Polymer Colloids: Current Challenges, Emerging Applications, and New Developments.

Polymer colloids are complex materials that have the potential to be used in a vast array of applications. One of the main reasons for their continued growth in commercial use is the water-based emulsion polymerization process through which they are generally synthesized. This technique is not only highly efficient from an industrial point of view but also extremely versatile and permits the large-scale production of colloidal particles with controllable properties. In this perspective, we seek to highlight the central challenges in the synthesis and use of polymer colloids, with respect to both existing and emerging applications. We first address the challenges in the current production and application of polymer colloids, with a particular focus on the transition toward sustainable feedstocks and reduced environmental impact in their primary commercial applications. Later, we highlight the features that allow novel polymer colloids to be designed and applied in emerging application areas. Finally, we present recent approaches that have used the unique colloidal nature in unconventional processing techniques.

Assessing the Effect of CeO2 Nanoparticles as Corrosion Inhibitor in Hybrid Biobased Waterborne Acrylic Direct to Metal Coating Binders.

CeO2 nanoparticles were incorporated in waterborne binders containing high biobased content (up to 70%) in order to analyze the anticorrosion performance for direct to metal coatings. Biobased binders were synthesized by batch miniemulsion polymerization of 2-octyl acrylate and isobornyl methacrylate monomers using a phosphate polymerizable surfactant (Sipomer PAM200) that lead to the formation of phosphate functionalized latexes. Upon the direct application of such binders on steel, the functionalized polymer particles were able to interact with steel, creating a thin phosphatization layer between the metal and the polymer and avoiding flash rust. The in situ incorporation of the CeO2 nanoparticles during the polymerization process led to their homogeneous distribution in the final polymer film, which produced outstanding anticorrosion performance according to the Electrochemical Impedance Spectroscopy measurements. In fact, steel substrates coated with the hybrid polymer film (30-40 µm thick) showed high barrier corrosion resistance after 41 days (~1000 h) of immersion in NaCl water solution and active inhibition capabilities thanks to the presence of the CeO2 nanoparticles. This work opens the door to the fabrication of sustainable hybrid anticorrosion waterborne coatings.

Green Electrospinning of Polymer Latexes: A Systematic Study of the Effect of Latex Properties on Fiber Morphology.

Green electrospinning is a relatively new promising technology in which a polymer (latex) can be spun from an aqueous dispersion with the help of a template polymer. This method is a green, clean and safe technology that is able to spin hydrophobic polymers using water as an electrospinning medium. In this article, a systematic study that investigates the influence of the template polymer molar mass, the total solids content of the initial dispersion and the particle/template ratio is presented. Furthermore, the influence of the surfactant used to stabilize the polymer particles, the surface functionality of the polymer particles and the use of a bimodal particle size distribution on the final fiber morphology is studied for the first time. In green electrospinning, the viscosity of the initial complex blend depends on the amount and molar mass of the template polymer but also on the total solids content of the dispersion to be spun. Thus, both parameters must be carefully taken into account in order to fine-tune the final fiber morphology. Additionally, the particle packing and the surface chemistry of the polymer particles also play an important role in the obtained nanofibers quality.

Water dynamics and self-assembly of single-chain nanoparticles in concentrated solutions.

Single-chain polymer nanoparticles (SCNPs) are soft nano-objects consisting of uni-macromolecular chains collapsed to a certain degree by intramolecular crosslinking. The similarities between the behaviour of SCNPs and that of intrinsically disordered proteins suggest that SCNPs in concentrated solutions can be used as models to design artificial micro-environments, which mimic many of the general aspects of cellular environments. In this work, the self-assembly into SCNPs of an amphiphilic random copolymer, composed by oligo(ethylene glycol)methyl ether methacrylate (OEGMA) and 2-acetoacetoxy ethyl methacrylate (AEMA), has been investigated by means of the dielectric relaxation of water. Direct evidence of segregation of the AEMA repeating units is provided by comparison with the dielectric relaxation of water in similar solutions of the linear hydrophilic polymer, P(OEGMA). Furthermore, the results of comparative studies with similar water solutions of an amphiphilic block copolymer forming multi-chain micelles support the single-chain character of the self-assembly of the random copolymer. The overall obtained results highlight the suitability of the dielectric spectroscopy to confirm the self-assembly of the amphiphilic random copolymers into globular like core-shell single-chain nanoparticles at a concentration well above the overlap concentration.

Excellent Stability in Water of Single-Chain Nanoparticles against Chain Scission by Sonication.

In this study the superior stability against degradation induced by ultrasound irradiation of water-soluble single-chain polymer nanoparticles when compared to their parent precursor polymers is reported, and a loop scission mechanism in support of such behavior is suggested.

Advances in Single-Chain Nanoparticles for Catalysis Applications.

Enzymes are the most efficient catalysts known for working in an aqueous environment near room temperature. The folding of individual polymer chains to functional single-chain nanoparticles (SCNPs) offers many opportunities for the development of artificial enzyme-mimic catalysts showing both high catalytic activity and specificity. In this review, we highlight recent results obtained in the use of SCNPs as bioinspired, highly-efficient nanoreactors (3-30 nm) for the synthesis of a variety of nanomaterials (inorganic nanoparticles, quantum dots, carbon nanodots), polymers, and chemical compounds, as well as nanocontainers for CO2 capture and release.

Advances in Fluorescent Single-Chain Nanoparticles.

Fluorophore molecules can be monitored by fluorescence spectroscopy and microscopy, which are highly useful and widely used techniques in cell biology, biochemistry, and medicine (e.g., biomarker analysis, immunoassays, cancer diagnosis). Several fluorescent micro- and nanoparticle systems based on block copolymer micelles and cross-linked polymer networks, quantum dots, π-conjugated polymers, and dendrimers have been evaluated as optical imaging systems. In this review, we highlight recent advances in the construction of fluorescent single-chain nanoparticles (SCNPs), which are valuable artificial soft nano-objects with a small tunable size (as small as 3 nm). In particular, the main methods currently available to endow SCNPs with fluorescent properties are discussed in detail, showing illustrative examples.

Fabrication of thermo-responsive cotton fabrics using poly(vinyl caprolactam-co-hydroxyethyl acrylamide) copolymer.

A thermo-responsive polymer with hydrophilic to hydrophobic transition behavior, poly(vinyl caprolactam-co-hydroxyethyl acrylamide) P(VCL-co-HEAA), was prepared by copolymerization of vinyl caprolactam and N-hydroxyethyl acrylamide via free radical solution polymerization. The resulting copolymer was characterized by Fourier transform infrared spectroscopy (FTIR), 1H nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The lower critical solution temperature (LCST) of P(VCL-co-HEAA) was determined at 34.5°C. This thermo-responsive polymer was then grafted onto cotton fabrics using 1,2,3,4-butanetetracarboxylic acid (BTCA) as crosslinker and sodium hypophosphite (SHP) as catalyst. FTIR and energy dispersive X-ray spectroscopy (EDS) studies confirmed the successful grafting reaction. The modified cotton fabric exhibited thermo-responsive behavior as evidenced by water vapor permeability measurement confirming decreased permeability at elevated temperature. This is the first demonstration that a PVCL based copolymer is grafted to cotton fabrics. This study provides a new thermo-responsive polymer for fabrication of smart cotton fabrics with thermally switchable hydrophilicity.

Increasing Stability of Biotin Functionalized Electrospun Fibers for Biosensor Applications.

This paper describes the effects of both solvent and copolymer block lengths on the stability of electrospun poly(lactic acid)/poly(lactic acid)-b-poly(ethylene glycol) (PLA/PLA-b-PEG) and PLA/PLA-b-PEG-Biotin fibers in water. By tailoring the block length of copolymers PLA-b-PEG, water stability of electrospun fibers is improved over fibers reported previously. The solvent used also influenced the stability and hydrophilicity of resulting fibers. Fibers formed using 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) have greater water stability, but less PEG at the surface of fibers than fibers spun from dimethylformamide (DMF). Attaching biotin to the end of PLA(3600)-b-PEG(2000) and spinning from DMF resulted, initially, in 7.6% of the total biotin incorporated into the fiber, assuming every PEG terminal had one biotin attached (1.1 mg of biotin per gram of fiber) available at the fibers' surface. In addition, PLA/PLA(3600)-b-PEG(2000)-Biotin spun from DMF hindered biotin migration to the aqueous phase, leaving 2% of the incorporated biotin remaining at the surface of fibers after 7 days of water exposure. The water wicking ability of DMF spun fibers also increased significantly with the biotin attachment to the PEG terminal. While HFIP spun fibers lost little biotin from fibers, there was no detectable surface available biotin, indicating biotin was at the interior. With biotin and PEG at the interior of the fibers spun from HFIP, the water wicking remained the same for PLA/PLA(3600)-b-PEG(2000) spun samples and decreased for PLA/PLA(5700)-b-PEG(1000). The dissimilarities observed in water wicking for HFIP spun samples are primarily the result of differences in fiber morphology.

Surface Functional Poly(lactic Acid) Electrospun Nanofibers for Biosensor Applications.

In this work, biotin surface functionalized hydrophilic non-water-soluble biocompatible poly(lactic acid) (PLA) nanofibers are created for their potential use as biosensors. Varying concentrations of biotin (up to 18 weight total percent (wt %)) were incorporated into PLA fibers together with poly(lactic acid)-block-poly(ethylene glycol) (PLA-b-PEG) block polymers. While biotin provided surface functionalization, PLA-b-PEG provided hydrophilicity to the final fibers. Morphology and surface-available biotin of the final fibers were studied by Field Emission Scanning Electron Microscopy (FESEM) and competitive colorimetric assays. The incorporation of PLA-b-PEG block copolymers not only decreased fiber diameters but also dramatically increased the amount of biotin available at the fiber surface able to bind avidin. Finally, fiber water stability tests revealed that both biotin and PLA-b-PEG, migrated to the aqueous phase after relatively extended periods of water exposure. The functional hydrophilic nanofiber created in this work shows a potential application as a biosensor for point-of-care diagnostics.

New evidence for hybrid acrylic/TiO2 films inducing bacterial inactivation under low intensity simulated sunlight.

This study addresses the preparation and characterization of hybrid films prepared from Titanium dioxide (TiO2) Pickering stabilized acrylic polymeric dispersion as well as their bacterial inactivation efficiency under sunlight irradiation. Complete bacterial inactivation under low intensity simulated solar light irradiation (55 mW/cm(2)) was observed within 240 min for the films containing 10 weight based on monomers (wbm) % of TiO2, whereas 360 min were needed for the films containing 20 wbm% of TiO2. The hybrid films showed repetitive Escherichia coli (E. coli) inactivation under light irradiation. TiO2 released from the films surfaces was measured by inductively coupled plasma mass spectrometry (IPC-MS), obtaining values of ∼ 0.5 and 1 ppb/cm(2) for the films containing 10 wbm% and 20 wbm% of TiO2, respectively, far below the allowed cytotoxicity level for TiO2 (200 ppb). Transmission electron microscopy (TEM) of the hybrid films showed that TiO2 nanoparticles (NPs) were located at the polymer particle's surface forming a continuous inorganic network inside the film matrix. Atomic force microscopy (AFM) images showed differences in the TiO2 dispersion between the air-film and film-substrate interfaces. Films containing 10 wbm% of TiO2 had higher roughness (Rg) at both interfaces than the one containing 20 wbm% of TiO2 inducing an increase in the bacterial adhesion as well as the bacterial inactivation kinetics. The highly oxidative OH-radicals participating in the bacterial inactivation were determined by fluorescence.

Use of a Routh-Russel deformation map to achieve film formation of a latex with a high glass transition temperature.

In the film formation of latex, particle deformation can occur by processes of wet sintering, dry sintering, or capillary action. When latex films dry nonuniformly and when particles deform and coalesce while the film is still wet, a detrimental skin layer will develop at the film surface. In their process model, Routh and Russel proposed that the operative particle deformation mechanism can be determined by the values of control parameters on a deformation map. Here, the film formation processes of three methyl methacrylate/butyl acrylate copolymer latexes with high glass transition temperatures (T(g)), ranging from 45 to 64 °C, have been studied when heated by infrared radiation. Adjusting the infrared (IR) power density enables the film temperature, polymer viscosity, and evaporation rate during latex film formation to be controlled precisely. Different polymer particle deformation mechanisms have been demonstrated for the same latex under a variety of film formation process conditions. When the temperature is too high, a skin layer develops. On the other hand, when the temperature is too low, particles deform by dry sintering, and the process requires extended time periods. The deduced mechanisms can be interpreted and explained by the Routh-Russel deformation maps. Film formation of hard (high T(g)) coatings is achieved without using coalescing aids that emit volatile organic compounds (VOCs), which is a significant technical achievement.

Determination of the coalescence temperature of latexes by environmental scanning electron microscopy.

A new methodology for quantitative characterization of the coalescence process of waterborne polymer dispersion (latex) particles by environmental scanning electron microscopy (ESEM) is proposed. The experimental setup has been developed to provide reproducible latex monolayer depositions, optimized contrast of the latex particles, and a reliable readout of the sample temperature. Quantification of the coalescence process under dry conditions has been performed by image processing based on evaluation of the image autocorrelation function. As a proof of concept the coalescence of two latexes with known and differing glass transition temperatures has been measured. It has been shown that a reproducibility of better than 1.5 °C can be obtained for the measurement of the coalescence temperature.