Investigation of the phase separation of PNIPAM using infrared spectroscopy together with multivariate data analysis

The use of vibrational spectroscopy to investigate complex structural changes in polymers yields chemically rich data, but interpretation can be challenging and subtle but meaningful spectral changes may be missed through visual inspection alone. Multivariate analysis is an efficient approach to gain an oversight of small but systematic spectral differences anywhere within the spectra, providing further insight into structural changes and associated transformation mechanisms. In this study, the novel analytical approach of infrared spectroscopy combined with principal component analysis and Gaussian peak fitting was used to investigate the structural changes in aqueous solutions of a polymer, using poly(N-isopropyl acrylamide) (PNIPAM) in the atactic form and with controlled tacticity as a model system. Subtle spectral changes associated with the dehydration and phase separation upon heating included peak shifts, an area ratio change of the amide I band to the amide II band and formation of a new peak in the amide I band were efficiently detected. Dehydration and phase separation of PNIPAM occurred in two temperature ranges, one for the atactic and one for isotactic rich part, both involving a complex re-organization of the hydrogen bonds and change of the hydration layer. The changes agreed with existing results from other techniques, and new insights were gained into the effect of controlled tacticity on phase transformation behaviour. The study demonstrates that infrared spectroscopy combined with the multivariate analytical method principal component analysis and Gaussian peak fitting is an efficient approach to probing structural change in polymers during heating. The simplicity of the presented approach could find excellent use in analysing and understanding the molecular environment of a range of stimuli-responsive polymers, for instance block or grafted types of polymers, as well as those with controlled tacticity.     

Investments into forest biorefineries under different price and policy structures

Increasing scarcity of oil reserves and the high CO₂ emissions from using oil have contributed to the development of renewable biofuels. Pulp and paper mill integrated forest biorefineries offer one important means to increase biofuel production. This study analyzes the effects of policies to support biofuel production in the pulp and paper sector. We study the relative effectiveness of three biofuel supporting policy instruments, namely production subsidy, input subsidy and investment subsidy. We present a partial equilibrium pulp and paper market model with a biorefinery investment option. A numerical model is used to evaluate the impacts of policy instruments on wood prices, as well as input choices and investment strategies of pulp and paper industries. The data represent the Finnish pulp and paper sector. We evaluate the values and direct costs of the policy instruments in a situation of exogenous biofuel production targets. The direct costs of input and investment subsidies are higher than those of a production subsidy. With all the policy instruments, Finnish pulp and paper mills would invest in wood-gasifying technology, instead of black liquor based one. The number of biorefinery units is dependent on the subsidy type — investment and input subsidies are likely to result in more numerous but smaller biofuel production units than a production subsidy. With all the policy instruments the demand for wood increases in Finland leading to higher wood prices. This, in turn, could reflect negatively on the profitability of the pulp and paper industries. To a significant degree, the model and the results can be generalized to other countries and markets where integrated pulp and paper mills are operating.     

Unique Decipherability in the Monoid of Languages: An Application of Rational Relations

We attack the problem of deciding whether a finite collection of finite languages is a code, that is, possesses the unique decipherability property in the monoid of finite languages. We investigate a few subcases where the theory of rational relations can be employed to solve the problem. The case of unary languages is one of them and as a consequence, we show how to decide for two given finite subsets of nonnegative integers, whether they are the nth root of a common set, for some n≥1. We also show that it is decidable whether a finite collection of finite languages is a Parikh code, in the sense that whenever two products of these sets are commutatively equivalent, so are the sequences defining these products. Finally, we consider a nonunary special case where all finite sets consist of words containing exactly one occurrence of the specific letter.     

Methane oxidation on alumina supported palladium catalysts: Effect of Pd precursor and solvent

Palladium precursors and solvents were studied for their effects on the activities of alumina-based palladium catalysts in methane combustion and the resistance of the catalysts to thermal aging. The properties of the catalysts were compared with those of a commercial reference. The palladium precursors were Pd(propionate)₂, Pd(acetate)₂ and Pd(acetyl acetonate)₂ and the solvents were acetone, acetic acid, propionic acid and toluene. Catalysts were prepared by the wet impregnation method.Catalysts were characterized by powder X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and energy dispersive X-ray spectroscopy (EDS). The surface areas were measured by Brunauer–Emmett–Teller method (BET). Acidity of the alumina support was measured by NH₃ desorption. Activities of the catalysts in methane oxidation were screened under lean burn conditions.In methane oxidation with fresh catalyst, the best performance was obtained with a combination of Pd(acetate)₂ and acetic or propionic acid. The light-off temperatures of the fresh catalysts (562 K and 557 K, respectively) were slightly lower than the light-off temperature (567 K) of the commercial reference. Differences between the light-off temperatures of the aged and fresh catalysts were least when the catalysts were prepared with Pd(acetyl acetonate)₂ as Pd precursor and in acetic or propionic acid as solvent: +12 K and +18 K, respectively. The corresponding value for the reference was +64 K. For several of the fresh catalysts, conversion in methane oxidation at 623 K was over 90%. A comparison of methane combustion and NH₃ desorption results indicated that acidity of the support material affects catalysts activity.     

Observation of NMR Signals from a Thin 3He Slab

NMR free precession signals from a slab of normal ³ He of thickness comparable to the superfluid coherence length have been observed using a SQUID NMR spectrometer at a frequency of 880 kHz. This spectrometer is based on a SQUID with Additional Positive Feedback, directly coupled to a low noise room temperature amplifier, and operated in flux locked loop mode using the direct offset integration technique, with a bandwidth of several MHz. The sensitivity is such that the signal from a 100 nm slab on a 1 cm ² surface, corresponding to 2×10 ¹⁷ spins, is clearly resolved.     

Effect of glycerol on blood flow distribution in tumoral and peritumoral brain tissue

The effect of glycerol on blood flow in tumoral and peritumoral tissue was measured in 32 patients with brain tumor, 17 gliomas and 15 meningiomas. Blood flow before and after the administration of glycerol was measured by stable xenon-enhanced computed tomography. The tumor part of glioma was significantly hypoperfused. In contrast, the tumor part of meningioma was significantly hyperperfused. Peritumoral edema of both glioma and meningioma was hypoperfused. After the administration of glycerol, blood flow increased in all regions except for the tumor part of glioma. Vascular responses to glycerol may be different in these two tumor types. The steal phenomena of blood flow might occur in cases of glioma.     

Measuring strain distributions in amorphous materials.

A number of properties of amorphous materials including fatigue, fracture and component performance are governed by the magnitude of strain fields around inhomogeneities such as inclusions, voids and cracks. At present, localized strain information is only available from surface probes such as optical or electron microscopy. This is unfortunate because surface and bulk characteristics in general differ. Hence, to a large extent, the assessment of strain distributions relies on untested models. Here we present a universal diffraction method for characterizing bulk stress and strain fields in amorphous materials and demonstrate its efficacy by work on a material of current interest in materials engineering: a bulk metallic glass. The macroscopic response is shown to be less stiff than the atomic next-neighbour bonds because of structural rearrangements at the scale of 4-10 A. The method is also applicable to composites comprising an amorphous matrix and crystalline inclusions.     

Do Dislocation Loops Destroy Facet Flatness?

Following our discovery of a new surface state near the facet edges of ⁴ He crystals, it was argued that thermally excited dislocation loops could destroy the facet flatness. Recent measurements of facet profiles of very small ⁴ He crystals indicate that the activation energy of these loops would have to be more than 20 K, which is quite high. The possible consequences of this result are discussed.