FSPCMs with excellent phase change performances and multifunctional properties.

Sorption of picolinic acid by Cu(II)-containing sulfocationite KU-2-8

Objectives. To study the equilibrium distribution of components between KU-2-8 sulfocationite and an aqueous solution containing picolinic acid and Cu(II); to show the possibility of immobilization of cations of picolinic acid and Cu2+ in sulfonic cation exchanger KU-2-8; to calculate the component compositions of the equilibrium solution, in order to obtain the required ionic composition of the KU-2-8 sulfonic cation exchanger according to the selectivity coefficients of binary ion exchange, and the constants of formation of such complexes in water.Methods. The concentrations of the individual components in multicomponent solutions were calculated using the HySS 2009 program (Hyperquad Simulaton and Speciation). The calculation of the equilibrium ionic compositions of KU-2-8 sulfocationite was performed using the selectivity coefficients of binary ion exchanges and the formation constants of complexes of picolinic acid with Cu2+ and H+ cations. Experimental study of the equilibrium distribution of components between aqueous solutions of picolinic acid, copper nitrate, and KU-2-8 sulfocationite was carried out by means of the dynamic method at a temperature of 298 K. Fourier-transform infrared spectroscopy and electron paramagnetic resonance spectroscopy were used, in order to determine the ionic forms of the components contained in the sulfocationite.Results. It was shown that the equilibrium solution contains H+ protons, Cu2+ cations, LH picolinic acid molecules, protonated picolinic acid cations [H2L]+, deprotonated picolinic acid anions L-, Cu2+ complexes with the deprotonated picolinic acid anion [CuL]+, and Cu2+ complexes with two anions of deprotonated picolinic acid [CuL2]. The concentration of H+, Cu2+, and [H2L]+ cations in the solution significantly exceeds the concentration of other components at pH values from 0 to 0.5. The content of [CuL]+ cations and neutral complexes [CuL2] increases significantly in the solution, while the [H2L]+ cations disappear at pH greater than 1. It was experimentally established that the concentrations of picolinic acid and copper in the polymer phase are many times higher than the concentrations of these components in an aqueous solution. The partition coefficients are about 24 and 210 for picolinic acid and Cu(II), respectively. The calculated dependencies of the concentrations of Cu2+, [H2L]+, H+, [CuL]+ cations in the polymer vs pH of an equilibrium solution containing picolinic acid were obtained. The experimental data on the concentrations of all cations in the ion exchanger is in the intervals of the calculated compositions within the limits of measurement errors.Conclusions. KU-2-8 sulfocationite is proposed as a container for obtaining drugs based on picolinic acid and Cu2+ cations. It was shown that the selectivity coefficients of binary ion exchanges and the formation constants of [H2L]+, [CuL]+ complexes can be used to precalculate the ionic compositions of the equilibrium solution, in order to obtain the required compositions of the sulfocationite.

Separation and purification of phycobiliproteins from Thermosynechococcus PCC 6715 by foam fractionation and aqueous twophase extraction

The use of foam fractionation followed by aqueous two-phase extraction has emerged as a potential alternative to traditional liquid chromatography, hitherto irreplaceable in the purification of phycobiliproteins. The crude extracts of C-phycocyanin and allophycocyanin were obtained after Thermosynechococcus PCC 6715 biomass disintegration. The FF process with air flow of 2.4 L·h -1 resulted in purification factors up to 1.47 and partitioning coefficients of about 39, and did not require the addition of surfactants. A temperature of 35˚C allowed for the highest partitioning coefficient of 67.6 and yield of 76%; however, the purity of C-PC in condensate at this temperature was lower than at 25˚C. ATPE was tested in 20 different systems consisting of polyethylene glycol and phosphate or citrate salts, of which PEG1500-citrate gave the highest purification factor value of 2.31. Conversely, a partitioning coefficient of 2416 and 1094 were obtained for the PEG1500-phosphate and PEG3000-phosphate systems, respectively. Interestingly, the use of FF condensate in subsequent ATPE step resulted, for the first time, in the separation of the polymer phase into two fractions, one contained C-phycocyanin and the other allophycocyanin. It can be concluded that the use of a two-step system of FF and ATPE is a viable way to separate phycobiliproteins.

Porous Polymeric Nanofilms for Recreating the Basement Membrane in an Endothelial Barrier-on-Chip.

Organs-on-chips (OoCs) support an organotypic human cell culture in vitro. Precise representation of basement membranes (BMs) is critical for mimicking physiological functions of tissue interfaces. Artificial membranes in polyester (PES) and polycarbonate (PC) commonly used in in vitro models and OoCs do not replicate the characteristics of the natural BMs, such as submicrometric thickness, selective permeability, and elasticity. This study introduces porous poly(d,l-lactic acid) (PDLLA) nanofilms for replicating BMs in in vitro models and demonstrates their integration into microfluidic chips. Using roll-to-roll gravure coating and polymer phase separation, we fabricated transparent ∼200 nm thick PDLLA films. These nanofilms are 60 times thinner and 27 times more elastic than PES membranes and show uniformly distributed pores of controlled diameter (0.4 to 1.6 μm), which favor cell compartmentalization and exchange of large water-soluble molecules. Human umbilical vein endothelial cells (HUVECs) on PDLLA nanofilms stretched across microchannels exhibited 97% viability, enhanced adhesion, and a higher proliferation rate compared to their performance on PES membranes and glass substrates. After 5 days of culture, HUVECs formed a functional barrier on suspended PDLLA nanofilms, confirmed by a more than 10-fold increase in transendothelial electrical resistance and blocked 150 kDa dextran diffusion. When integrated between two microfluidic channels and exposed to physiological shear stress, despite their ultrathin thickness, PDLLA nanofilms upheld their integrity and efficiently maintained separation of the channels. The successful formation of an adherent endothelium and the coculture of HUVECs and human astrocytes on either side of the suspended nanofilm validate it as an artificial BM for OoCs. Its submicrometric thickness guarantees intimate contact, a key feature to mimic the blood-brain barrier and to study paracrine signaling between the two cell types. In summary, porous PDLLA nanofilms hold the potential for improving the accuracy and physiological relevance of the OoC as in vitro models and drug discovery tools.

Toughening 3D printed biomimetic hydroxyapatite scaffolds: Polycaprolactone-based self-hardening inks

The application of 3D printing to calcium phosphates has opened unprecedented possibilities for the fabrication of personalized bone grafts. However, their biocompatibility and bioactivity are counterbalanced by their high brittleness. In this work we aim at overcoming this problem by developing a self-hardening ink containing reactive ceramic particles in a polycaprolactone solution instead of the traditional approach that use hydrogels as binders. The presence of polycaprolactone preserved the printability of the ink and was compatible with the hydrolysis-based hardening process, despite the absence of water in the ink and its hydrophobicity. The microstructure evolved from a continuous polymeric phase with loose ceramic particles to a continuous network of hydroxyapatite nanocrystals intertwined with the polymer, in a configuration radically different from the polymer/ceramic composites obtained by fused deposition modelling. This resulted in the evolution from a ductile behavior, dominated by the polymer, to a stiffer behavior as the ceramic phase reacted. The polycaprolactone binder provides two highly relevant benefits compared to hydrogel-based inks. First, the handleability and elasticity of the as-printed scaffolds, together with the proven possibility of eliminating the solvent, opens the door to implanting the scaffolds freshly printed once lyophilized, while in a ductile state, and the hardening process to take place inside the body, as in the case of calcium phosphate cements. Second, even with a hydroxyapatite content of more than 92 wt.%, the flexural strength and toughness of the scaffolds after hardening are twice and five times those of the all-ceramic scaffolds obtained with the hydrogel-based inks, respectively. Statement of significanceOvercoming the brittleness of ceramic scaffolds would extend the applicability of synthetic bone grafts to high load-bearing situations. In this work we developed a 3D printing ink by replacing the conventional hydrogel binder with a water-free polycaprolactone solution. The presence of polycaprolactone not only enhanced significantly the strength and toughness of the scaffolds while keeping the proportion of bioactive ceramic phase larger than 90 wt.%, but it also conferred flexibility and manipulability to the as-printed scaffolds. Since they are able to harden upon contact with water under physiological conditions, this opens up the possibility of implanting them immediately after printing, while they are still in a ductile state, with clear advantages for fixation and press-fit in the bone defect.

Evaluation of Thermodynamic and Kinetic Contributions to Over-Extraction of Extractables by Nonpolar Organic Solvents in Comparison to Lipids in Exhaustive and Exaggerated Extractions of Medical Devices Based on Abraham Solvation Model and Solvent–Material Interactions Using Low-Density Polyethylene as a Representative Material

The thermodynamic and kinetic contributions to the over-extraction of extractables by nonpolar organic solvents relative to biological lipids in exhaustive and exaggerated extractions of medical devices are studied based on the Abraham solvation model and solvent–material interactions, using low-density polyethylene (LDPE) as an exemplary material. The thermodynamic effect is evaluated by the partition constant of extractables between LDPE and extraction solvents, hexane and lipids, defined as the concentration in the polymer phase divided by the concentration in the solvent phase. The Abraham solvation model is used to correlate the measured LDPE-lipid partition constant (log10Pldpe/lipid) to construct the predictive model. Similar models are also derived from the thermodynamic cycle conversion, using the system constants of LDPE-water and Lipid-water partition systems. These constructed models, together with the predictive LDPE-hexane (log10Pldpe/hexane) model established from a previous study, are used to predict and compare the ranges and values of Pldpe/s (s = lipids and hexane) for the observed LDPE extractables over a wide hydrophobicity range in log10Po/w from zero to 30. The solvent-LDPE interactions are examined by the degree of swelling of LDPE by hexane (or other nonpolar solvents) and lipids, including the solvent diffusion rates into the material. These parameters allow the evaluation of kinetic effect on the over-extraction. The extent of over-extraction is compiled directly by experimental “overall” or “specific” migration data or indirectly calculated by the diffusion coefficient of extractables when extracted by hexane or lipids. It is concluded from this study that the extractables distribution between LDPE and lipids highly favors the lipid phase thermodynamically (Pldpe/lipid<1), and the values of Pldpe/lipid are always lower than those of Pldpe/hexane, thereby indicating that the thermodynamic effect is not the cause of over-extraction. It is the kinetic effect that dominantly contributes to the over-extraction, as supported by the material swelling and solvent diffusion rates. Finally, the extent of over-extraction has been established from a few folds to over a hundred-fold, and the median value is 7. Furthermore, the methods adopted and developed in this study can be invaluable tools in other disciplines such as the reliable prediction of extractables from other device materials and environmental sampling.

Carbon nanotubes in high internal phase emulsion polymer composite for packed-cartridge micro-solid-phase extraction of fluoroquinolones in urine

Aim of this study stands in the evaluation of a carbon nanotubes-based polymerized high internal phase emulsion composite (CNT/polyHIPE) as sorptive phase in biological sample preparation. A micro-solid-phase extraction procedure (µSPE) was developed for trace fluoroquinolone (FQ) antimicrobials, namely Ciprofloxacin, Levofloxacin, Lomefloxacin, Moxifloxacin, Norfloxacin and Sparfloxacin, in human urine samples. PolyHIPEs modified by incorporation of different concentrations of nanotubes (0.2–0.8 wt %) were one-pot synthesized and applied in the packed-cartridge setting. The sorption affinity for the drugs was investigated in tap water and buffered aqueous solutions, demonstrating the key role of the nanotubes embedded in the polymer. The 0.5 wt % CNT composite was selected to develop a straightforward µSPE procedure directly in raw urine (1 mL sample), followed by HPLC-MS/MS. Targets were retained on the sorbent at near neutral pH and, after an aqueous washing (0.1 % v/v formic acid), eluted in a single-step with 4 % v/v ammonia aqueous solution (15 % v/v acetonitrile), thus combining extraction and clean-up. The method allowed accurate quantification of FQs, as evidenced by the recoveries (74–116 %, n = 3) obtained on blank pooled urine samples spiked with 40, 75, 150 µg L−1, accompanied by good inter-day precision (RSD < 14 %, n = 3). To confirm the applicability of the analytical method, some real-life blind samples were processed as a proof of concept.

Polyethylene glycol-impregnated carbon quantum dots-phenolic phase change composites for highly efficient thermal energy storage

The development of stable smart thermal energy storage systems is the key to reaching breakthroughs in thermal management technologies based on phase change composites (PCC). In this study, high-performance PCC is developed by impregnating polyethylene glycol (PEG), as a polymeric phase change material (PCM), into the porous structure of modified resorcinol-formaldehyde (RF) hydrogels. Carbon quantum dots (CQDs) and 3-chlorophenol are introduced into the RF structure during the synthesis process to increase energy storage properties and impregnation efficiency. A sol-gel polymerization method is used to synthesize the hydrogels, followed by the impregnation of liquid PEG600 into the hydrogel structure. The low PEG leakage of optimal PCC consisting of 3-chlorophenol and 0.2 wt% CQDs is related to the presence of surface functional groups in the structure of the modified RF hydrogels resulting in the formation of hydrogen bonding and electrostatic forces. The melting enthalpy of the optimal PCC is 67 % higher than the unmodified RF-based PCC, while the encapsulation efficiency is 92.5 %. Our results confirm that thermal energy storage performance can be improved by 40 % through the addition of CQDs and 3-chlorophenol into the polymeric material. These PCC systems show long-term stability in terms of storage/release cycles and have the potential to be used as thermal regulator systems.

One-step sorting of nearly single-chiral carbon nanotubes with (10,9) chirality of 1.3 nm diameter by backbone planarization of polydioctylfluorenes

The conjugated polymer wrapping method has been developed to sort semiconducting single-walled carbon nanotubes (sc-SWNTs). However, the method has rarely been applied in sorting nearly single-chiral SWNTs with large diameter despite the necessity of separating sc-SWNT with homogeneous optoelectrical characteristics for high-performance devices. In this study, nearly single-chiral sc-SWNTs with a 1.3 nm diameter are sorted via only conjugated polymer wrapping method using poly (9,9-dioctylfluorenyl-2,7-diyl) (PFO) in tetralin, without additional process. The PFO backbone chain is extended with a torsion angle of 180° in tetralin owing to strong intermolecular forces from the viscous solvent. Consequently, the backbone planarization of PFO enables the sorting of SWNTs of specific chirality. The phase of the wrapping polymer results in an enhanced chiral selectivity, with over 70 % of the sorted SWNTs in tetralin having a chirality of (10,9). These findings clarify the relationship between the conformation and chiral selectivity of the wrapping polymer in the conjugated polymer wrapping method and contribute to the development of highly uniform SWNT-based devices, which require single-chiral SWNTs with homogeneous optoelectrical characteristics.

Efficient incorporation of protein into waterborne hybrid acrylic based nanoparticles

The use of raw materials from natural sources as substitutes for petrochemical monomers is of high interest in the polymer science, to comply with the increasing social awareness of pollution and environmental regulations. Natural proteins emerge as particularly promising candidates to be combine with synthetic polymers, offering the prospect of enhancing the product sustainability. Nonetheless, protein-based hybrid materials still present some drawbacks such as high susceptibility to water, due to the incorporation of hydrophilic protein and the resulting morphology of hybrid particles. In the present study, we propose a novel approach for synthesizing biphasic hybrid particles with a controlled morphology that tend to optimize the synergy between both phases. Here, protein phase forms the core of hybrid particles, which is surrounded by an acrylic polymer phase. To achieve this particular morphology, a seeded semibatch emulsion polymerization strategy was designed by employing preformed zein-casein bioparticles (BPs) as seed. This paper encompassed a comprehensive exploration of the key variables impacting on both the synthesis of BPs and the subsequent formation of hybrid latex particles. The outcomes of this research not only contribute to a deeper understanding of the synthesis process but also broaden the potential applications of acrylic-protein hybrid films, particularly as coatings.

Composite Bioprinted Hydrogels Containing Porous Polymer Microparticles Provide Tailorable Mechanical Properties for 3D Cell Culture.

The mechanical and architectural properties of the three-dimensional (3D) tissue microenvironment can have large impacts on cellular behavior and phenotype, providing cells with specialized functions dependent on their location. This is especially apparent in macrophage biology where the function of tissue resident macrophages is highly specialized to their location. 3D bioprinting provides a convenient method of fabricating biomaterials that mimic specific tissue architectures. If these printable materials also possess tunable mechanical properties, they would be highly attractive for the study of macrophage behavior in different tissues. Currently, it is difficult to achieve mechanical tunability without sacrificing printability, scaffold porosity, and a loss in cell viability. Here, we have designed composite printable biomaterials composed of traditional hydrogels [nanofibrillar cellulose (cellulose) or methacrylated gelatin (gelMA)] mixed with porous polymeric high internal phase emulsion (polyHIPE) microparticles. By varying the ratio of polyHIPEs to hydrogel, we fabricate composite hydrogels that mimic the mechanical properties of the neural tissue (0.1-0.5 kPa), liver (1 kPa), lungs (5 kPa), and skin (10 kPa) while maintaining good levels of biocompatibility to a macrophage cell line.

Structural forming of soil composites using as a pavement subgrade strengthening

The article substantiates the possibility of obtaining composite materials with improved functional properties to strengthen the subgrade, containing technogenic soil stabilized by an additive based on a gelling polymer. The introduction of technogenic soils into composites will not only reduce the consumption of expensive materials, but also solve a complex of acute environmental problems. Composite materials can be used in the construction of structural layers of road pavements, foundations of buildings and structures, sites for various purposes, for the prevention and elimination of defects in the foundations of engineering structures during their construction, reconstruction and repair, including in permafrost areas. Stabilized technogenic soils are more durable, frost-resistant and waterproof, which makes them applicable for creating impervious curtains in hydraulic structures and sealing storage facilities for hazardous substances. The cryogenic effect on a composite material allows one to vary its properties within a wide range and modify its macroporous structure. Studying the process of structure formation of the resulting organic-inorganic materials, consisting of macromolecules of high-molecular substances and inorganic inclusions that have undergone cryogenic treatment, will make it possible to specifically regulate their performance characteristics. The best values of strength characteristics were obtained for samples with a stabilizing additive concentration of 100 g/l. The resulting composite materials are hydrophobic, frost-resistant, characterized by a compressive strength of 2.3–6.5 MPa and a thermal conductivity of 0.19–0.20 W/(m·K). Data from differential scanning calorimetry and thermogravimetry and IR spectroscopy revealed that the binding of mineral particles by a stabilizing additive occurs due to the formation of organomineral complexes with the participation of clay minerals and the restructuring of hydration shells. SEM data indicate that crystallinity zones formed due to hydrogen bonds of hydroxyl groups of neighboring polymer chains can participate in the formation of the composite structure. An increase in the number of cryogenic treatment cycles promotes additional structuring and strengthening of the polymer phase due to the formation of additional nodes of the supramolecular network, ordering of crystallinity zones and the appearance of compacted areas in the structure. Computed X-ray tomography revealed an increase in the density of the composite upon drying, which helps to increase its strength characteristics. The structure of the sample is characterized by heterogeneity of the pore space, which is characterized by the presence of both fine-porous and large-porous regions, which determines its thermophysical properties.

Two-stage thermocatalytic conversion of waste XLPE to diesel-like fuel

Cross-linked polyethylenes (XLPE) are not preferred in industrial pyrolysis applications and mechanical recovery methods due to great thermochemical resistance to heat and deformation. The studies on pyrolysis of XLPE up to 600?C on obtaining fuel have generally yielded high levels of wax and have not been of interest to the energy sector. In this study, two-stage pyrolysis of XLPE was carried out catalytically and also without catalyst (thermal, T- -pyr) under 500?C with heating rates of 5 and 10?C min-1. In the pyrolysis experiments, three different catalytic studies were performed by adding MCM- -41 + HZSM-5 catalyst mixture to the polymer phase only (PPC-pyr), by filling Cu(I)-MAS + HZSM-5 catalyst mixture to the gas outlet column only (GPC- -Pyr) and adding catalyst mixtures in both polymer phase and gas phase (MPC- -pyr). The highest diesel-like fuel (91.40 wt. %) was obtained in multiphase catalytic pyrolysis experiments at 460?C with a heating rate of 5?C min-1. The calorific value, kinematic viscosity, density, flash point and cetane number of the fuel were found as 45.97 MJ kg-1, 2.72 cSt, 832.5 kg m-3, 57 and 59?C, respectively. The results of the two-stage catalytic cracking and the heating rate profile will be a guide for industrial pyrolysis applications. The simple feasibility for industrial applications showed that it would be a very profitable investment.

ИССЛЕДОВАНИЕ ФИЗИКО-МЕХАНИЧЕСКИХ СВОЙСТВ КОМПОЗИТОВ С ПОЛИМЕРНОЙ ФАЗОЙ ПОЛИЛАКТИДА И КОСТРОЙ КОНОПЛИ

As a result of the study the indicators of key physical and mechanical properties and biodegradation potential of composites with polymer phase of polylactide and technical hemp shives were determined, the properties of composites based on polylactide with technical hemp shives and reference materials with wood flour were compared. It is established that composites with hemp shives demonstrate on the average higher values of density, Shore hardness and bending strength, as well as lower water absorption at higher values of the wetting angle. The stiffness of samples with hemp shives practically does not change when the filler content is increased up to 30 wt. %, and increases with further increase in the degree of filling. The impact toughness of composites with hemp shives significantly exceeds the parameters of analogs based on polylactide and wood flour. In addition, the increase in the content of hemp shives, in contrast to technical wood flour, has practically no negative effect on the impact toughness of composites. Introduction of wood flour into the composition of polylactide leads to a sharp increase in water absorption, while the water absorption of samples with hemp shives does not exceed 2% regardless of the degree of filling. Replacement of wood filler with hemp shives in the composition of the composite leads to a significant decrease in the mass loss index after aging in the active soil for 30 days. In general, composites with polylactide polymer phase and hemp shives are superior to analogs with wood flour in terms of physical and mechanical properties. Lower biodegradation potential can be both an advantage and a significant disadvantage for composites with technical hemp shives.