Structural descriptor and surrogate modeling for design of biodegradable scaffolds.

Biodegradable scaffolds are important to regenerative medicine in that they provide an amicable environment for tissue regrowth. However, establishing structure-property (SP) relationships for scaffold design is challenging due to the complexity of the three-dimensional porous scaffold geometry. The complexity requires high-dimensional geometric descriptors. The training of such a SP surrogate model will need a large amount of experimental or simulation data. In this work, a schema of constructing SP relationship surrogates is developed to predict the degraded mechanical properties from the initial scaffold geometry. A new structure descriptor, the extended surfacelet transform (EST), is proposed to capture important details of pores associated with the degradation of scaffolds. The efficiency is further enhanced with principal component analysis to reduce the high-dimensional EST data into a low-dimensional representation. The schema also includes a kinetic Monte Carlo biodegradation model to simulate the biodegradation of polymer scaffolds and to generate the training data for the formation of SP relationships. The schema is demonstrated with the design of polycaprolactone biodegradable scaffolds by connecting the initial scaffold geometry to the degraded compressive modulus.

Scaled Production of Functionally Gradient Thin Films Using Slot Die Coating on a Roll-to-Roll System.

Polymer thin films with a cross-web gradient structure is a burgeoning area of research, having received more attention in the last two decades, for improvements in the performance and material properties. Such patterned films have been fabricated using several techniques, but in practice these techniques are non-scalable, material-dependent, wasteful, and not highly efficient. Slot die coating, a well-known scalable manufacturing process, is used to fabricate gradient polymer thin films which will be investigated herein. By incorporating slot die with the custom roll-to-roll imaging system, gradient thin films are successfully fabricated by forcing two fluidic materials into the slot die simultaneously and by manipulating the viscous, diffusive, and inertial forces. The materials will be allowed to intermix, with the aim of having approximately a 50% mix along the centerline of any two contiguous stripes. Moreover, several characterizations such as FTIR, UV-vis spectroscopy, and SEM are performed to assess the quality of the gradient polymer thin films. The gradient structure fabricated using functional and nonfunctional materials has successfully improved the functional properties compared to fully blended two materials. This work will provide an understanding of the mechanisms to obtain gradient polymer thin-film structures that exhibit the desired geometric structure and performance.

Roll-to-Roll, Dual-Layer Slot Die Coating of Chitin and Cellulose Oxygen Barrier Films for Renewable Packaging.

Cellulose and chitin are the two most abundant naturally produced biopolymers and are being extensively studied as candidates for renewable oxygen barrier films used in packaging. It has been shown that bilayers formed from cellulose nanocrystals (CNCs) and chitin nanofibers (ChNFs) exhibit oxygen barrier properties similar to polyethylene terephthalate (PET). However, this prior work explored only coating each layer individually in sequence through techniques such as spray coating. Here, we demonstrate the viability of dual-layer slot die coating of CNC/ChNF bilayers onto cellulose acetate (CA) substrates. The dual-layer slot die method enables significantly lower oxygen permeability versus spray coating while using a roll-to-roll system that applies the bilayer in a single pass. This work discusses suspension properties, wetting, and drying conditions required to achieve well-controlled ChNF/CNC bilayers. Spray-coated bilayer films were on average 25% thinner than the dual-layer bilayer film; however, the thickness-normalized oxygen permeability (OP) of the dual-layer-coated ChNF/CNC bilayer film on CA was 20 times better than that of the spray-coated bilayers. It has been shown that ChNF contributes to the wetting and barrier properties. Values of OP for the slot die-coated bilayers under optimized drying conditions were as low as 1.2 cm3·µm·m-2·d-1·kPa-1, corresponding to a normalized oxygen transmission rate of 0.32 cm3·m-2·d-1 at 23 °C and 50% relative humidity. It is also noted that the adhesive properties of the dual-layer coating are also improved when films are air-dried and that ChNF contributes to the wetting and barrier properties.

Polymers and Solvents Used in Membrane Fabrication: A Review Focusing on Sustainable Membrane Development.

(1) Different methods have been applied to fabricate polymeric membranes with non-solvent induced phase separation (NIPS) being one of the mostly widely used. In NIPS, a solvent or solvent blend is required to dissolve a polymer or polymer blend. N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), dimethylformamide (DMF) and other petroleum-derived solvents are commonly used to dissolve some petroleum-based polymers. However, these components may have negative impacts on the environment and human health. Therefore, using greener and less toxic components is of great interest for increasing membrane fabrication sustainability. The chemical structure of membranes is not affected by the use of different solvents, polymers, or by the differences in fabrication scale. On the other hand, membrane pore structures and surface roughness can change due to differences in diffusion rates associated with different solvents/co-solvents diffusing into the non-solvent and with differences in evaporation time. (2) Therefore, in this review, solvents and polymers involved in the manufacturing process of membranes are proposed to be replaced by greener/less toxic alternatives. The methods and feasibility of scaling up green polymeric membrane manufacturing are also examined.

Coarse-Grained Force Field Calibration Based on Multiobjective Bayesian Optimization to Simulate Water Diffusion in Poly-ε-caprolactone.

Molecular dynamics at the atomistic scale is increasingly being used to predict material properties and speed up the material design and development process. However, the accuracy of molecular dynamics predictions is sensitively dependent on the force fields. In the traditional force field calibration process, a specific property, predicted by the model, is compared with the experimental observation and the force field parameters are adjusted to minimize the difference. This leads to the issue that the calibrated force fields are not generic and robust enough to predict different properties. Here, a new calibration method based on multiobjective Bayesian optimization is developed to speed up the development of molecular dynamics force fields that are capable of predicting multiple properties accurately. This is achieved by reducing the number of simulation runs to generate the Pareto front with an efficient sequential sampling strategy. The methodology is demonstrated by generating a new coarse-grained force field for polycaprolactone, where the force field can predict the mechanical properties and water diffusion in the polymer.

Scalable, Alternating Narrow Stripes of Polyvinyl Alcohol Support and Unmodified PEDOT:PSS with Maintained Conductivity Using a Single-Step Slot Die Coating Approach.

Slot die coating has been established as an economical approach for deposition of parallel narrow stripes, a constituent pattern feature in many printed device applications. However, the minimum feature size that can be achieved using this approach is constrained by wetting and liquid bridge phenomena at the deposition region. We hypothesize that pattern resolution and process control can be improved by co-depositing a support fluid to stabilize the pattern. Electrically conductive poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) is slot die-coated in parallel stripes on flexible poly(ethylene terephthalate) substrate, without wettability-enhancing dopants or substrate pretreatment. A miscible liquid phase, polyvinyl alcohol, is used as the support material. Feature size performance and conductivity of PEDOT:PSS stripe regions are evaluated across a range of process conditions. Narrow PEDOT:PSS stripes produced using our technique range from 400 to 850 µm and exhibit conductivity approaching 1.5 S cm-1. This electrical performance falls within the upper range expected prior to standard conductivity-enhancing post-treatments. Significantly, dewetting effects normally present with undoped PEDOT:PSS on the plastic substrate are fully mitigated with our deposition technique. These results indicate high ease of processing and good feature size performance, with few inherent drawbacks to the functional properties of the patterned films.