A laser induced fluorescence-based instrument for in-situ measurements of atmospheric formaldehyde.

Direct, in situ detection of gas phase formaldehyde (HCHO) via laser induced fluorescence in a White-type multipass cell is demonstrated with a (3sigma) limit of detection of approximately 0.051 parts per billion by volume in a 1 s sampling time. Calibration is performed in two ways: using permeation tubes and with air bubbled through an aqueous solution of HCHO. The concentration of HCHO output from the bubbler is measured by cavity ring-down spectroscopy. Measurement of ambient HCHO is carried out at the University of Wisconsin, Madison for a period of several days.

Laser-induced phosphorescence for the in situ detection of glyoxal at part per trillion mixing ratios.

Glyoxal is a molecule of emerging importance to the atmospheric chemistry community because of its role in aerosol formation and utility as an indicator for oxidative chemistry. We describe the Madison laser-induced phosphorescence (LIP) instrument, an instrument based on LIP for direct, in situ measurement of gas-phase glyoxal with a S/N = 3 limit of detection (LOD) of 18 ppt(v)/min, with planned upgrades to reduce the LOD to 5 ppt(v)/min. By employing this technique, we have built an instrument with exceptional in situ limits of detection, tremendous selectivity, and the considerable advantage of direct, fast measurements that requires neither derivatization nor ex situ analysis. The instrument is equally well-suited for laboratory and field measurements. It was deployed for the first time to the BEARPEX 2007 field campaign in Georgetown, CA, producing nearly one month of continuous data with mixing ratios ranging from 20 to 250 ppt(v) glyoxal. To the authors' knowledge, this represents the first use of LIP for a field measurement.

Morphological evolution in dewetting polystyrene/polyhedral oligomeric silsesquioxane thin film bilayers.

Morphological evolution in dewetting thin film bilayers of polystyrene (PS) and a polyhedral oligomeric silsesquioxane (POSS), trisilanolphenyl-POSS (TPP), was studied as a function of annealing temperature and annealing time. The results demonstrate unique dewetting morphologies in PS/TPP bilayers at elevated temperatures that are significantly different from those typically observed in dewetting polymer/polymer bilayers. During temperature ramp studies by optical microscopy (OM) in the reflection mode, PS/TPP bilayers form cracks with a weak optical contrast at approximately 130 degrees C. The crack formation is attributed to tensile stresses within the upper TPP layer. The weak optical contrast of the cracks observed in the bilayers for annealing temperatures below approximately 160 degrees C is consistent with the cracking and dewetting of only the upper TPP layer from the underlying PS layer. The optical contrast of the morphological features is significantly enhanced at annealing temperatures of >160 degrees C. This observation suggests dewetting of both the upper TPP and the lower PS layers that results in the exposure of the silicon substrate. Upon annealing the PS/TPP bilayers at 200 degrees C in a temperature jump experiment, the upper TPP layer undergoes instantaneous cracking as observed by OM. These cracks in the upper TPP layer serve as nucleation sites for rapid dewetting and aggregation of the TPP layer, as revealed by OM and atomic force microscopy (AFM). X-ray photoelectron spectroscopy (XPS) results indicated that dewetting of the lower PS layer ensued for annealing times >5 min and progressed up to 90 min. For annealing times >90 min, OM, AFM, and XPS results revealed complete dewetting of both the layers with the formation of TPP encapsulated PS droplets.

Blends of amphiphilic poly(dimethylsiloxane) and nonamphiphilic octaisobutyl-POSS at the air/water interface.

Brewster angle microscopy (BAM) shows that a nonamphiphilic polyhedral oligomeric silsesquioxane (POSS) nanofiller, octaisobutyl-POSS, forms aggregates at all surface concentrations at the air/water interface. When amphiphilic poly(dimethylsiloxane) (PDMS) is blended with the octaisobutyl-POSS (>10 wt % PDMS), the degree of POSS aggregation dramatically decreases. Thermodynamic analyses and morphology studies through surface pressure-area per monomer isotherm data and BAM, respectively, exhibit three distinct composition regimes: (1) Blends with >70 wt % POSS have unstable isotherms whose shapes deviate from those of PDMS and form large rigid domains comparable to but smaller than pure, octaisobutyl-POSS films. (2) At compositions between approximately 40 and 70 wt % POSS, the isotherms' features are qualitatively similar to those of pure PDMS, and extensive nanofiller "networks" are observed by BAM. (3) For compositions < or = approximately 30 wt % POSS, the isotherms are essentially those of pure PDMS with small POSS domains dispersed in the PDMS matrix. These results provide further insight into nanofiller aggregation mechanisms and dispersion that may be present in thicker films and bulk systems.

Polyhedral oligomeric silsesquioxane amphiphiles: isotherm and brewster angle microscopy studies of trisilanolisobutyl-POSS at the air/water interface.

A trisilanol derivative of polyhedral oligomeric silsesquioxanes (POSS), trisilanolisobutyl-POSS, has recently been reported to form stable monolayers at the air/water interface. Moreover, the trisilanolisobutyl-POSS monolayer undergoes a nonequilibrium structural transition (collapse) around a surface pressure of Rho approximately 18 mN.m(-1). This paper explores the mono- and multilayer properties of POSS molecules at the air/water interface by the Wilhelmy plate technique and Brewster angle microscopy. Surface concentrations are controlled by four mechanisms: (1) compression at a constant rate, (2) stepwise compression followed by surface pressure relaxation to an "equilibrium" value, (3) successive additions of spreading solution followed by relaxation to a stable surface pressure value, and (4) hysteresis loops to test the reversibility of the structural transitions. Results show that both an increasing compression rate and a decreasing temperature lead to an increase in the surface pressure of the structural transition, which is consistent with the formation of solidlike multilayer domains during the collapse process. For the case of compression at a constant rate, small domains initially form and later aggregate to form large solid masses. Cessation of compression allows these large solid masses to relax into equilibrium ringlike structures with a lower surface pressure, Rho approximately 13 mN.m(-1). In contrast, if the film is expanded rapidly, these large solidlike domains relax into "spaghetti" like networks with a residual surface pressure that depends on the initial amount of the solidlike collapsed phase. Finally, successive addition and stepwise compression isotherm experiments lead to different and time-dependent morphologies. Understanding these surface properties of POSS molecules affords an excellent opportunity to design and study POSS/polymer blends for coating applications where POSS molecules with rigid inorganic cores, soft organic coronae, and dimensions comparable to polymeric monolayers can serve as perfectly monodisperse nanofillers.

Polyhedral oligomeric silsesquioxanes: a new class of amphiphiles at the air/water interface.

Insoluble films of trisilanolisobutyl-POSS and octaisobutyl-POSS at the air/water interface are investigated by means of surface pressure - area per molecule isotherm (Pi - A) and Brewster angle microscopy (BAM). Analysis of the experimental results shows the partial cage molecule, trisilanolisobutyl-POSS, is a surface-active molecule that self-assembles into uniform monolayer upon compression; but the fully condensed cage molecule, octaisobutyl-POSS, is nonamphiphilic.