Bulk Polymer Materials Research Articles

Preferential Mechanochemical Activation of Short Chains in Bidisperse Triblock Elastomers.

Polymer mechanochemistry offers attractive opportunities for using macroscopic forces to drive molecular-scale chemical transformations, but achieving efficient activation in bulk polymeric materials has remained challenging. Understanding how the structure and topology of polymer networks impact molecular-scale force distributions is critical for addressing this problem. Here we show that in block copolymer elastomers the molecular-scale force distributions and mechanochemical activation yields are strongly impacted by the molecular weight distribution of the polymers. We prepare bidisperse triblock copolymer elastomers with spiropyran mechanophores placed in either the short chains, the long chains, or both and show that the overall mechanochemical activation of the materials is dominated by the short chains. Molecular dynamics simulations reveal that this preferential activation occurs because pinning of the ends of the elastically effective midblocks to the glassy/rubbery interface forces early extension of the short chains. These results suggest that microphase segregation and network strand dispersity play a critical role in determining molecular-scale force distributions and suggest that selective placement of mechanophores in microphase-segregated polymers is a promising design strategy for efficient mechanochemical activation in bulk materials.

Responsive polymer thin films

Responsive polymer thin films

Single-Chain Mechanics at Low Temperatures: A Study of Three Kinds of Polymers from 153 to 300 K

The single-chain mechanics of three kinds of polymers (i.e., polydimethylsiloxane, polyoxymethylene, and poly(methyl methacrylate)) has been investigated from room temperature to 153 K by atomic force microscopy-based single-molecule force spectroscopy in high vacuum and a theoretical model. The stretched part of the individual polymer chain can be regarded as an isolated chain. In the broad range of temperature, the isolated chain shows a gradual change in single-chain mechanics, which can be depicted nicely by an elastic model. Further analysis shows that with thermal fluctuation, the single bonds (e.g., Si–O or C–O) in the backbone of an isolated chain can rotate freely in the temperature range in the timescale of single-molecule manipulation. To our best knowledge, this is the first experimental study on the single-chain mechanics at cryogenic temperatures, which validates the theoretical prediction that the transition temperature of an isolated chain is much lower than that of the corresponding bulk polymer material.

Investigating the Physicochemical Property Changes of Plastic Packaging Exposed to UV Irradiation and Different Aqueous Environments

A wide range of weathering processes contributes to the degradation of plastic litter items which leads to the formation of microplastics that may be detrimental to marine ecosystems and the organisms inhabiting them. In this study, the impact of UV exposure on the degradation of clear polypropylene (CPP), black polypropylene (BPP), and polyethylene terephthalate (PET) packaging materials was investigated over a period of 6 weeks under dry air conditions representing the terrestrial environment. The exposure was conducted using differently sized and shaped samples at irradiation intensities of 65 W/m2 and 130 W/m2. Results indicated that UV irradiation led to changes in the properties of PET, BPP, and CPP that were proportional to the intensity delivered, leading to a higher level of mass loss, carbonyl indices, crystallinities, and microhardness in all polymer types at 130 W/m2 relative to 65 W/m2. However, material shape and size did not have a significant influence on any property for any of the test materials. Increased mass loss over time was accompanied by considerable increases in carbonyl index (CI) for both PPs. Clear PP (CPP) underwent the most severe degradation, resulting in the highest mass loss, increase in crystallinity, and CI. BPP was less degraded and modified by the UV irradiation than the CPP, indicating that the colorant, carbon black, provided some degree of protection to the bulk polymer material. PET was the least degraded of the three materials, suggesting this polymer type is more resistant to UV degradation. The differences in the degradation behaviours of the three test materials under dry environmental conditions indicate that the UV exposure history of plastic litter might play an important role in its potential for further degradation once it reaches the marine environment. Furthermore, analysis of samples exposed to UV in aqueous media reveals a more irregular set of trends for most material properties measured. Overall, the degree of degradation resulting from UV irradiation in dry environments was more pronounced than in aqueous environments, although the most significant property changes were observed for materials without previous UV exposure histories. Samples with previous UV histories showed higher resistance to further crystallinity changes, which appeared to be due to crosslinking in the pretreatment exposures inhibiting chain alignment into crystalline structures. The effect of solution medium was insignificant, although the presence of water allowed hydrolytic degradation to proceed simultaneously with UV degradation for PET. The reduction of CI in pretreated materials in the aqueous exposures, combined with the mass loss, suggest that the degraded surface layer erodes or products dissolve into surrounding solution medium, leaving a fresh surface of plastic exposed.

Investigation of Insulation Properties Using Microwave Nondevastating Methodology to Predict the Strength of Polymer Materials

The study was extended and developed to predict the roughness of polymer-based materials using the latest data mining techniques. Different types of particles are used in polymer-based materials, which characterize the roughness of polymer-based materials. The research study focused on predicting the roughness of bulk polymer materials using fly ash. Fly ash is an alternative material that is used to replace both cement and fine aggregate to some extent. Particles such as silica fume, limestone, and slag have been used in place of concrete, but flash has received more attention than other elements. It is important to express the insulation properties of polymer materials using the microwave nondevastative method. Finally, this article concludes by predicting the strength of polymer materials by measuring insulation properties using the microwave nondevastative method.

Unclonable Features via Electrospraying of Bulk Polymers

The ability to encode unclonable information using low-cost materials and processes is of significant interest for anti-counterfeiting and information security applications. In this study, we present a versatile approach based on electrospraying of polymer solutions to generate randomly positioned complex features as a form of physically unclonable function (PUF). The key advantage of this approach is that readily available low-cost bulk polymeric materials can form small and complex features using a simple process. Polymers of varying composition and molecular weight, together with different solvents and electrospraying conditions, are systematically explored to construct the parameter space for PUFs of varying characteristics. Besides the randomness in the spatial positions and sizes of features, the key advantage of the presented approach is the ability to generate complex 3D shapes, which are very difficult, if not impossible to fabricate with the most advanced fabrication techniques. The inclusion of photoluminescent molecules establishes an additional security layer. The additive nature of operation enables multiplexing, i.e., deposition of multiple materials on the same substrate. The fabricated PUFs have an average uniformity of 0.533 and uniqueness of 0.495, which are highly close to an ideal value of 0.5. The authentication is effectively performed using a feature detection algorithm without the need for markers and precisely defined rotation angles, greatly relaxing constraints associated with the imaging. Direct application of PUFs on the label of goods and authentication via a handheld microscope demonstrate the practical utility of the presented approach.

Nanoarchitectonics and applications of artificial molecular machines in smart polymer materials

Artificial molecular machine is one of the most brilliant areas in the last half a century. They represent people's control abilities to the microscopic molecules in solution. Beside the hard works in the proof-of-concept research on the exploration of fundamental principles, the wide hybrid of them with diverse materials was confirmed. Through the coupling of these movable molecules with various materials, the microscopic motion of molecular machines could be easily translated and amplified to macroscopic world to produce useful work. The integration further improves the ability of us to control the molecules in solid state. Among the various materials, polymers have the widest applications in many areas. The incorporation of artificial molecular machines into the bulk polymer materials would produce more influence on our life in the near future. In this review, we summarized the proofed hybrid strategies of polymers with different molecular machines. We hope that the summarization could provide a research roadmap for the related researchers.

Unraveling Sequence Effect on Glass Transition Temperatures of Discrete Unconjugated Oligomers.

Sequence plays a critical role in enabling unique properties and functions of natural biomolecules, which has promoted the rapid advancement of synthetic sequence-defined polymers in recent decades. Particularly, investigation of short chain sequence-defined oligomers (also called discrete oligomers) on their properties has become a hot topic. However, most studies have focused on discrete oligomers with conjugated structures. In contrast, unconjugated oligomers remain relatively underexplored. In this study, three pairs of discrete oligomers with the same composition but different sequence for each pair are employed for investigating their glass transition temperatures (Tg s). The resultant Tg s of sequenced oligomers in each pair are found to be significantly different (up to 11.6°C), attributable to variations in molecular packing as demonstrated by molecular dynamics and density function theory simulations. Intermolecular interaction is demonstrated to have less impact on Tg s than intramolecular interaction. The mechanistic investigation into two model dimers suggests that monomer sequence caused the difference in intramolecular rotational flexibility of the sequenced oligomers. In addition, despite having different monomer sequence and Tg s, the oligomers have very similar solubility parameters, which supports their potential use as effective oligomeric plasticizers to tune the Tg s of bulk polymer materials.

A molecular view of plasticization of polyvinyl alcohol.

Although macromolecules such as polymers are in widespread industrial use, pure formulations rarely have precisely the properties new applications demand. Pure polymer is often too brittle and inflexible, necessitating plasticizers to soften or toughen films and bulk polymer materials. In practice, new formulations are developed by extensive trial-and-error methods, as no general molecular explanations exist for the mechanism of plasticization to aid in determining the optimal structure and concentration of plasticizers. Here, through atomistic molecular simulations augmented with advanced sampling techniques, we develop an atomic-level picture of the processes in plasticization by directly calculating free energies that govern the interaction between polymers and small-molecule plasticizers. This work focuses on the influence of two common plasticizer molecules-glycerol and sorbitol-interacting with polyvinyl alcohol (PVA), a frequently used component of polymer films. In particular, we focus on conformational and hydrogen bond structure changes induced in globules of PVA by the plasticizer molecules, with the hypothesis that hydrogen bonding plays a role in the incorporation of these plasticizers into PVA and, thus, in the observed mechanical properties. While we focus on nanoscopic systems, we observe distinct preferences in the conformational free energy that can be connected to the performance of polymer materials at laboratory and industrial scales. This work presents a new molecular perspective from which effective plasticizers can be developed and presents a firm basis from which important analyses of plasticization in complex chemical environments relevant to industry may be developed.

Entropy-Driven Ultratough Blends from Brittle Polymers.

Polymer blends with synergetic performance play an integral part in modern society. The discovery of compatible polymer systems often relies on strong chemical interactions. By contrast, the role of entropy in polymers is often neglected. In this work, we show that entropy effect could control the phase structure and mechanical behaviors of polymer blends. For weakly interacting polymer pairs, the seemingly small mixing entropy favors the formation of nanoscale cocontinuous structures. The abundant nanointerfaces could initiate large plastic deformations by crazing or shear, thus, transforming brittle polymers (elongation < 9%) into superductile materials (elongation ∼ 146%). The resultant polymer blends display high transparency, strength (∼70 MPa), and toughness (∼60 MJ/m3) beyond most engineering plastics. The principle of entropy-driven blends may also be applied in other polymer systems, offering a strategy to develop mechanically robust bulk polymeric materials for emerging applications such as biomedicine and electronics.

Damage in extrusion additive manufactured biomedical polymer: Effects of testing direction and environment during cyclic loading

Although biodegradable polymers were widely researched, this is the first study considering the effect of combined testing environments and cyclic loading on the most important aspect related to additive manufacturing: the interfacial bond between deposited layers. Its results give confidence in applicability of the material extrusion additive manufacturing technology for biomedical fields, by demonstrating that the interface behaves in a manner similar to that of the bulk-polymer material. To do this, especially designed tensile specimens were used to analyse the degradation of 3D-printed polymers subjected to constant-amplitude and incremental cyclic loads when tested in air at room temperature (control) and submerged at 37 °C (close to in-vivo conditions). The mechanical properties of the interface between extruded filaments were compared against the bulk material, i.e. along filaments. In both cases, cyclic loading caused only a negligible detrimental effect compared to non-cyclic loading (less than 10 % difference in ultimate tensile strength), demonstrating the suitability of using 3D-printed components in biomedical applications, usually exposed to cyclic loading. For cyclic tests with a constant loading amplitude, larger residual deformation (>100 % greater) and energy dissipation (>15 % greater) were found when testing submerged in solution at 37 °C as opposed to in laboratory conditions (air at room temperature), as used by many studies. This difference may be due to plasticisation effects of water and temperature. For cyclic tests with incrementally increasing loading amplitudes, the vast majority of energy dissipation happened in the last two cycles prior to failure, when the polymer approached the yield point. The results demonstrate the importance of using an appropriate methodology for biomedical applications; otherwise, mechanical properties may be overestimated.

Kinetically Controlled Formation of Semi-crystalline Conjugated Polymer Nanostructures

Conjugated polymer (CP) materials that are considered as an attractive choice for various electronic and optoelectronic applications possess highly heterogeneous complex structures that can span several orders of magnitude in length scale. This is due to the intricate coupling effects of weak secondary interactions and entropic forces that determine molecular organization in bulk polymer materials. Understanding the influence of molecular interactions on the emergence and evolution of nano- and microscale structures is of paramount importance to the guided design and development of condensed CP materials. Such understanding is even more critical for the rational design of hierarchical systems away from equilibrium, where weak molecular interactions can guide the system along competing kinetic pathways toward local energy minima and metastable architectures. In this work, we studied a promising concept for accessing various kinetically stabilized semi-crystalline CP nanostructures that are formed in the process of controlled chain-growth Kumada catalyst-transfer polymerization initiated by a small-molecule catalytic species which can exist in equilibrium between free and aggregated states. Specifically, we chose a small-molecule perylenedicarboximide (PDCI) polymerization catalytic initiator which has a strong tendency toward reversible supramolecular assembly–disassembly that can be controlled by temperature. Addition of a thiophene monomer to a solution of the PDCI initiator starts the chain-growth polymerization process, which produces distinct nanoscale semi-crystalline polythiophene structures formed under predominant kinetic control. We demonstrated that, depending on the reaction temperature (which affects the fine balance between the position of PDCI assembly–disassembly equilibrium, rate of polymerization, and solvent–solute interactions for the growing polythiophene chains), a range of kinetically trapped hierarchically organized semi-crystalline CP systems with substantially varying optoelectronic properties could be obtained. In addition to spectroscopic and electron microscopic studies, in order to better reveal the structural aspects of the generated polymer nanoscale systems, we carried out a series of X-ray diffraction and neutron scattering experiments which indicated complex hierarchical organization in these kinetically stabilized CP assembled materials. We expect that this in situ polymerization-based approach can lead to a general way to expand access to various semi-crystalline CP nanostructured materials with broadly tunable electronic and optical properties.

Phosphonium Tetraphenylborate: A Photocatalyst for Visible-Light-Induced, Nucleophile-Initiated Thiol-Michael Addition Photopolymerization.

A photoinitiation system that utilizes phosphonium tetraphenylborate as the key component was developed for the visible light-triggered nucleophile-catalyzed thiol-Michael addition reaction. This highly reactive catalyst was composed of a photocaged phosphine (methyldiphenylphosphonium tetraphenylborate, MDPP·HBPh4), a photosensitizer (isopropylthioxanthone, ITX), and a radical scavenger (TEMPO). Unlike the prevailing photobase catalysts, this photoactivatable phosphine system triggers the thiol-Michael addition polymerization by a nucleophile-catalyzed mechanism and provides a controlled stoichiometric reaction between the thiol and the vinyl precursors. This approach enables the formation of homogeneous polymer networks upon low-energy visible light exposure and, thus, broadens its potential applications in bulk polymer materials synthesis and UV-sensitive bioscaffold formation.

Mechanical performance of 3D printed polylactide during degradation

Although widely-used biodegradable polymers have been extensively studied for conventional manufacturing processes, this is the first study considering the effect of interfacial bonds between extruded filaments – the most important aspect related to additive manufacturing – on degradation at 37 °C. Its results improve the confidence in the material extrusion additive manufacturing process and negate one of the crucial unknown factors for bioresorbable products, by demonstrating that the interface degrades in a similar manner to the bulk polymer material. To do this, specially designed micro-tensile specimens were developed to analyse the degradation of 3D-printed parts for the first time at 37 °C and accelerated temperatures. The mechanical properties of the interface between extruded filaments (Z specimen) were compared against the control, i.e. along filaments (F specimen), under medically relevant testing conditions (submerged at 37 °C). Monitoring the degradation of tensile strength showed that both specimen types behaved similarly, exhibiting an initial delay followed by a reduction in properties. Comparison of thermal and chemical properties revealed that during the early stage of degradation, crystallinity was the dominating factor, whilst at later stages, mechanical properties were mainly defined by the molecular weight and autocatalytic degradation. The findings suggest that understanding developed in the long-standing field of polymer degradation can be applied to additive-manufactured medical devices, which unavoidably contain interlayer interfaces.

Poly(2-oxazoline) Matrices with Temperature-Dependent Solubility-Interactions with Water and Use for Cell Culture.

In this work, we studied the stability of matrices with temperature-dependent solubility and their interactions with water at physiological temperature for their application in cell culture in vitro. Gradient copolymers of 2-isopropyl- with 2-n-propyl-2-oxazoline (P(iPrOx-nPrOx)) were used to prepare the matrices. The comonomer ratio during polymerization was chosen such that the cloud point temperature (TCP) of the copolymer was below 37 °C while the glass transition (Tg) was above 37 °C. The role of the support for matrices in the context of their stability in aqueous solution was examined. Therefore, matrices in the form of both self-supported bulk polymer materials (fibrillar mats and molds) and polymer films supported on the silica slides were examined. All of the matrices remained undissolved when incubated in water at a temperature above TCP. For the self-supported mats and molds, we observed the loss of shape stability, but, in the case of films supported on silica slides, only slight changes in morphology were observed. For a more in-depth investigation of the origin of the shape deformation of self-supported matrices, we analyzed the wettability, thickness, and water uptake of films on silica support because the matrices remained undeformed under these conditions. It was found that, above the TCP of P(iPrOx-nPrOx), the wettability of the films decreased, but at the same time the films absorbed water and swelled. We examined how this specific behavior of the supported films influenced the culture of fibroblasts. The temperature-dependent solubility of the matrices and the possibility of noninvasive cell separation were also examined.

Persistence of plastic debris and its colonization by bacterial communities after two decades on the abyssal seafloor

The fate of plastic debris entering the oceans is largely unconstrained. Currently, intensified research is devoted to the abiotic and microbial degradation of plastic floating near the ocean surface for an extended period of time. In contrast, the impacts of environmental conditions in the deep sea on polymer properties and rigidity are virtually unknown. Here, we present unique results of plastic items identified to have been introduced into deep-sea sediments at a water depth of 4150 m in the eastern equatorial Pacific Ocean more than two decades ago. The results, including optical, spectroscopic, physical and microbial analyses, clearly demonstrate that the bulk polymer materials show no apparent sign of physical or chemical degradation. Solely the polymer surface layers showed reduced hydrophobicity, presumably caused by microbial colonization. The bacterial community present on the plastic items differed significantly (p < 0.1%) from those of the adjacent natural environment by a dominant presence of groups requiring steep redox gradients (Mesorhizobium, Sulfurimonas) and a remarkable decrease in diversity. The establishment of chemical gradients across the polymer surfaces presumably caused these conditions. Our findings suggest that plastic is stable over extended times under deep-sea conditions and that prolonged deposition of polymer items at the seafloor may induce local oxygen depletion at the sediment-water interface.

Tuning CO2-induced reversible redispersion or irreversible destabilisation for latex separation

HypothesisThe CO2-sensitive dispersion/precipitation transition of polymer latexes fabricated based on a responsive emulsifier is a promising way to conveniently acquire bulk polymer materials. Nevertheless, the tedious synthesis procedures for switchable surfactants and the harsh operating requirements for the sensitive latexes constrain the applicability of the approach for latex preparation. Therefore, a new strategy for generating latexes with tunable CO2 responsiveness in a maneuverable way is urgently needed. ExperimentsIn this work, a CO2-switchable electrostatic interaction is introduced to construct responsive latexes. A series of lightly crosslinked poly(diethylaminoethyl methacrylate-styrene) [P(DEA-St)] latexes with different PDEA contents were fabricated via one-pot emulsion copolymerization, with divinylbenzene and sodium dodecylsulfate (SDS) used as the crosslinker and anionic emulsifier, respectively. The influence of the DEA feeding ratio on the resulting P(DEA-St) colloids was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. Then, a cyclic CO2/N2 input was introduced to verify the response transitions of polymer latexes. FindingsAccompanied by the stepwise decrease of DEA feeding ratio, the morphology of the resulting copolymerized nanoparticles changed from an ambiguous bulge to the typical spherical pattern. In addition, the P(DEA-St) latexes treated by cyclic CO2/N2 exhibit four different types of response modes, namely (i) CO2-switchable swelling/deswelling transition, (ii) CO2-reversible dispersion/coagulation transition, (iii) CO2-induced irreversible destabilisation and (iv) CO2-insensitive latexes. The CO2-responsive destabilisation is highly applicable in the separation and transportation fields of commercial latex products, such as poly(methyl methacrylate), poly(n-butyl acrylate) and poly(butyl methacrylate) colloids.

Mechanical Reactivity of Two Different Spiropyran Mechanophores in Polydimethylsiloxane

We investigate the effect of pulling point location on the mechanochemical activation of two isomers of spiropyran in cross-linked polymeric materials through computational calculations and in situ fluorescence measurements. The threshold stress and strain required to activate the spiropyran mechanophores under tensile load are characterized. For both spiropyran isomers, applied stress favors the activated merocyanine states; however, despite differences in mechanochemical behavior predicted by quantum chemical calculations and previous single molecule experiments, both spiropyran isomers exhibit similar mechanochemical reactivity in bulk polymeric materials. The kinetics of the spiropyran–merocyanine transition under different tensile stresses are also examined. Overall, we find that varying the pulling geometry on the spiropyran mechanophore has only a minimal effect on the mechanical activation in bulk polymeric materials due to the complex nature of the macroscopic system.

Mechanochemical Activation of Fluorogenic CuAAC "Click" Reactions for Stress-Sensing Applications.

Strategies for visualizing stress within polymeric materials are of growing interest during the past decade. In this paper, stress-sensing materials, triggered by a mechanoresponsive catalytic system based on latent copper(I)bis(N-heterocyclic carbene) mechanophores, are reported, which can be activated by compression force to trigger a fluorogenic copper(I)-catalyzed alkyne/azide "click" cycloaddition reaction, activating a fluorescent dye useful for stress-sensing applications in bulk polymeric materials. The focus is placed on the polymeric architecture, which is responsible for an efficient stress transmission, revealing the greatest activation for network-based mechanocatalysts, observing "click" conversions up to 44%, while chain-extended and linear mechanocatalysts activate either in a less efficient manner or are not completely latent in the initial state. The developed catalysts enable "irreversible" mechanochromic systems for stress-sensing devices.

Diffusion of Sites versus Polymers in Polyelectrolyte Complexes and Multilayers.

It has long been assumed that the spontaneous formation of materials such as complexes and multilayers from charged polymers depends on (inter)diffusion of these polyelectrolytes. Here, we separately examine the mass transport of polymer molecules and extrinsic sites-charged polyelectrolyte repeat units balanced by counterions-within thin films of polyelectrolyte complex, PEC, using sensitive isotopic labeling techniques. The apparent diffusion coefficients of these sites within PEC films of poly(diallyldimethylammonium), PDADMA, and poly(styrenesulfonate), PSS, are at least 2 orders of magnitude faster than the diffusion of polyelectrolytes themselves. This is because site diffusion requires only local rearrangements of polyelectrolyte repeat units, placing far fewer kinetic limitations on the assembly of polyelectrolyte complexes in all of their forms. Site diffusion strongly depends on the salt concentration (ionic strength) of the environment, and diffusion of PDADMA sites is faster than that of PSS sites, accounting for the asymmetric nature of multilayer growth. Site diffusion is responsible for multilayer growth in the linear and into the exponential regimes, which explains how PDADMA can mysteriously "pass through" layers of PSS. Using quantitative relationships between site diffusion coefficient and salt concentration, conditions were identified that allowed the diffusion length to always exceed the film thickness, leading to full exponential growth over 3 orders of magnitude thickness. Both site and polymer diffusion were independent of molecular weight, suggesting that ion pairing density is a limiting factor. Polyelectrolyte complexes are examples of a broader class of dynamic bulk polymeric materials that (self-) assemble via the transport of cross-links or defects rather than actual molecules.