Polymer-particle Interactions Research Articles

Application of Cyrene solvent for the fabrication of polymethyl methacrylate, polyethyl methacrylate and composite films containing hydroxyapatite and diamonds

AbstractCyrene is a new biodegradable solvent, which represents a green alternative to many traditional toxic solvents for advanced polymers. Therefore, this investigation is motivated by interest in applications of Cyrene for polymer processing. The feasibility of solubilization of polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA) in Cyrene is demonstrated. The ability to form relatively concentrated solutions of the high molecular mass polymers is an important factor for the formation of PMMA and PEMA films by a dip coating method. It was found that the polymer coatings provide corrosion protection of stainless steel in 30 g L−1 NaCl solutions. Another important finding is that the use of Cyrene facilitates the fabrication of stable suspensions of hydroxyapatite (HAp), microdiamond, and nanodiamond particles. Therefore, the problems of the dispersant selection for dispersion of chemically inert diamond and development of biocompatible dispersants are avoided using Cyrene. For the fabrication of composite films, HAp nanorods with reduced particle size are obtained using rutin as a chelating capping agent. Composite films containing HAp, microdiamond and nanodiamond in the PMMA or PEMA matrix are obtained. The composite films are promising for biomedical applications. It was found that the film morphology, composition and microstructure are influenced by the solvent–particle–polymer interactions and processing conditions.

Biomimetic Non-ergodic Aging by Dynamic-to-covalent Transitions in Physical Hydrogels.

Hydrogels are soft materials engineered to suit a multitude of applications that exploit their tunable mechanochemical properties. Dynamic hydrogels employing noncovalent, physically cross-linked networks dominated by either enthalpic or entropic interactions enable unique rheological and stimuli-responsive characteristics. In contrast to enthalpy-driven interactions that soften with increasing temperature, entropic interactions result in largely temperature-independent mechanical properties. By engineering interfacial polymer-particle interactions, we can induce a dynamic-to-covalent transition in entropic hydrogels that leads to biomimetic non-ergodic aging in the microstructure without altering the network mesh size. This transition is tuned by varying temperature and formulation conditions such as pH, which allows for multivalent tunability in properties. These hydrogels can thus be designed to exhibit either temperature-independent metastable dynamic cross-linking or time-dependent stiffening based on formulation and storage conditions, all while maintaining structural features critical for controlling mass transport, akin to many biological tissues. Such robust materials with versatile and adaptable properties can be utilized in applications such as wildfire suppression, surgical adhesives, and depot-forming injectable drug delivery systems.

Filled Elastomers: Mechanistic and Physics-Driven Modeling and Applications as Smart Materials.

Elastomers are made of chain-like molecules to form networks that can sustain large deformation. Rubbers are thermosetting elastomers that are obtained from irreversible curing reactions. Curing reactions create permanent bonds between the molecular chains. On the other hand, thermoplastic elastomers do not need curing reactions. Incorporation of appropriated filler particles, as has been practiced for decades, can significantly enhance mechanical properties of elastomers. However, there are fundamental questions about polymer matrix composites (PMCs) that still elude complete understanding. This is because the macroscopic properties of PMCs depend not only on the overall volume fraction (ϕ) of the filler particles, but also on their spatial distribution (i.e., primary, secondary, and tertiary structure). This work aims at reviewing how the mechanical properties of PMCs are related to the microstructure of filler particles and to the interaction between filler particles and polymer matrices. Overall, soft rubbery matrices dictate the elasticity/hyperelasticity of the PMCs while the reinforcement involves polymer-particle interactions that can significantly influence the mechanical properties of the polymer matrix interface. For ϕ values higher than a threshold, percolation of the filler particles can lead to significant reinforcement. While viscoelastic behavior may be attributed to the soft rubbery component, inelastic behaviors like the Mullins and Payne effects are highly correlated to the microstructures of the polymer matrix and the filler particles, as well as that of the polymer-particle interface. Additionally, the incorporation of specific filler particles within intelligently designed polymer systems has been shown to yield a variety of functional and responsive materials, commonly termed smart materials. We review three types of smart PMCs, i.e., magnetoelastic (M-), shape-memory (SM-), and self-healing (SH-) PMCs, and discuss the constitutive models for these smart materials.

Particle–polymer interactions for 3D printing material design

Embedded ink writing (EIW) and direct ink writing (DIW) constitute the primary strategies for three-dimensional (3D) printing within the realm of material extrusion. These methods enable the rapid fabrication of complex 3D structures, utilizing either yield-stress support baths or self-supporting inks. Both these strategies have been extensively studied across a range of fields, including biomedical, soft robotics, and smart sensors, due to their outstanding print fidelity and compatibility with diverse ink materials. Particle additives capable of forming volume-filling 3D networks are frequently incorporated into polymer solvents. This integration is crucial for engineering the requisite microstructures essential for the formulation of successful support bath and ink materials. The interplay between the particle additives and polymer solvents is critical for achieving rheological tunability in various 3D printing strategies, yet this area has not been systematically reviewed. Therefore, in this critical review, we examined various mechanisms of particle–polymer interactions, the resulting microstructures, and their subsequent impact on mechanical and rheological properties. Overall, this work aims to serve as a foundational guideline for the design of next-generation materials in the field of extrusion additive manufacturing, specifically for EIW and DIW.

Light-Scattering Analysis of Drying Behavior in Suspension Droplets with Silica and Polystyrene Particles and a Hydrosoluble Polymer.

The coffee-ring structure, which is the final drying pattern of a sessile suspension droplet, is a key factor in controlling the uniformity of the particulate deposits in various coatings. Two light-scattering methods, diffusing wave spectroscopy (DWS) and multispeckle DWS (MSDWS), were used to quantitatively distinguish temporal changes in particle mobility in evaporating suspension droplets containing micrometer-sized silica and polystyrene (PS) particles. The characteristic particle mobility was measured in terms of the mean square displacement in the early stage of drying, and the local particle dynamics around the edge and center regimes of the droplets during drying were analyzed using MSDWS. Hydroxyethyl cellulose (HEC), a hydrosoluble polymer, was added to the silica and PS suspensions to further investigate its role in suppressing or enhancing coffee-ring patterns based on particle-polymer interactions. Consequently, dried microstructures can be directly correlated with real-time drying dynamics, as well as the interactions between solutes by comprehensive light-scattering methods.

Effects of sodium carboxymethyl cellulose and poly (acrylic acid) on the agglomeration behavior of aqueous silicon suspensions

We investigate the effects of carboxymethyl cellulose (CMC) and poly (acrylic acid) (PAA) on the dispersion state of silicon particles and the mechanism thereof. Here, we report severe agglomeration of silicon particles induced by the hydrophobic interaction arising from CMC(degree of substitution; DS 0.7). Although the adsorption amount of CMC (DS 0.7) onto the silicon surface is comparable to that of PAA, its effect on particle dispersion is significantly different. The agglomeration mechanism is systematically explored in terms of polymer-polymer and particle-polymer interactions by varying the DS of CMC and the pH of the suspensions. We demonstrate that the attraction between polymers adsorbed on the silicon surface and the affinity between the particle and polymer determine the degree of silicon agglomeration. The hydrophobic attraction of CMC(DS 0.7) promotes silicon agglomeration significantly, whereas CMC(DS 1.2) deficient in attraction disperses silicon particles well. Silicon particles weakly agglomerate in Si/PAA suspensions due to hydrogen bonding between PAA chains and due to the high affinity between PAA and the silicon surface. The dispersion of Si/CMC(DS 0.7 or 1.2)/PAA suspensions is primarily dominated by PAA through its high affinity with silicon and corresponding favorable adsorption on the silicon surface. This is the first attempt to quantitatively assess and compare the impact of CMC and PAA on the agglomeration behavior of silicon particles and reveal the underlying mechanism. This paper provides a fundamental understanding to control the dispersion homogeneity and stability of silicon-containing electrodes.

How Tuning Interfaces Impacts the Dynamics and Structure of Polymer Nanocomposites Simultaneously

Fundamental understanding of the macroscopic properties of polymer nanocomposites (PNCs) remains difficult due to the complex interplay of microscopic dynamics and structure, namely interfacial layer relaxations and three-dimensional nanoparticle (NP) arrangements. The effect of surface modification by alkyl methoxysilanes at different grafting densities has been studied in PNCs made of poly(2-vinylpyridine) and spherical 20 nm silica NPs. The segmental dynamics has been probed by broadband dielectric spectroscopy and the filler structure by small-angle X-ray scattering and reverse Monte Carlo simulations. By combining the particle configurations with the interfacial layer properties, it is shown how surface modification tunes the attractive polymer-particle interactions: bare NPs slow down the polymer interfacial layer dynamics over a thickness of ca. 5 nm, while grafting screens these interactions. Our analysis of interparticle spacings and segmental dynamics provides unprecedented insights into the effect of surface modification on the main characteristics of PNCs: particle interactions and polymer interfacial layers.

Understanding the Rheology of Polymer–Polymer Interfaces Covered with Janus Nanoparticles: Polymer Blends versus Particle Sandwiched Multilayers

Interfacial rheology is crucial in dictating morphology and ultimate properties of particle-stabilized polymer blends, but is challenging to be determined. In this study, a fully polymeric dumbbell-shaped Janus nanoparticle (JNP) of polymethyl methacrylate (PMMA) and polystyrene (PS) spheres with equal sizes (∼80 nm) was prepared and used as an efficient compatibilizer for PMMA/PS blends. The JNPs were preferentially localized at the PMMA/PS interface, thereby reducing the interfacial tension and refining the morphology in both droplet-matrix and co-continuous type blends, whereby a JNP concentration ∼2.5 wt % is sufficient to reach a saturation in droplet size reduction due to compatibilization. Based on the linear viscoelastic moduli and corresponding relaxation spectra (H(τ)*τ) of JNP-compatibilized droplet-matrix blends, besides the droplet shape relaxation time (τF), a longer relaxation time (τβ), typically related to interfacial viscoelasticity, was readily identified. The dependence of τβ on the JNP concentration (WJNPs) was significantly dominated by the droplet size reduction induced by the JNP compatibilization, with τβ decreasing with increasing WJNPs. The viscoelastic properties extracted from τβ typically originate from a combination of gradients in interfacial tension due to the particle redistribution at the droplet interface (Marangoni stresses) and the deviatoric stresses of intrinsic rheological origin. The latter originate from the intrinsic viscoelasticity of the particle-laden interface, which is enhanced by particle jamming and particle–polymer interactions, such as entanglements between chains from the polymeric spheres and those penetrating from the bulk into the spheres. To address the challenge of isolating these contributions, a JNP-sandwiched PMMA/PS multilayer structure was designed to exclude the effect of Marangoni stresses and droplet curvature, thus having no τF but a new relaxation (τ′β), which characterizes the contribution of intrinsic interfacial viscoelasticity. The τ′β was observed to increase with JNP coverage (Σ) following the Vogel–Fulcher–Tammann model that is typically used to describe the divergent behavior of the “cage” effect in classical colloidal glasses. Moreover, a multimode Maxwell model fitting allows to split the interfacial relaxation into the confined diffusion of JNPs within their cage and the entanglements between the JNPs and the bulk.

Investigation into Mechanical Behavior of Air-Hardening Organic Polymer-Stabilized Silty Sand

Air-hardening organic polymer (AHOP), a new soil stabilizer, can form a cross-link among soil particles with high strength and toughness. In this study, the effect of the polymer content and density on the mechanical behavior of stabilized silty sand was investigated. The results indicate that the unconfined compressive strength and tensile strength of stabilized silty sand keep a prominent linear relationship with AHOP content that increases with the increment in density; the increment in AHOP content also leads to a higher elastic modulus of stabilized silty sand. The cohesion was also significantly enhanced by the increase in AHOP content and density; the internal friction angle of loose specimens (ρ≤1.50 g/cm3) keeps increasing with AHOP content; however, for dense specimens (ρ≥1.55 g/cm3), 3% polymer content is a turning point, at which the internal friction angle changes nonmonotonically. AHOP film can connect loose silty sand particles and adhere to the surface of particles, leading to silty sand with good strength properties. Based on failure modes, the failure of polymer–particle interactions can be divided into four modes, including (1) tensile fracture at membrane, (2) tensile fracture at polymer–particle interface, (3) shear at membrane, and (4) shear at polymer–particle interface.

Heterogeneous Percolation in Poly(methylvinylsiloxane)/Silica Nanocomposites: The Role of Polymer–Particle Interaction

Agglomeration and linking of nanoparticles or aggregates lead to the formation of percolated particle networks and alter the mechanical enhancement in polymer nanocomposites. Although critical behaviors have been widely studied, the solidlike behavior is only well described under the condition of the uniform dispersion of nanoparticles. In this work, we illustrate the role of particle–polymer interaction in the uniformity of particle dispersion and mechanical enhancement. Two types of silica with different interfacial adhesion energies with poly(methylvinylsiloxane) were adopted, resulting in different uniformities of particle dispersion. The critical percolation concentrations from the yield shear stress and yield first normal stress difference are identical. A lower interfacial adhesion energy leads to a higher critical concentration. The preshear stress only affects the critical concentration but does not change the critical exponents, which rely on the particle–polymer interaction. The mechanical enhancement, expressed as the power-law dependence of the yield stresses on the filler content, exhibits extraordinarily large power-law exponents for nanocomposites with lower interfacial adhesion energy, seriously deviating from the theoretical prediction in homogeneous dispersion systems. Based on the structural information from small-angle X-ray scattering (SAXS)/ultrasmall-angle X-ray scattering (USAXS) and transmission electron microscopy (TEM), we propose a model describing the heterogeneous percolation of loose aggregates in the presence of compact aggregates. This model shows that the heterogeneity of aggregates, including the fraction of compact aggregates and their fractal dimension, is the key factor in the scaling relationship between the yield stress and the particle volume fraction.

Network‐Nanostructured ZIF‐8 to Enable Percolation for Enhanced Gas Transport

AbstractMembrane‐based separations offer energy‐efficient solutions for various applications, but commercial polymer membranes show limited performance and stability. Mixed‐matrix membranes (MMMs), incorporating nanoporous inorganic materials in polymer matrices, have been of great interest to circumvent these polymer‐specific issues. However, reaching the percolation threshold is crucial to leverage high‐performing inorganic phases fully, yet the traditional sphere‐like nanofillers require high loadings that easily result in agglomerations and non‐selective defects. Here, a branch‐shaped zeolitic imidazole framework‐8 (ZIF‐8) nanoparticle is synthesized where its unique morphology automatically interconnects, readily forming percolated networks within the polymer matrix at loadings as low as 20 wt.%. Because of the high surface‐area‐to‐volume ratios of branched ZIF‐8 (BZ), strong polymer–particle interactions suppress polymer chain dynamics and the rotation of the ZIF‐8 ligand. This interphase confinement results in enhanced membrane stability and a smaller diffusion cut‐off than traditional ZIF‐8. With pre‐connected diffusion pathways and confined ZIF pores, BZ MMMs significantly outperformed MMMs with sphere‐like ZIF‐8 for H2‐based separations. Overall, the findings provide a novel approach to enhance filler effects in MMMs even at low loadings without any alignment, which can enable the development of advanced membranes in fields where percolation is desired, including separations, sensors, conductors, and batteries.

Hybrid Time-Dependent Ginzburg-Landau Simulations of Block Copolymer Nanocomposites: Nanoparticle Anisotropy.

Block copolymer melts are perfect candidates to template the position of colloidal nanoparticles in the nanoscale, on top of their well-known suitability for lithography applications. This is due to their ability to self-assemble into periodic ordered structures, in which nanoparticles can segregate depending on the polymer–particle interactions, size and shape. The resulting coassembled structure can be highly ordered as a combination of both the polymeric and colloidal properties. The time-dependent Ginzburg–Landau model for the block copolymer was combined with Brownian dynamics for nanoparticles, resulting in an efficient mesoscopic model to study the complex behaviour of block copolymer nanocomposites. This review covers recent developments of the time-dependent Ginzburg–Landau/Brownian dynamics scheme. This includes efforts to parallelise the numerical scheme and applications of the model. The validity of the model is studied by comparing simulation and experimental results for isotropic nanoparticles. Extensions to simulate nonspherical and inhomogeneous nanoparticles are discussed and simulation results are discussed. The time-dependent Ginzburg–Landau/Brownian dynamics scheme is shown to be a flexible method which can account for the relatively large system sizes required to study block copolymer nanocomposite systems, while being easily extensible to simulate nonspherical nanoparticles.

Simultaneous effects of agglomeration and interfacial defects on gas transport properties in nanocomposites: A novel modeling approach

In this study, a novel modeling approach for gas permeability predictionhas been proposed. For the first time, simultaneous effects of particle agglomeration andinterfaciallayerhave been considereddirectly in the model formula. The results show that the model fits well with the experimental data due to considering both particle agglomeration andinterfacialshell layer. For instance, average absolute relative error (AARE) has been decreased from 51% to 0.73% for O2 permeability throughpolyethersulfone(PES)/Zeolite4Amixed matrix membrane (MMM). Also,the precision ofthe proposed model is nearly more than 95% forall thestudied cases showing the great potential of this modelin the prediction ofMMMspermeability.The output of this study will help chemical engineers tofabricateMMMswith optimal permeability and selectivity and togeta better insight into particle–particle and particle-polymer interactions.

Rigid Amorphous Fraction as an Indicator for Polymer-Polymer Interactions in Highly Filled Plastics.

Above a percolation threshold a flow restriction has to be overcome by higher pressure in plastic processing. Besides amount and geometry of fillers, the interactions of polymer and filler are important. By differing the amorphous phase of polymers into a rigid amorphous and a mobile amorphous fraction, predictions about interactions are possible. The objective is the generation of a flow restriction and the combined investigation of polymer–particle interaction. SiO2 was used up to 50 vol.% in different spherical sizes in PLA and PP. A capillary-rheometer was used as a tool to create a yield point and by that investigations into the state of the flow restriction were possible. All produced compounds showed, in plate-plate rheometry, an increase in viscosity for lower shear rates and a significant change in the storage modulus. In DSC, hardly any specific rigid amorphous fraction was detectable, which suggests that there is a minor interaction between macromolecules and filler. This leads to the conclusion that the change in flow behavior is mainly caused by a direct interaction between the particles, even though they are theoretically too far away from each other. First images in the state of the yield point show a displacement of the particles against each other.

Nanoparticle Assembly in High Polymer Concentration Solutions Increases Superlattice Stability.

Polymer nanocomposites are made by combining a nanoscale filler with a polymer matrix, where polymer-particle interactions can enhance matrix properties and introduce behaviors distinct from either component. Manipulating particle organization within a composite potentially allows for better control over polymer-particle interactions, and the formation of ordered arrays can introduce new, emergent properties not observed in random composites. However, self-assembly of ordered particle arrays typically requires weak interparticle interactions to prevent kinetic traps, making these assemblies incompatible with most conventional processing techniques. As a result, more fundamental investigations are needed into methods to provide additional stability to these lattices without disrupting their internal organization. The authors show that the addition of free polymer chains to the assembly solution is a simple means to increase the stability of nanoparticle superlattices against thermal dissociation. By adding high concentrations (>50mgmL-1 ) of free polymer to nanoparticle superlattices, it is possible to significantly elevate their thermal stability without adversely affecting ordering. Moreover, polymer topology, molecular weight, and concentration can also be used as independent design handles to tune this behavior. Collectively, this work allows for a wider range of processing conditions for generating future nanocomposites with complete control over particle organization within the material.

Tailoring Therapeutic Responses via Engineering Microenvironments with a Novel Synthetic Fluid Gel.

This study reports the first fully synthetic fluid gel (SyMGels) using a simple poly(ethylene glycol) polymer. Fluid gels are an interesting class of materials: structured during gelation via shear-confinement to form microparticulate suspensions, through a bottom-up approach. Structuring in this way, when compared to first forming a gel and subsequently breaking it down, results in the formation of a particulate dispersion with particles "grown" in the shear flow. Resultantly, systems form a complex microstructure, where gelled particles concentrate remaining non-gelled polymer within the continuous phase, creating an amorphous-like interstitial phase. As such, these materials demonstrate mechanical characteristics typical of colloidal glasses, presenting solid-like behaviors at rest with defined yielding; likely through intrinsic particle-particle and particle-polymer interactions. To date, fluid gels have been fabricated using polysaccharides with relatively complex chemistries, making further modifications challenging. SyMGels are easily functionalised, using simple click-chemistry. This chemical flexibility, allows the creation of microenvironments with discrete biological decoration. Cellular control is demonstrated using MSC (mesenchymal stem cells)/chondrocytes and enables the regulation of key biomarkers such as aggrecan and SOX9. These potential therapeutic platforms demonstrate an important advancement in the biomaterial field, underpinning the mechanisms which drive their mechanical properties, and providing a versatile delivery system for advanced therapeutics.

Toward Optimizing Electrospun Nanofiber Fuel Cell Catalyst Layers: Polymer–Particle Interactions and Spinnability

We investigate the effect of the poly(acrylic acid) (PAA) carrier polymer concentration on the microstructure and rheological properties of catalyst inks for electrospun polymer–electrolyte membran...

Mechanical and thermal properties of modified Georgian and Brazilian clay infused biobased epoxy nanocomposites

This study focuses on the preparation and characterization of nanocomposite system with bio-based epoxy resin (Super SAP 100/1000, contains 37% bio-based carbon content) and natural clays including Georgian clay and Brazilian clay. Georgian clay was surface modified using an ultrasound processing in presence of Decalin. Brazilian clay was modified to organophilic bentonite using quaternary ammonium salts. The resulting nano clay particles were characterized using XRD and TEM to confirm the particle size reduction and uniform distribution. The as-fabricated nanocomposites were characterized using flexure, DMA, TMA and TGA. The flexure analysis showed that the modified clay composites have significant improvement in strength (23–38%) and modulus (28–37%). Delayed thermal degradation was observed from TGA analysis which showed that the major degradation temperatures improved from 7°-25°C. DMA and TMA analysis showed improvements in storage moduli (4–6%) and coefficient of thermal expansion (CTE) (6–64%), respectively. The notable improvement in thermal and mechanical properties suggested the effective dispersion and the high degree of polymer particle interaction. The bio based content present in the Super Sap 100/1000 acts as plasticizer resulting in the extensive ductility of the polymer.

Silica particles incorporated into PLGA-based in situ-forming implants exploit the dual advantage of sustained release and particulate delivery

Poly (lactic-co-glycolic acid) (PLGA) in situ-forming implants are well-established drug delivery systems for controlled drug release over weeks up to months. To prevent initial burst release, which is still a major issue associated with PLGA-based implants, drugs attached to particulate carriers have been encapsulated. Unfortunately, former studies only investigated the resulting release of the soluble drugs and hence missed the potential offered by particulate drug release. In this study, we developed a system capable of releasing functional drug-carrying particles over a prolonged time. First, we evaluated the feasibility of our approach by encapsulating silica particles of different sizes (500 nm and 1 μm) and surface properties (OH or NH2 groups) into in situ-forming PLGA implants. In this way, we achieved sustained release of particles over periods ranging from 30 to 70 days. OH-carrying particles were released much more quickly when compared to NH2-modified particles. We demonstrated that the underlying release mechanisms involve size-dependent diffusion and polymer-particle interactions. Second, particles that carried covalently-attached ovalbumin (OVA) on their surfaces were incorporated into the implant. We demonstrated that OVA was released in association with the particles as functional entities over a period of 30 days. The released particle-drug conjugates maintained their colloidal stability and were efficiently taken up by antigen presenting cells. This system consisting of particles incorporated into PLGA-based in situ-forming implants offers the dual advantage of sustained and particulate release of drugs as a functional unit and has potential for future use in many applications, particularly in single-dose vaccines.

Characterization of the polymer/particle interphase in composite materials by molecular probing

In this study, a new method was developed for the characterization of the interface morphology in polymer/particle composites. This method, not limited to a specific polymer or particle, utilizes the gas permeability of the composites to determine the interfacial properties such as the type of polymer-particle interactions as well as the thickness and the transport properties of the interphase. Moreover, it can be employed to determine the size of the aggregates in the case of particle aggregation. The proposed method was evaluated by comparing its results with the findings of the small-angle X-ray scattering (SAXS) analysis for polyethersulfone (PES)-based composites containing pristine and fumed silica nanoparticles. Our method was also evaluated by analyzing the results of other studies obtained from the literature.