Current trends in interfacial polymerization chemistry

Interfacial polymerization is an enabling technique for the large-scale production of ultrathin layers, hollow nanospheres and nanofibers. The availability of a wide range of suitable monomer reactants allows for the synthesis of an impressive collection of polymers, including polyamides, polyurethanes, polyureas, polyanilines, polyimides, and polycarbonates. In addition, the technique has been used to prepare defect-free, ultrathin films of metal organic frameworks, organic-inorganic hybrids, and bio-hybrids. This review provides an overview of the chemistry that is used in interfacial polymerization, discusses the (dis)advantages of derived material types, and assesses the future prospects for synthesis of ultrathin functional materials via interfacial polymerization.     

Chemical and interfacial design in the visible-light-absorbing ferroelectric thin films

Ferroelectric thin films with switchable polarization and anomalous photoelectric effects have received extensive attention recently. However, the improvement of photoelectric performance is accompanied by the weakening of ferroelectricity. Here, both chemical and interlayer design are used to regulate the polarization and optical properties of BiFeO₃-based ferroelectric films. We achieved an improvement in both ferroelectricity and bandgap by chemical composition. The remanent polarization has been enhanced to 73.8 μC/cm² from 0.2 μC/cm², ascribed to the structural transition. The band gap of Eu-BiFeO₃ films has been reduced to 2.23 eV from 2.42 eV due to the unique energy level from Eu 4f, indicating the enhanced visible-light-absorbing capability. We have designed a "sandwich" interfacial structure of homogeneous Eu-BiFeO₃ films. A clever combination between optimal ferroelectricity and narrow band gap with near Eu contents of BFO films would generate an interfacial layer with a homogeneous gradient component, which should favor the switching of ferroelectric domains. The results show that the remanent polarization improved by 17 % to 86.2 μC/cm² while the band gap has also improved. Intriguingly, the short-circuit current density (J_sc) and open circuit (V_oc) of the photovoltaic signal of the optimal films are 89.0 nA and 0.412 V, respectively. This provides a simple and intelligent way to design the ferroelectric-photoelectric thin films and lays the foundation for optical information storage devices.     

Impact of molecular mass on the elastic modulus of thin polystyrene films

Surface wrinkling was used to determine the elastic modulus at ambient temperature of polystyrene (PS) films of varying thickness and relative molecular mass (M_n). A range of M_n from 1.2 kg/mol to 990 kg/mol was examined to determine if the molecular size impacts the mechanical properties at the nanoscale. Ultrathin films exhibited a decrease in modulus for all molecular masses studied here compared to the bulk value. For M_n > 3.2 kg/mol, the fractional change in modulus was statistically independent of molecular mass and the modulus began to deviate from the bulk as the thickness is decreased below ≈50 nm. An order of magnitude decrease in the elastic modulus was found when the film thickness was ≈15 nm, irrespective of M_n. However, an increase in the length scale for nanoconfinement was observed as the molecular mass was decreased below this threshold. The modulus of thin PS films with a molecular mass of 1.2 kg/mol deviated from bulk behavior when the film thickness was decreased below ≈100 nm. This result illustrates that the modulus of thin PS films does not scale with molecular size. Rather, the quench depth into the glass appears to correlate well with the length scale at which the modulus of the films deviates from the bulk, in agreement with molecular simulations from de Pablo and coworkers [31] and recent experimental work [35].     

Morphological study of thin films: Simulation and experimental insights using horizontal visibility graph

We studied the morphological nature of various thin films such as silicon carbide (SiC), diamond (C), germanium (Ge), and gallium nitride (GaN) on silicon substrate Si(100) using the pulsed laser deposition (PLD) method and Monte Carlo simulation. We, for the first time, systematically employed the visibility algorithm graph to meticulously study the morphological features of various PLD grown thin films. These thin-film morphologies are investigated using random distribution, Gaussian distribution, patterned heights, etc. The nature of the interfacial height of individual surfaces is examined by a horizontal visibility graph (HVG). It demonstrates that the continuous interfacial height of the silicon carbide, diamond, germanium, and gallium nitride films are attributed to random distribution and Gaussian distribution in thin films. However, discrete peaks are obtained in the brush and step-like morphology of germanium thin films. Further, we have experimentally verified the morphological nature of simulated silicon carbide, diamond, germanium, and gallium nitride thin films were grown on Si(100) substrate by pulsed laser deposition (PLD) at elevated temperature. Various characterization techniques have been used to study the morphological, and electrical properties which confirmed the different nature of the deposited films on the Silicon substrate. Decent hysteresis behavior has been confirmed by current-voltage (IV) measurement in all the four deposited films. The highest current has been measured for GaN at ～60 nA and the lowest current in SiC at ～30 nA level which is quite low comparing with the expected signal level (μA). The HVG technique is suitable to understand surface features of thin films which are substantially advantageous for the energy devices, detectors, optoelectronic devices operating at high temperatures.     

Influence of extrinsic and intrinsic parameters onto the formation of surface relief gratings in polar azo molecular glasses

Polar azo derivatives exhibiting stable glass-forming properties displayed efficient migration properties as thin films when subjected to interferential illumination, and formed time-stable and rewritable surface relief gratings as high as the initial film thickness. Intrinsic (film thickness, structure bulkiness) as well as extrinsic (laser fluence and polarization) parameters dramatically influenced the rate of the relief growth as well as the maximum relief amplitude. The superimposition of +45°/−45°-polarized beams unexpectedly conducted to a diffraction efficiency ten times as high as the combination of two p/p (parallel to the incident plane) polarized beams. The introduction of bulky anthryl Diels-Alder substituents showed net increase in the modulation amplitude due to the creation of large free volume around each azo unit, facilitating the azo migration within the less densely packed material.     

Molecular dynamics studies on the effects of water speciation on interfacial structure and dynamics in silica-filled PDMS composites

The effect of chemisorbed and physisorbed water on the interfacial structure and dynamics in silica-filled polydimethylsiloxane (PDMS) based composites have been investigated. Toward this end, we have combined molecular dynamics simulations and experimental studies employing dynamic mechanical analysis and nuclear magnetic resonance analysis. Our results suggest that the polymer-silica contact distance and the mobility of interfacial polymer chains significantly decreased as the hydration level at the interface was reduced. The reduced mobility of the PDMS chains in the interfacial domain reduced the overall, bulk, motional properties of the polymer, thus causing an effective ‘stiffening’ of the polymer matrix. The role of the long-ranged Coulombic interactions on the structural features and chain dynamics of the polymer were also examined. Both are found to be strongly influenced by the electrostatic interactions as identified by the bond orientation time correlation function, local density distribution and radial distribution functions. These results have important implications for the design and life performance behavior of nanocomposite silica-siloxane materials.     

Understanding interfacial polycondensation: Experiments on polyurea system and comparison with theory

Interfacial polycondensation, with its multiphase character and the involvement of several rate and equilibrium processes, presents unique challenges to our ability to understand and design processes for achieving desired properties. In a recent study [1], we have presented a detailed model for the process and shown that it explains the salient features as reported in the literature for several interfacial systems. In the present paper, we report extensive experimental studies on the polyurea system and their comparison with the model. Two geometries - the spherical geometry of the microcapsule and the flat-film geometry - have been used to study qualitative and quantitative features of the polycondensation and the nature of the film that forms. While some aspects, such as the manner in which the solvent influences the kinetics, confirm earlier findings, inadequacies have been identified in the sample preparation protocols followed in earlier work, because of which property estimations may carry a large error. Improved protocols have accordingly been developed and used to study the development of film properties in time and as a function of the important preparation variables. Detailed molecular weight distributions have been determined using a GPC technique and used to derive important properties of the polyurea (such as Mark-Houwink parameters) as well as to gain insights into mechanisms. The data have been used to determine the rate parameters in the Dhumal and Suresh [1] model. The predictions of the model, as far as trends are concerned, are shown to be satisfactory given the level of uncertainty about parameter values and the complexity of the system being studied. Where discrepancies exist, the reasons have been established and the areas for improvement of the model identified. The findings reported are of interest to applications such as controlled release and membrane separations, in which permeation rate through the membrane is of importance and depends upon various membrane properties like crystallinity, morphology, etc.     

Vapour induced ordering phenomena in syndiotactic polystyrene amorphous films

Summary Films of amorphous syndiotactic polystyrene were exposed to dichloromethane vapour at varying activity, up to a=1. Infrared analysis and wide angle X-ray scattering were used to follow the development of ordered structures, induced by the vapour. It has been found that characteristic bands in the infrared spectrum appear after activity a=0.45, whereas X-rays show that the sample is still amorphous. The appearance of the crystalline reflections occurs at higher activities and a continuous improvement up to a=1 in the X-ray pattern is observed.     

Influence of water content in mixed solvent on surface morphology,wettability, and photoconductivity of ZnO thin films

ZnO thin films have been synthesized by means of a simple hydrothermal method with different solvents. The effect of deionized water content in the mixed solvents on the surface morphology, crystal structure, and optical property has been investigated by scanning electron microscopy, X-ray diffraction, and UV-Vis spectrophotometer. A large number of compact and well-aligned hexagonal ZnO nanorods and the maximal texture coefficient have been observed in the thin film, which is grown in the mixed solvent with x = 40%. A lot of sparse, diagonal, and pointed nanorods can be seen in the ZnO thin film, which is grown in the 40-mL DI water solution. The optical band gap decreases firstly and then increases with the increase of x. Reversible wettability of ZnO thin films were studied by home-made water contact angle apparatus. Reversible transition between hydrophobicity and hydrophilicity may be attributed to the change of surface chemical composition, surface roughness and the proportion of nonpolar planes on the surface of ZnO thin films. Photocurrent response of ZnO thin films grown at different solvents were measured in air. The response duration of the thin film, which is grown in the solvent with x = 40%, exhibits a fast growth in the beginning but cannot approach the saturate current value within 100 s. The theoretical mechanism for the slower growth or decay duration of the photocurrent has been discussed in detail.     

Influence of Na and F doping on microstructures,optical and magnetic properties of ZnO films synthesized by sol-gel method

Undoped, Na-doped, and Na-F codoped ZnO films were synthesized using sol-gel method. Na⁺ and F⁺ ions were used as two different dopants that yielded a synergistic doping effect. This effect was measurable using XRD, accompanied by a redshift in the optical bandgap from 3.284 to 3.261?eV in ZnO, ZnO-F, and ZnO-Na-F thin films, respectively. We then studied the resulting photoluminescent changes, which were attributed to O-related defects. Ferromagnetism measurements revealed that magnetic orderings decreased significantly with F doping. However, increased Na doping enhanced the oxygen-vacancy mediated ferromagnetic state.     

Influence of WS2 content on high temperature wear performance of magnetron sputtered TiN-WSx thin films

TiN-WS_x thin films with varying WS_x content were co-deposited by reactive magnetron sputtering. GAXRD analyses showed that the addition of 4 at.% WS_x led to loss of crystallinity of TiN phase and a complete amorphous characteristic was manifested upon incorporation of 19 at.% WS_x. Nanohardness results indicated that TiN-WS_x containing 4 and 19 at.% WS_x presented 19.7 GPa and 18.4 GPa, respectively, following the rule of mixtures. Friction coefficient and wear rates measured in reciprocated tribological tests revealed that TiN-WS_x coatings present an improved tribological performance when compared to pure TiN thin film at room temperature, registering friction coefficient of 0.42 ± 0.05 and 0.19 ± 0.03 for samples with 4 and 19 at.% WS_x, respectively. Wear tests at high temperatures evidenced that sample with 4 at.% WS_x did not provide advanced protection to substrate at 343 K and above due to deterioration. On the other hand, coating with 19 at.% WS_x maintained low friction coefficient up to 343 K, registering an optimum wear rate of 0.86 × 10⁻¹⁷ m²/N with no cracking occurrence.     

Moisture absorption into ultrathin hydrophilic polymer films on different substrate surfaces

Moisture absorption into ultrathin poly(vinyl pyrrolidone) (PVP) films with varying thickness was examined using X-ray reflectivity (XR) and quartz crystal microbalance (QCM) measurements. Two different surfaces were used for the substrate: a hydrophilic silicon oxide (SiO_x) and a hydrophobic hexamethyldisilazane (HMDS) treated silicon oxide surface. The total equilibrium moisture absorption (solubility) was insensitive to the surface treatment in the thickest films (≈150 nm). However, strong reductions in the equilibrium uptake with decreasing PVP film thickness were observed on the HMDS surfaces, while the SiO_x surface exhibited thickness independent equilibrium absorption. The decreased absorption with decreasing film thickness is attributed a depletion layer of water near the polymer/HMDS interface, arising from hydrophobic interactions between the surface and water. The diffusivity of water decreased when the film thickness was less than 60 nm, independent of the surface treatment. Changes in the properties of ultrathin polymer films occur even in plasticized films containing nearly 50% water.     

Transition behavior of PS-b-PMMA films on the balanced interfacial interactions

The thickness dependence of the order-to-disorder transition (ODT), measured by in situ grazing-incidence small-angle X-ray scattering (GISAXS), has been investigated in thin films of a symmetric polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) on a random copolymer (P(S-r-MMA)) grafted to the substrate where the interfacial interactions are balanced. With decreasing film thickness less than 25L₀, the ODT significantly decreases to 193 °C for film of 10L₀ in thickness, because the interfacial interactions by a random copolymer grafted to the substrate provide a surface-induced compatibilization toward two block components. However, a plateau of the ODT at ∼213 °C for films thicker than 25L₀ was observed above the bulk value of 200 °C. The elevation of this ODT indicates a suppression of compositional fluctuations normal to the film surface, more than likely because the dominant orientation of the lamellar microdomains was found to be parallel to the film surface.     

Influence of oxygen pressure on microstructure and dielectric properties of lead-free BaTi0.85Sn0.15O3 thin films prepared by pulsed laser deposition

Lead-free barium tin titanate BaTi_0.85Sn_0.15O₃ (BTS) ferroelectric thin films have been deposited on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition. The structure and dielectric properties of thin films deposited at various oxygen pressures are investigated systematically. By optimizing the oxygen pressure during the deposition, the structure and dielectric properties are improved. The thin films grown at 15 Pa have the best crystal quality and the largest grain size, which result in the enhancement of the dielectric properties. The dielectric constant and loss tangent show the similar trend in the entire oxygen pressure range. The influence mechanisms of the oxygen pressure on the structure and dielectric properties are proposed. The BTS thin films deposited at 15 Pa with large figure of merit (FOM) of 81.1, high tunability of 72.1%, moderate dielectric constant of 341, low loss tangent of 0.009 are considered to be appropriate as a field tunable ferroelectric material for electrically tunable devices.     

The effects of latex coalescence and interfacial crosslinking on the mechanical properties of latex films

The effects of latex coalescence and interfacial crosslinking on the mechanical properties of latex films were extensively investigated by means of several series of model latexes with varying backbone polymer crosslinking density and interfacial crosslinking functional groups. It was found that the tensile strength of crosslinked model latex films increased with increasing gel content (i.e. crosslinking density) of latex backbone polymers up to about 75% and then decreased with further increase in gel, while their elongation at break steadily decreased with increasing gel content. These findings showed that latex particle coalescence was retarded above a gel content of about 75% so that the limited coalescence of latex particles containing gel contents higher than 75% prevented the tensile strength of crosslinked latex films from increasing by further crosslinking the latex backbone polymers. This was contrary to the theory of rubber elasticity that the tensile strength increases with increasing molecular weight and crosslinking density. This limitation was found to be overcome by the interfacial crosslinking among latex particles during film formation and curing. This paper will discuss the effects of both latex backbone polymer and interfacial crosslinking on latex film properties. It will also discuss the development of self-curable latex blends and structured latexes containing co-reactive groups: oxazoline and carboxylic groups.     

Scandium effect on the luminescence of Er-Sc silicates prepared from multi-nanolayer films

Polycrystalline Er-Sc silicates (Er _x Sc_2-x Si₂O₇ and Er _x Sc_2-x SiO₅) were fabricated using multilayer nanostructured films of Er₂O₃/SiO₂/Sc₂O₃ deposited on SiO₂/Si substrates by RF sputtering and thermal annealing at high temperature. The films were characterized by synchrotron radiation grazing incidence X-ray diffraction, cross-sectional transmission electron microscopy, energy-dispersive X-ray spectroscopy, and micro-photoluminescence measurements. The Er-Sc silicate phase Er _x Sc_2-x Si₂O₇ is the dominant film, and Er and Sc are homogeneously distributed after thermal treatment because of the excess of oxygen from SiO₂ interlayers. The Er concentration of 6.7 × 10²¹ atoms/cm³ was achieved due to the presence of Sc that dilutes the Er concentration and generates concentration quenching. During silicate formation, the erbium diffusion coefficient in the silicate phase is estimated to be 1 × 10^-15 cm²/s at 1,250°C. The dominant Er _x Sc_{2 - x} Si₂O₇ layer shows a room-temperature photoluminescence peak at 1,537 nm with the full width at half maximum (FWHM) of 1.6 nm. The peak emission shift compared to that of the Y-Er silicate (where Y and Er have almost the same ionic radii) and the narrow FWHM are due to the small ionic radii of Sc³⁺ which enhance the crystal field strength affecting the optical properties of Er³⁺ ions located at the well-defined lattice sites of the Sc silicate. The Er-Sc silicate with narrow FWHM opens a promising way to prepare photonic crystal light-emitting devices.     

Conformational rearrangements in interfacial region of polydimethylsiloxane melt films

Synchrotron X-ray reflectivity (XRR) confirms the formation of a quasi-immobilized layer in thin films of polydimethylsiloxane (PDMS) melts near silica surfaces. This layer (40-60 Å) has a lower density than the bulk value, and its thickness varies slightly with PDMS molecular weight. Formation of this layer is very rapid for PDMS melts with low molecular weights (below entanglement limit for these molecules) but takes 5-10 h for higher molecular weights (close to and above their entanglement value).     

Influence of coalescence and interfacial tension on the morphology of PP/HDPE compatibilized blends

In this paper, the compatibilization of polypropylene (PP)/high-density polyethylene (HDPE) blend was studied through morphological and interfacial tension analysis. Three types of compatibilizers were tested: ethylene-propylene-diene copolymer (EPDM), ethylene-vinylacetate copolymer (EVA) and styrene-ethylene/butylene-styrene triblock copolymer (SEBS). The morphology of the blends was studied by scanning electron microscopy. The interfacial tension between the components of the blends was evaluated using small amplitude oscillatory shear analysis. Emulsion curves relating the average radius of the dispersed phase and the interfacial tension to the compatibilizer concentration added to the blend were obtained. It was shown that EPDM was more efficient as an emulsifier for PP/HDPE blend than EVA or SEBS. The relative role of interfacial tension reduction and coalescence reduction to particle size reduction was also addressed. It was observed that the role of coalescence reduction is small, mainly for PP/HDPE (90/10) blends compatibilized by EPDM, EVA or SEBS. The results indicated that the role of coalescence reduction to particle size reduction is lower for blends for which interfacial tension between its components is low at compatibilizer saturation.     

Modulation of ferroelectricity and antiferroelectricity of nanoscale ZrO2 thin films using ultrathin interfacial layers

In this study, tailoring the microstructures and ferroelectric(FE)/antiferroelectric(AFE) properties of nanoscale ZrO₂ thin films is demonstrated with an intentional introduction of sub-nanometre interfacial layers. The ferroelectricity of ZrO₂ thin films is significantly enhanced by the HfO₂ interfacial layers, while the TiO₂ interfacial layers lead to a dramatic transformation of ZrO₂ from ferroelectricity into antiferroelectricity. The HfO₂ and TiO₂ interfacial layers boost the formation of the polar orthorhombic phase with (111)-texture and the non-polar tetragonal phase with (110)-texture in the FE/AFE ZrO₂ thin films, respectively, as evidenced by grazing incidence, out-of-plane, and in-plane X-ray diffraction measurements. Furthermore, the modulation of ferroelectricity and antiferroelectricity of nanoscale ZrO₂ thin films by the HfO₂/TiO₂ interfacial layers can be achieved without high-temperature annealing, which is highly advantageous to process integration. The findings demonstrate the important role of the interfaces in the effective tuning of FE/AFE properties of nanoscale thin films.     

Carbon dioxide plasticization of thin glassy polymer films

We have demonstrated in previous studies that thin glassy polymer films exhibit complex responses to highly sorbing penetrants, such as CO₂, relative to their thick film counterparts. In this paper, we apply similar experiments to two new polymers, including a polysulfone made from bisphenol A (PSF), and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO), and compare their responses to Matrimid^® to understand better CO₂ plasticization behavior of these materials when in thin film form. As expected, the extent of plasticization response tracks with CO₂ solubility; CO₂ diffusivity may also be an important factor at shorter exposure times. Experiments at longer CO₂ exposure times revealed that each polymer experiences the permeability maximum observed in our previous work as well. However, polymers that are not as highly sorbing to CO₂, like polysulfone, may not at some conditions exhibit a distinct permeability maximum but will still decrease in permeability after a long period of CO₂ exposure owing to physical aging.