Polymer Microstructure Research Articles

The Spatial Distribution of Lipophilic Cations in Gradient Copolymers Regulates Polymer-pDNA Complexation, Polyplex Aggregation, and Intracellular pDNA Delivery.

Here, we demonstrate that the spatial distribution of lipophilic cations governs the complexation pathways, serum stability, and biological performance of polymer-pDNA complexes (polyplexes). Previous research focused on block/statistical copolymers, whereas gradient copolymers, where the density of lipophilic cations diminishes (gradually or steeply) along polymer backbones, remain underexplored. We engineered gradient copolymers that combine the polyplex colloidal stability of block copolymers with the transfection efficiency of statistical copolymers. We synthesized length- and compositionally equivalent gradient copolymers (G1-G3) along with statistical (S) and block (B) copolymers of 2-(diisopropylamino)ethyl methacrylate and 2-hydroxyethyl methacrylate. We mapped how polymer microstructure governs pDNA loading per polyplex, pDNA conformational changes, and polymer-pDNA binding thermodynamics via static light scattering, circular dichroism spectroscopy, and isothermal titration calorimetry, respectively. While gradient steepness is a powerful design handle to improve polyplex physical properties, augment pDNA delivery capacity, and attenuate polycation-triggered hemolysis, microstructural contrasts did not elicit differences in complement activation.

Reverse Mode Polymer Stabilized Cholesteric Liquid Crystal Flexible Films with Excellent Bending Resistance.

The reverse-mode smart windows, which usually fabricated by polymer stabilized liquid crystal (PSLC), are more practical for scenarios where high transparency is a priority for most of the time. However, the polymer stabilized cholesteric liquid crystal (PSCLC) film exhibits poor spacing stability due to the mobility of CLC molecules during the bending deformation. In this work, a reverse-mode PSCLC flexible film with excellent bending resistance was fabricated by the construction of polymer spacer columns. The effect of the concentration of the polymerizable monomer C6M and chiral dopant R811 on the electro-optical properties and polymer microstructure of the film were studied. The sample B2 containing 3 wt% of C6M and 3 wt% R811 presented the best electro-optical performance. The electrical switch between transparent and opaque state of the flexible PSCLC film after bending not only indicated the excellent electro-optical switching performance, but also demonstrated the outstanding bending resistance of the sample with polymer spacer columns, which makes the PSCLC film containing polymer spacer columns have a great potential to be applied in the field of flexible devices.

Synthesis of Polycyclic Olefinic Monomers from Norbornadiene for Inverse Vulcanization: Structural and Mechanistic Consequences.

The preparation of high-sulfur content organosulfur polymers has generated considerable interest as an emerging area in polymer science that has been driven by advances in the inverse vulcanization polymerization of elemental sulfur with organic comonomers. While numerous new inverse vulcanized polysulfides have been made over the past decade, insights into the mechanism of inverse vulcanization and structural characterization of the high-sulfur-content copolymers remain limited in scope. Furthermore, the exploration of new molecular architectures for organic comonomer synthesis remains an important frontier to enhance the properties of these new polymeric materials. In the current report, the first detailed study on the synthesis and inverse vulcanization of polycyclic rigid comonomers derived from norbornadiene was conducted, affording a quantitative assessment of polymer microstructure for these organopolysulfides and insights into the inverse vulcanization polymerization mechanism for this class of monomers. In particular, a stereoselective synthesis of the endo-exo norbornadiene cyclopentadiene adduct (Stillene) was achieved, which enabled direct comparison with the known exo-exo norbornadiene dimer (NBD2) previously used for inverse vulcanization. Reductive degradation of these sulfur copolymers and detailed structural analysis of the recovered sulfurated organic fragments revealed that remarkable exo-stereospecificity was achieved in the inverse vulcanization of elemental sulfur with both these polycyclic dienyl comonomers, which correlated to the robust thermomechanical properties associated with organopolysulfides made from NBD2 previously. Melt processing and molding of these sulfur copolymers were conducted to fabricate free-standing plastic lenses for long-wave infrared thermal imaging.

Synergistic Effects of Magnesium Oxide and SBR Latex Additives on Cement Sheath Stability in Oil Well Operations.

Leaks through cement sheaths remain a complex and challenging issue in the oil industry, representing a persistent obstacle that has endured for decades. The drying shrinkage, an inherent characteristic of Portland cement, substantially exacerbates this problem, driving the formation of microcracks and heightened permeability under variable stress conditions. In this context, additives emerge as significant elements in addressing this issue, offering a pathway to mitigate the adverse effects of leaks. Among these additives, magnesium oxide (MgO) stands out for its ability to reduce drying shrinkage through structural modifications in the cement matrix. Simultaneously, SBR Latex, another important additive, acts to minimize gas migration due to its polymeric microstructure while also strengthening acid resistance and enhancing microstructural cohesion. This study aims to deepen the understanding of the interaction between MgO and SBR Latex additives in cement slurries, employing an experimental design to substantiate and expand upon the analyses conducted. The results reveal a synergistic integration of these additives, with MgO acting as an effective agent in reducing drying shrinkage and gel formation, thereby contributing to the strengthening of shear strength. Conversely, SBR Latex provides elasticity to the slurry, although with a slight compromise in compressive strength, with a relatively limited effect on shear strength. The strategic combination of these additives results in improvements in the mechanical integrity of cement slurries, a positive advancement in the context of petroleum well cementing operations. Thus, this study not only highlights the individual properties of MgO and SBR Latex but also offers valuable perspectives for the careful formulation of cements, with potential applications in challenging operational environments in the oil industry.

(Invited) Probing the Influence of the Dielectric Environment on Charge Carrier Dynamics in Semiconducting Polymers

Pi-conjugated semiconducting polymers have garnered attention for a variety of electronic and optoelectronic applications, such as field-effect transistors, thermoelectric generators, and photovoltaic devices. In these systems, the charge carrier dynamics are primarily governed by the properties of the polaron and the polymer microstructure. More recently, there has been growing interest in the suitability of these polymer for electrochemical transistors and (photo)electrochemical applications, where the understanding is further complicated by the presence of ions and solvent molecules, as well as the dynamic transport of these species into the semiconducting polymer. Here, we will employ steady-state and transient spectroscopic techniques to probe the influence of charge carrier doping, as well as the extrinsic and local dielectric environments, on charge carrier generation, transport, and recombination in prototypical semiconducting polymer(s). Incorporation of electrochemical techniques enables in-situ spectroscopic measurements that mimic operando conditions. Our observations will provide a better understanding of the factors that control the carrier dynamics in these compositionally complex systems and will have implications for their viability and optimization for (photo)electrochemical applications.

Overcoming Challenges of Incorporation of Biobased Dibutyl Itaconate in (Meth)acrylic Waterborne Polymers.

Polymeric derivatives of itaconic acid are gaining interest as biobased alternatives to petroleum-based monomers due to their versatility, renewable nature, commercial availability, and cost-effectiveness. Itaconate ester monomer's challenges incorporating in (meth)acrylic waterborne polymers are the low propagation rate, unfavorable reactivity ratios, and the depropagation process. To overcome these challenges, the seeded semibatch emulsion polymerization of 100% biobased dibutyl itaconate, methyl methacrylate, and butyl acrylate was investigated at different temperatures. Consequently, 30 wt % DBI was successfully incorporated within waterborne (meth)acrylates in short reaction times (4 h), obtaining high DBI incorporation (>90%). The results demonstrate that DBI incorporation influences the instantaneous monomer conversion, polymer's microstructure, and mechanical properties. By incorporating a biobased itaconate cross-linker, kinetics and mechanical characteristics of the polymers were improved. This combined approach can be implemented without altering industrial processes, resolving the commercialization dilemma for itaconate monomers to synthesize high-performance biobased polymers for adhesive and coating industries.

Shape Memory Polymers in 4D Printing: Investigating Multi-Material Lattice Structures

This paper evaluates the design and fabrication of a thermoplastic polyurethane (TPU) shape memory polymer (SMP) using fused deposition modeling (FDM). The commercially available SMP filament was used to create parts capable of changing their shape following the application of an external heat stimulus. The characterization of thermal and viscoelastic properties of the SMP TPU revealed a proportional change in shape fixity and recovery with respect to heating and cooling rates, as well as a decreasing softening temperature with increasing shape memory history due to changes in the polymer microstructure. Inspired by the advancements in 3D and 4D printing, we investigated the feasibility of creating multi-material lattice structures using SMP and another thermoplastic with poor adhesion to TPU. A variety of interlocking lattice structures were evaluated by combining SMP with another thermoplastic that have poor adhesion with TPU. The tensile strength and failure modes of the fabricated multi-material parts were compared against homogenous SMP TPU specimens. It was found that the lattice interface failed first at approximately 41% of the ultimate strength of the homogenous part on average. The maximum recorded ultimate strength of the multi-material specimens reached 62% of SMP TPU’s ultimate strength. These characterizations can make 4D printing technology more accessible to common users and make it available for new markets.

Tunable Dual Self-Healing Composite Coatings with Self-Assembled Structures Regulated by Janus Nanoparticles.

The durability of concrete structures can be enhanced in a convenient and permanent manner through the surface protection of cementitious materials with composite polymer coatings. However, polymer coatings are susceptible to various mechanical and physical deterioration in complex and variable environments. In this paper, the theory of polymer microstructure regulation was employed to improve the sustainability of the protective performance of composite coatings. The self-assembled core-shell structure regulated by amphiphilic Janus nanoparticles is employed to modify the tunable polystyrene acrylate-polysiloxane self-healing coatings. The results demonstrate that the adhesion strength of the prepared self-assembled coating reached 3.7 MPa, which is sufficient to resist the damage to the microstructure of cementitious materials caused by physical erosion, seepage, and ionic corrosion. The self-healing coating, regulated by Janus particles, exhibited a residual creep of only 57.03% and a maximum loss angle tangent of 0.381. Furthermore, the material exhibited a superior shape memory function due to the presence of strong hydrogen bonding. The regulated self-healing coating repaired the polymer structural damage under mechanical and thermal deformation by bridging and filling effects. The coating demonstrated a tensile strength recovery of up to 71.23% in a wetted state, accompanied by a rapid restoration of its electrochemical properties and corrosion resistance. Furthermore, the self-healing emulsion penetrates the substrate defects and forms numerous polymer crystalline particles that effectively fill the microcracks.

An Algorithm for Modeling Thermoplastic Spherulite Growth Using Crystallization Kinetics.

Crystallization kinetics were used to develop a spherulite growth model, which can determine local crystalline distributions through an optimization algorithm. Kinetics were used to simulate spherulite homogeneous nucleation, growth, and heterogeneous nucleation in a domain discretized into voxels. From this, an overall crystallinity was found, and an algorithm was used to find crystallinities of individual spherulites based on volume. Then, local crystallinities within the spherulites were found based on distance relative to the nucleus. Results show validation of this model to differential scanning calorimetry data for polyether ether ketone at different cooldown rates, and to experimental microscopic images of spherulite morphologies. Application of this model to various cooldown rates and the effect on crystalline distributions are also shown. This model serves as a tool for predicting the resulting semi-crystalline microstructures of polymers for different manufacturing methods. These can then be directly converted into a multiscale thermomechanical model.

Simultaneously enhancing the flow properties and mechanical strength of polyphenylene sulfide via in‐mold ultrasonic‐assisted injection molding

AbstractInjection molding is widely used for making intricate plastic products due to its precision, cost efficiency, and fast production. Industries like consumer electronics, aerospace, and medical, demand high mechanical properties from these parts. However, high‐performance polymers face challenges in flowability. Ultrasonic‐assisted injection molding offers a solution, but its impact on flowability and mechanical properties is not fully understood. We propose a novel injection mold design with in‐mold ultrasonic vibration to address this. By applying high‐frequency shear forces to the melt, it alters polymer chain alignment, enhancing flow and microstructure. Employing polyphenylene sulfide (PPS) resin as the primary material, this study systematically explores the impact of varying ultrasonic vibration durations and stages on melt filling behavior and product performance. Compared with conventional molds, ultrasonic‐assisted molds reduce melt viscosity by 38% and improve mechanical properties by 10.21%, with a 17.1% increase in crystallinity. This technology shows promise for improving flowability and mechanical properties in injection molding, with potential for wide industrial application.

Subsurface Profiling of Ion Migration and Swelling in Conducting Polymer Actuators with Modulated Electrochemical Atomic Force Microscopy.

Understanding the dynamics of ion migration and volume change is crucial to studying the functionality and long-term stability of soft polymeric materials operating at liquid interfaces, but the subsurface characterization of swelling processes in these systems remains elusive. In this work, we address the issue using modulated electrochemical atomic force microscopy as a depth-sensitive technique to study electroswelling effects in the high-performance actuator material polypyrrole doped with dodecylbenzenesulfonate (Ppy:DBS). We perform multidimensional measurements combining local electroswelling and electrochemical impedance spectroscopies on microstructured Ppy:DBS actuators. We interpret charge accumulation in the polymeric matrix with a quantitative model, giving access to both the spatiotemporal dynamics of ion migration and the distribution of electroswelling in the electroactive polymer layer. The findings demonstrate a nonuniform distribution of the effective ionic volume in the Ppy:DBS layer depending on the film morphology and redox state. Our findings indicate that the highly efficient actuation performance of Ppy:DBS is caused by rearrangements of the polymer microstructure induced by charge accumulation in the soft polymeric matrix, increasing the effective ionic volume in the bulk of the electroactive film for up to two times the value measured in free water.

Assessing the reinforcement effect by response surface methodology of holocellulose from spent coffee grounds on biopolymeric films as food packaging materials.

The pollution caused by petroleum-derived plastic materials has become a major environmental problem that has encouraged the development of new compostable and environmentally friendly materials for food packaging based on biomodified polymers with household residues. This study aims to design, synthesize, and characterize a biobased polymeric microstructure film from polyvinyl alcohol and chitosan reinforced with holocellulose from spent coffee grounds for food-sustainable packaging. Chemical isolation with a chlorite-based solution was performed to obtain the reinforced holocellulose from the spent coffee ground, and the solvent casting method was used to obtain the films to study. Physicochemical and microscopic characterizations were conducted to identify and select the best formulations using a simplex-centroid design analysis. The response surface methodology results indicate that the new packaging material obtained with equal amounts of polymers and reinforced material (1:1:1) possesses the appropriate barrier properties and microstructural character to prevent water attack and hydrophobic behavior and thus could be used as an alternative for food packaging materials.

Study on the properties and microstructure of polymer modified waste printed circuit board cement-based materials

Waste printed circuit boards (WPCB) are solid waste, and the current disposal of WPCB in landfills has raised environmental concern. Existing studies used ground WPCB as a replacement of fine aggregate in cement-based materials, but the performances of those materials were notably decreased. This paper aims to improve the performance of WPCB-bearing cementitious materials using styrene butadiene rubber (SBR) latex and chloroprene rubber (CR) latex. For this purpose, cement-based materials with ground WPCB as fine aggregates were prepared, and the effects of SBR latex and CR latex on the mechanical properties of WPCB-bearing samples with varying dosages were studied. The influence mechanism was studied using SEM, hydration heat, XRD, and FTIR tests. The results showed that the incorporation of ground WPCB tends to significantly reduce the compressive strength of cement-based materials, while the addition of SBR and CR latex can prevent the strength loss. For instance, with the optimal dosage of 5 % for SBR latex or 7.5 % for CR, the 28-d compressive strength of the latex-modified sample was 42.6 MPa and 45.3 MPa, which was 26.78 % and 34.82 % higher than that of the unmodified samples. Through microstructure analysis, it was found that the incorporation of WPCB had a negative impact on the densification of cement-based materials. SBR latex and CR latex promoted the hydration reaction and formed continuous film products inside the structure, which improved the bonding performance of WPCB cement-based materials.

Effect of Thermo- and pH-Sensitive Block Copolymer Structure and Composition on the Synthesis and Stabilization of Gold Nanoparticles.

Homopolymers of poly[N-(2-(diethylamino)ethyl) acrylamide] exhibit the ability to adsorb onto the surface of preformed or growing gold nanoparticles. The resulting hybrid materials possess a pH and thermo-sensitive nature. Consequently, their optical properties can be modulated by manipulating either the temperature or the pH. Moreover, introducing monomers based on poly(N-isopropyl acrylamide) into block or random statistical polymers enables further modulation of the thermosensitive properties. These copolymers, employed for the in-situ synthesis and/or stabilization of gold nanoparticles, lead to hybrid materials whose properties and/or particle size depend on the polymer composition and microstructure: statistical polymers emerge as superior stabilizing agents compared to their block counterparts at a constant composition.

Nickel‐ and Palladium‐Catalyzed Copolymerizations of Norbornene with Polar α‐Olefins

AbstractRecent progress regarding the copolymerization of norbornene with various polar α‐olefins catalyzed by nickel and palladium catalysts is reviewed here with special attention paid to the diverse catalyst frameworks, polar monomer scopes as well as polymer microstructures. Both the influences of steric effect and electron property of ligand substituents and the type of polar monomers on the catalytic behaviors (activity, stability, polarity tolerance, etc.) and the polymer microstructures (molecular weight and distribution, comonomer contents, etc.) have been summarized. The introduction of noncyclic‐olefins, such as polar vinyl monomers, polar higher α‐olefins, and polar styrenes, into rigid cyclic‐based polynorbornene chain resulted in significant modifications on the polarity, compatibility, thermostability, processibility, transparency, and many other properties of the material, which has also been discussed in the review. The contents of this review have been classified according to the type of polar monomers involved in the norbornene copolymerization, and each section included nickel and palladium catalysts bearing different ligand structures, which will be meaningful for the development of new types of catalysts and new families of norbornene‐based cyclic olefin copolymer materials in the future.

Field Emission from Carbon Nanotubes on Titanium Nitride-Coated Planar and 3D-Printed Substrates.

Carbon nanotubes (CNTs) are well known for their outstanding field emission (FE) performance, facilitated by their unique combination of electrical, mechanical, and thermal properties. However, if the substrate of choice is a poor conductor, the electron supply towards the CNTs can be limited, restricting the FE current. Furthermore, ineffective heat dissipation can lead to emitter-substrate bond degradation, shortening the field emitters' lifetime. Herein, temperature-stable titanium nitride (TiN) was deposited by plasma-enhanced atomic layer deposition (PEALD) on different substrate types prior to the CNT growth. A turn-on field reduction of up to 59% was found for the emitters that were generated on TiN-coated bulk substrates instead of on pristine ones. This observation was attributed exclusively to the TiN layer as no significant change in the emitter morphology could be identified. The fabrication route and, consequently, improved FE properties were transferred from bulk substrates to free-standing, electrically insulating nanomembranes. Moreover, 3D-printed, polymeric microstructures were overcoated by atomic layer deposition (ALD) employing its high conformality. The results of our approach by combining ALD with CNT growth could assist the future fabrication of highly efficient field emitters on 3D scaffold structures regardless of the substrate material.

Deep convolutional generative adversarial network for generation of computed tomography images of discontinuously carbon fiber reinforced polymer microstructures

Computed tomography images are of utmost importance when characterizing the heterogeneous and complex microstructure of discontinuously fiber reinforced polymers. However, the devices are expensive and the scans are time- and energy-intensive. Through recent advances in generative adversarial networks, the instantaneous generation of endless numbers of images that are representative of the input images and hold physical significance becomes possible. Hence, this work presents a deep convolutional generative adversarial network trained on approximately 30,000 input images from carbon fiber reinforced polyamide 6 computed tomography scans. The challenge lies in the low contrast between the two constituents caused by the close proximity of the density of polyamide 6 and carbon fibers as well as the small fiber diameter compared to the necessary resolution of the images. In addition, the stochastic, heterogeneous microstructure does not follow any logical or predictable rules exacerbating their generation. The quality of the images generated by the trained network of 256 pixel ×\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\ imes$$\\end{document} 256 pixel was investigated through the Fréchet inception distance and nearest neighbor considerations based on Euclidean distance and structural similarity index measure. Additional visual qualitative assessment ensured the realistic depiction of the complex mixed single fiber and fiber bundle structure alongside flow-related physically feasible positioning of the fibers in the polymer. The authors foresee additionally huge potential in creating three-dimensional representative volume elements typically used in composites homogenization.

Preparation and Characterization of Polymeric Microparticles Based on Poly(ethylene brassylate-co-squaric Acid) Loaded with Norfloxacin.

In recent years, increasing interest has been accorded to polyester-based polymer microstructures, driven by their promising potential as advanced drug delivery systems. This study presents the preparation and characterization of new polymeric microparticles based on poly(ethylene brassylate-co-squaric acid) loaded with norfloxacin, a broad-spectrum antibiotic. Polymacrolactone was synthesised in mild conditions through the emulsion polymerization of bio-based and renewable monomers, ethylene brassylate, and squaric acid. The microparticles were obtained using the precipitation technique and subsequently subjected to comprehensive characterization. The impact of the copolymer/drug ratio on various properties of the new system was systematically evaluated, confirming the structure of the copolymer and the encapsulation of norfloxacin. The microspheres are approximately spherical and predominantly homogeneously distributed. The average hydrodynamic diameter of the microparticles falls between 400 and 2000 nm, a decrease that is observed with the increase in norfloxacin content. All samples showed good encapsulation efficiency and drug loading capacity, with the highest values obtained for microparticles synthesised using an equal ratio of copolymer and drug. In vitro drug release results disclose that norfloxacin molecules are released in a sustained biphasic manner for up to 24 h. Antimicrobial activity was also studied, with samples showing very good activity against E. coli and moderate activity against S. aureus and E. faecalis. In addition, HDFA human fibroblast cell cultures demonstrated the cytocompatibility of the microparticles.

Enhancing the Thermoelectric Properties of Conjugated Polymers by Suppressing Dopant-Induced Disorder.

Doping is a crucial strategy to enhance the performance of various organic electronic devices. However, in many cases, the random distribution of dopants in conjugated polymers leads to the disruption of the polymer microstructure, severely constraining the achievable performance of electronic devices. Here, it is shown that by ion-exchange doping polythiophene-based P[(3HT)1-x-stat-(T)x] (x=0 (P1), 0.12 (P2), 0.24 (P3), and 0.36 (P4)), remarkably high electrical conductivity of >400S cm-1 and power factor of >16µWm-1K-2 are achieved for the random copolymer P3, ranking it among highest ever reported for unaligned P3HT-based films, significantly higher than that of P1 (<40Scm-1, <4µWm-1K-2). Although both polymers exhibit comparable field-effect transistor hole mobilities of ≈0.1cm2V-1s-1 in the pristine state, after doping, Hall effect measurements indicate that P3 exhibits a large Hall mobility up to 1.2cm2V-1s-1, significantly outperforming that of P1 (0.06cm2V-1s-1). GIWAXS measurement determines that the in-plane π-π stacking distance of doped P3 is 3.44Å, distinctly shorter than that of doped P1 (3.68Å). These findings contribute to resolving the long-standing dopant-induced-disorder issues in P3HT and serve as an example for achieving fast charge transport in highly doped polymers for efficient electronics.

Access to Stereoblock Polyesters via Irreversible Chain-Transfer Ring-Opening Polymerization (ICT-ROP).

Precise control over polymer microstructure can enable the molecular tunability of material properties and represents a significant challenge in polymer chemistry. Stereoblock copolymers are some of the simplest stereosequenced polymers, yet the synthesis of stereoblock polyesters from prochiral or racemic monomers outside of "simple" isotactic stereoblocks remains limited. Herein, we report the development of irreversible chain-transfer ring-opening polymerization (ICT-ROP), which overcomes the fundamental limitations of single catalyst approaches by using transmetalation (e.g., alkoxide-chloride exchange) between two catalysts with distinct stereoselectivities as a means to embed temporally controlled multicatalysis in ROP. Our combined small-molecule model and catalytic polymerization studies lay out a clear molecular basis for ICT-ROP and are exploited to access the first examples of atactic-syndiotactic stereoblock (at-sb-st) polyesters, at-sb-st polyhydroxyalkanoates (PHAs). We achieve high levels of control over molecular weight, tacticity, monomer composition, and block structures in a temporally controlled manner and demonstrate that stereosequence control leads to polymer tensile properties that are independent of thermal properties.