Thin Polymer Films Research Articles

Responsive polymer thin films

Responsive polymer thin films

Portovenography Findings Following Partial Polypropylene Versus Thin Film Band Attenuation of a Single Congenital Extrahepatic Portosystemic Shunt: A Prospective Randomized Study in Dogs.

The objective was to conduct a prospective, randomized study to compare mesenteric portovenogram findings following partial polypropylene suture versus thin film band extrahepatic portosystemic shunt attenuation in dogs. Dogs with extrahepatic portosystemic shunts that could not tolerate complete acute shunt closure received a partial attenuation with either a polypropylene suture or synthetic polymer thin film band. At a routine second surgery three months after shunt patency, missed shunt branches and/or development of multiple acquired shunts were assessed using intra-operative mesenteric portovenography. Twenty-four dogs were enrolled, 12 received partial polypropylene suture ligation, and 12 received partial thin film band shunt attenuation. Intra-operative mesenteric portovenography three months later demonstrated that nine dogs (75%) in the thin film band group had achieved complete shunt closure versus two dogs (16.7%) in the polypropylene suture group, which was significantly different (p = 0.004). No dogs in the polypropylene suture group and two dogs (16.7%) in the thin film band group developed multiple acquired shunts. This is the first study directly comparing follow-up intra-operative mesenteric portovenography imaging findings between two methods of partial portosystemic shunt attenuation in dogs. The study provides accurate information on the rates of complete anatomical shunt closure and development of multiple acquired shunts following partial shunt attenuation with either synthetic polymer thin film band or polypropylene suture.

Tailoring the Wettability and Substrate Adherence of Thin Polymer Films with Surface-Segregating Bottlebrush Copolymer Additives.

We developed "reactive" bottlebrush polymers based on styrene (S) and t-butyl acrylate (tBA) as additives for polystyrene (PS) coatings. The bottlebrush polymers spontaneously bloom to both the air and substrate interfaces during solution casting. While neat PS films are hydrophobic and poorly adhere to the native oxide on clean silicon wafers, the hydrophilicity and substrate adherence of bottlebrush-incorporating PS films can be tailored through the thermally activated deprotection of tBA to produce acrylic acid (AA) and acrylic anhydride (AH). A critical design parameter is the manner by which tBA is incorporated into the bottlebrush: When the bottlebrush side chains are copolymers of S and tBA, the extent of deprotection is extremely low, even after prolonged thermal annealing at elevated temperature. However, when the bottlebrush contains a mixture of poly(t-butyl acrylate) (PtBA) and PS side chains, nearly all tBA is converted to AA and AH. Consequently, using the "mixed-chain" bottlebrush design with thermal processing and appropriate conditioning, the water contact angle is reduced from over 90° on unmodified PS down to 75° on bottlebrush-incorporating PS films, and the substrate adherence is improved in proportion to the extent of tBA deprotection.

Autonomous Self-healable Scratch-free Bilayer Anti-corrosion Film

Thin hydrophobic polymer film, which physically prevents an approach of corrosive media, has been widely used as an anti-corrosion coating for metals. Though polymer film effectively passivates surface of metal, it loses its anti-corrosion property once the film is peeled off by physical damage, such as scratches. Corrosion can be propagated from the exposed area even if the area is small. Therefore, for long-term anti-corrosion, the film should be seamless and completely cover the entire metal surface without scratches. In this study, we introduce an autonomously self-healable hydrophobic coating with superior anti-corrosion property by a combination of self-healable/fluorinated polymers. Schiff-base linkages based polydimethylsiloxane (SC-PDMS) is used as a primary protection layer against corrosive media. The SC-PDMS matrix with the dynamic imine bonds allows scratch-free metal protection layer by reproducible damage healing property. In addition, we applied polytetrafluoroethylene (PTFE) thin film at the surface of the SC-PDMS, which suppresses the reaction of imine bond with water and helps to maintain long-term anti-corrosion property. Eventually, this simple coating of bilayer structure with SC-PDMS and PTFE shows an effective scratch-free corrosive resistance, providing a new way of long-term use of metals.

Dependence of Slippery and Elastic Properties of Thin Polymer Films on the Grafted Flexible Sidechain Amount

In modern life, people face a wide number of sticky problems when adhesion is highly undesirable: water and dirt stick to clothes, useful materials stick to the walls of their containers and cannot be fully used, water sticking and freezing on airplane wings affects handling and can be dangerous, biological liquids can stick and form clots inside medical devices threatening patients' lives, etc. Slippery liquid-infused porous surfaces (SLIPSs) with pressure stable omniphobicity could help to solve these issues. Lubricant depletion from porous surface and subsequent degradation of omniphobic properties is the major problem for SLIPS. It could be resolved by attaching flexible, liquid-like sidechains to the polymer matrix. Understanding the relationship between the structure of such polymer films and wetting effects is therefore of great importance. The present work is devoted to the study of droplet pinning on crosslinked polydimethylsiloxane (PDMS) polymer films with varied amounts of attached flexible PDMS sidechains and clarification of the relationship between slippery and viscoelastic properties of the films. An one-stage approach to the synthesis of such slippery coatings on smooth and porous substrates in "eco-friendly" pressurized CO2 solutions is proposed. Pinning force and Young's modulus (E) of the films on silicon substrates with variation of the grafted sidechains amount (x) are measured. The non-monotonic dependence of the pinning force on the amount of sidechains is obtained: the pinning force decreases at small x values (region I) and starts to increase at higher x (region II). The effects of the grafted sidechains amount, as well as matrix softening, are discussed for each case. It is demonstrated that the proposed method of film synthesis allows one to obtain thin, uniform coatings on fabrics without gluing the fibers. Such coatings with an optimal amount of PDMS sidechains demonstrate decreased sliding angles for droplets of water and aqueous alcohol solutions, as compared to PDMS coatings without grafted sidechains. The proposed technique may be of interest for deposition of coatings on porous surfaces having a complex morphology, such as textiles, aerogels, porous electrodes, etc.

Reducing the Bulk Fragility and Suppressing the Fragility-Confinement Effect in Polystyrene with Very Low Levels of 2-Ethylhexyl Acrylate Comonomer

The effects of nanoconfinement on the glass-transition temperature (Tg) and fragility index (m) of thin polymer films, e.g., polystyrene (PS), can be substantial. We recently demonstrated the elimination of the Tg-confinement effect in supported PS films by including 2–6 mol % 2-ethylhexyl acrylate comonomer (Macromolecules 2022, 55, 9601). Here, we use spectroscopic ellipsometry and differential scanning calorimetry to characterize how m is affected by inclusion of low levels of 2-ethylhexyl acrylate (EHA), n-butyl acrylate (nBA), or n-octyl acrylate (nOA) in styrene (S)-based random copolymers. Relative to PS, the inclusion of 1 mol % EHA or 5 mol % nBA or nOA in S-based copolymers has no effect within uncertainty on bulk fragility, mbulk. In contrast, 98/2 mol % and 94/6 mol % S/EHA copolymers exhibit ∼21% and ∼30% reductions in mbulk relative to PS. In thin films supported on silicon, PS, 99/1 mol % S/EHA, 95/5 mol % S/nOA, and 95/5 mol % S/nBA exhibit similar, strong confinement effects on Tg and m. In contrast, 98/2 mol % S/EHA exhibits weak m-confinement effects in sub-100 nm thick films, and 94/6 mol % S/EHA shows no effect down to 22 nm. The strengths of the Tg-confinement effect for various systems are in accord with the m-confinement effects. Thus, the role of the EHA comonomer in suppressing or eliminating Tg- and m-confinement effects cannot be generalized to other acrylates. These results support previously reported correlations between the susceptibilities of Tg- and m-perturbations caused by nanoconfinement and provide a very simple route to suppress or eliminate confinement effects in linear polymers.

Monitoring Cell Adhesion on Polycaprolactone-Chitosan Films with Varying Blend Ratios by Quartz Crystal Microbalance with Dissipation.

A detailed understanding of the cell adhesion on polymeric surfaces is required to improve the performance of biomaterials. Quartz crystal microbalance with dissipation (QCM-D) as a surface-sensitive technique has the advantage of label-free and real-time monitoring of the cell-polymer interface, providing distinct signal patterns for cell-polymer interactions. In this study, QCM-D was used to monitor human fetal osteoblastic (hFOB) cell adhesion onto polycaprolactone (PCL) and chitosan (CH) homopolymer films as well as their blend films (75:25 and 25:75). Complementary cell culture assays were performed to verify the findings of QCM-D. The thin polymer films were successfully prepared by spin-coating, and relevant properties, i.e., surface morphology, ζ-potential, wettability, film swelling, and fibrinogen adsorption, were characterized. The adsorbed amount of fibrinogen decreased with an increasing percentage of chitosan in the films, which predominantly showed an inverse correlation with surface hydrophilicity. Similarly, the initial cell sedimentation after 1 h resulted in lesser cell deposition as the chitosan ratio increased in the film. Furthermore, the QCM-D signal patterns, which were measured on the homopolymer and blend films during the first 18 h of cell adhesion, also showed an influence of the different interfacial properties. Cells fully spread on pure PCL films and had elongated morphologies as monitored by fluorescence microscopy and scanning electron microscopy (SEM). Corresponding QCM-D signals showed the highest frequency drop and the highest dissipation. Blend films supported cell adhesion but with lower dissipation values than for the PCL film. This could be the result of a higher rigidity of the cell-blend interface because the cells do not pass to the next stages of spreading after secretion of their extracellular matrix (ECM) proteins. Variations in the QCM-D data, which were obtained at the blend films, could be attributed to differences in the morphology of the films. Pure chitosan films showed limited cell adhesion accompanied by low frequency drop and low dissipation.

UV-shielding properties of a cost-effective hybrid PMMA-based thin film coatings using TiO2 and ZnO nanoparticles: a comprehensive evaluation

This study aimed to assess the UV-shielding features of the PMMA-based thin film coatings with the addition of TiO2 and ZnO nanoparticles as nanofillers considering different contents. Furthermore, the effect of TiO2/ZnO nanohybrids at different ratios and concentrations was examined. The XRD, FTIR, SEM, and EDX analyses characterized the prepared films' functional groups, structure, and morphology. Meanwhile, the coatings' optical properties and UV-protecting capability were investigated by ultraviolet–visible (UV–Vis) spectroscopy. The UV–Vis spectroscopic study revealed that as the concentration of nanoparticles increased in the hybrid-coated PMMA, the absorption in the UVA region increased. Overall, it can be concluded that the optimal coatings for PMMA were 0.1 wt% TiO2, 0.1 wt% ZnO, and 0.025:0.025 wt% TiO2: ZnO nanohybrid. Considering the acquired FT-IR of PMMA with different content of nanoparticles before and after exposure to the UV irradiation, for some films, it was confirmed that the polymer-based thin films degraded after 720 h, with either decreasing or increasing intensity of the degraded polymer, peak shifting, and band broadening. Notably, the FTIR results were in good agreement with UV–Vis outcomes. In addition, XRD diffraction peaks demonstrated that the pure PMMA matrix and PMMA coating films did not show any characteristic peaks indicating the presence of nanoparticles. All diffraction patterns were similar with and without any nanoparticles. Therefore, it depicted the amorphous nature of polymer thin film.

Controlling the electrocatalytic activities of conducting polymer thin films toward suitability as cost-effective counter electrodes of dye-sensitized solar cells

Role dopant anions and solvents in electropolymerized conducting polymers (CPs) on controlling the morphology of thin films and electrocatalytic activities to judge their suitability as low-cost counter electrodes (CE) of dye-sensitized solar cells ( DSSCs) was systematically investigated. Amongst various CPs such as polyaniline (PANI), polypyrrole (PPy), and PEDOT with sodium dodecyl sulfate (SDS) as a dopant, PEDOT was found to exhibit the best photovoltaic performance with a photoconversion efficiency (PCE) of 6.99 %. This was attributed to the best electrocatalytic activity due to the smallest ΔEp, most minor R1, and nano-morphology-assisted high surface area, as confirmed by CV, EIS, and FE-SEM investigations. Using PEDOT as CP, the nature of dopants such as SDS, TFSI, and ClO4 has also been found to control the electrocatalytic activities and the morphology of the fabricated thin films affecting overall photovoltaic performance DSSCs. Amongst the various CP-based CE fabricated using different dopants and solvents, PEDOT:TFSI thin films prepared in acetonitrile solvent and used as CE exhibited not only the best electrocatalytic activity as CE but also demonstrated the best photovoltaic performance with PCE of 7.0 %, which almost similar to that of DSSC utilizing Pt as CE with PCE of 7.1 %. Therefore, it was concluded that the nature of CP and dopant ions were vital factors in governing the electrocatalytic activities of the thin films to ensure their suitability as CE for optimal functioning and controlling the DSSC performance.

Photoinduced Solubility Modulation in the Copolymers of Fluoroalkyl, Spiropyranyl, and Isobornyl Methacrylates

This article reports photoinduced solubility modulation in copolymer thin films derived from spiropyranyl, perfluoroalkyl, and isobornyl methacrylates. A random copolymer of spiropyranyl methacrylate (SPMA) and 1H,1H,2H,2H-perfluorooctyl methacrylate (FOMA) was first prepared in the absence of isobornyl methacrylate (IBMA). The resulting as-prepared thin film could be dissolved in highly fluorinated or fluorous solvents but became insoluble following exposure to UV light (λ = 365 nm) via the photoisomerization transformation of spiropyran units into merocyanine moieties. On the other hand, the incorporation of IBMA into the copolymer structure above a certain threshold resulted in copolymers exhibiting the opposite dissolution behavior. UV–vis spectroscopic measurements on the copolymer films and solutions indicated that dipolar attraction between the photoisomerized merocyanine moieties contributed to the decrease in solubility. The incorporation of IBMA into the copolymer chains diluted the merocyanine moieties and increased their glass-transition temperature, resulting in the disruption of the intermolecular attraction and an increase in the solubility of the UV-exposed polymer chains. These results suggested that stencils could be developed without additives to generate strong acid molecules or free radicals in polymer thin films. The proposed processing technique for fluoroalkylated copolymers was thus tested in the fabrication of orthogonal copolymer stencils and demonstrated to be a useful tool for the pixel patterning of chemically vulnerable organic light-emitting diodes.

Surface Functionalization of 4D Printed Substrates Using Polymeric and Metallic Wrinkles.

Wrinkle topographies have been studied as simple, versatile, and in some cases biomimetic surface functionalization strategies. To fabricate surface wrinkles, one material phenomenon employed is the mechanical-instability-driven wrinkling of thin films, which occurs when a deforming substrate produces sufficient compressive strain to buckle a surface thin film. Although thin-film wrinkling has been studied on shape-changing functional materials, including shape-memory polymers (SMPs), work to date has been primarily limited to simple geometries, such as flat, uniaxially-contracting substrates. Thus, there is a need for a strategy that would allow deformation of complex substrates or 3D parts to generate wrinkles on surfaces throughout that complex substrate or part. Here, 4D printing of SMPs is combined with polymeric and metallic thin films to develop and study an approach for fiber-level topographic functionalization suitable for use in printing of arbitrarily complex shape-changing substrates or parts. The effect of nozzle temperature, substrate architecture, and film thickness on wrinkles has been characterized, as well as wrinkle topography on nuclear alignment using scanning electron microscopy, atomic force microscopy, and fluorescent imaging. As nozzle temperature increased, wrinkle wavelength increased while strain trapping and nuclear alignment decreased. Moreover, with increasing film thickness, the wavelength increased as well.

Photo-Crosslinkable Polymeric Coatings Providing Chemically Versatile Reactive Surfaces on Various Substrates

We demonstrate a chemical route to attain simple, clean, scalable, photopatternable, chemically adjustable, and versatile systems to fabricate reactive organic thin films. Their surfaces exhibit effective biocompatibility, controlled reactivity, and processability on various surface types, i.e., photo-crosslinkable polymeric thin films with various functionalities, further applicable for the definition of surface activity for interfacing biological objects. The copolymers were synthesized with three monomers: a poly(ethylene glycol)-containing monomer, a monomer releasing a primary amine upon exposure to UV light, and a monomer bearing cyclic dithiocarbonate or glycidyl groups that are highly reactive with the amine. The resulting copolymers were processed with polar solvents such as water or alcohol for coating and were readily crosslinked under UV light illumination to form a highly stable molecular network, beneficial for defining selective reactive surfaces in a desired region on a variety of organic and inorganic substrates. The designed system was chemically versatile in immobilizing biologically relevant molecules on the surfaces by (i) post-crosslinking modification through the reaction of bovine serum albumin on the remaining surface reactive group with a primary amine in the protein and (ii) pre-crosslinking formulation with reactive gelatin that has the functionality to crosslink in the composite thin film. We further showed that the resulting coating on a glass or polystyrene substrate provided excellent biocompatibility and growth of C2C12 murine myocytes.

Preparation and Evaluation of Caffeine Orodispersible Films: The Influence of Hydrotropic Substances and Film-Forming Agent Concentration on Film Properties.

This study aimed to develop caffeine (CAF) orodispersible films (ODFs) and verify the effects of different percentages of film-forming agent and hydrotropic substances (citric acid-CA or sodium benzoate-SB) on various film properties. Hydroxypropyl methylcellulose E 5 (HPMC E 5) orodispersible films were prepared using the solvent casting method. Four CAF-ODF formulations were prepared and coded as CAF1 (8% HPMC E 5, CAF), CAF2 (8% HPMC E 5 and CAF:CA-1:1), CAF3 (9% HPMC E 5 and CAF:CA-1:1), and CAF4 (9% HPMC E 5 and CAF:SB-1:1). The CAF-ODFs were evaluated in terms of disintegration time, folding endurance, thickness, uniformity of mass, CAF content, thickness-normalized tensile strength, adhesiveness, dissolution, and pH. Thin, opaque, and slightly white CAF-ODFs were obtained. All the formulations developed exhibited disintegration times less than 3 min. The dissolution test revealed that CAF1, CAF2, and CAF3 exhibited concentrations of active pharmaceutical ingredients (APIs) released at 30 min that were close to 100%, whilst CAF4 showed a faster dissolution behaviour (100% of the CAF was released at 5 min). Thin polymeric films containing 10 mg of CAF/surface area (3.14 cm2) were prepared.

Damage-free X-ray spectroscopy characterization of oxide thin films

Thin polymer or oxide films are ubiquitous components in many devices, including membranes for filtration or electrodes in electrochemical energy storage. High energy electron or x-ray probes for microscopy and spectroscopy are useful to characterize and understand these materials. However, irreversible damage by the probe radiation remains a challenge. Here, we show that graphene serves as an x-ray and electron transparent substrate that substantially reduces radiation damage of an oxide thin film. We demonstrate this using highly focused x-ray beams, which show that compared to oxide thin films supported on a substrate, graphene-supported regions show minimal changes in the x-ray spectra as a function of x-ray dose. These results pave the way for the development of experimental setups that allow for long exposure time measurements with limited sample damage and substrate-directed radiation patterning.

Chain length dependence of ZnO nanofiller–polystyrene blend coating nanofilm: Morphology, surface mechanics, photochemistry, and chain packing

Based on that chain packing which is associated with the number of entanglements per chain and thereby chain length is an influential factor closely related to the properties of polymeric coating film, the nanothin film of zinc oxide (ZnO) nanofiller–incorporated polystyrene (PS) coated on Si substrate important to electronic packaging for protecting electronic material surface is fabricated with different PS molecular weights primarily for heat–resistant coating. Synergistically, through directly–measurable film characteristics obtained using atomic force microscopy (AFM) and spectroscopy (AFS) in conjunction with Raman spectroscopy (RS), the internal structures of the films are evaluated which helps indicate the corresponding film properties tested afterwards. Considering mechanical responses of individual nanoscale surface features together with surface morphology, the optimal PS–ZnO film is pointed out which indicates improved resistance to thermal dewetting compared to pure PS films while providing sub–nanometer roughness and the highest contact area of relatively low–surface–energy sites. Correlated with Raman analysis, chain packing structure encouraging multiple amplification of incident light is ascribed to the films made of the optimal chain length which indicates and describes the observed enhancement of photocatalytic self–cleaning. This study not only contributes to the development of PS–ZnO composite for multi–function coating but also to the design of structure and inspection of nanoparticle–reinforced polymer thin films.

Thermal Characterization of Micrometric Polymeric Thin Films by Photoacoustic Spectroscopy

In materials science, the knowledge of the thermal properties of thin films on thick substrates is crucial in determining the role of the film in the physical properties of the entire system. Even though the role of the film can be very important, the determination of its thermal properties is a challenging task due to the fact that its contribution to heat transfer is generally hard to single out from the influence of the substrate. Herein, a simple analytical methodology, based on the photoacoustic technique, useful in the thermal characterization of thin films on thick substrates, is presented. The approach is based on illuminating one side of the substrate with a modulated laser beam and monitoring the thermal contrast when a thin film is formed on the opposite side. This methodology allows to unambiguously determine the volumetric heat capacity of micrometric polymeric thin films. The limits of applicability of the method as well as the possibility of performing a full characterization of the thermal properties of the film are discussed.

Marangoni‐Driven Patterning in Polymer Thin Film Supported on Shrinking Substrate for Resolution Enhancement

AbstractThe Marangoni effect causes liquids to flow toward localized regions with higher surface tension. In a polymer thin film, the flow induced by photochemically programmed surface tension gradients can be harnessed to manufacture patterned surfaces. Patterned polymer films are particularly useful for controlling adhesion, improving photonic device efficiency, and directing cellular alignment. In general, a broader range of accessible pattern resolutions and/or aspect ratios ensures a broader range of applications. However, because of the process flow for pattern formation, the final pattern periodicity of the Marangoni‐driven features matches that of the initially prescribed surface energy pattern. To achieve better resolution without using sophisticated and complex tools, a shrinking (or pre‐strained) polymer film is used as a substrate. The shrinking substrate can “contract or densify” the features along the substrate plane. Consequently, the resolution of the patterns formed on the shrinking substrate is improved by the shrinkage rate of the substrate compared with those formed on the non‐shrinking substrate (i.e., silicon wafer).

Photothermal switch of drug release from polydopamine-modified nanosheets

Colorectal cancer, which is difficult to treat and has a high recurrence rate, is a challenging target. Here, we propose a novel multi-layered sheet-like device with photothermal switching for the achievement of both hyperthermia and local chemotherapy. The device was fabricated by modifying polydopamine on the surface of a polymer thin film (nanosheet) and combining it with a drug-loaded poly(lactic acid) nanosheet, and was demonstrated to control the drug release reversibly. It is suggested that several percent of loaded drug was repeatedly released by irradiating near-infrared light, indicating the high potential of minimally invasive long-term treatment of colorectal cancer.Graphical abstract

Dewetting Behavior of PS-ZnO Thin Film Coated on Ultrathin Au Layer Grown on Si Substrate

Electronic packaging by coating device component surfaces with polymer thin film is an important step to protect the components from harsh environments. However, along with the device miniaturization to improve its performance, scaling down the coating film can cause a decrease in film durability. Therefore, the thermal stability of pure polystyrene (PS) and zinc oxide-incorporated polystyrene (PS-ZnO) nano-thin films coated on gold (Au) layer with different nano thicknesses on Si substrate were examined to determine the smallest Au thickness at which the polymer films would exhibit optimal stability, and to investigate the effects of the Au component on film resistance to thermal dewetting. With the requirement of having a transparent and conductive Au electrode, the thickness of 20 nm was identified as the optimal value for the Au layer on which both the PS and PS-ZnO films could withstand environment temperatures at 150oC for up to a few hours while the PS-ZnO film exhibited outstanding thermal stability for over 10 days. Such excellent durability was ascribed to the physio-chemical framework in which the coating film can experience forces from the coated layers which potentially affect the mobility of polymer chains. Considering the increase of Au content and Au film roughness with increasing Au film thickness and realizing the similar surface adhesion forces of these Au layers, several possible influences of the Au material on the stability of PS matrix were discussed. The findings provide an insight into heat-resistant coatings for nano-thin Au layers grown on Si, which may also be of benefit in the design and understanding of relevant electronic protection and functional polymeric coatings.

Molecular Simulation Strategies for Understanding the Degradation Mechanisms of Acrylic Polymers.

Acrylic polymers, commonly used in paints, can degrade over time by several different chemical and physical mechanisms, depending on structure and exposure conditions. While exposure to UV light and temperature results in irreversible chemical damage, acrylic paint surfaces in museums can also accumulate pollutants, such as volatile organic compounds (VOCs) and moisture, that affect their material properties and stability. In this work, we studied the effects of different degradation mechanisms and agents on properties of acrylic polymers found in artists' acrylic paints for the first time using atomistic molecular dynamics simulations. Through the use of enhanced sampling methods, we investigated how pollutants are absorbed into thin acrylic polymer films from the environment around the glass transition temperature. Our simulations suggest that the absorption of VOCs is favorable (-4 to -7 kJ/mol depending on VOCs), and the pollutants can easily diffuse and be emitted back into the environment slightly above glass transition temperature when the polymer is soft. However, typical environmental fluctuations in temperature (<16 °C) can lead for these acrylic polymers to transition to glassy state, in which case the trapped pollutants act as plasticizers and cause a loss of mechanical stability in the material. This type of degradation results in disruption of polymer morphology, which we investigate through calculation of structural and mechanical properties. In addition, we also investigate the effects of chemical damage, such as backbone bond scission and side-chain cross-linking reactions on polymer properties.