Double layer structure of ionic liquids at the Au(111) electrode interface : an atomic force microscopy investigation

The double layer structure of two ionic liquids (ILs), 1-butyl-1- methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate ([Py ₁,₄]FAP) and 1-ethyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate ([EMIm]FAP) at the polarized Au(111) electrode interface is probed using Atomic Force Microscopy force measurements. The force-separation profiles suggest a multilayered morphology is present at the electrified Au(111)-IL interface, with more near surface layers detected at higher potentials. At the (slightly negative) open circuit potential, multiple ion layers are present, and the innermost layer, in contact with the Au(111) surface, is enriched in the cation due to electrostatic adsorption. Upon applying negative electrode potentials (-1.0 V, -2.0 V), stronger IL near surface structure is detected: both the number of ion layers and the force required to rupture these layers increases. Positive electrode potentials (+1.0 V, +2.0 V) also enhance IL near surface structure, but not as much as negative potentials, because surface-adsorbed anions are less effective at templating structure in subsequent layers than cations. This interfacial structure is not consistent with a double layer in the Stern-Gouy-Chapman sense, as there is no diffuse layer. The structure is consistent with a capicitative double-layer model, with a very small separation distance between the planes of charge.

Manufacturing influence on the delamination fracture behavior of the T800H/3900-2 carbon fiber reinforced polymer composites

'Torayca' T800H/3900-2 is the first material qualified on Boeing Material Specification (BMS 8-276) which utilizes the thermoplastic-particulate interlayer toughening technology. Two manufacturing processes, the autoclave process and the fast heating rated Quickstep™ process, were employed to cure this material. The Quickstep process is a unique composite production technology which utilizes the fast heat transfer rate of fluid to heat and cure polymer composite components. The manufacturing influence on the mode I delamination fracture toughness of laminates was investigated by performing double cantilever beam tests. The composite specimens fabricated by two processes exhibited dissimilar delamination resistance curves (R-curves) under mode I loading. The initial value of fracture toughness GIC-INIT was 564 J/m2 for the autoclave specimens and 527 J/m2 for the Quickstep specimens. However, the average propagation fracture toughness GIC-PROP was 783 J/m2 for the Quickstep specimens, which was 2.6 times of that for the autoclave specimens. The mechanism of fracture occurred during delamination was studied under scanning electron microscope (SEM). Three types of fracture were observed: the interlayer fracture, the interface fracture, and the intralaminar fracture. These three types of fracture played different roles in affecting the delamination resistance curves during the crack growth. More fiber bridging was found in the process of delamination for the Quickstep specimens. Better fiber/matrix adhesion was found in the Quickstep specimens by conducting indentation-debond tests.

Transparent uv-shielding films from organic small molecule-intercalated layered double hydroxide nanoplatelets/polymer composite

In this study, layered double hydroxide (LDH) with nitrate as the interlayer anion has been partially exfoliated in dimethyl sulfoxide (DMSO). Atomic force microscopy (AFM) images showed that both the lateral size and the thickness of the LDH nanoplatelets were decreased after DMSO treatment. Formation of transparent LDH suspension in DMSO was observed. Taking this advantage, we have prepared transparent LDH/ethylene-vinyl alcohol copolymer (EVOH) nanocomposite films using DMSO as the processing solvent. Organic small molecules, UV absorbers, were intercalated into the LDH interlayers to incorporate the UV-shielding property into the transparent composite films. The thermal stability of UV absorbers was considerably improved after intercalation, which was attributed to the electrostatic interaction between the guest UV absorbers and the host LDH layers. The prepared composite films were flexible and exhibited excellent UV-shielding capability, but had transmittance as high as 90% in the visible region. The effect of LDH filler on thermal and mechanical properties of the composite films was also examined.

Partial exfoliation of layered double hydroxides in DMSO : a route to transparent polymer nanocomposites

Layered double hydroxides (LDHs), either having nitrate counter anions or intercalated with organic molecules, have been for the first time partially exfoliated in dimethyl sulfoxide (DMSO) to form a transparent suspension. Atomic force microscopy (AFM) images showed that both the lateral size and the thickness of the LDH nanoplatelets were decreased after the exfoliation. The organic-LDHs maintained their intercalation characteristics, i.e. the thermal stability improvement of the incorporated organic anions, after the exfoliation in DMSO. Transparent ethylene-vinyl alcohol copolymer (EVOH) nanocomposite films containing partially exfoliated LDHs intercalated with UV absorbers were prepared using DMSO as the processing solvent. As the first reported example of a highly transparent LDH/polymer composite, the obtained composite film had a visible light transmittance of 90% (comparable to that of the pure matrix), was flexible and exhibited an excellent UV-shielding capability and thermal stability.

Synthesis, characterization, and multilayer assembly of pH sensitive graphene−polymer nanocomposites

pH sensitive graphene−polymer composites have been prepared by the modification of graphene basal planes with pyrene-terminated poly(2-N,N′-(dimethyl amino ethyl acrylate) (PDMAEA) and poly(acrylic acid) (PAA) via π−π stacking. The pyrene-terminal PDMAEA and PAA were synthesized using reversible addition−fragmentation chain transfer (RAFT) polymerization with a pyrene-functional RAFT agent. The graphene−polymer composites were found to demonstrate phase transfer behavior between aqueous and organic media at different pH values. Atomic force microscopy (AFM) analysis revealed that the thicknesses of the graphene−polymer sheets were approximately 3.0 nm when prepared using PDMAEA (M_n: 6800 and PDI: 1.12). The surface coverage of polymer chains on the graphene basal plane was calculated to be 5.3 × 10⁻¹¹ mol cm⁻² for PDMAEA and 1.3 × 10⁻¹⁰ mol cm⁻² for PAA. The graphene−polymer composites were successfully characterized using X-ray photoelectron spectroscopy (XPS), attenuated total reflection infrared (ATR-IR) spectroscopy, and thermogravimetric analysis (TGA). Self-assembly of the two oppositely charged graphene−polymer composites afforded layer-by-layer (LbL) structures as evidenced by high-resolution scanning electron microscopy (SEM) and quartz crystal microbalance (QCM) measurements.

Study on the oriented recrystallization of carbon-coated polyethylene oriented ultrathin films

It is confirmed that a layer of vacuum-evaporated carbon on the surface of a preoriented ultrathin polymer film can lead to an oriented recrystallization of the polymer film. This has been attributed to a strong fixing effect of vacuum-evaporated carbon layer on the film surface of the polymer. To study the origin of the strong fixing effect of vacuum-evaporated carbon layer on the polymer films, the melting and recrystallization behaviors of the preoriented ultrathin PE film with a vacuum-evaporated carbon layer were studied by using atomic force microscopy, electron diffraction, Fourier transform infrared spectroscopy, and Raman spectroscopy. We found that there exists some extent of chain orientation of carbon-coated polyethylene (PE) preoriented ultrathin film above its melting temperature. These oriented PE chain sequences act as nucleation sites and induce the oriented recrystallization of preoriented PE film from melt. Raman spectroscopy results suggest that new carbon-carbon bonds between the carbon layer and the oriented PE film are created during the process of vacuum carbon evaporation. As a result, some of the PE chain stems are fixed to the coated carbon substrate via covalent bond. Such a bonding has retarded the relaxation of the PE chains at the spot and, therefore, preserves the original orientation of the PE stems at high temperature, which in turn derives the recrystallization of the PE chains in an oriented structure.

Self-assembled multimicellar vesicles via complexation of a rigid conjugated polymer with an amphiphilic block copolymer

A viable method of encapsulating block copolymer micelles inside vesicles using a conjugated polymer is reported in this study. Self-assembly and complexation between an amphiphilic block copolymer poly(methyl methacrylate)-b-poly(acrylic acid) (PMMA-b-PAA) and a rod-like conjugated polymer polyaniline (PANI) in aqueous solution were studied using transmission electron microscopy, atomic force microscopy and dynamic light scattering. The complexation and morphology transformation were driven by electrostatic interaction between PANI and the PAA block of the block copolymer. Addition of PANI to PMMA-b-PAA induced the morphology transformation from micelles to irregular vesicles through vesicles, thick-walled vesicles (TWVs) and multimicellar vesicles (MMVs). Among the observed morphologies, MMVs were observed for the first time. Morphology transformation was studied as a function of aniline/acrylic acid molar ratio ([ANI]/[AA]). Micelles were observed for the pure block copolymer, while vesicles and TWVs were observed at [ANI]/[AA] = 0.1 and 0.3, respectively. MMVs were observed at [ANI]/[AA] = 0.5 and irregular vesicles were observed for molar ratios at 0.7 and above. Clearly, a conjugated polymer like polyaniline can induce a morphology transformation even at its lower concentrations and produce complex morphologies.

Large compound vesicles from amphiphilic block copolymer/rigid-rod conjugated polymer complexes

Morphology evolution in complexes of amphiphilic block copolymers poly(styrene)-b-poly(acrylic acid) (PS-b-PAA) and poly(styrene)-b-poly(ethylene oxide) (PS-b-PEO) in the presence of polyaniline (PANI) in aqueous solution is reported. Transmission electron microscopy, atomic force microscopy, and dynamic light scattering techniques were used to study the morphologies at various PANI contents [aniline]/[acrylic acid] ([ANI]/[AA]) ranging from 0.1 to 0.7. The interpolyelectrolyte complex formed between PAA and PANI plays a key role in the morphology transformation. Spherical micelles formed from pure block copolymers were transformed into large compound vesicles upon increasing PANI concentration due to internal block copolymer segregation. In addition to varying PANI content, the kinetic pathway of nanoparticle formation was controlled through different water addition methods and was critical in the formation of multigeometry nanoparticles.

Removal of Pb (II) ions using polymer based graphene oxide magnetic nano-sorbent

Graphene oxide (GO) based magnetic nano-sorbent was synthesized by assembling the Fe3O4 and GO on the surface of polystyrene (denoted as PS@Fe3O4@GO). The morphology of the nano-sorbent was studied using scanning electron microscopy (SEM), while their individual nano-components were characterized using UV-visible spectroscopy, atomic force microscopy (AFM), zeta potential, transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The assembled nano-sorbent was further investigated for Pb (II) ions removal by optimizing the parameters including pH, temperature and contact time. The obtained data was modelled for adsorption kinetics, adsorption isotherms and thermodynamics. Kinetic experiments indicated the Pb (II) adsorption followed first order kinetics. The adsorption equilibrium data fits Langmuir isotherm model well and the adsorption process was found to be spontaneous. The adsorption capacity of the prepared nano-sorbent was estimated to be 73.52mgg-1, with a maximum removal of 93.78% at pH 6. The nano-sorbent can be regenerated by nitric acid (HNO3) for reuse. FT-IR and X-ray photoelectron spectroscopy (XPS) studies confirmed the interactions between the Pb (II) ions and the nano-sorbent.

Selective hydrogen bonding and hierarchical nanostructures in poly(hydroxyether of bisphenol A)/poly(ε-caprolactone)-block-poly(2-vinyl pyridine) blends

The phase behavior, hydrogen bonding interactions and morphology of poly(hydroxyether of bisphenol A) (phenoxy) and poly(var epsilon-caprolactone)-block-poly(2-vinyl pyridine) (PCL-b-P2VP) were investigated using differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, optical microscopy and atomic force microscopy (AFM). In this A-b-B/C type block copolymer/homopolymer system, both P2VP and PCL blocks have favorable intermolecular interaction towards phenoxy via hydrogen bonding. However, the hydrogen bonding between P2VP and phenoxy is significantly stronger than that between PCL and phenoxy. Selective hydrogen bonding between phenoxy/P2VP pair at lower phenoxy contents and co-existence of two competitive hydrogen bonding interactions between phenoxy/P2VP and phenoxy/PCL pairs at higher phenoxy contents were observed in the blends. This leads to the formation of a variety of composition dependent nanostructures including wormlike, hierarchical and core–shell morphologies. The blends became homogeneous at 95 wt% phenoxy where both blocks of the PCL-b-P2VP were miscible with phenoxy due to hydrogen bonding. In the end, a model was proposed to explain the microphase morphology of blends based on the experimental results obtained. The swelling of the PCL-b-P2VP block copolymer by phenoxy due to selective hydrogen bonding causes formation of different microphases

Nanostructure and hydrogen bonding in interpolyelectrolyte complexes of poly(ε-caprolactone)-block-poly(2-vinyl pyridine) and poly(acrylic acid)

Nanostructured poly(ε-caprolactone)-block-poly(2-vinyl pyridine) (PCL-b-P2VP)/poly(acrylic acid) (PAA) interpolyelectrolyte complexes (IPECs) were prepared by casting from THF/ethanol solution. The morphological behaviour of this amphiphilic block copolymer/polyelectrolyte complexes with respect to the composition was investigated in a solvent mixture. The phase behaviour, specific interactions and morphology were investigated using differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, optical microscopy (OM), dynamic light scattering (DLS) and atomic force microscopy (AFM). Micelle formation occurred due to the aggregation of hydrogen bonded P2VP block and polyelectrolyte (PAA) from non-interacted PCL blocks. It was observed that the hydrodynamic diameter (D_h) of the micelles in solution decreased with increasing PAA content up to 40 wt%. After 50 wt% PAA content, D_h again increased. The micelle formation in PCL-b-P2VP/PAA IPECs was due to the strong intermolecular hydrogen bonding between PAA homopolymer units and P2VP blocks of the block copolymer. The penetration of PAA homopolymers into the shell of the PCL-b-P2VP block copolymer micelles resulted in the folding of the P2VP chains, which in turn reduced the hydrodynamic size of the micelles. After the saturation of the shell with PAA homopolymers, the size of the micelles increased due to the absorption of added PAA onto the surface of the micelles.

The miscibility of poly(d,l-lactide-co-glycolide) with amphiphilic molecules and the interaction of their mixtures with DNA at air/water interface

The miscibility of poly(d,l-lactide-co-glycolide) (PLG) with three amphiphilic molecules and the interaction of the PLG/surfactant mixtures with DNA at air/water interface are investigated by π-A isotherms, Brewster angle microscopy (BAM) and atomic force microscopy (AFM) techniques. The π-A isotherms of the PLG mixtures with cationic C12AzoC6PyBr, and C12AzoC6N(CH3)3Br, are quite different from the π-A isotherm of pure PLG on water subphase. In contrast to the case, the π-A isotherm of PLG mixed with nonionic C12AzoC6OPy is almost identical to the pure PLG except some increasing of molecular area. Similar phenomena are observed on DNA subphase. The in situ BAM and ex situ AFM observations demonstrate that the dispersion of PLG at air/water interface becomes good when it mixes with the two cationic surfactants, whereas quite poor due to the phase separation when it mixes with the nonionic amphiphilic molecule. Based on these results we conclude that the cationic surfactants can affect the conformation change of PLG at air/water interface and figure a well miscibility with polymer whereas the nonionic amphiphilic molecule presents poor miscibility. In addition, the even mixing of the PLG and the cationic surfactants is favorable for the adsorption to DNA more effectively.

Competitive hydrogen bonding and self-assembly in Poly(2-vinyl pyridine)-block-Poly(methyl methacrylate)/ Poly(hydroxyether of bisphenol A) blends

Blends of poly(2-vinyl pyridine)-block-poly(methyl methacrylate) (P2VP-b-PMMA) and poly(hydroxyether of bisphenol A) (phenoxy) were prepared by solvent casting from chloroform solution. The specific interactions, phase behavior and nanostructure morphologies of these blends were investigated by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), dynamic light scattering (DLS), atomic force microscopy (AFM), and transmission electron microscopy (TEM). In this block copolymer/homopolymer blend system, it is established that competitive hydrogen bonding exists as both blocks of the P2VP-b-PMMA are capable of forming intermolecular hydrogen bonds with phenoxy. It was observed that the interaction between phenoxy and P2VP is stronger than that between phenoxy and PMMA. This imbalance in the intermolecular interactions and the repulsions between the two blocks of the diblock copolymer lead to a variety of phase morphologies. At low phenoxy concentration, spherical micelles are observed. As the concentration increases, PMMA begins to interact with phenoxy, leading to the changes of morphology from spherical to wormlike micelles and finally forms a homogenous system. A model is proposed to describe the self-assembled nanostructures of the P2VP-b-PMMA/phenoxy blends, and the competitive hydrogen bonding is responsible for the morphological changes.

Extending the surface force apparatus capabilities by using white light interferometry in reflection

The application of surface force apparatus (SFA) capabilities in measuring interactions between surfaces over nanometer separations was described. The technique is used when both the materials are transparent. It was observed that the poorly reflecting surface produce fringes that have low contrast and low finesse. The results show that the technique is successful when the visibility of the interference fringes is maximized.