Transition temperature of poly(methyl methacrylate) determined by time-of-flight secondary ion mass spectrometry and contact angle measurements.

The surface chain conformations of poly(methyl methacrylate) (PMMA) at different temperatures were extensively studied by time-of-flight secondary ion mass spectrometry (ToF-SIMS). Similar to our previous experimental studies on polystyrene (PS) and poly(2, 3, 4, 5, 6-pentafluorostyrene) (5FPS), a transition temperature (TT) could be identified through the principal component analysis (PCA) of the ToF-SIMS spectra obtained from the PMMA samples annealed at different temperatures. Interestingly, our results show that the TT depended on molecular weight and was about 50-60˚C below the bulk glass transition temperature (Tg) and therefore could possibly be related to the surface glass transition temperature (TgS). These results were confirmed by contact angle measurements. ToF-SIMS results showed higher peak intensities of several low-mass oxygen-containing positive ions, hydrocarbon positive ions and OCH3- negative ion at higher temperatures, which can be interpreted by a higher surface concentration of methoxy groups at the surface.

Detection of surface mobility of poly (2, 3, 4, 5, 6-pentafluorostyrene) films by in situ variable-temperature ToF-SIMS and contact angle measurements.

Poly (2, 3, 4, 5, 6-pentafluorostyrene) (5FPS) was prepared by bulk radical polymerization. The spin-cast films of this polymer were analyzed using time-of-flight secondary ion mass spectrometry (ToF-SIMS) at various temperatures ranging from room temperature to 120°C. Principal component analysis (PCA) of the ToF-SIMS data revealed a transition temperature (T(T)) at which the surface structure of 5FPS was rearranged. A comparison between the results of the PCA of ToF-SIMS spectra obtained on 5FPS and polystyrene (PS) indicate that the pendant groups of 5FPS and PS moved in exactly opposite directions as the temperature increased. More pendant groups of 5FPS and PS migrated from the bulk to the surface and verse versa, respectively, as the temperature increased. These results clearly support the view that the abrupt changes in the normalized principal component 1 value was caused by the surface reorientation of the polymers and not by a change in the ion fragmentation mechanism at temperatures above the T(T). Contact angle measurement, which is another extremely surface sensitive technique, was used to monitor the change in the surface tension as a function of temperature. A clear T(T) was determined by the contact angle measurements. The T(T) values determined by contact angle measurements and ToF-SIMS were very similar.

Evidence of enhanced mobility at the free surface of supported polymer films by in situ variable-temperature time-of-flight-secondary ion mass spectrometry.

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) spectra of polystyrene (PS) films supported on silicon wafers were obtained at temperatures ranging from room temperature to 100 °C. Principal component analysis (PCA) of the TOF-SIMS data revealed a transition temperature (TT) at which the surface structure of PS was rearranged. The TT of a 120-nm thick PS (weight-average molecular weight of 3,000 g/mol) thin film was determined to be about 36 °C, which is approximately 30 °C lower than the bulk glass transition temperature (Tg) of that PS. Similar TTs were observed on PSs with different molecular weights. As the TT is strongly related to the Tg and dependent on the molecular weight, it is believed that the TT determined by TOF-SIMS is related to the surface glass transition temperature (Tg(S)) measured by other techniques. This suggests that TOF-SIMS combined with PCA can be used to determine the Tg(S) of polymer films. Furthermore, the detailed PCA analyses indicate that the phenyl groups of PS tended to move away from the surface at temperatures above TT. This conclusion was further confirmed by contact angle and XPS measurements.

Hollow interior structure of spin-coated polymer thin films revealed by ToF-SIMS three-dimensional imaging.

Surface patterns were observed on spin-coated poly(bisphenol A decane ether) (BA-C10) films prepared with chloroform and tetrahydrofuran as the solvents. The interior structure of these surface patterns were analyzed using a time-of-flight secondary ion mass spectrometry (ToF-SIMS) equipped with a bismuth cluster source for ion imaging and a C(60)(+) cluster source for depth profiling. For the first time, the surface patterns have been shown to be hollow rather than solid using ToF-SIMS three-dimensional (3D) analysis and optical techniques. Moreover, the microarea depth profiling analysis indicated that the hollow structure was sandwiched between two polymer layers rather than sitting on the substrate. The height of the hollow structure and the thicknesses of the polymer layers above and below the hollow structure were also estimated from the depth profiling results.

High-impact polystyrene/halloysite nanocomposites prepared by emulsion polymerization using sodium dodecyl sulfate as surfactant.

High-impact polystyrene (PS) nanocomposites filled with individually dispersed halloysite nanotubes (HNTs) were prepared by emulsion polymerization of styrene in the presence of HNTs with sodium dodecyl sulfate (SDS) as the emulsifier. The SDS is a good dispersing agent for HNTs in aqueous solution. The emulsion polymerization resulted in the formation of polystyrene nanospheres separating individual HNTs. Transmission electron microscopy revealed that the HNTs were uniformly dispersed in the PS matrix. Differential scanning calorimetry, Fourier-transform infrared spectroscopy and thermogravimetry were used to characterize the PS/HNT nanocomposites. The impact strength of the PS/HNTs nanocomposites was 300% higher than that of the neat PS. This paper presents a simple yet feasible method for the preparation of high-impact PS/halloysite nanocomposites.

Time-of-flight-secondary ion mass spectrometry and principal component analysis: determination of structures of lamellar surfaces.

In this article, we addressed the applicability of time-of-flight secondary ion mass spectrometry (TOF-SIMS) to examine the effects of molecular weight and of flexible-segment length on the polymer chain arrangement at the folding surfaces of the lamellae. Poly(bisphenol A-etheralkane) (Cn) contains both rigid aromatic and flexible aliphatic CH(2) segments. The number of CH(2) units per flexible segment, n, varies from 8 to 12. Principal component analysis (PCA) of TOF-SIMS data revealed the chemical and structural variations of the folding surfaces of these polymers and identified the ion peaks contributing to these variations. We highlighted the discriminating power of PCA to distinguish the structural conformations of the amorphous and flat-on lamellar surfaces of these polymers. PCA loadings analyses showed that relatively more flexible structures were deposited on the folding surfaces when the flexible-segment length increased from 8 to 10 CH(2) units. The concentration of short loops at folding surfaces and the disorder of folding surfaces increased when the molecular weight increased. All these results led us to conclude that TOF-SIMS has great potential for probing the chemical composition of the folding surfaces of polymers.

Induction of molecular organization of oligomers by low-energy electrons.

We reveal that a beam of low-energy electrons (18 eV) can directly trigger long-range molecular ordering of an amorphous, semi-flexible oligomer in a few minutes without the prerequisite of pre-orientation. A strong endothermic transition was detected with a micro-thermal analyzer on the areas that had been exposed to the electron irradiation while the areas that were shielded from the irradiation by a protective mask remained amorphous as usual. This result suggests that long-range molecular ordering only develops in the area of the oligomer film under electron irradiation. This is the first-time effort to use electron irradiation to control the long-range ordering of an amorphous organic thin film above the glass transition temperature.

Control of the fold surface conformation of the lamellae of an oligomer.

Small-angle X-ray scattering revealed that a semirigid oligomer of bisphenol-A-co-ether-octane with a monodisperse chain length is capable of forming ciliated-folded, once-folded, ciliated-extended and fully extended lamellar structures. Isothermal crystallization studies suggested a sequence of structures with increasing crystallization temperature, from a ciliated-folded to a once-folded form and then to a ciliated-extended form as the degree of supercooling is decreased. The crystal surface thus changed from octane cilia to bisphenol A segments and then back to octane cilia as the lamellar structure changed. The results of time-of-flight secondary ion mass spectrometry analyses strongly supported the fold structural models.

Concentric-ringed structures in polymer thin films.

Novel polymer crystalline structures containing micrometer-sized concentric rings (or bands) were observed in thin poly(bisphenol A hexane ether) (BA-C6) films. The origin of the banded structures was found to be different from that of traditional banded spherulites in polymer systems. Analyses based on optical microscopy (OM) and atomic force microscopy (AFM) revealed that the banded structures contained alternating ridge and valley bands of polymer crystals in the flat-on orientation. No lamellar twisting was observed within the concentric-ringed structures, which were developed as a result of the formation of a depletion zone during crystallization. The formation of a depletion zone was determined to be caused by the specific volume decrement between the crystal and the melt and by the diffusion of polymer chains to the fold surfaces of the flat-on lamellae. The height of the ridges and the interband widths could be adjusted by controlling the diffusion rate. Time-of-flight secondary ion mass spectrometry ion images showed higher concentrations of low-molecular-weight polymer chains on the surfaces of the ridges than in the valleys.

Real-time observation of lamellar branching induced by an AFM tip and the stability of induced nuclei.

Branching of edge-on lamellae of poly(bisphenol A octane ether) (BA-C8) was studied at room temperature (21 +/- 1 degrees C) using real-time tapping mode atomic force microscopy (AFM). Lamellar branches were shown to develop from induced nuclei that had originated from lamellar defects, namely protruding cilia and loose loops, of parent lamellae. Induced nuclei appeared and also disappeared-a phenomenon observed first time by AFM. Induced nuclei are one of the possible origins for the branching of lamellae. Branching of edge-on lamellae can be induced by an AFM tip though the adjustment of the set-point amplitude ratio (r(sp)). Using an r(sp) smaller than 0.65, defects could be created on the lamellar surface, which gave rise to lamellar branches.