Two-component Polymer Research Articles

Photoluminescence color-tuning with polymer-dispersed fluorescent films containing two fluorinated diphenylacetylene-type fluorophores.

The development of organic light-emitting devices has driven demand for new luminescent materials, particularly after the 2001 discovery of aggregation-induced emission. This study focuses on fluorinated diphenylacetylene-based luminescent molecules, revealing that specific molecular modifications can enhance fluorescence and achieve a wide range of photoluminescence colors. A simple and effective luminescence color-tuning method is proposed to investigate the photoluminescence behavior of two-component polymer dispersion films blended with two types of fluorinated diphenylacetylenes, namely blue- and yellow- or red-fluorescent fluorinated diphenylacetylenes. It is confirmed that if blue and green-yellow or yellow fluorophores are blended in appropriate ratios, a binary blend with color coordinates (0.20, 0.32) can be achieved, which approaches the white point of pure white emission. These findings contribute to the development of effective lighting and display devices as new white-light-emitting materials.

A Co-MOF encapsulated microneedle patch activates hypoxia induction factor-1 to pre-protect transplanted flaps from distal ischemic necrosis

Avoiding ischemic necrosis after flap transplantation remains a significant clinical challenge. Developing an effective pretreatment method to promote flap survival postoperatively is crucial. Cobalt chloride (CoCl2) can increase cell tolerance to ischemia and hypoxia condition by stimulating hypoxia-inducible factor-1 (HIF-1) expression. However, the considerable toxic effects severely limit the clinical application of CoCl2. In this study, cobalt-based metal-organic frameworks (Co-MOF) encapsulated in a microneedle patch (Co-MOF@MN) was developed to facilitate the transdermal sustained release of Co2+ for rapid, minimally invasive rapid pretreatment of flap transplantation. The MN patch was composed of a fully methanol-based two-component cross-linked polymer formula, with a pyramid structure and high mechanical strength, which satisfied the purpose of penetrating the skin stratum corneum of rat back to achieve subcutaneous vascular area administration. Benefiting from the water-triggered disintegration of Co-MOF and the transdermal delivery via the MN patch, preoperative damage and side effects were effectively mitigated. Moreover, in both the oxygen-glucose deprivation/recovery (OGD/R) cell model and the rat dorsal perforator flap model, Co-MOF@MN activated the HIF-1α pathway and its associated downstream proteins, which reduced reperfusion oxidative damage, improved blood supply in choke areas, and increased flap survival rates post-transplantation. This preprotection strategy, combining MOF nanoparticles and the MN patch, meets the clinical demands for trauma minimization and uniform administration in flap transplantation. Statement of significanceCobalt chloride (CoCl2) can stimulate the expression of hypoxia-inducible factor (HIF-1) and improve the tolerance of cells to ischemia and hypoxia conditions. However, the toxicity and narrow therapeutic window of CoCl2 severely limit its clinical application. Herein, we explored the role of Co-MOF as a biocompatible nanocage for sustained release of Co2+, showing the protective effect on vascular endothelial cells in the stress model of oxygen-glucose deprivation. To fit the clinical needs of minimal trauma in flap transplantation, a Co-MOF@MN system was developed to achieve local transdermal delivery at the choke area, significantly improving blood supply opening and flap survival rate. This strategy of two-step delivery of Co2+ realized the enhancement of biological functions while ensuring the biosafety.

Modern two-component modifiers inhibiting the aging process of road bitumen

The bitumen physicochemical properties of are constantly changing during both the production of asphalt mixtures and the service of road pavements. These changes involve bitumen hardening which consequently cause formation of defects and cracks in road pavements. Therefore, in recent years, prolonging road pavement life by inhibiting the bitumen aging process is a key trend in road engineering, bringing many economic, environmental and social benefits. In line with these trends, the main objective of this research was inhibition of short-term bitumen aging by two-component chitosan-based polymer composites containing ligands with different chemical structures, i.e. polyaniline, methacrylamide and 2-acrylamido-2-methylpropanesulfonic acid. This paper presents their effect on the TFOT aging process, as well as physicochemical and structural changes. Studies show that the strongest anti-aging properties are demonstrated by the chitosan:polyaniline composite. Its use at 2 % w/w allows it to maintain 90 % of the primary penetration value, increase the softening point by only 2°C and increase dynamic viscosity by 17% in comparison to non-aged modified bitumen. In addition, the use of the composite makes it possible to reduce the degree of bitumen components oxidation, which is seen from the reduction of carbonyl and sulfoxide indices by more than 33 % and 47 %, respectively.

Two-component polymer sorting to obtain high-purity s-SWCNTs for all-carbon photodetectors.

The advancement of carbon-based electronics is reliant on the development of semiconducting carbon nanotubes with high purity and yield. We developed a new extraction strategy to efficiently sort SWCNTs with superior yields and purity. The approach uses two polymers, poly[N-(1-octylnonyl)-9H-carbazol-2,7-diyl](PCz) and poly(9,9-n-dihexyl-2,7-fluorene-alt-9-phenyl-3,6-carbazole)(PDFP), and two sonication processes to eliminate surface polymer contamination. PCz selectively wraps large-diameter s-SWCNTs, with PDFP added as an enhancing molecule to increase sorting efficiency at 4-fold compared to the efficiency of only PCz alone sorting. The purity of the sorted s-SWCNTs was confirmed to be above 99 % using absorption and Raman spectra. Field-effect transistors and photodetectors made from the sorted s-SWCNTs exhibited excellent semiconductor properties and broad-spectrum detection, with good long-term stability. Furthermore, a photodetector using large-tube diameter s-SWCNTs achieved broad-spectrum detection, which the photoresponsivity is 0.35 mA/W and the detectivity is 4.7×106 Jones. The s-SWCNTs/graphene heterojunction photodetector achieved a photoresponsivity of 3 mA/W and a detectivity of 6.3×106 Jones. This new strategy provides a promising approach to obtain high-purity and high-yield s-SWCNTs for carbon-based photodetectors.

Benzoxazine/amine-based polymer networks featuring stress-relaxation and reprocessability

Amines as additives in benzoxazines are known to beneficially affect the polymerization temperature and furthermore to allow for partially reversible reaction steps yielding however a non-dynamic polybenzoxazine network. This contribution proves that the polymerization behavior of a two-component polymer of the polyetheramine Jeffamine® ED-600 and a bisphenol-A-based benzoxazine features stress-relaxation and reprocessability usually known from vitrimers. With the aim to gain a deeper understanding of the material properties of this system and the corresponding polymer structure, the reaction mechanism of a monofunctional benzoxazine and monoamine model system was studied revealing at first primary, and then secondary amine induced opening of oxazine rings, leading at first to linear polymer chains and then to covalently crosslinked networks. Both consist of repeated phenolic benzoxazine/amine motifs with permanently incorporated polyetheramine chains that do not impact the mechanical properties, compared to pure polybenzoxazine. Thermal, spectroscopic, and extraction analyses show that the addition of Jeffamine® reduces the polymerization temperature and introduces material properties such as reprocessability at the same time. Stress-relaxation measurements support the assumption that the reprocessability point to vitrimer-like molecular processes. The material shows rapid stress-relaxation of up to 11 s, a corresponding bond-exchange activation energy of 146 kJ/mol, and a topology freezing temperature of 97°C.

Dynamic centrifuge test of shield tunnels with non-water reacting two-component polymer buffer layer

A buffer layer is one of the countermeasures to promote the anti-seismic performance of tunnels. A newly invented non-water reacting two-component polymer (NRTCP) is superior in impermeability and durability. The construction process of the NRTCP is time-saving and labor-saving. In this study, in order to verify the seismic isolation efficiency of the NRTCP around a shield tunnel model, a dynamic centrifuge test with several dynamic input signals was conducted. The seismic responses of shield tunnel models with and without the NRTCP layer were compared. The results show that the bending moments of the tunnel model with an NRTCP layer were lower than those without an NRTCP layer. Thus, this indicates that the NRTCP layer positively reduced the bending moment in the tunnel model. The axial strain in the tunnel model with the NRTCP layer was lower than that without the NRTCP layer. In addition, the frequency contents of the acceleration response of the tunnel models were rarely influenced by the NRTCP layer. These findings demonstrated the positive effects of the NRTCP buffer layer on seismic isolation in shield tunnels.

A micromechanical damage-healing model for encapsulation-based self-healing polymer composites under tensile loading

In this study, a novel micromechanics-based damage model is proposed for the damage evolution of a two-component microencapsulated-based self-healing polymer composite. In this way, a representative volume element (RVE) including an epoxy matrix with randomly distributed poly(methyl methacrylate) (PMMA) microcapsules is modeled in DigimatTM software and analyzed in Abaqus®. A new technique is developed to investigate the progressive damage by pre-inserted cohesive elements along all element boundaries of the epoxy matrix, PMMA shell, and capsule-matrix interfaces with the bilinear traction–separation law. Moreover, the impact of interface bonding strength, interface fracture energy, and PMMA microcapsules volume fraction on the load-carrying capacity of the RVEs under uniaxial tension loading was studied. The results indicated that the tensile strength of the self-healing polymer composite increased as the interfacial strength and fracture energy increased from 10 to 60 MPa and 100 to 1000 J/m2, respectively. Furthermore, the higher volume fraction of 5% PMMA microcapsules results in a lower load-carrying capacity of self-healing polymer composite with a strength of 4.9 N. A similar trend of Young’s modulus was observed for microcapsule-loaded epoxy composite compared to the pristine epoxy matrix. The micromechanical model has proper accuracy in predicting the tension behavior of self-healing composite in comparison to experimental results. Finally, two healing strategies are considered for the damaged RVE.

Rock Reinforcement by Stepwise Injection of Two-Component Silicate Resin

Our research aims to improve the efficiency of the reinforcement of loose rocks with two-component polymer resins. The standard approach consists of the injection of two pre-mixed components into a rock massive. We propose a stepwise injection of individual components of a resin into the rock and deep extrusion of the solutions into the rock by gas between the injection stages. The experimental results indicate that the proposed method provides a reduction of polymer consumption per unit volume of the rock, and an increase in the impregnation depth, area of the resin impact, and the reinforced rock volume in comparison with the conventional method of prepared resin solution injection. The cured resin partially fills the sand rock pore space, binds the grains, and acts as a reinforcing frame. The highest reinforcement is achieved with the sequential stepwise injection of the resin by separate small portions of each component. We have shown the uniaxial compressive strength is on average more than twice as high that obtained with the conventional injection method. This can be explained by higher fracture toughness of the reinforced rock with a flexible hardened network of the cured resin in the structure.

A grafting-from strategy for the synthesis of bottlebrush nanofibers from organic semiconductors

Bottlebrush polymers with optoelectronic function show promise for applications in photonic crystals, nanomedicine, and encoding of information. In particular, bottlebrush polymers formed from organic semiconductors give wire-like nanoparticles where band gaps, fluorescence, and energy transfer can be tuned. To date, such bottlebrush polymers have largely been prepared by grafting-through polymerization of organic semiconductor macromonomers, where pre-synthesized side chains are polymerized along a bottlebrush backbone. While this approach provides high side-chain grafting densities, the length of bottlebrush polymers that is possible to obtain is limited by steric crowding at the propagating chain end. Here, we describe methods for preparing ultralong bottlebrush nanofibers from organic semiconductors, with backbone lengths approaching 800 repeating units and molecular weights in excess of 4 MDa. By combining reversible addition fragmentation chain transfer and Cu(0) reversible deactivation radical polymerization, a “grafting-from” protocol is described where monomers can be grown from a pre-synthesized backbone. Bottlebrush polymers were prepared from organic semiconductors used as n-type, p-type, and host materials in multilayer organic devices. Finally, a two-component bottlebrush polymer exhibiting deep blue emission, two-photon fluorescence, and a quantum yield of unity is also prepared by this method.

Bio-Based Polymer Developments from Tall Oil Fatty Acids by Exploiting Michael Addition.

In this study, previously developed acetoacetates of two tall-oil-based and two commercial polyols were used to obtain polymers by the Michael reaction. The development of polymer formulations with varying cross-link density was enabled by different bio-based monomers in combination with different acrylates—bisphenol A ethoxylate diacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate. New polymer materials are based on the same polyols that are suitable for polyurethanes. The new polymers have qualities comparable to polyurethanes and are obtained without the drawbacks that come with polyurethane extractions, such as the use of hazardous isocyanates or reactions under harsh conditions in the case of non-isocyanate polyurethanes. Dynamic mechanical analysis, differential scanning calorimetry, thermal gravimetric analysis, and universal strength testing equipment were used to investigate the physical and thermal characteristics of the created polymers. Polymers with a wide range of thermal and mechanical properties were obtained (glass transition temperature from 21 to 63 °C; tensile modulus (Young’s) from 8 MPa to 2710 MPa and tensile strength from 4 to 52 MPa). The synthesized polymers are thermally stable up to 300 °C. The suggested method may be used to make two-component polymer foams, coatings, resins, and composite matrices.

Polarity Nano-Mapping of Polymer Film Using Spectrally Resolved Super-Resolution Imaging.

With the rapid development of the nanofabrication of polymer materials, the local measurement of the chemical properties of polymer nanostructures has become crucial because they can be highly heterogeneous at the nanoscale. We developed a spectroscopic imaging approach to characterize the nanoscale local polarity of polymer films via spectrally resolved super-resolution microscopy. We demonstrate the capability of the recently developed single-molecule sensing and imaging method to probe the polarity of polymers either inside a polymer matrix or on the external surface of a polymer. The nanoscale polarity sensing capability of our method facilitates the differentiation of various polymer surfaces based on chemical polarities, and it can further differentiate the polarity of functional side chain groups. Moreover, we demonstrate that a two-component polymer mixture can be locally distinguished based on the contrasting polarities of the lateral phase separation, further allowing for the investigation of nanoscale phase separation depending on the composition of the polymer blend film. This approach is anticipated to open the door to further characterizations of various nanocomposite materials.

Statistical damage constitutive model for the two-component foaming polymer grouting material

Abstract Two-component foaming polymer (TFPU) grouting material is increasingly used in civil engineering. Its compressive strength is key to achieving the desired enhancing effect. The constitutive model of TFPU grouting material is a theoretical basis to evaluate the strength performance, which, however, is not fully understood. Here the uniaxial compression experiment of TFPU samples of different densities (0.11–0.53 g·cm−3) was conducted. Based on the stress–strain curves, the damage evolution equation of each sample was obtained by function fitting, followed by the establishment of statistical damage constitutive model. The model was simplified to a universal function with density as the argument. Results show that the stress–strain curves contain the initial compression stage, linear elastic stage, yield stage, yield plateau stage, and strain hardening stage regardless of the varied density. The variation laws of the damage with strain conform to the form of first-order decay exponential function. The theoretical stress–strain curves are in good agreement with the experimental ones, indicating that the statistical damage constitutive model can well reflect the mechanical behavior of TFPU grouting material. With this constitutive model, the mechanical properties of TFPU grouting material can be obtained according to the density alone, which is more convenient for practical engineering applications.

The Shear Damage Model of the Two-Component Forming Polymer Grouting Material-Bentonite Contact Surface

The newly developed two-component polymer (TFPU) cut-off walls have great application potential in civil engineering for water-seepage prevention. Investigating the mechanical interactions between TFPU and soil from the theoretical perspective can provide a basis for furtherly evaluating the stability of TFPU cut-off walls, which, however, has not been conducted. In this study, based on the shear testing results, the shear damage model of the TFPU-bentonite contact surface was established. Studies show that the TFPU-bentonite contact surface performs strain-softening behavior under shear and that the strain-softening behavior becomes less and less obvious when the normal stress increases. The theoretical shear stress-strain curves are in good consistent with the experimental ones, and the maximum differences between the theoretical shear stress and shear strain at yield and the experimental ones are about 3.88% and 3.40%, respectively, indicating that the shear damage model can reflect the mechanical properties of the TFPU-bentonite contact surface. The critical damage of the contact surface increases from 0.05 to 0.50 in the power function way when normal stress increases from 75 to 1200 kPa, implying that the shear failure of the contact surfaces changes from brittleness to ductility. This study provides a theoretical base for evaluating the influences of the TFPU-soil contact surface on the stability of the TFPU cut-off wall structures.

Removal of Acetic Acid from Bacterial Culture Media by Adsorption onto a Two-Component Composite Polymer Gel.

Organic acids, including acetic acid, are the metabolic products of many microorganisms. Acetic acid is a target product useful in the fermentation process. However, acetic acid has an inhibitory effect on microorganisms and limits fermentation. Thus, it would be beneficial to recover the acid from the culture medium. However, conventional recovery processes are expensive and environmentally unfriendly. Here, we report the use of a two-component hydrogel to adsorb dissociated and undissociated acetic acid from the culture medium. The Langmuir model revealed the maximum adsorption amount to be 44.8 mg acetic acid/g of dry gel at neutral pH value. The adsorption capacity was similar to that of an ion-exchange resin. In addition, the hydrogel maintained its adsorption capability in a culture medium comprising complex components, whereas the ion-exchange did not adsorb in this medium. The adsorbed acetic acid was readily desorbed using a solution containing a high salt concentration. Thus, the recovered acetic acid can be utilized for subsequent processes, and the gel-treated fermentation broth can be reused for the next round of fermentation. Use of this hydrogel may prove to be a more sustainable downstream process to recover biosynthesized acetic acid.

Nematic Structures under Conical Anchoring at Various Director Tilt Angles Specified by Polymethacrylate Compositions.

Dependence of the director tilt angle of nematic liquid crystal (LC) under conical anchoring from the two-component polymer mixture composition has been studied. We varied the ratio of poly(isobutyl methacrylate) (PiBMA), which specifies a conical anchoring for the nematic liquid crystal LN-396, and poly(methylmethacrylate) (PMMA) assigning a tangential alignment for the same nematic. An oblique incidence light technique to determine a tilt angle has been used. It has been shown that the tilt angle increases from to when PiBMA:PMMA ratio changes in the range 30:70 to 100:0. The specific optical textures viewed under the polarizing microscope and proper orientational structures have been considered for various compositions of the polymer films. An electric field action on the formed orientational structures has been investigated. The obtained results are promising for the application in various electro-optical LC devices with a conical anchoring in which the director tilt angle is a crucial parameter: a controlled diffraction gratings, an electrically operated achromatic rotators of linear light polarization, etc.

Estimation of the Filled Two-Component Cold Curing Polymer System Performance as a Coating for Protecting Concrete Surfaces from the Aggressive Environment Exposure

A filled two-component polymer cold curingsystem (FTCPS) is discussed in the article. To assess its corrosion resistance and durability, the indexes of reagent resistance were determined in accordance with the sorption method. What is optimal, since this value depends on the parameters of mass transfer, the intensity of the reaction, the size of the product, the duration of exposure to aggressive media and other factors. As aggressive media were taken: water, 5% hydrochloric acid solution, 25% aqueous ammonia solution, 10% sodium hydroxide solution, saturated sodium chloride solution. The exposure time was 360 days. Reagent resistance evaluation of the developed FTCPScompositionswas carried out on the basis of guidelines for determining the anticorrosive properties of protective coatings of concrete and laboratory test methods. Changes in the mass of the samples and their reagent resistance as a result of exposure to chemical reagents simulating an aggressive environment during operation were evaluated. The change in the index of reagent resistance in laboratory conditions did not go beyond the value of 0.80, which makes it possible to ensure reliable protection and operation of polymer-coated products under conditions of exposure to these aggressive environments.

LAB-SCALE TESTS OF INCOHERENT ROCK REINFORCEMENT USING TWO-COMPONENT POLYMER BLENDS

The study addresses improvement of physical and mechanical properties of incoherent sediments by means of their chemical reinforcement using two-component resins. The lab-scale testing data on reinforcement of fine-grained quartz sand using two-component activated mineral and polyurethane resin blends are presented. Resins were injected by two ways on the tests. The first method was sequential injection of the polymer blend components in rock samples. The second method was injection of finished polymer blends. The two-component activated mineral and polyurethane resin blends ensure more effective reinforcement of incoherent sediment rocks as against foamed polyurethane blends. The uniaxial compression strength of reinforced fine-grained sand is 2.5-3 times higher in case of sequential injection of the components than in injection of finished mixtures. The elasticity modulus of the reinforced samples is 5.5-6 times higher in sequential injection than in injection of finished blends. The test results are useful for selection and optimization of injection method for two-component polymer blends in stabilization of broken rocks and in water-proofing of underground excavations.

Test Method for the Solubility Model of Physical Blowing Agent of Self-Expanding Polymer

This paper aims to present a solubility model of physical blowing agent (PBA) for a kind of commonly used self-expanding polymer on engineering. The self-expanding polymer contains Component A (isocyanate) and Component B (polyhydric alcohol, PBA, water, and catalyst). Component B grout of the polymer, which contains PBA, was heated to measure its temperature and volume variations. Based on the principle of mass conservation and Clapeyron equation, the solubility curve of PBA with respect to temperature was calculated. The solubility curve was then applied to simulate the foaming process. A two-component polymer grout foaming experiment was then carried out to verify the applicability of the measured solubility curve. The simulated changes of temperature and density with respect to time of polymer grout were analyzed and compared with experimental results. The error of both sets of curves is within 5%, which shows a good agreement among them and proves the feasibility of the solubility model. This study provides a relatively complete test and verification process for the solubility model of PBA, which lays a theoretical foundation for both the polymer grouting diffusion mechanism and engineering application.

Processability and Mechanical Properties of Thermoplastic Polylactide/Polyhydroxybutyrate (PLA/PHB) Bioblends.

This work considers the application of eco-friendly, biodegradable materials based on polylactide (PLA) and polyhydroxybutyrate (PHB), instead of conventional polymeric materials, in order to prevent further environmental endangerment by accumulation of synthetic petro-materials. This new approach to the topic is focused on analyzing the processing properties of blends without incorporating any additives that could have a harmful impact on human organisms, including the endocrine system. The main aim of the research was to find the best PLA/PHB ratio to obtain materials with desirable mechanical, processing and application properties. Therefore, two-component polymer blends were prepared by mixing different mass ratios of PLA and PHB (100/0, 50/10, 50/20, 40/30, 50/50, 30/40, 20/50, 10/50 and 0/100 mass ratio) using an extrusion process. The prepared blends were analyzed in terms of thermal and mechanical properties as well as miscibility and surface characteristics. Taking into account the test results, the PLA/PHB blend with a 50/10 ratio turned out to be most suitable in terms of mechanical and processing properties. This blend has the potential to become a bio-based and simultaneously biodegradable material safe for human health dedicated for the packaging industry.

Mixed-flow design for microfluidic printing of two-component polymer semiconductor systems

The rational creation of two-component conjugated polymer systems with high levels of phase purity in each component is challenging but crucial for realizing printed soft-matter electronics. Here, we report a mixed-flow microfluidic printing (MFMP) approach for two-component π-polymer systems that significantly elevates phase purity in bulk-heterojunction solar cells and thin-film transistors. MFMP integrates laminar and extensional flows using a specially microstructured shear blade, designed with fluid flow simulation tools to tune the flow patterns and induce shear, stretch, and pushout effects. This optimizes polymer conformation and semiconducting blend order as assessed by atomic force microscopy (AFM), transmission electron microscopy (TEM), grazing incidence wide-angle X-ray scattering (GIWAXS), resonant soft X-ray scattering (R-SoXS), photovoltaic response, and field effect mobility. For printed all-polymer (poly[(5,6-difluoro-2-octyl-2H-benzotriazole-4,7-diyl)-2,5-thiophenediyl[4,8-bis[5-(2-hexyldecyl)-2-thienyl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl]-2,5-thiophenediyl]) [J51]:(poly{[N,N'-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)}) [N2200]) solar cells, this approach enhances short-circuit currents and fill factors, with power conversion efficiency increasing from 5.20% for conventional blade coating to 7.80% for MFMP. Moreover, the performance of mixed polymer ambipolar [poly(3-hexylthiophene-2,5-diyl) (P3HT):N2200] and semiconducting:insulating polymer unipolar (N2200:polystyrene) transistors is similarly enhanced, underscoring versatility for two-component π-polymer systems. Mixed-flow designs offer modalities for achieving high-performance organic optoelectronics via innovative printing methodologies.