Flory-Huggins Interaction Parameter Research Articles

Solvent Vapor Annealing, Defect Analysis, and Optimization of Self-Assembly of Block Copolymers Using Machine Learning Approaches.

Self-assembly of block copolymers (BCPs) is an alternative patterning technique that promises high resolution and density multiplication with lower costs. The defectivity of the resulting nanopatterns remains too high for many applications in microelectronics and is exacerbated by small variations of processing parameters, such as film thickness, and fluctuations of solvent vapor pressure and temperature, among others. In this work, a solvent vapor annealing (SVA) flow-controlled system is combined with design of experiments (DOE) and machine learning (ML) approaches. The SVA flow-controlled system enables precise optimization of the conditions of self-assembly of the high Flory-Huggins interaction parameter (χ) hexagonal dot-array forming BCP, poly(styrene-b-dimethylsiloxane) (PS-b-PDMS). The defects within the resulting patterns at various length scales are then characterized and quantified. The results show that the defectivity of the resulting nanopatterned surfaces is highly dependent upon very small variations of the initial film thicknesses of the BCP, as well as the degree of swelling under the SVA conditions. These parameters also significantly contribute to the quality of the resulting pattern with respect to grain coarsening, as well as the formation of different macroscale phases (single and double layers and wetting layers). The results of qualitative and quantitative defect analyses are then compiled into a single figure of merit (FOM) and are mapped across the experimental parameter space using ML approaches, which enable the identification of the narrow region of optimum conditions for SVA for a given BCP. The result of these analyses is a faster and less resource intensive route toward the production of low-defectivity BCP dot arrays via rational determination of the ideal combination of processing factors. The DOE and machine learning-enabled approach is generalizable to the scale-up of self-assembly-based nanopatterning for applications in electronic microfabrication.

Understanding what determines the organic solar cell stability

Understanding the fundamental origin of morphological degradation in non-fullerene acceptor-based organic solar cells is challenging. In the April 2021 issue of <i>Nature Materials</i>, Ghasemi et al. reveal that the most thermodynamically unstable and low-miscibility systems with high Flory-Huggins interaction parameter (χ) exhibit the most kinetically stable (low diffusion) morphology for superior device operation stability under thermal stress.

Surpassing 13% Efficiency for Polythiophene Organic Solar Cells Processed from Nonhalogenated Solvent.

Benefiting from low cost and simple synthesis, polythiophene (PT) derivatives are one of the most popular donor materials for organic solar cells (OSCs). However, polythiophene-based OSCs still suffer from inferior power conversion efficiency (PCE) than those based on donor-acceptor (D-A)-type conjugated polymers. Herein, a fluorinated polythiophene derivative, namely P4T2F-HD, is introduced to modulate the miscibility and morphology of the bulk heterojunction (BHJ)-active layer, leading to a significant improvement of the OSC performance. The Flory-Huggins interaction parameters calculated from the surface energy and differential scanning calorimetry results suggest that P4T2F-HD shows moderate miscibility with the popular nonfullerene acceptor Y6-BO (2,2'-((2Z,2'Z)-((12,13-bis(2-butyloctyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2',3':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile), while poly(3-hexylthiophene) (P3HT) is very miscible with Y6-BO. As a result, the P4T2F-HD case forms desired nanoscale phase separation in the BHJ film while the P3HT case forms a completely mixed BHJ film, as revealed by transmission electron microscopy (TEM) and grazing-incidence wide-angle X-ray scattering (GIWAXS). By optimizing the cathode interface and the morphology of the P4T2F-HD:Y6-BO films processed from nonhalogenated solvents, a new record PCE of 13.65% for polythiophene-based OSCs is demonstrated. This work highlights the importance of controlling D/A interactions for achieving desired morphology and also demonstrates a promising OSC system for potential cost-effective organic photovoltaics.

An empirical model for sorption by glassy polymers: An assessment of thermodynamic parameters

A new fitting model for sorption by glassy polymers is suggested based on the Flory–Huggins (FH) equation with a composite formula for the FH interaction parameter, χ, which is applicable if sorption experimental data shows a single-maximum variation of the FH parameter. Namely, a power-like and a linear approximation is assumed for χ(φ1), as a function of solvent volume fraction φ1, before and after the point of its maximum. After determining the maximum point from a direct inspection of the sorption data, the three fitting parameters are evaluated by solving two independent least-square minimization problems. Several sorption studies of biopolymers taken from the literature show that the endset of the glass transition region is correlated with the position of the maximum of the FH interaction parameter. Based on this hypothesis and the Vrentas–Vrentas model for sorption of glassy polymers, a theoretical framework for the glass transition analysis is developed. In particular, the solvent-induced glass transition temperature variation can be estimated from the sorption isotherm as a function of the solvent content corresponding to temperatures above the temperature of sorption.

Critical Depletion, Adsorption, and Intersurface Interaction in Polymer Solutions: A Mean-Field Theory Study

Using a self-consistent field theory, we examine the thermodynamics and interfacial properties of a homopolymer solution, either close to a single hard surface or confined between two parallel surfaces, in equilibrium with a bulk reservoir. We focus on the bulk critical regime and find that various physical quantities therein exhibit qualitatively different behaviors from those in the off-critical regime. For the single-surface system, the surface-excess Γ diverges as ln|ϕb – ϕc| and ln|χc – χ| when approaching the bulk critical point, where χ and ϕb are the Flory–Huggins interaction parameter and the volume fraction of polymer segment in bulk solution, respectively, and χc and ϕc are their respective values at the critical point. Γ diverges to +∞ when the surface–polymer interaction eₛ is larger than the depletion–adsorption transition (DAT) point ec, and to −∞ when eₛ < ec. As such, the DAT at ec in the critical regime is rather sharp and ec = 0.1824 + 0.1359N–¹/² at large N. For the two-surface system, the intersurface potential W at the critical point is purely attractive for both depleted and adsorbed cases and follows a D–³ power-law decay at large intersurface separations D; when eₛ is close to ec, the strength of W becomes rather weak. This nonmonotonic dependence of W on eₛ has important experimental implications on the stability of colloidal suspensions.

Biomechanically Tunable Nano-Silica/P-HEMA Structural Hydrogels for Bone Scaffolding

Innovative tissue engineering biomimetic hydrogels based on hydrophilic polymers have been investigated for their physical and mechanical properties. 5% to 25% by volume loading PHEMA-nanosilica glassy hybrid samples were equilibrated at 37 °C in aqueous physiological isotonic and hypotonic saline solutions (0.15 and 0.05 M NaCl) simulating two limiting possible compositions of physiological extracellular fluids. The glassy and hydrated hybrid materials were characterized by both dynamo-mechanical properties and equilibrium absorptions in the two physiological-like aqueous solutions. The mechanical and morphological modifications occurring in the samples have been described. The 5% volume nanosilica loading hybrid nanocomposite composition showed mechanical characteristics in the dry and hydrated states that were comparable to those of cortical bone and articular cartilage, respectively, and then chosen for further sorption kinetics characterization. Sorption and swelling kinetics were monitored up to equilibrium. Changes in water activities and osmotic pressures in the water-hybrid systems equilibrated at the two limiting solute molarities of the physiological solutions have been related to the observed anomalous sorption modes using the Flory-Huggins interaction parameter approach. The bulk modulus of the dry and glassy PHEMA-5% nanosilica hybrid at 37 °C has been observed to be comparable with the values of the osmotic pressures generated from the sorption of isotonic and hypotonic solutions. The anomalous sorption modes and swelling rates are coherent with the difference between osmotic swelling pressures and hybrid glassy nano-composite bulk modulus: the lower the differences the higher the swelling rate and equilibrium solution uptakes. Bone tissue engineering benefits of the use of tuneable biomimetic scaffold biomaterials that can be “designed” to act as biocompatible and biomechanically active hybrid interfaces are discussed.

Phase Diagrams of Ternary π-Conjugated Polymer Solutions for Organic Photovoltaics.

Phase diagrams of ternary conjugated polymer solutions were constructed based on Flory-Huggins lattice theory with a constant interaction parameter. For this purpose, the poly(3-hexylthiophene-2,5-diyl) (P3HT) solution as a model system was investigated as a function of temperature, molecular weight (or chain length), solvent species, processing additives, and electron-accepting small molecules. Then, other high-performance conjugated polymers such as PTB7 and PffBT4T-2OD were also studied in the same vein of demixing processes. Herein, the liquid-liquid phase transition is processed through the nucleation and growth of the metastable phase or the spontaneous spinodal decomposition of the unstable phase. Resultantly, the versatile binodal, spinodal, tie line, and critical point were calculated depending on the Flory-Huggins interaction parameter as well as the relative molar volume of each component. These findings may pave the way to rationally understand the phase behavior of solvent-polymer-fullerene (or nonfullerene) systems at the interface of organic photovoltaics and molecular thermodynamics.

Synthesis and characterization of novel 4-benzyloxyphenyl 4-[4-(n-dodecyloxy)benzoyloxy]benzoate liquid crystal.

Liquid crystal (LC) compound 4-Benzyloxyphenyl 4-[4-( n -dodecyloxy)benzoyloxy]benzoate (BDBB) was prepared and characterized. Inverse gas chromatography (IGC) was to be a beneficial analysis method for the research of thermodynamic characteristics of the new LC. Acetate and alcohol isomers were used to examine LC selectivity via the IGC technique at temperatures between 333.2 K and 483.2 K. The retention diagrams of n -heptane, n -octane, n -nonane, n -decane, undecane, dodecane, tridecane, n -butyl acetate, isobutyl acetate, ethyl acetate, n -propylbenzene, isopropylbenzene, ethylbenzene, chlorobenzene, and toluene on BDBB were plotted with temperatures of 483.2–493.2 K. Flory–Huggins interaction parameter and weight fraction activity coefficient at infinite dilution were researched for BDBB.

Separation of phenyl acetic acid and 6-aminopenicillanic acid applying aqueous two-phase systems based on copolymers and salts

6-Aminopenicillanic acid (6-APA) is used for synthesis of semisynthetic antibiotics. Polymer-salt aqueous two-phase systems (ATPSs) were applied for separation of 6-APA and phenyl acetic acid (PAA), as the products of hydrolyzation reaction of Penicillin G/Penicillin V. The binodal curves of ATPS composed of a copolymer (reverse Pluronic 10R5, Pluronic L35 and PEG-ran-PPG) and a salt (Tri-sodium citrate, tri-potassium citrate, di-potassium phosphate, sodium sulphate and magnesium sulphate) were obtained. The results show that, at a fixed PPG/PEG ratio, block copolymers have larger two-phase region compared with random copolymer. After screening on the partition coefficient of PAA and 6-APA separately, Na2SO4 was selected for studying the effect of the copolymer structure and the composition of salt and copolymer on partitioning, considering higher selectivity of PAA and 6-APA. 10R5-Na2SO4 ATPS was selected as the most appropriate system for separation of 6-APA and PAA. This system was used for separation of mixture of 6-APA and PAA. The results show that selectivity was approx 53 and smaller in a system, containing a mixture of 6-APA and PAA. This observation can be justified by the interaction between 6-APA and PAA. Molecular interaction between these two molecules were investigated by the Flory–Huggins interaction parameter.

Organic Photovoltaics: Understanding the Preaggregation of Polymer Donors in Solution and Its Morphological Impact.

In bulk-heterojunction organic solar cells, it is well established that the active-layer morphology significantly impacts device performance. However, morphology control remains very challenging. An interesting step in that direction was recently provided by the development of polymer donors that display a temperature-dependent aggregation behavior in solution; the aggregation characteristics were found indeed to play a determining role in the eventual active-layer morphology. Here, a combination of thermodynamic analyses, molecular dynamics simulations, and long-range corrected density functional theory calculations enables us (i) to establish the Flory-Huggins interaction parameter, χ, as a useful figure of merit that allows us to integrate the contributions from all inter-related molecular interactions and to describe the extent of polymer preaggregation in solution at room temperature; (ii) to correlate the χ values for various polymer solutions to the extent of polymer aggregation and the morphological characteristics of the active layers; and (iii) to assess how polymer-polymer and polymer-solvent intermolecular interactions contribute to the variations in χ values among different polymer solutions. We have chosen to examine four representative polymer donors (PBT4T-2OD, PBTff4T-2OD, PffBT4T-2OD, and PffBTff4T-2DT) in solution in chlorobenzene or dichlorobenzene. With χ as a robust bridge, our results provide an unprecedented, detailed description of the relationships among intermolecular interactions, extent of polymer solution aggregation, and morphological features of the active layers.

Plasticization of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with an Oligomeric Polyester: Miscibility and Effect of the Microstructure and Plasticizer Distribution on Thermal and Mechanical Properties.

In the last few decades, many efforts have been made to make poly(3-hydroxybutyrate) (PHB) and its copolymers more suitable for industrial production and large-scale use. Plasticization, especially using biodegradable oligomeric plasticizers, has been one of the strategies for this purpose. However, PHB and its copolymers generally present low miscibility with plasticizers. An understanding of the plasticizer distribution between the mobile and rigid amorphous phases and how this influences thermal, mechanical, and morphological properties remains a challenge. Herein, formulations of poly(hydroxybutyrate-co-valerate) (PHBV) plasticized with an oligomeric polyester based on lactic acid, adipic acid, and 1,2-propanediol (PLAP) were prepared by melt extrusion. The effects of the PLAP content on the processability, miscibility, and microstructure of the semicrystalline PHBV and on the thermal, morphological, and mechanical properties of the formulations were investigated. The compositions of the mobile and rigid amorphous phases of the PHBV/PLAP formulations were easily estimated by combining dynamic mechanical data and the Fox equation, which showed a heterogeneous distribution of PLAP in these two phases. An increase in the PLAP mass fraction in the formulations led to progressive changes in the composition of the amorphous phases, an increase of both crystalline lamellae and interlamellar layer thickness, and a decrease in the melting and glass transition temperatures as well as the PHBV stiffness. The Flory–Huggins interaction parameter varied with the formulation composition in the range of −0.299 to −0.081. The critical PLAP mass fraction of 0.37 obtained from thermodynamic data is close to the value estimated from dynamic mechanical analysis (DMA) data and the Fox equation. The mechanical properties showed a close relationship with the distribution of PLAP in the rigid and mobile amorphous phases as well as with the microstructure of the crystalline phase of PHBV in the formulations.

Effect of Added Salt on Disordered Poly(ethylene oxide)-Block-Poly(methyl methacrylate) Copolymer Electrolytes

We studied the effect of salt addition on a diblock copolymer system with a negative Flory–Huggins interaction parameter, χ, indicative of attractive interactions between the two blocks. The system studied is poly(ethylene oxide)-block-poly(methyl methacrylate) (PEO-PMMA) with added lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. We studied two asymmetric block copolymers, PEO-PMMA(10–33) and PEO-PMMA(10–64), where the numbers refer to the molar masses of the blocks in kg mol–1. The small-angle X-ray scattering (SAXS) profiles for PEO-PMMA(10–33) were featureless at all salt concentrations. In contrast, PEO-PMMA(10–64) exhibited SAXS peaks when the salt concentration was between 0.22 ≤ m (mol Li/kg polymer) ≤ 0.44. The appearance of SAXS peaks only in PEO-PMMA(10–64) is consistent with the predictions of ionic self-consistent field theory developed by de la Cruz and co-workers, which predicts that in systems with negative χ, ordered phases are only found when the volume fraction of the ionic block is about 10%.

Solution Lithography for Colloidal Crystal Patterning: Revisiting Flory–Huggins Interaction Parameters and Co‐Nonsolvent Systems

AbstractFor fundamental studies and practical applications, colloidal crystal patterns on substrates are typically fabricated through etching and conventional lithography. However, a wet‐chemical based method is necessary for simplifying the procedure, preserving the substrate structure, and reproducibly fabricating the colloidal crystal patterns. The present study demonstrates that colloidal crystal patterns can be conveniently generated using thermodynamic relationships between a polymer colloid and surrounding solvents. Close‐packed colloidal monolayers in good solvents that cause colloidal swelling spontaneously transform into non–close‐packed crystal patterns when non‐solvents that cause their shrinkage replace the good solvents. The colloid diameter in the close‐packed monolayer decreases significantly when the polymer in the colloid is passing thermodynamic theta conditions (when Flory–Huggins interaction parameters increase to higher than ≈0.5). The close‐packed monolayers also transform into the patterns in co‐nonsolvent conditions. The “solution lithography” might be particularly useful for patterning colloids on curved microstructures and plastic/flexible films. The colloidal shapes in the patterns vary with the solvent pairs and substrates. The method does not require special facilities to reproducibly fabricate the patterns. The study further suggests methods simultaneously fixing the patterns. The patterns exhibit anti‐reflection properties. Therefore, the solution lithography is applicable to optics, electronics, analytical science, and energy systems.

Calculation aided miscibility manipulation enables highly efficient polythiophene:nonfullerene photovoltaic cells

Polythiophenes, with merits of low cost and high scalability of synthesis, have received growing interest in organic solar cells. To date, the best-performing polythiophene:nonfullerene solar cells exhibit typical power conversion efficiencies (PCEs) of 10%–12%, which is much lower than those employing PM6- and D18-type polymers. This inferior performance is mostly limited by the improper miscibility between polythiophene and acceptors. Efforts on engineering the molecular structure to systematically tune the miscibility are required. With the aid of group contribution calculations, the miscibility of polythiophene:nonfullerene blend system was finely tuned by varying the ratios of siloxane-terminated chains and alkyl chains in ester-substituted polythiophenes through random copolymerization. Based on a series of the polythiophene and nonfullerene acceptors, the detailed analysis of blend miscibility and performance reveals a surprising anticorrelation between the Flory-Huggins interaction parameter ( χ aa) and the optimal time of solvent vapor annealing for device performance across these systems. Primarily due to the slightly higher χ aa, the blend of PDCBT-Cl-Si5 and ITIC-Th1 results in a record-high PCE of 12.85% in polythiophene:nonfullerene solar cells. The results not only provide a calculation-guided approach for molecular design but also prove that precise control of the miscibility is an effective way to design high-performance polythiophene:nonfullerene blends and beyond.

Thermodynamic studies on tert-amine modified polystyrene based polymer/solvent systems by inverse gas chromatography method

In the present work, vinyl benzyl chloride (VBC) was polymerized by using free radical polymerization. The obtained PVBC was reacted with dibutyl amine to obtain tertiary amine modified polystyrene based polymer (PVBC-Dibutyl amine). The inverse gas chromatography (IGC) method was used to examine the thermodynamic properties of the polymer. Firstly, the retention diagrams of some polar and non-polar solvents on PVBC-Dibutyl amine were obtained over a temperature range from 135 to 160° C. Then, the thermodynamic parameters, including Flory–Huggins interaction parameter, weight fraction activity coefficient, partial molar heat of sorption, and partial molar heat of mixing were determined via interactions between the polymer and selected solvents at infinite dilution. The results reveal that the alkanes are poor solvents for the polymer whereas n-butyl acetate, i-butyl acetate, ethyl acetate, n-propylbenzene, i-propylbenzene, and ethylbenzene are moderately solvents in the studied temperature range.

Alternating aligned conductive stripes in polypropylene film with remarkable anisotropy for sensing application

Abstract Anisotropic conductive films (ACFs) are of great significance in miniaturized sensing devices, however it still is a huge challenge to fabricate ACFs via a facile and cost-effective method. Herein, ACFs containing aligned conductive stripes have been developed based on polypropylene (PP)/multi-walled carbon nanotubes (MWCNTs) composite. Compared with their isotropic counterparts, they demonstrate quick response, high responsivity and excellent reversibility for volatile organic vapors. The maximum responsivity toward three organic vapors is in the order of cyclohexane > dichloromethane > ethyl acetate, which is consistent with the calculated Flory-Huggins interaction parameter. The superior organic vapor sensing behavior of anisotropic PP/MWCNTs film (A-P/M-F) can be ascribed to the clear interfaces between stripes, which can accelerate the rapid absorption/desorption of vapors at such interfaces. Moreover, the spatial confining forced effect between the neighboring stripes is beneficial for reconstructing and stabilizing the internal conductive network, endowing A-P/M-F containing aligned conductive stripes with a good sensing stability. Furthermore, their vapor sensing behavior shows temperature dependence, that is, it increases with the increasing temperature because of higher absorption activation energy at higher temperature. This work provides a facile but cost-effective way to fabricate ACFs, enabling its industrial-scale application as organic vapor sensor with high stability and satisfied reliability.

Synthesis and thermodynamic characterization of poly(methyl methacrylate)/multiwall carbon nanotube nanocomposite

In the first part of this study, poly(methyl methacrylate) (PMMA)/multiwall carbon nanotube (MWCNT) nanocomposite was synthesized by adding carbon nanotube before polymerization with bulk polymerization. Surface morphology of the PMMA/MWCNT nanocomposite and the PMMA/MWCNT nanocomposite with Chromosorb W was characterized by scanning electron microscopy (SEM). Surface and thermodynamic properties of the PMMA/MWCNT nanocomposite were investigated by inverse gas chromatography (IGC). The surface acid base character and dispersed surface energy of the PMMA/MWCNT were determined at infinite dilution. The entropy of adsorption, ∆SS, the specific free energy of adsorption, ∆GS, and the enthalpy of adsorption, ∆HS, of selected polar solvents were determined on the PMMA/MWCNT nanocomposite. The values of ∆HS were correlated with both the acceptor and donor numbers of the solvents to determine the Lewis acidic constant KA and the Lewis basic constant KD of the PMMA/MWCNT nanocomposite. The PMMA/MWCNT nanocomposite selectivity was investigated using the acetate and alcohol isomers by IGC at temperatures between 393.2 and 403.2 K. Glass transition temperature (Tg) was determined using differential scanning calorimetry (DSC) and IGC method.The interactions between the PMMA/MWCNT nanocomposite and 12 solvents were propped at a temperature range (423.2–448.2 K). The Flory–Huggins interaction parameter, and the weight fraction activity coefficient, of the PMMA/MWCNT nanocomposite solvent system were estimated at temperatures between 423.2 and 448.2 K. The solubility parameter of the PMMA/MWCNT nanocomposite, δ2, was calculated as 14.0 (cal/cm3)1/2.

A molecular scale analysis of TEMPO-oxidation of native cellulose molecules

The native cellulose, through TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical)-mediated oxidation, can be converted into individual fibers. It has been observed that oxidized fibers disperse completely and individually in water. It is believed that electrostatic repulsive forces might be responsible for such observations. In order to study the TEMPO-oxidation of cellulose molecules, we used Density Functional Theory (DFT) calculations and Flory-Huggins theory combined with molecular dynamics (MD). The surface electrostatic potential in native cellulose and TEMPO-oxidized cellulose were calculated using DFT calculations. We found that TEMPO-oxidized cellulose accommodates a threefold screw conformation where the negatively charged (–COO–) functional groups are pointed away from the surface in all spatial directions. This spatial orientation causes that TEMPO-oxidized cellulose molecules repulse each other due to strong negatively charged surface. At the same time, the spatial orientation increases the hydrophilicity in TEMPO-oxidized cellulose molecules. These observations explain the improved dispersion in water and separability of TEMPO-oxidized cellulose molecules. We obtained large and positive Flory–Huggins interaction parameters for TEMPO-oxidized cellulose molecules indicating their higher dispersion once in water.

Tunable Optical Property of Plasmonic-Polymer Nanocomposites Composed of Multilayer Nanocrystal Arrays Stacked in a Homogeneous Polymer Matrix.

Layer-by-layer (LbL) synthetic technique has been used to deposit multilayers composed of a wide range of materials including polymers, colloidal particles, and biomolecules. A more complex organization of nanocomponents-within layers (intralayer) and across layers (interlayer)-beyond simple deposition is required for manufacturing next-generation materials and devices. Recently, LbL was used to fabricate multilayer stacked polymer-nanocrystal nanocomposites composed of a stacking sequence of two immiscible polymer thin films. However, the requirement of two immiscible polymers limits its widespread use for the fabrication of various nanocomposites. Here, we presented a new and simplified synthetic method for the fabrication of multilayer stacked nanocomposites composed of multilayer plasmonic nanocrystal arrays stacked in a homogeneous polymer matrix via iterative sequential LbL deposition of polymer thin films and nanocrystal arrays. This novel fabrication technique requires strong attractive interaction between the "ligand shell" on the nanocrystal surface and the polymer matrix [Flory-Huggins interaction parameter of the ligand shell-polymer matrix (χ) < 0], which can dramatically enhance the stability of nanocomposites during the LbL deposition. The optical properties of plasmonic nanocomposites can be manipulated by the adjustment of the intrinsic property of the nanocrystal and/or coupling effect between adjacent nanocrystals from the same layer (intralayer) and/or the neighboring layer (interlayer). Taking advantage of this novel LbL fabrication technique, the properties of multilayer plasmonic nanocrystal arrays stacked in a homogeneous matrix can be manipulated via tuning the interlayer or intralayer coupling between nanocrystals, which can be achieved by sophisticated control of the packing density of two-dimensional nanocrystal arrays in each individual layer or the thickness of the polymer thin film between two adjacent nanocrystal arrays, respectively. These results provide a facile and effective way of designing a more complex multilayer nanostructure with controllable properties in a homogeneous polymer matrix.

Surface chain engineering of chitin nanocrystals towards tailoring the nucleating capacities for poly(β-hydroxybutyrate)

Chitin nanocrystal (ChNC) is good nucleation agent for aliphatic polyesters because of its high-energy surface. To moderate its nucleation activity, silane coupling agents with different chain lengths or functional groups were used to modify ChNCs in this work, and biodegradable poly(β-hydroxybutyrate) (PHB) was used as target polymer for crystallization study. Surface coupling of ChNCs improves their phase adhesion to PHB chain and weakens their nucleation activities. The alterations strongly depend on the surface chain structure of ChNCs: sulfhydryl silane-coupled ChNC shows lowered nucleation activity, whereas amino silane-coupled ChNCs even become antinucleation agents. The interfacial compatibility is vital to altered role of ChNCs and to following changes in spherulite growth and ring-banded morphology, which is further disclosed using Flory-Huggins interaction parameters and rheological responses as probes. This work provides useful information on tailoring the functions of ChNCs as nanoadditive for biodegradable aliphatic polyesters by the way of surface chain engineering.