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Single use plastic packaging and its environmental impacts have received much attention over the last few years from governments, businesses and consumers. One option to reduce plastic packaging waste and its associated environmental impacts is to shift towards circular business models, supplying reusable packaging options that are used many times before being recycled. One technical barrier to the implementation of plastic food packaging reuse is the need to effectively clean the packs and provide cleaning assurance to prevent the possibility of product crossover. This research investigated the feasibility of using Ultraviolet Fluorescence imaging to optically detect residual food fouling and thus assuring cleanliness in the case example of margarine spread tubs. Processing of obtained images was carried out using MATLAB® applying Otsu’s thresholding method. It was established that for the current setup the minimum detectable quantity of fouling was of the order 10–4 g/mm2. The assessment process was correlated against that of Adenosine Triphosphate assay, an industry-standard process for assessing the cleanliness of food contact surfaces. The implications of the investigated technique overcome one barrier to plastic food packaging reuse on an industrial scale. Fast and reliable fouling evaluation of every pack will underpin business and consumer trust in such a circular material flow. The established technique has the potential to form part of the wider reuse system for polymer packaging. Implications on optical detection optimization, packaging design, and suitability for automation are discussed alongside wider food supply chain considerations.

Electrostatic adsorption of cationic polyelectrolytes onto anionic cellulosic substrates is an attractive route for facile surface modification of biorenewable materials. Recently, attention has focused on adsorbing cationic spherical diblock copolymer nanoparticles onto model cellulose and/or nanocellulosic substrates. Herein, we investigate physical adsorption of highly anisotropic copolymer worms bearing either anionic or cationic charge onto planar silica, cellulose nanocrystal (CNC) or cellulose nanofibril (CNF) surfaces using quartz crystal microbalance with dissipation monitoring. Electrostatic interactions dominate in the case of anionic silica and CNC surfaces because the adsorbed mass of cationic worms was greater than that of anionic worms. However, either anionic or cationic worms could be adsorbed onto in situ generated CNF substrates, suggesting that additional interactions were involved: hydrogen bonding, van der Waals forces, and possibly covalent bond formation. Scanning electron and atomic force microscopy studies of the dried planar substrates after adsorption experiments confirmed the presence of adsorbed copolymer worms. Finally, composite worm/CNF films exhibited restricted swelling behavior when immersed in water compared to reference CNF films, suggesting that the worms reinforce CNF films by acting as a physical crosslinker. This study is the first investigation of the physical adsorption of highly anisotropic diblock copolymer worms onto cellulosic surfaces.

Stimuli-responsive polymers have attracted academic interest over the last 60 years due to their potential use in developing systems with a range of functionalities that can be activated by external artificial triggers. The diversity of responses and stimuli, which can be achieved through careful polymer selection and processing, opens up applications in nearly every sector. In particular, the use of responsive polymers for the controlled delivery of drugs and bioactive compounds has been heavily researched. This review provides an overview of the recent advancements in electrospinning of temperature- and pH-responsive polymers to create networks of nanofibres with controlled drug delivery profiles for biomedical applications.

The design and preparation of sustainable materials has received considerable interest in recent years due to growing environmental concerns and diminishing crude oil reserves. In this Minireview, the polymerization of renewable monomers by reversible addition–fragmentation chain transfer (RAFT) polymerization is discussed. Specifically, small molecules extracted from biomass and their conversion to polymerizable vinyl monomers is examined. Applications of these renewable RAFT polymers are also highlighted and the future outlook for this area of research is considered.

The rational synthesis of epoxy-functional diblock copolymer nano-objects has been achievedviaRAFT aqueous emulsion polymerisation of glycidyl methacrylate (GlyMA; aqueous solubility similar to 22 g dm(-3)at 50 degrees C) by utilising relatively mild conditions (pH 7, 50 degrees C) to preserve the epoxy groups. High monomer conversions were achieved within 1 h when using a poly(glycerol monomethacrylate) chain transfer agent with a mean degree of polymerisation (DP) of 28, with GPC analysis indicating relatively narrow molecular weight distributions (M-w/M-n< 1.40) when targeting PGlyMA DPs up to 80. A phase diagram was constructed to identify the synthesis conditions required to access pure spheres, worms or vesicles. Transmission electron microscopy, dynamic light scattering and small-angle X-ray scattering (SAXS) studies indicated the formation of well-defined worms and vesicles when targeting relatively long PGlyMA blocks. These epoxy-functional nano-objects were derivatisedviaepoxy-thiol chemistry by reaction withl-cysteine in aqueous solution. Finally, anin situSAXS study was conducted during the RAFT aqueous emulsion polymerisation of GlyMA at 50 degrees C to examine the nucleation and size evolution of PGMA(48)-PGlyMA(100)diblock copolymer spheres using a bespoke stirrable reaction cell.

Owing to the overconsumption of petroleum-based resources and growing demand for fossil-based fuels and chemicals, it has become imperative to adopt alternative resources that are renewable. With the availability of biomass, it is believed that this technology has the capability to valorize waste into wealth. Recently, efficient utilization of plant biomass, a chief renewable resource, has gained tremendous attention in research as it offers distinct social, economic, and sustainable benefits. The present review focuses on the various biomass from waste resources. Subsequently, the applications of these polymeric biomass composites are reviewed in catalysis, drug delivery, and food applications. Finally, corrosion studies along with DFT calculations and theoretical aspects have also been reviewed. Naturally occurring carbohydrate polymers found in lignocellulosic biomass are biopolymers have been used for various physical and chemical applications; as catalyst, coatings, drug delivery, corrosion inhibitors etc. This review reports these material applications of carbohydrate polymers. In this review we focus on new and emerging applications of polymers from lignocellulosic biomass.

Polymerization-induced self-assembly (PISA) is a powerful platform technology for the rational and efficient synthesis of a wide range of block copolymer nano-objects (e.g., spheres, worms or vesicles) in various media. In situ small-angle X-ray scattering (SAXS) studies of reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization have previously provided detailed structural information during self-assembly (see M. J. Derry et al., Chem. Sci. 2016, 7, 5078-5090). However, conducting the analogous in situ SAXS studies during RAFT aqueous emulsion polymerizations poses a formidable technical challenge because the inherently heterogeneous nature of such PISA formulations requires efficient stirring to generate sufficiently small monomer droplets. In the present study, the RAFT aqueous emulsion polymerization of 2-methoxyethyl methacrylate (MOEMA) has been explored for the first time. Chain extension of a relatively short non-ionic poly(glycerol monomethacrylate) (PGMA) precursor block leads to the formation of sterically-stabilized PGMA-PMOEMA spheres, worms or vesicles, depending on the precise reaction conditions. Construction of a suitable phase diagram enables each of these three morphologies to be reproducibly targeted at copolymer concentrations ranging from 10 to 30% w/w solids. High MOEMA conversions are achieved within 2 h at 70 degrees C, which makes this new PISA formulation well-suited for in situ SAXS studies using a new reaction cell. This bespoke cell enables efficient stirring and hence allows in situ monitoring during RAFT emulsion polymerization for the first time. For example, the onset of micellization and subsequent evolution in particle size can be studied when preparing PGMA(29)-PMOEMA(30) spheres at 10% w/w solids. When targeting PGMA(29)-PMOEMA(70) vesicles under the same conditions, both the micellar nucleation event and the subsequent evolution in the diblock copolymer morphology from spheres to worms to vesicles are observed. These new insights significantly enhance our understanding of the PISA mechanism during RAFT aqueous emulsion polymerization.

Nitroxide-functional polymers have garnered considerable interest in recent years and appear to hold promise for energy storage applications. However, their synthesis can be both expensive and time-consuming. Here, we propose a highly convenient method for the preparation of TEMPO-functional diblock copolymer nanoparticles directly in water. Epoxy-functional diblock copolymer worms are synthesized from a single monomer, glycidyl methacrylate (GlyMA), using a three-step, one-pot protocol in aqueous solution via polymerization-induced self-assembly (PISA). First, an initial aqueous emulsion of GlyMA was heated at 85 °C for 9 h to afford an aqueous solution of glycerol monomethacrylate (GMA). Then reversible addition–fragmentation chain transfer (RAFT) polymerization of GMA was conducted in aqueous solution using a dicarboxylic acid-based RAFT agent to produce a water-soluble PGMA homopolymer. Finally, chain extension of this precursor block via RAFT aqueous emulsion polymerization of GlyMA at 50 °C produced amphiphilic diblock copolymer chains that self-assembled in situ to form a 15% w/w aqueous dispersion of diblock copolymer worms. These worms can be derivatized directly using 4-amino-TEMPO in aqueous solution, affording novel crosslinked anisotropic nanoparticles that contain a relatively high density of stable nitroxide radicals for potential charge storage applications.

High-pressure microfluidization is used to prepare a series of oil-in-water Pickering nanoemulsions using sterically-stabilized diblock copolymer nanoparticles as the Pickering emulsifier. The droplet phase comprised either n-octane, n-decane, n-dodecane, or n-tetradecane. This series of oils enabled the effect of aqueous solubility on Ostwald ripening to be studied, which is the primary instability mechanism for such nanoemulsions. Analytical centrifugation (LUMiSizer instrument) was used to evaluate the long-term stability of these Pickering nanoemulsions over time scales of weeks/months. This technique enables convenient quantification of the fraction of growing oil droplets and confirmed that using n-octane (aqueous solubility = 0.66 mg dm-3 at 20 °C) leads to instability even over relatively short time periods. However, using n-tetradecane (aqueous solubility = 0.386 μg dm-3 at 20 °C) leads to significantly improved long-term stability with respect to Ostwald ripening, with all droplets remaining below 1 μm diameter after 6 weeks storage at 20 °C. In the case of n-dodecane, the long-term stability of these new copolymer-stabilized Pickering nanoemulsions is significantly better than the silica-stabilized Pickering nanoemulsions reported in the literature by Persson et al. ( Colloids Surf., A, 2014, 459, 48-57). This is attributed to a much greater interfacial yield stress for the former system, as recently described in the literature (see P. J. Betramo et al. Proc. Natl. Acad. Sci. U.S.A., 2017, 114, 10373-10378).

In this work we describe the grafting of cellulose nanocrystals (CNCs) by surface-initiated photoinduced Cu-mediated reversible-deactivation radical polymerization (RDRP). Initially, CNCs obtained through sulfuric acid hydrolysis were functionalized with a tertiary bromo-ester moiety as an initiating group for the subsequent RDRP of methyl acrylate, targeting three different degrees of polymerization for the polymer grafts: 50, 300 and 600. The polymerizations proceeded in DMSO in the presence of CuBr 2 and Me 6 TREN as the catalytic system utilizing a UV source (λ max ≈ 360 nm). The technique proved highly versatile for the modification of CNCs with poly(methyl acrylate), where considerably high grafting was achieved in short reaction times (90 min), with simple purification steps. CNC morphology was maintained and polymer grafts were evident through FT-IR spectroscopy, thermal analysis, contact angle measurements, X-ray photoelectron microscopy and x-ray diffraction.

Herein, we report a novel class of latex particles composed of a hemicellulose, xyloglucan (XG), and poly(methyl methacrylate) (PMMA), specially designed to enable a biomimetic modification of cellulose. The formation of the latex particles was achieved utilizing reversible addition-fragmentation chain transfer (RAFT) mediated surfactant-free emulsion polymerization employing XG as a hydrophilic macromolecular RAFT agent (macroRAFT). In an initial step, XG was functionalized at the reducing chain end to bear a dithioester. This XG macroRAFT was subsequently utilized in water and chain extended with methyl methacrylate (MMA) as hydrophobic monomer, inspired by a polymerization-induced self-assembly (PISA) process. This yielded latex nanoparticles with a hydrophobic PMMA core stabilized by the hydrophilic XG chains at the corona. The molar mass of PMMA targeted was varied, resulting in a series of stable latex particles with hydrophobic PMMA content between 22 and 68 wt % of the total solids content (5-10%). The XG-PMMA nanoparticles were subsequently adsorbed to a neutral cellulose substrate (filter paper), and the modified surfaces were analyzed by FT-IR and SEM analyses. The adsorption of the latex particles was also investigated by quartz crystal microbalance with dissipation monitoring (QCM-D), where the nanoparticles were adsorbed to negatively charged model cellulose surfaces. The surfaces were analyzed by atomic force microscopy (AFM) and contact angle (CA) measurements. QCM-D experiments showed that more mass was adsorbed to the surfaces with increasing molar mass of the PMMA present. AFM of the surfaces after adsorption showed discrete particles, which were no longer present after annealing (160 °C, 1 h) and the roughness (Rq) of the surfaces had also decreased by at least half. Interestingly, after annealing, the surfaces did not all become more hydrophobic, as monitored by CA measurements, indicating that the surface roughness was an important factor to consider when evaluating the surface properties following particle adsorption. This novel class of latex nanoparticles provides an excellent platform for cellulose modification via physical adsorption. The utilization of XG as the anchoring molecule to cellulose provides a versatile methodology, as it does not rely on electrostatic interactions for the physical adsorption, enabling a wide range of cellulose substrates to be modified, including neutral sources such as cotton and bacterial nanocellulose, leading to new and advanced materials.

Recently development of high-performance polymer composites made from natural resources in the various sectors is increasing tremendously due to the environmental issues and health hazard possessed by the synthetic fibers during disposal and manufacturing. Among the many different types of natural resources, kenaf fibers have been extensively investigated as an alternative reinforcement for polymer composites over the past few years due to their low cost, good mechanical properties, high specific strength, nonabrasive, eco-friendly, and biodegradability characteristics. Kenaf is regarded as an industrial crop in Malaysia and grown commercially in other parts of the world for different applications. It is certainly one of the important plants cultivated for natural fibers globally which has great potential to use as automotive and construction materials. In many research studies, kenaf fibers have been used as reinforcement in unsaturated polyester (UPE) which perfectly improved the features of the polyester resin. The tensile properties of kenaf fiber reinforced UPE are mainly influenced by the interfacial adhesion between the fibers and the polyester resin. Several chemical modifications are employed to improve the interfacial bonding between kenaf fibers and polyester, resulting in the enhancement of mechanical properties of the composites. Therefore, this paper explores and highlights of the previous studies around kenaf fiber reinforced UPE composites, in terms of processing methods, mechanical, water absorption, and morphological properties to provide a perfect source of literature for doing further research in this topic.

Reversible addition-fragmentation chain transfer (RAFT) aqueous dispersion polymerization is used to prepare epoxy-functional PGMA-P(HPMA- stat-GlyMA) diblock copolymer worms, where GMA, HPMA, and GlyMA denote glycerol monomethacrylate, 2-hydroxypropyl methacrylate, and glycidyl methacrylate, respectively. The epoxy groups on the GlyMA residues were ring-opened using 3-aminopropyltriethoxysilane (APTES) in order to cross-link the worm cores via a series of hydrolysis-condensation reactions. Importantly, the worm aspect ratio can be adjusted depending on the precise conditions selected for covalent stabilization. Relatively long cross-linked worms are obtained by reaction with APTES at 20 °C, whereas much shorter worms with essentially the same copolymer composition are formed by cooling the linear worms from 20 to 4 °C prior to APTES addition. Small-angle X-ray scattering (SAXS) studies confirmed that the mean aspect ratio for the long worms is approximately eight times greater than that for the short worms. Aqueous electrophoresis studies indicated that both types of cross-linked worms acquired weak cationic surface charge at low pH as a result of protonation of APTES-derived secondary amine groups within the nanoparticle cores. These cross-linked worms were evaluated as emulsifiers for the stabilization of n-dodecane-in-water emulsions via high-shear homogenization at 20 °C and pH 8. Increasing the copolymer concentration led to a reduction in mean droplet diameter, indicating that APTES cross-linking was sufficient to allow the nanoparticles to adsorb intact at the oil/water interface and hence produce genuine Pickering emulsions, rather than undergo in situ dissociation to form surface-active diblock copolymer chains. In surfactant challenge studies, the relatively long worms required a thirty-fold higher concentration of a nonionic surfactant (Tween 80) to be displaced from the n-dodecane-water interface compared to the short worms. This suggests that the former nanoparticles are much more strongly adsorbed than the latter, indicating that significantly greater Pickering emulsion stability can be achieved by using highly anisotropic worms. In contrast, colloidosomes prepared by reacting the hydroxyl-functional adsorbed worms with an oil-soluble polymeric diisocyanate remained intact when exposed to high concentrations of Tween 80.

It is well known that polymerization-induced self-assembly (PISA) offers an efficient synthetic route for the production of highly anisotropic diblock copolymer worms. When prepared in aqueous media, such worms form thermoresponsive free-standing hydrogels that are (i) readily sterilizable, (ii) can act as a 3D matrix for the culture of normal mammalian cells and (iii) can induce stasis in human stem cell colonies. Herein we critically examine the gelation behavior of two types of diblock copolymer worms in terms of recent advances in percolation theory for rigid rods, which explicitly account for the effect of rod length polydispersity. More specifically, we use small-angle X-ray scattering (SAXS) to determine the weight-average worm contour length, Lw, and the mean worm cross-sectional radius, R. This approach enables a direct comparison to be made between the theoretical critical worm volume fraction, φc, required for gelation and the experimental values indicated by rheological measurements and tube inversion experiments. Given that these diblock copolymer worms are relatively flexible rather than truly rod-like, reasonably good agreement between these two parameters is observed, particularly for shorter, relatively stiff worms. For longer, more flexible worms a proportionality constant of approximately two is required to reconcile theory with experimental values for φc. These findings are expected to have important implications for the aqueous gelation behavior exhibited by various other anisotropic nanoparticles, such as cellulose nanocrystals and semicrystalline block copolymer rods, and also fibril-forming small molecule (e.g. dipeptide) gelators.

The formation of inorganic–organic magnetic nanocomposites using reactive chemistry often leads to a loss of super-paramagnetisim when conducted in the presence of iron oxide nanoparticles. We present here a low energy and chemically-mild process of co-nanoprecipitation using SPIONs and homopolymers or amphiphilic block copolymers, of varying architecture and hydrophilic/hydrophobic balance, which efficiently generates near monodisperse SPION-containing polymer nanoparticles with complete retention of magnetism, and highly reversible aggregation and redispersion behaviour. When linear and branched block copolymers with inherent water-solubility are used, a SPION-directed nanoprecipitation mechanism appears to dominate the nanoparticle formation presenting new opportunities for tailoring and scaling highly functional systems for a range of applications.

The utilization and modification of cellulose, in particular nanocelluloses, for applications in bioplastics and biocomposites has been well studied in recent years. There is an increasing need for materials with good mechanical properties from renewable resources to replace current polymeric materials derived from fossil fuels. The modification of cellulose is essential to improve compatibility with hydrophobic matrices. For this purpose, various modification techniques have been employed such as physical adsorption of polymers to cellulosic substrates. This review aims to summarize the existing literature describing the physical adsorption of tailor-made copolymers to cellulosic surfaces. This area of cellulose modification incorporates a broad range of polymeric materials, and the expansion of this method of cellulose modification is promising for future sustainable, renewable and ‘green’ material development.

Nanopreciptation of hydrophobic polymers into aqueous media is still a relatively poorly understood phenomenon. Here we present the first model studies of branched vinyl polymer nanoprecipitation and the co-nanoprecipitation of the branched polymers with linear amphiphilic A–B block copolymers. The instantaneous formation of nanoprecipitates is shown after addition of polymers in a good solvent to the aqueous antisolvent, and the limits of the solvent mixtures are determined. Multiple nanoprecipitations are also shown to be possible through direct addition of polymer solutions to aqueous nanoparticle dispersions after solvent removal, leading to particle concentration increase without modification of the initial nanoprecipitate size. When nanoprecipitation of branched polymer/A–B block copolymer mixtures were studied, variation of the ratio of the two polymer architectures led to varying z-average diameters, narrow particle size distributions, tunable stability to salt addition and storage within aqueous ...

Latex nanoparticles comprising cationically charged coronas and hydrophobic cores with different glass transition temperatures (Tg) have been prepared by surfactant-free, RAFT-mediated emulsion polymerization, where the particles form through a polymerization-induced self-assembly (PISA) type mechanism. Poly(2-dimethylaminoethyl methacrylate-co-methacrylic acid) (P(DMAEMA-co-MAA)) was utilized as a hydrophilic macroRAFT agent for the polymerization of methyl methacrylate (MMA) or n-butyl methacrylate (nBMA), respectively, resulting in two different latexes, with either a core of high (PMMA) or low (PnBMA) Tg polymer. By varying the molar mass of the hydrophobic block, latexes of different sizes were obtained (DHca. 40–120 nm). The adsorption of the latexes to cellulose model surfaces and cellulose nanofibrils (CNF) was studied using quartz crystal microbalance with dissipation monitoring (QCM-D). The surfaces with adsorbed PnBMA latexes yielded hydrophobic surfaces both before and after annealing, whereas surfaces with adsorbed PMMA latex became hydrophobic only after annealing, clearly showing the influence of the Tg of the core. The latexes were also used to modify macroscopic cellulose in the form of filter papers. Similar to the CNF surfaces, no annealing was required to achieve hydrophobic surfaces with PnBMA latexes. Finally, nanocomposites of CNF and the polymer nanoparticles were prepared through a one-pot mixing procedure. It was found that the largest synthesized PMMA latex (120 nm) facilitated a more strainable CNF network at 50% relative humidity, with a nearly 200% increase in strain at break compared to the neat CNF reference film as well as to the composite films with PnBMA latexes or to the smaller sized PMMA latexes. This difference was attributed to the spherical shape and rigidity of the large PMMA latex nanoparticles during composite formation. This highly interesting result should indeed be considered in the future design of novel biocomposites.

The new macromolecular architecture, hyperbranched polydendrons, are composed of a broad distribution of molecular weights and architectural variation; however, nanoprecipitation of these materials yields highly uniform, dendron-functional nanoparticles. By isolating different fractions of the diverse samples, the key role of the most highly branched structures in directing nucleation and growth has been explored and determined.