Polyethylene terephthalate (PET) bulk film analysis using C60+, Au3+, and Au+ primary ion beams

The damage characteristics of polyethylene terephthalate (PET) have been studied under bombardment by C₆₀+, Au₃+ and Au+ primary ions. The observed damage cross-sections for the three ion beams are not dramatically different. The secondary ion yields however were significantly enhanced by the polyatomic primary ions where the secondary ion yield of the [M + H]+ is on average 5× higher for C₆₀+ than Au₃+ and 8× higher for Au₃+ than Au+. Damage accumulates under Au+ and Au₃+ bombardment while C₆₀+ bombardment shows a lack of damage accumulation throughout the depth profile of the PET thick film up to an ion dose of 1 ~ 10¹⁵ ions cm⁻². These properties of C₆₀+ bombardment suggest that the primary ion will be a useful molecular depth profiling tool.

Amine enrichment of thin-film composite membranes via low pressure plasma polymerization for antimicrobial adhesion

Thin-film composite membranes, primarily based on poly(amide) (PA) semipermeable materials, are nowadays the dominant technology used in pressure driven water desalination systems. Despite offering superior water permeation and salt selectivity, their surface properties, such as their charge and roughness, cannot be extensively tuned due to the intrinsic fabrication process of the membranes by interfacial polymerization. The alteration of these properties would lead to a better control of the materials surface zeta potential, which is critical to finely tune selectivity and enhance the membrane materials stability when exposed to complex industrial waste streams. Low pressure plasma was employed to introduce amine functionalities onto the PA surface of commercially available thin-film composite (TFC) membranes. Morphological changes after plasma polymerization were analyzed by SEM and AFM, and average surface roughness decreased by 29%. Amine enrichment provided isoelectric point changes from pH 3.7 to 5.2 for 5 to 15 min of plasma polymerization time. Synchrotron FTIR mappings of the amine-modified surface indicated the addition of a discrete 60 nm film to the PA layer. Furthermore, metal affinity was confirmed by the enhanced binding of silver to the modified surface, supported by an increased antimicrobial functionality with demonstrable elimination of E. coli growth. Essential salt rejection was shown minimally compromised for faster polymerization processes. Plasma polymerization is therefore a viable route to producing functional amine enriched thin-film composite PA membrane surfaces.

The last 10 amino acid residues beyond the hydrophobic motif are critical for the catalytic competence and function of protein kinase Cá*

The segment C-terminal to the hydrophobic motif at the V5 domain of protein kinase C (PKC) is the least conserved both in length and in amino acid identity among all PKC isozymes. By generating serial truncation mutants followed by biochemical and functional analyses, we show here that the very C terminus of PKCα is critical in conferring the full catalytic competence to the kinase and for transducing signals in cells. Deletion of one C-terminal amino acid residue caused the loss of ~60% of the catalytic activity of the mutant PKCα, whereas deletion of 10 C-terminal amino acid residues abrogated the catalytic activity of PKCα in immune complex kinase assays. The PKCα C-terminal truncation mutants were found to lose their ability to activate mitogen-activated protein kinase, to rescue apoptosis induced by the inhibition of endogenous PKC in COS cells, and to augment melatonin-stimulated neurite outgrowth. Furthermore, molecular dynamics simulations revealed that the deletion of 1 or 10 C-terminal residues results in the deformation of the V5 domain and the ATP-binding pocket, respectively. Finally, PKCα immunoprecipitated using an antibody against its C terminus had only marginal catalytic activity compared with that of the PKCα immunoprecipitated by an antibody against its N terminus. Therefore, the very C-terminal tail of PKCα is a novel determinant of the catalytic activity of PKC and a promising target for selective modulation of PKCα function. Molecules that bind preferentially to the very C terminus of distinct PKC isozymes and suppress their catalytic activity may constitute a new class of selective inhibitors of PKC.

Bleaching and dyeing of superfine wool powder/polypropylene blend film

Fibers based regenerated protein draw much attention for recycling discarded protein resources and can produce biodegradable and environmental friendly polymers. In this study, superfine wool powder is blended with polypropylene (PP) to produce wool powder/PP blend film through extrusion and hot-pressing. Hydrogen peroxide is used to bleach the black colored surface of the blend films. The effects of peroxide concentration, bleaching time and powder content on the final whiteness and mechanical properties of the blend films are investigated.

The bleached films are dyed with acid red dyes and the dyed color is evaluated using a Computer Color Matching System. Color characters of dyed films, such as L*, a*, b*, ΔE*ab, C*ab and K/S values are measured and analyzed. The study not only reuses discarded wool resources into organic powder, widens the application of superfine wool powder on polymers, but also improves the dyeing properties of PP through the addition of protein content.

Thermoplastic film from superfine wool powder

In this paper a research work is described in which superfine wool powder was plasticised by glycerol and hot-pressed into a kind of thermoplastic film. SEM photos show that the powder is moulded into a smooth surface and is conglutinated into a continuous phase in the cross-section of the film. The glycerol content, moulding pressure, temperature and moulding time were changed in the moulding process. The sizes and thickness aw well as tensile strength, modulus, breaking elongation and breaking energy of the films were also tested to investigate the thermoplasticity and mechanical properties of the films. The best moulding techniques included a glycerol content of 30%, a moulding pressure of 5 MPa, a temperature of 160 °C and a moulding time of 5 minutes.

Women's cognitive and emotional processing during sexual arousal : the effects of erotic film and absorption

Sexual arousal is a complex and dynamic element of women’s sexuality. Accounts vary, however most multidimensional models highlight the cognitive, affective and physiological components of the female sexual arousal response. While literature examining the peripheral physiological changes that occur during female sexual arousal abounds, there has been a dearth of literature pertaining to the cognitive and affective components. Thus, while many authors have included cognitive and emotions as independent components of the female sexual arousal response, there has been little empirical research to validate this approach. The aim of the current thesis was to examine the cognitive and affective components of female sexual arousal in more depth, investigating the nature of the relationship between these components under various experimental conditions. In order to do so, two integrated studies were conducted, each highlighting the effects of either external or internal variables on women’s subjective sexual arousal, absorption, positive affect and negative affect. Study One was designed to evaluate women’s emotional and cognitive processing of two elements of erotic film – foreplay and erotic context. 60 women were asked to report their subjective sexual arousal, absorption, positive affect and negative affect in response to one of four erotic film excerpts. The erotic excerpts varied in accordance with the degree of foreplay (low vs. high) depicted and the context in which the sexual activities took place (novel vs. habitual context). Women in the study responded more favourably to the high foreplay erotic film excerpt, subsequently reporting higher degrees of subjective sexual arousal, absorption and positive affect. Women also responded favourably to the erotic excerpt filmed in a novel context, reporting greater subjective sexual arousal as a result. The environment in which the sexual encounters were filmed failed to have an effect however, on women’s absorption or their positive or negative affect. The results of Study One suggest that stimulus specific variables, such as the degree of foreplay depicted, have a significant influence on female cognitive and emotional processing of erotic film. The results also suggest that a relationship exists between absorption, subjective sexual arousal and positive affect, albeit a correlational one. Specifically, there was evidence of parallel processing during sexual arousal, as participant reported sexual arousal, absorption and positive affect all increased and decreased in unison. Based on the results it was suggested that future research attempt to experimentally manipulate one of these variables, to examine its direct effect on the remaining variable. Thus, Study Two aimed to examine the effects of absorption on women’s cognitive and emotional processing of erotica. Study Two manipulated absorption at two levels (high vs. low), examining the impact of these states on participants’ subsequent absorption, subjective sexual arousal and positive and negative affect. 62 women were asked to read one of two sets of test session instructions. The first, participant-oriented instruction set, instructed participants to immerse themselves in the erotic film excerpt, as if they were active participants in the sexual exchange. The second, spectator-oriented instruction set, directed participants to observe and evaluate the erotic film. These instructions were designed to elicit high and low degrees of absorption, respectively. The utility of this approach when manipulating female absorption, was demonstrated by self reported ratings of absorption, given at the conclusion of the film presentation. Participants were also asked to report their subjective sexual arousal and positive and negative affect at the conclusion of the erotic film presentation. The findings of this study suggest that the adoption of a participant-oriented (high absorption) perspective elicits more favourable responses from participants than a spectator-oriented (low absorption) perspective, with participants in the former experimental group reporting greater degrees of subjective sexual arousal and positive affect. Negative affect was equivalent across experimental conditions, with the participants reporting that they experienced little to no aversive feelings during either of the experimental conditions. The results suggest that the degree to which a women immerses and absorbs herself in a sexual stimulus has a significant impact in her subsequent cognitive and affective processing of that stimulus. More specifically, it appears that women respond more favourably when they are highly absorbed and immersed in a stimulus, reporting greater subjective sexual arousal and positive affect. Overall, the results of Studies One and Two highlight the dynamic and complex nature of female sexual arousal. It appears that women have definite cognitive and affective responses to sexual stimuli. The magnitude of these responses may be mediated by a number of factors however, including the intrinsic qualities of the stimulus and the degree to which the woman attends to the stimulus. Both these variables act to either enhance or inhibit the sexual arousal response. There results have important implications for current sexuality literature. While women’s cognitions and emotions in response to erotic film were generally highly correlated, in some instances they differed, warranting their inclusion as separate elements in models of female sexual arousal. Furthermore, it might be suggested that the inclusion of an additional variable – absorption – into current models of female sexual arousal would prove beneficial, aiding researchers to better understand and predict the arousal process. As such, recommendations are made for a revised model of female sexual arousal. In terms of future directions, the results of the present thesis have implications for the treatment of sexual dysfunctions, suggesting that clinicians need to understand the internal and external variables that might contribute to the aetiology and maintenance of their presenting problems.

Self-assembly and film stability of a micelle of a single-chain quaternary ammonium amphiphile containing azobenzene on mica

The self-assembling behavior of a single-chain quaternary ammonium amphiphile bearing azobenzene (C₁₂AzoC₆N⁺) on freshly cleaved mica sheet has been investigated by atomic force microscopy (AFM) method. Confocal microscopic Raman spectra confirm the adsorption of the self-assembled monolayer structure. Ex-situ AFM reveals that C₁₂AzoC₆N⁺ forms branch-like stripes indicating the fusion and reorganization of the micelles during drying in air as the in-situ AFM has revealed that surfactant forms spherical micelles on the mica surface. The nano-sized surface structure is strongly dependent on the change of molecular structure, which resulted from photo-induced isomerization. The nano-sized stripe is quite stable even being annealed at 90 °C for 4 h.

The nature of the surface film on steel treated with cerium and lanthanum cinnamate based corrosion inhibitors

The corrosion inhibition mechanisms of new cerium and lanthanum cinnamate based compounds have been investigated through the surface characterisation of the steel exposed to NaCl solution of neutral pH. Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopy was used to identify the nature of the deposits on the metal surface and demonstrated that after accelerated tests the corrosion product commonly observed on steel (i.e. lepidocrocite, γ-FeOOH) is absent. The cinnamate species were clearly present on the steel surface upon exposure to NaCl solution for short periods and appeared to coordinate through the iron. At longer times the Rare Earth Metal (REM) oxyhydroxide species are proposed to form as identified through the bands in the 1400–1500 cm⁻¹ region. These latter bands have been previously assigned to carbonate species adsorbed onto REM oxyhydroxide surfaces. The protection mechanism appears to involve the adsorption of the REM–cinnamate complex followed by the hydrolysis of the REM to form a barrier oxide on the steel surface.

Ordering and stability in conducting polypyrrole

X-ray diffraction (XRD) was employed to characterize electrochemically synthesized polypyrrole (PPy) films with 1,5-naphthalene disulfonate (1,5-NDS) counterions treated with simple acid and base. Results show that the as-synthesized film is amorphous with short-range ordering in the polymer backbone. This ordering is soon lost after thermal ageing at 150°C for 60 days and there is evidence of counterion degradation. Base treatment of the PPy/1,5-NDS films has similar effects leading to a complete loss of ordering in the polymer backbone and dedoping of the polymer. Acid treatment at high temperatures increases the ordering of the polymer backbone and results in the development of a secondary interdopant peak confirming that ion exchange has occurred. Conductivity of the PPy was also increased substantially. The enhanced ordering was maintained even after thermal ageing. Room-temperature acid treatment also results in improved ordering of the polymer as well as the counterion but the increase in conductivity is only marginal and most of the ordering is soon lost after thermal ageing. Increase in ordering of the polymer structure seems to lead to better conductivity, although not necessarily improved thermal stability.

A potential novel rapid screening NMR approach to boundary film formation at solid interfaces in contact with ionic liquids

The boundary films generated on a series of inorganic compounds, typical of native films on metal and ceramic surfaces, when exposed to various ionic liquids (ILs) based on the trihexyl(tetradecyl)phosphonium cation have been characterized using multinuclear solid-state NMR. The NMR results indicate that SiO₂ and Mg(OH)₂ interact strongly with the anion and cation of each IL through a mechanism of adsorption of the anion and subsequent close proximity of the cation in a surface double layer (as observed through ¹H−²⁹Si cross polarization experiments). In contrast, Al₂O₃, MgO, ZnO, and ZrO₂ appear less active, strongly suggesting the necessity of hydroxylated surface groups in order to enhance the generation of these interfacial films. Using solid-state NMR to characterize such interfaces not only has the potential to elucidate mechanisms of wear resistance and corrosion protection via ILs, but is also likely to allow their rapid screening for such durability applications.

New insights into the fundamental chemical nature of ionic liquid film formation on magnesium alloy surfaces

Ionic liquids (ILs) based on trihexyltetradecylphosphonium coupled with either diphenylphosphate or bis(trifluoromethanesulfonyl)amide have been shown to react with magnesium alloy surfaces, leading to the formation a surface film that can improve the corrosion resistance of the alloy. The morphology and microstructure of the magnesium surface seems critical in determining the nature of the interphase, with grain boundary phases and intermetallics within the grain, rich in zirconium and zinc, showing almost no interaction with the IL and thereby resulting in a heterogeneous surface film. This has been explained, on the basis of solid-state NMR evidence, as being due to the extremely low reactivity of the native oxide films on the intermetallics (ZrO₂ and ZnO) with the IL as compared with the magnesium-rich matrix where a magnesium hydroxide and/or carbonate inorganic surface is likely. Solid-state NMR characterization of the ZE41 alloy surface treated with the IL based on (Tf)₂N− indicates that this anion reacts to form a metal fluoride rich surface in addition to an organic component. The diphenylphosphate anion also seems to undergo an additional chemical process on the metal surface, indicating that film formation on the metal is not a simple chemical interaction between the components of the IL and the substrate but may involve electrochemical processes.

Potentiostatic control of ionic liquid surface film formation on ZE41 magnesium alloy

The generation of potentially corrosion-resistant films on light metal alloys of magnesium have been investigated. Magnesium alloy, ZE41 [Mg−Zn−Rare Earth (RE)-Zr, nominal composition 4 wt % Zn, 1.7 wt % RE (Ce), 0.6 wt % Zr, remaining balance, Mg], was exposed under potentiostatic control to the ionic liquid trihexyl(tetradecyl)phosphonium diphenylphosphate, denoted [P_6,6,6,14][DPP]. During exposure to this IL, a bias potential, shifted from open circuit, was applied to the ZE41 surface. Electrochemical impedance spectroscopy (EIS) and chronoamperometry (CA) were used to monitor the evolution of film formation on the metal surface during exposure. The EIS data indicate that, of the four bias potentials examined, applying a potential of −200 mV versus OCP during the exposure period resulted in surface films of greatest resistance. Both EIS measurements and scanning electron microscopy (SEM) imaging indicate that these surfaces are substantially different to those formed without potential bias. Time of flight-secondary ion mass spectrometry (ToF-SIMS) elemental mapping of the films was utilized to ascertain the distribution of the ionic liquid cationic and anionic species relative to the microstructural surface features of ZE41 and indicated a more uniform distribution compared with the surface following exposure in the absence of a bias potential. Immersion of the treated ZE41 specimens in a chloride contaminated salt solution clearly indicated that the ionic liquid generated surface films offered significant protection against pitting corrosion, although the intermetallics were still insufficiently protected by the IL and hence favored intergranular corrosion processes.

An electrochemical impedance study of ionic liquid film formation and aqueous corrosion of magnesium alloy ZE41

Ionic liquid surface treatments are proposed as a method of controlling corrosion processes on magnesium alloys. An important magnesium alloy, ZE41 (nominally 4% Zn and 1% rare earth), was treated with the ionic liquid trihexyl(tetradecyl)phosphonium diphenylphosphate (P₆₆₆₁₄DPP). Impedance spectra were acquired at intervals during the treatment, indicating the development of a film and allowing a measure of the film formation process to be obtained over time. Mechanically polished and electro-polished surfaces were prepared; these surfaces, treated and untreated, were subsequently exposed to 0.1 M NaCl aqueous solutions. The corrosion behavior of the prepared surfaces were assessed using impedance spectroscopy and optical microscopy. The results indicated a significant role for the method of surface preparation used and, in both cases, the ionic liquid treatment produced a more corrosion-resistant surface.

Transient responses of a wetting film to mechanical and electrical perturbations

This article reports real-time observations and detailed modeling of the transient response of thin aqueous films bounded by a deformable surface to external mechanical and electrical perturbations. Such films, tens to hundreds of nanometers thick, are confined between a molecularly smooth mica plate and a deformable mercury/electrolyte interface on a protuberant drop at a sealed capillary tube. When the mercury is negatively charged, the water forms a wetting film on mica, stabilized by electrical double layer forces. Mechanical perturbations are produced by driving the mica plate toward or by retracting the mica plate from the mercury surface. Electrical perturbations are applied to change the electrical double layer interaction between the mica and the mercury by imposing a step change of the bias voltage between the mercury and the bulk electrolyte. A theoretical model has been developed that can account for these observations quantitatively. Comparison between experiments and theory indicates that a no-slip hydrodynamic boundary condition holds at the molecularly smooth mica/electrolyte surface and at the deformable mercury/electrolyte interface. An analysis of the transient response based on the model elucidates the complex interplay between disjoining pressure, hydrodynamic forces, and surface deformations. This study also provides insight into the mechanism and process of droplet coalescence and reveals a novel, counterintuitive mechanism that can lead to film instability and collapse when an attempt is made to thicken the film by pulling the bounding mercury and mica phases apart.

Electrophoretic deposition of YSZ thin-film electrolyte for SOFCs utilizing electrostatic-steric stabilized suspensions obtained via high energy ball milling

This manuscript describes a facile alternative route to make thin-film yttria-stabilized zirconia (YSZ) electrolyte by liquid-phase assisted electrophoretic deposition utilizing electrostatic-steric stabilized YSZ suspension followed by sintering. Very fine YSZ particles in ball-milled suspension facilitate their sustained dispersion through electrostatic mechanism as evidenced by their higher zeta potentials. Binder addition into the ball-milled suspension is also demonstrated to contribute complementary steric hindrance effects on suspension stability. As the consequence, the film quality and sinterability improve in the sequence of film made from non ball-milled suspension, film made from ball-milled suspension and film made from ball-milled suspension with binder addition. The specific deposition mechanisms pertaining to each suspension are also postulated and discussed below. A very thin dense electrolyte layer of ∼10 μm can be achieved via electrophoretic deposition route utilizing ball-milled suspension and binder addition. This in turn, makes the electrolyte resistance a more negligible part of the overall cell resistance. Further on, we also tested the performance of SOFC utilizing as-formed 10 μm YSZ electrolyte i.e. YSZ-NiO|YSZ|LSM (La0.8Sr0.2MnO3-δ), whereby a maximum power density of ∼850 mW cm−2 at 850 °C was demonstrated.