A compendium of comparison function results

The use of comparison functions has become standard in systems and control theory, particularly for the purposes of studying stability properties. The use of these functions typically allows elegant and succinct statements of stability properties such as asymptotic stability and input-to-state stability and its several variants. Furthermore, over the last 20 years several inequalities involving these comparison functions have been developed that simplify their manipulation in the service of proving more significant results. Many of these inequalities have appeared in the body of proofs or in appendices of various papers. Our goal herein is to collect these inequalities in one place.     

Biomimetic strain hardening in interpenetrating polymer network hydrogels

In this paper, we present the systematic development of mechanically enhanced interpenetrating polymer network (IPN) hydrogels with Young's moduli rivaling those of natural load-bearing tissues. The IPNs were formed by synthesis of a crosslinked poly(acrylic acid) (PAA) network within an end-linked poly(ethylene glycol) (PEG) macromonomer network. The strain-hardening behavior of these PEG/PAA IPNs was studied through uniaxial tensile testing and swelling measurements. The interaction between the independently crosslinked networks within the IPN was varied by (1) changing the molecular weight of the PEG macromonomer, (2) controlling the degree of PAA ionization by changing pH, and (3) increasing the polymer content in the PAA network. Young's moduli and the maximum stress-at-break of the swollen hydrogels were normalized on the basis of their polymer content. Strain hardening in the IPNs exhibited a strong dependence on the molecular weight of the first network macromonomer, the pH of the swelling buffer, as well as the polymer content of the second network. The results indicate that the mechanical enhancement of these IPNs is mediated by the strain-induced intensity of physical entanglements between the two networks. The strain can be applied either by mechanical deformation or by changing the pH to modulate the swelling of the PAA network. At pHs below the pK_a of PAA (4.7), entanglements between PEG and PAA are reinforced by interpolymer hydrogen bonds, yielding IPNs with high fracture strength. At pHs above 4.7, a “pre-stressed” IPN with dramatically enhanced modulus is formed due to ionization-induced swelling of the PAA network within a static PEG network. The modulus enhancement ranged from two-fold to over 10-fold depending on the synthesis conditions used. Variation of the network parameters and swelling conditions enabled “tuning” of the hydrogels' physical properties, yielding materials with water content between 58% and 90% water, tensile strength between 2.0 MPa and 12.0 MPa, and initial Young's modulus between 1.0 MPa and 19.0 MPa. Under physiologic pH and salt concentration, these materials attain “biomimetic” values for initial Young's modulus in addition to high tensile strength and water content. As such, they are promising new candidates for artificial replacement of natural tissues such as the cornea, cartilage, and other load-bearing structures.     

Biochemical activities during lipid accumulation inCandida curvata

Intracellular and extracellular concentrations of citrate and the specific activities of ten different enzymes in Candida curvata D were examined in relation to lipid biosynthesis in batch and continuous culture. Citrate was found to accumulate prior to lipid production and declined markedly as lipid accumulated in batch culture. The cells excreted citrate as the culture became nitrogen-limiting after 30 hr of growth, but little more was expelled after 40 hr when lipid accumulation was more marked. In continuous culture, only low levels of citrate were detected at the lower dilution rates and citrate was completely absent from both the cells and medium above a dilution rate of 0.1/hr. The activity of malic enzyme, malate dehydrogenase and ATP:citrate lyase increased in batch culture on lipid accumulated and, in continuous culture, both malic enzyme and ATP:citrate lyase varied in parallel with the specific rate of lipid synthesis which increased with increasing dilution rate. Activity of malate dehydrogenase, citrate synthase and glucose-6-phosphate dehydrogenase decreased with increasing dilution rate. The regulatory significance of these enzymes in lipid accumulation by C. curvata is discussed.     

Characterisation of the adsorption sites of hydrogen on Pt/C fuel cell catalysts

A key component of a hydrogen fuel cell is a catalyst to dissociate dihydrogen to hydrogen atoms. In the present study, the adsorption of hydrogen on Pt/C fuel cell catalysts has been investigated by inelastic neutron scattering spectroscopy.

Monitoring a clean Pt(50%)/C catalyst with low energy neutron spectroscopy, after exposure to dihydrogen at 20 K, as it was heated to room temperature, showed three distinct temperature regimes: (i) a decrease in intensity from 10 to 60 K, (ii) a rise to a maximum between 60 and 120 K and then (iii) a slow fall-off towards room temperature. We assign the three regions as: (i) desorption of physisorbed dihydrogen, (ii) dissociation of dihydrogen to give an adsorbed layer and (iii) damping of the response by an increasing Debye–Waller factor.

The vibrational INS spectra of a series of Pt/C catalysts prepared under varying conditions were similar indicating that the same types of site are common to all the catalysts, although the relative proportions of each site are sample dependent. Features at 520, 950 and part of the intensity at 1300 cm⁻¹ are assigned to hydrogen on (1 1 1) faces, in good agreement with single crystal data. The mode at 640 cm⁻¹ is assigned as the doubly degenerate asymmetric stretch of Pt(1 0 0) faces with the symmetric stretch near 550 cm⁻¹.

We assign the bending mode of the on-top site to the feature at 470 cm⁻¹. The Pt–H stretch mode was observed at 2079 cm⁻¹. This is a significant result: this is the first time that hydrogen on the on-top sites has been observed on nanosized platinum particles supported on high surface area carbon black. The width of the INS peak is surprisingly large and may give additional information on the type and relative proportions of the crystallographic faces present on the catalyst particles.     

THE ADHESION OF ISOCYANATE-BASED POLYMERS TO STEEL

Isocyanate-based materials have been used for decades as the basis for high performance adhesives, coatings, and primers. The origin of the excellent adhesion of these materials to metals such as steel has been generally assumed to derive from the condensation of isocyanates with metal hydroxyls to form metal oxide-cyanate esters analogous to urethanes. In this work Fourier transform infrared reflection (FTIR) was used to demonstrate that these esters do indeed form, but that the esterification is preceded by the formation of carbamate salts between the isocyanate and the hydrated metal oxide.

Isocyanate pMDI Polyurethane Steel Adhesion Interface     

Image analysis for interfacial area and cocontinuity detection in polymer blends

A novel image processing method was developed to extract interfacial area concentration measurements from 2D micrographs of immiscible polymer blends. Although this method can be used for analyzing different types of 2D micrographs such as optical or transmission electron microscopy images, it was designed for analyzing scanning electron microscopy (SEM) images. The method operates by detecting edges within the images and using standard image processing operations to selectively eliminate false edges. SEM images of polyethylene oxide/polystyrene (PEO/PS) blends were analyzed using this image processing method to measure the amount of interfacial area in the samples. Interfacial area per unit volume exhibits maxima for blend compositions at the boundary between droplet and cocontinuous morphologies. In addition to the detection of cocontinuity, the interfacial area measurements facilitated by this method may be used in future investigations of blend dynamics, including coalescence, drop deformation, and blend rheology studies. These measurements may also be used to quantify the effects of compatibilizers on blend morphology.     

Effect of Dyebath Additives on Decolorization Efficiency in the Ozonation of Dyehouse Effluent

It is necessary to study the effect of dyebath additives on decolorization efficiency in order to optimize ozone-based decolorization processes as the consumption of ozone can be reduced through selecting ozone favorable additives. The effect of 5 dyebath additives viz. electrolytes (sodium chloride and sodium sulfate), chelating agent (ethylene diamine tetra acetic acid or EDTA), reducing agent (sodium dithionite), optical brightener (Uvitex BHT), and dispersing agent (Zetex DNVL) was investigated. All of the additives showed synergistic effect as addition of sodium chloride, sodium dithionite and Zetex DN-VL markedly improved decolorization efficiency, but EDTA and optical brightener showed negative effect. Sodium sulfate did not show any positive or negative effect on decolorization efficiency.     

Dose and enantiospecific responses of white pine cone beetles,Conophthorus coniperda,to alpha-Pinene in an eastern white pine seed orchard

The white pine cone beetle, Conophthorus coniperda, exhibited dose and enantiospecific responses to -pinene in stands of mature eastern white pine, Pinus strobus, in a seed orchard near Murphy, North Carolina, USA. (–)--Pinene significantly increased catches of cone beetles to traps baited with (± )-trans-pityol. (+)--Pinene did not increase catches of beetles to pityol-baited traps and interrupted the response of beetles to traps baited with (±)-trans-pityol and (–)--pinene. Maximal attraction of cone beetles to pityol-baited traps was obtained with lures releasing (–)--pinene at a rate of 103 mg/day at 23^°C. Lures releasing (–)--pinene at rates lower or higher than 103 mg/day resulted in reduced catches to traps baited with (±)-trans-pityol. The sex ratio in all catches was heavily male biased. Attraction of the clerid predator, Thanasimus dubius, to traps baited with (±)-trans-pityol increased significantly with the presence of -pinene, irrespective of enantiomeric composition. Maximal attraction of T. dubius to pityol-baited traps occurred with devices releasing (–)--pinene at the highest rate tested, 579 mg/d at 23^°C, a sub optimal rate for cone beetles.     

Processing of mesocarbon microbeads to high-performance materials: Part II. Reaction bonding by in situ silicon carbide and nitride formation

The processing of carbon-ceramic composites by utilizing the unique sintering ability of mesocarbon microbeads (MCMB) is reported. The ceramic constituents (silicon nitride and silicon carbide) are formed in situ by reactions between MCMB and silicon in different atmospheres. In comparison with direct addition of ceramic (SiC, Si₃N₄) phases, in situ formation shows several appealing features. By inducing the reaction of silicon with MCMB, the sintering ability of the composite is enhanced via reaction bonding mechanisms. Similarly, it is demonstrated that composite porosity is limited owing to silicon reaction with nitrogen. The reactive formation of nanoscale ceramic reinforcements via decomposition of the silicon-containing polymer (e.g. poly-carbomethyl-silane) is also reported. This approach results in formation of uniform nanosized (>100 nm) SiC layers strongly bonded to the surface of the carbon particles. The presented results contribute to the development of carbon-ceramic materials with high-operational properties.     

Extension of Master Sintering Curve Theory to Organic Decomposition

The ability to predict and control organic decomposition of a material under arbitrary thermal treatments is one of the main objectives of thermogravimetric studies. The development of this ability provides significant potential to ensure reliability and reproducibility for a given processing method and can be used in planning optimized thermal treatment strategies. Based on this report, the master sintering curve theory has been successfully extended to similar kinetically controlled phenomena. The theory has been applied to organic decomposition reaction kinetics to develop a master organic decomposition curve. The fundamental kinetics are assumed to be governed by an Arrhenius-type reaction rate, making master sintering and decomposition curves analogous to one another. The formulation and construction of a master decomposition curve are given in this paper. Simultaneous thermogravimetric and differential thermal analysis of a low-temperature co-fire glass/ceramic dielectric tape (Dupont 951 Green Tape^TM) is analyzed and used to demonstrate this new concept. The results reveal two independent organic decomposition reactions, the first occurring at ≈245°C and the second at ≈365°C. The analysis is used to produce a master decomposition curve and to calculate the activation energy for these reactions, at 86±6 and 142±4 kJ/mol, respectively. In addition, the weight loss of product and the rate of decomposition can be predicted under varying thermal paths (time–temperature trajectories) following a minimal set of preliminary experiments.