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Polydispersity affects physical properties of polymeric materials, such as solubility in solvents. Most biobased, synthetic, recycled, mixed, copolymerized, and self-assembled polymers vary in size and chemical structure. Using solvent fractionation, this variety in molecular features can be reduced and a selection of the sizes and molecular features of the polymers can be made. The significant chemical and physical dispersity of these polymers, however, complicates theoretical solubility predictions. A theoretical description of the fractionation process can guide experiments and material design. During solvent fractioning of polymers, a part of the polydisperse distribution of the polymers dissolves. To describe this process, this paper presents a theoretical tool using Flory-Huggins theory combined with molecular mass distributions and distributions in the number of functional groups. This paper quantifies how chemical and physical polydispersity of polymers affects their solubility. Comparison of theoretical predictions with experimental measurements of lignin in a mixture of solvents shows that multiple molecular features can be described well using a single set of parameters, giving a tool to theoretically predict the selective solubility of polymers.

The fabrication of a soft actuator with a dampened actuation response is presented. This was achieved via the incorporation into an actuating hydrogel of urease-loaded pH-responsive bicontinuous nanospheres (BCNs), whose membrane was able to regulate the permeability and thus conversion of fuel urea into ammonia. The dampened response of these nanoreactors to the enzymatically induced pH change was translated to a pH-responsive soft actuator. In hydrogels composed of a pH-responsive and nonresponsive layer, the transient pH gradient yielded an asymmetric swelling behavior, which induced a bending response. The transient actuation profile could be controlled by varying the external fuel concentrations. Furthermore, we showed that the spatial organization of the BCNs within the actuator had a great influence on the actuation response. Embedding the urease-loaded nanoreactors within the active, pH-responsive layer resulted in a reduced response due to local substrate conversion in comparison to embedding them within the passive layer of the bilayer hydrogel. Finally, we were able to induce transient actuation in a hydrogel comprising two identical active layers by the immobilization of the BCNs within one specific layer. Upon addition of urea, a local pH gradient was generated, which caused accelerated swelling in the BCN layer and transient bending of the device before the pH gradient was attenuated over time.

The rational development of sustainable polymeric materials demands tunable properties using mixtures of polymers with chemical variations. At the same time, the sheer number of potential variations and combinations makes experimentally or numerically studying every new mixture impractical. A direct predictive tool quantifying how material properties change when molecular features change provides a less time- and resource-consuming route to optimization. Numerically solving Flory–Huggins theory provides such a tool for mono-disperse mixtures with a limited number of components, but for multi-component systems the large number of equations makes numerical computations challenging. Approximate solutions to Flory–Huggins theory relating miscibility and solubility to molecular features are presented. The set of approximate relations show a wider range of accuracy compared to existing approximations. The combination of the analytical, lower-order, and more accurate higher-order approximations together contribute to a broader applicability and extensibility of Flory–Huggins theory.

In dynamic polyamide networks, 1,2,4,5-benzene tetraamide (B4A) units act simultaneously as a dynamic covalent cross-linker and as supramolecular stacking motif. This results in materials with a rubbery plateau modulus that is about 20 times higher than that of a corresponding reference network in which the supramolecular interaction is suppressed. In branched polyamides with the same B4A dynamic motif, hydrogen bonding and stacking lead to strong and reversible supramolecular networks, whereas a branched polyamide with the nonstacking reference linker is a viscous liquid under the same conditions. Wide-angle X-ray scattering and variable-temperature infrared experiments confirm that covalent cross-linking and stacking cooperatively contribute to the dynamics of the network. Stress relaxation in the reference network is dominated by a single mode related to the dynamic covalent chemistry, whereas relaxation in the B4A network has additional modes assigned to the stacking dynamics.

Lignin is the most abundant and sustainable source of aromatics on earth. However, its heterogeneous structure and hard-to-predict physicochemical properties complicate its valorization potential in many applications. We present a combined experimental and theoretical approach to quantify and predict the fractionation of lignin in binary solvent blends. This serves as an important way to reduce feedstock heterogeneity, obtaining lignin fractions with better defined molecular features. Our model predicts how the yield, in terms of amount of dissolved lignin, varies with the solvent composition. To explain the experimental results, it is essential that we invoke the physical and chemical polydispersity of lignin in our model. We obtain quantitative agreement with experimental results on various molecular features of the dissolved lignin fractions, including the yield, molecular mass, and the number of functional hydroxyl groups. This work shows that the amount and nature of dissolved lignin can be tuned predictably using a combination of solvents, which paves the way for a broader applicability of lignin as a bio-based material.

We demonstrate the construction of pH-responsive bicontinuous nanospheres (BCNs) with nonlinear transient permeability and catalytic activity. The BCNs were assembled from amphiphilic block copolymers comprising pH-responsive groups and were loaded with the enzymes urease and horseradish peroxidase (HRP). A transient membrane permeability switch was introduced by employing the well-known pH-increasing effect of urease upon conversion of urea to ammonia. As expected, the coencapsulated HRP displayed a transiently regulated catalytic output profile upon addition of urea, with no significant product formation after the pH increase. This transient process displayed a nonlinear “dampening” behavior, induced by a decrease in membrane permeability as a result of significant local ammonia production. Furthermore, the catalytic output of HRP could be modulated by addition of different amounts of urea or by altering the buffer capacity of the system. Finally, this nonlinear dampening effect was not observed in spherical polymersomes, even though the membrane permeability could also be inhibited by addition of urea. The specific BCN morphology therefore allows to optimally control catalytic processes by pH changes in the nanoreactor microenvironment compared to bulk conditions due to its unique permeability profile.

Determination of mechanical properties of (silica) thin films is important for the development of new applications. However, a versatile approach for small-scale sample fabrication and in situ mechanical testing of these materials is currently lacking which can overcome the existing difficulties in conventional testing approaches. Here, it is shown that by combining focused ion beam scanning electron microscopy (FIB-SEM) with micromanipulators free-standing silica beams of the desired dimensions can be fabricated. Using in situ bending tests on such beams inside the SEM and finite element method simulations, the Young's modulus of thin-film silica and the effects of gallium ion beam radiation on Young's modulus are determined. Furthermore, the effects of controlled relative humidity on the mechanical behavior of silica beams are investigated. The demonstrated FIB-SEM approach can be extended to other materials and preparation conditions to measure, model, and optimize mechanical properties of thin films for a wide range of (coating) applications.

Investigating and understanding the intrinsic material properties of biogenic materials, which have evolved over millions of years into admirable structures with difficult to mimic hierarchical levels, holds the potential of replacing trial-and-error-based materials optimization in our efforts to make synthetic materials of similarly advanced complexity and properties. An excellent example is biogenic silica which is found in the exoskeleton of unicellular photosynthetic algae termed diatoms. Because of the complex micro-and nanostructures found in their exoskeleton, deter-mining the intrinsic mechanical properties of biosilica in diatoms has only partly been accomplished. Here, a general method is presented in which a combination of in situ deformation tests inside an SEM with a realistic 3D model of the frustule of diatom Craspedostauros sp. (C. sp.) obtained by electron tomography, alongside finite element method (FEM) simulations, enables quantification of the Young’s modulus (E = 2.3 ± 0.1 GPa) of this biogenic hierarchical silica. The workflow presented can be readily extended to other diatom species, biominerals, or even synthetic hierarchical materials.

The diamide-imide equilibrium was successfully exploited for the synthesis of dynamic covalent polymer networks in which a dissociative bond exchange mechanism leads to high processibility at temperatures above ≈110 °C. Dynamic covalent networks bridge the gap between thermosets and thermoplastic polymers. At the operating temperature, when the network is fixed, dynamic covalent networks are elastic solids, while at high temperatures, chemical exchange reactions turn the network into a processible viscoelastic material. Upon heating a dissociative network, the viscosity may also decrease due to a shift of the chemical equilibrium; in such materials, the balance between processibility and excessive flow is important. In this study, a network is prepared that upon heating to above ≈110 °C dissociates to a significant extent due to a shift in the amide-imide equilibrium of a bisimide, pyromellitic diimide, in combination with poly(tetrahydrofuran) diamines. At room temperature, the resulting materials are elastic rubbers with a tensile modulus of 2-10 MPa, and they become predominantly viscous above a temperature of approximately 110 °C, which is dependent on the stoichiometry of the components. The diamide-imide equilibrium was studied in model reactions with NMR, and variable temperature infrared (IR) spectroscopy was used to investigate the temperature dependence of the equilibrium in the network. The temperature-dependent mechanical properties of the networks were found to be fully reversible, and the material could be reprocessed several times without loss of properties such as modulus or strain at break. The high processibility of these networks at elevated temperatures creates opportunities in additive manufacturing applications such as selective laser sintering.

Bond exchange via neighboring group-assisted reactions in dynamic covalent networks results in efficient mechanical relaxation. In Nature, the high reactivity of RNA toward nucleophilic substitution is largely attributed to the formation of a cyclic phosphate ester intermediate via neighboring group participation. We took inspiration from RNA to develop a dynamic covalent network based on β-hydroxyl-mediated transesterifications of hydroxyethyl phosphate triesters. A simple one-step synthetic strategy provided a network containing phosphate triesters with a pendant hydroxyethyl group. 31P solid-state NMR demonstrated that a cyclic phosphate triester is an intermediate in transesterification, leading to dissociative network rearrangement. Significant viscous flow at 60-100 °C makes the material suitable for fast processing via extrusion and compression molding.

The macroscopic friction behavior of water-swollen cross-linked poly(ethylene glycol)-based polyurethane coatings (PEG-based PU coatings) with varying PEG precursor mass is measured against a glass counter surface. Experimental data such as the water uptake and the indentation modulus are used to calculate an accurate value for the molar mass between cross-links Mc, which, in turn, is used for the estimation of the actual coating mesh size ξ. The friction, swelling and indentation data obtained are used to successfully deduce an empirical model for the quantitative description of the aqueous friction behavior of these coatings depending on the mesh size of the coatings and the sliding velocity only.

Polyamines play a major role in biosilicification reactions in diatoms and sponges. While the effects of polyamines on silicic acid oligomerization and precipitation are well known, the impact of polyamines chain length on silica particle growth is unclear. We studied the effects of polyamine chain length on silica particle growth and condensation in a known, simple, and salt-free biphasic reaction system; with tetraethyl orthosilicate as organic phase and polyamine dissolved in the aqueous phase. The particles at various growth stages were characterized by Cryo- Transmission Electron Microscopy, Scanning Electron Microscopy, Thermogravimetric Analysis, Zeta Potential, and solid-state NMR analysis. Polyamines were found co-localized within silica particles and the particle diameter increased with an increase in polyamine chain length, whereas silica condensation showed the opposite trend. Particle growth is proposed to progress via a coacervate intermediate while the final particles have a core shell structure with an amine-rich core and silica-rich shell. The results presented in this paper would of interest for researchers working in the field of bioinspired materials.

Biocomposite structures are difficult to characterize by bulk approaches due to their morphological complexity and compositional heterogeneity. Therefore, a versatile method is required to assess, for example, the mechanical properties of geometrically simple parts of biocomposites at the relevant length scales. Here, it is demonstrated how a combination of Focused Ion Beam Scanning Electron Microscopy (FIB-SEM) and micromanipulators can be used to isolate, transfer, and determine the mechanical properties of frustule constituents of diatom Thalassiosira pseudonana (T.p.). Specifically, two parts of the diatom frustule, girdle bands and valves, are separated by FIB milling and manipulated using a sharp tungsten tip without compromising their physical or chemical integrity. In situ mechanical studies on isolated girdle bands combined with Finite Element Method (FEM) simulations, enables the quantitative assessment of the Young's modulus of this biosilica; E = 40.0 GPa. In addition, the mechanical strength of isolated valves could be measured by transferring and mounting them on top of premilled holes in the sample support. This approach may be extended to any hierarchical biocomposite material, regardless of its chemical composition, to isolate, transfer, and investigate the mechanical properties of selected constituents or specific regions.

Diatoms are unicellular photosynthetic algae that produce a silica exoskeleton (frustule) which exposes a highly ordered nano to micro scale morphology. In recent years there has been a growing interest in modifying diatom frustules for technological applications. This is achieved by adding non-essential metals to the growth medium of diatoms which in turn modifies morphology, composition, and resulting properties of the frustule. Here, we investigate the frustule formation in diatom Pinnularia sp., including changes to overall morphology, silica thickness, and composition, in the presence of Al3+ ions at different concentrations. Our results show that in the presence of Al3+ the total silica uptake from the growth medium increases, although a decrease in the growth rate is observed. This leads to a higher inorganic content per diatom resulting in a decreased pore diameter and a thicker frustule as evidenced by electron microscopy. Furthermore, 27Al solid-state NMR, FIB-SEM, and EDS results confirm that Al3+ becomes incorporated into the frustule during the silicification process, thus, improving hydrolysis resistance. This approach may be extended to a broad range of elements and diatom species towards the scalable production of silica materials with tunable hierarchical morphology and chemical composition.

The present invention is directed to polyester powders suitable for use in 3D printing processes, methods of using such polyester powders in 3D printing processes, and processes for the manufacturing thereof. The polyester powders prepared in accordance with the present invention are easily recycled after such polyester powders have been subjected to 3D printing conditions. In addition, the present invention is directed to recycling processes that recondition waste polyester powders into polyester powders suitable for 3D printing.

Dynamic covalent bonds in a polymer network lead to plasticity, reshapability, and potential recyclability at elevated temperatures in combination with solvent-resistance and better dimensional stability at lower temperatures. Here we report a simple one-step procedure for the catalyst-free preparation and intramolecularly catalyzed stress-relaxation of dynamic polyester networks. The procedure is based on the coupling of branched OH-end functional polyesters (functionality ≥ 3) by pyromellitic dianhydride (PMDA) or 2,5-bis(methoxy-carbonyl) benzenesulfonic acid resulting in ester linkages with, respectively, a COOH or a SO3H group in a position ortho to the ester bond. This approach leads to an efficient external catalyst-free dynamic polyester network, in which the topology rearrangements occur via a dissociative mechanism involving anhydrides. The SO3H-containing network is particularly interesting, as it shows the fastest stress relaxation and does not suffer from unwanted additional transesterification reactions, as was observed in the COOH-containing network.

Defects in a polymer network complicate an accurate calculation of structural parameters such as the molar mass between cross-links Mc, typically obtained from experimental swelling data. In this paper the formation and structure of poly(ethylene glycol) (PEG)-based polyurethane networks containing PEG-mono methyl ether dangling chains are studied. The phantom network model can describe the swelling behavior of these networks only when a composition-dependent interaction parameter is used and the formation of allophanates is accounted for. A clear transition in the network formation is found at the PEG network precursor molar mass at which entanglements are formed in the melt. Correction factors based on structure calculations using the Miller-Macosko-Vallés probability approach are proposed and validated for an accurate calculation of the Mc of these defect-containing networks. This provides a new approach for studies that requires an accurate estimate of the Mc, only based on experimentally straightforward swelling experiments.

Described herein are methods and compositions for forming three-dimensional objects via material jetting processes, the methods including the repeated steps of selectively depositing a liquid thermoset material onto a surface from a nozzle of at least one jetting head in a first specified direction and exposing at least a portion of the liquid thermoset material to a source of actinic radiation in order to form a three-dimensional object from the cured thermoset material, wherein the jetting head is configured to eject droplets of o the liquid thermoset material from the nozzle at prescribed elevated operating temperatures, and wherein the liquid thermoset material is chosen so as to possessing prescribed viscosity and rheological characteristics.

Adhesive compositions comprising an aqueous dispersion of an acrylic polymer are disclosed, with such compositions having particular applicability in additive manufacturing processes, such as three-dimensional (3D) printing, including Fused Filament Fabrication (FFF). In particular, the compositions address drawbacks associated with an improper degree of adhesion between a ther­moplastic build material and build plate, which decrease the quality of printed objects. In representative aqueous dispersions, the solids content of at least about 5 wt.% and also most about 95 wt.% of the acrylic polymer is solubilized, with the balance of this polymer comprising dispersed solid particles.

A method of forming a three-dimensional object comprises the steps of forming a layer of a particulate composition, selectively depositing a liquid composition onto the layer of the particulate composition in accordance with computer data corresponding object. The particulate composition comprises a plurality of first particles that comprise a resin component comprising a first resin, the first resin comprising a first resin polymerizable group. Either or both of the particulate composition and the liquid composition comprise an initiator capable of initiating polymerization of at least the first resin. At least the first resin undergoes melting and polymerization in a plurality of the locations where the liquid composition has been selectively deposited

Hydrophilic coatings have recently emerged as a new approach to avoiding the adhesion of (bio)organisms on surfaces immersed in water. In these coatings the hydrophilic character is crucial for the anti-fouling (AF) performance. However, this property can be rapidly lost due to the inevitable damages which occur at the surface, reducing the long-term effectiveness of the AF functionality. We report hydrophilic polycarbonate-poly(ethylene glycol) methyl ether (mPEG) polyurethane coatings with tunable hydrophilic properties as well as an excellent and long-term stability in water. The coatings exhibit low protein adhesion values and are able to self-replenish their hydrophilicity after damage, due to the existence of a reservoir of hydrophilic dangling chains incorporated in the bulk. The combination of low Tg and sufficient mobility of the mPEG dangling chains (enabled by chains with higher molecular weight) proved to be crucial to ensure autonomous surface hydrophilicity recovery when the coatings were immersed in water. This coatings and design approach offers new possibilities towards high-performance AF coatings with an extended service life-time which can be used in several major applications areas, such as marine and biomedical coatings, with major economic and environmental benefits.

A method of marking substrates and marked containers are disclosed. A method comprises the steps of applying and curing a coating composition comprising (a) a matrix forming material comprising an inorganic ox­ ide or inorganic oxide precursor, and (b) an organic pore forming agent. The marking is provided by removing at least a portion of the organic pore forming agent in a selected location of the coating layer. The marking may be provided on a container with a product or heat-sensi­tive product inside. Additional embodiments relate to mul­tilayer coatings and methods for forming multi-layer coatings.

A kinetic Monte Carlo method to simulate photodegradation of a polymer coating is applied to the weathering process of a polyester-urethane clearcoat during artificial exposure under different conditions. Firstly, the optimised simulation parameters that yield the best match with experimentally measured results on the depth-resolved ester and urethane bond fractions are determined and compared for two different aerobic exposure experiments (one in a Weather-Ometer (WOM) and one in a Suntest equipment). Secondly, several other quantities that are obtained from the simulations, but cannot be determined experimentally, are compared, such as the fraction of newly formed crosslink bonds, absorptivity states, oxidised states, the fraction of radicals, the concentration of oxygen and the total amount of remaining material. Depth-inhomogeneity of the rate of photon absorption leads to the formation of distinct depth gradients in the WOM simulation, while a much more homogeneous evolution is obtained for the Suntest-air simulation. Photo-oxidative damage in the WOM simulation is more concentrated on the upper layer of the coating, resulting in the extensive evaporation of highly oxidised material, whereas degradation in the Suntest-air simulation is more spread out over the entire coating thickness, resulting in less material loss.

This paper is devoted to the surface analysis of a polyester-urethane coating during weathering under different conditions using artificial weathering machines. By means of atomic force microscopy (AFM), the evolution of the surface topology of the coatings is studied. Degradation is shown to be a laterally inhomogeneous process. The presence of water facilitates material removal and leads to an increase in the surface roughness and consequently a gloss loss. In addition, by comparing degradation under aerobic and anaerobic conditions, it is shown that oxidation reactions are the main cause of lateral inhomogeneous degradation of coatings.