Changes in the surface properties of plasma-modified polyfluoroolefin films during storage and heating

Changes in the wettability and surface contact properties of polytetrafluoroethylene (PTFE) and tetrafluoroethylene-ethylene copolymer films modified in a direct current discharge at the cathode and anode depending on the storage time in air at room temperature and on heating to 200°C have been studied. Changes in the chemical composition of film surfaces have been examined by X-ray photoelectron spectroscopy.     

Changes in curing behaviour of aminoresins during storage

Summary The curing behaviour of commercial UF and MUF resins, stored at room temperature nearly up to gelation, is studied by simultaneous TG-DTA technique and structural changes of resins are also followed during aging. On the basis of ¹³C NMR spectra, the main chemical reaction during UF resin storage is the formation of methylenes and dimethylene ethers linked to secondary amino groups. Aging of resins results in a decrease of cure rate which is related to lower concentration of active functional groups and decrease in molecular mobility. On DTA curve, the resin with higher content of methylol groups reveals the curing exotherm earlier. With decreasing methylol content during storage, the peak maximum of exotherm is shifted to higher temperature value. Advanced polycondensation and sedimentation processes during storage produce partly locked in macromolecule structure water, and the water evaporation endotherm on DTA curve shifts to considerably higher temperature. The aged MUF resins are chemically less changed than UF resins and the aging process mainly involves noncovalent network formation due to complex molecular structure.     

Changes in content and composition of dietary fiber in yellow onions and red delicious apples during commercial storage

Changes in pectin composition and solubility are part of the softening process in apples during ripening and postharvest storage. Lignification may also occur with long-term storage. In the United States, apples and onions are harvested once yearly and then stored and marketed for the next 12 months. The changes that occur in the dietary fiber content and composition in Red Delicious apples and yellow Spanish onions during storage were studied, and the loss of fiber in peeled apples was determined. Dietary fiber was extracted by the enzymatic-chemical method of Theander and Westerlund. Storage had no effect on total or insoluble fiber content of apples; Klason lignin concentration was greater in samples stored for 12 months than in those stored for 0, 4, or 8 months. Peeling reduced apple fiber concentration about 25% by decreasing neutral and acidic sugars and Klason lignin in the insoluble fraction. The total fiber content of onions increased with storage, primarily by increasing the insoluble fiber content of uronic acids. The results suggest that the standardized, environmentally controlled storage of apples, as used in Washington State, has little effect on dietary fiber content. In contrast, the less rigorously controlled storage conditions for yellow Spanish onions increases the insoluble fiber fraction and uronic acid content.     

Influence of membrane structure on fouling layer morphology during apple juice clarification

The flux behavior of 0.2 μm nylon, polysulfone (PS), polyvinylidene fluoride (PVDF) and polyethersulfone (PES) membranes was examined during dead-end microfiltration of commercial apple juice. On nylon membranes, a 0.1 μm thick surface fouling layer rapidly formed that acted as a secondary membrane. The colloidal particles retained by this surface layer aggregated to form a thick loose gel structure, producing an anisotropic fouling structure. In contrast, the 4 μm thick surface fouling layer of PES was slower to form and had a more open structure with a lower flux resistance per unit thickness. The morphology of the PES surface layer also did not differ dramatically from the loose gel structure that subsequently formed on top of this secondary membrane. The PS surface fouling layer was similar in structure to nylon whereas the PVDF layer more closely resembled that found with PES. The density of the surface fouling layer did not directly correlate to membrane surface hydrophobicity or pure water flux. Atomic force microscopy (AFM) indicated that surface roughness strongly influenced surface fouling layer morphology. The membrane surface appears to act as a template for the fouling process; therefore, smooth membranes (nylon and PS) produce a dense surface fouling layer whereas this same layer on rough membranes (PES and PVDF) is much more open. Consequently, the fluxes of PES and PVDF membranes are less affected by fouling formation.     

Amino acid composition of Pirus communis and its change during storage

M. V. Lomonosov Odessa Technological Institute of the Food Industry. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 142–143, January–February, 1989.     

Orientational transition in the cholesteric layer induced by electrically controlled ionic modification of the surface anchoring

A reorientation of cholesteric liquid crystal with a large helix pitch induced by the electrically controlled ionic modification of the surface anchoring has been studied. In initial state, the cholesteric helix is untwisted completely owing to the normal surface anchoring specified by the cations adsorbed at the substrates. As a result, the homeotropic director configuration is observed within the cell. Under the action of DC electric field, one of the substrates becomes free from the layer of surface active cations, therefore, setting the planar surface anchoring. The latter, in turn, leads to the formation of the hybrid chiral structure. The threshold value and dynamic parameters have been estimated for this process as well as the range of control voltages, which do not allow the electrohydrodynamic instabilities. The twisted hybrid director configuration observed in the experiment has been analysed by means of the simulation of polarisation change of light propagating through the cholesteric layer with asymmetric (planar and homeotropic) surface anchoring on the cell substrates.     

Changes in iron oxidation state and surface composition of iron-chromium catalyst reduced by hydrogen

X-ray photoelectron spectroscopic studies of the reduction of iron-chromium catalysts have been carried out to determine changes in the relative surface concentrations of iron(II) and (III) oxides and metallic iron and in its surface composition at 100–500°C.

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(II), (III) 100–500°C. .

     

Effect of irradiation and packaging on lipid fraction of Bulgarian salami during storage

The effect of γ-irradiation (4 and 9 kGy) and packaging on the lipolytic and oxidative processes in lipid fraction of Bulgarian fermented salami during storage at 5 °C was evaluated (1st, 15th and 30th days). No significant differences were observed in the amounts of total lipids (TL), total phospholipids (TPL) and acid number (AN) within the vacuum packed samples of salami treated with 4 and 9 kGy during storage. The changes in thiobarbituric acid reactive substances (TBARS) depended mainly on the irradiation dose applied and did not exceed 1.37 mg/kg in all groups. The most intensive lipolytic and oxidative processes and the lowest sensory assessment were found in the non-packed irradiated (9 kGy) samples.     

Changes in surface stress of gold electrode during underpotential deposition of copper

The changes in surface stress of the evaporated gold electrode (mainly oriented to the (111) plane) during underpotential deposition (UPD) of copper in 0.1 M sulfuric acid medium or 0.1 M perchloric acid medium with and without sulfate or chloride were measured using a bending beam method. The surface stress maximum of gold electrode appeared during Cu-UPD. The co-adsorption of (bi)sulfate or chloride ions with copper atoms induced the compressive surface stress to promote the Cu-UPD. The factors influencing the surface stress or surface elastic strain were discussed in relation to the Cu-UPD structure. Dedicated to Professor Su-Il Pyun on the occasion of his 65th birthday.     

Remarkable influence of surface composition and structure of oxidized iron layer on orange I decomposition mechanisms

Although the decomposition of water pollutants in the presence of metallic iron is known, the reaction pathways and mechanisms of the decomposition of azo-dyes have been meagerly investigated. The interface phenomena taking place during orange I decomposition have been investigated with the use of infrared external reflection spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. The studies presented in this paper establish that there are close relationships between the composition and structure of the iron surface oxidized layers and the kinetics and reaction pathway of orange decomposition. The influence of the molecular structure of azo-dye on the produced intermediates was also studied. There are remarkable differences in orange I decomposition between pH 3 and pH 5 at 30 degrees C. Decomposition at pH 3 is very fast with pseudo-first-order kinetics, whereas at pH 5 the reaction is slower with pseudo-zero-order kinetics. At pH 3, only one amine, namely 1-amino-4-naphthol, was identified as an intermediate that undergoes future decomposition. Sulfanilic acid, the second harmful reduction product, was not found in our studies. At pH 3, the iron surface is covered only by a very thin layer of polymeric Fe(OH)(2) mixed with FeO that ensures orange reduction by a combination of an electron transfer reaction and a catalytic hydrogenation reaction. At pH 5, the iron surface is covered up to a few micrometers thick, with a very spongy and porous layer of lepidocrocite enriched in Fe(2+) ions, which slows the electron transfer process. The fastest decomposition reaction was found at a potential near -300 mV (standard hydrogen electrode). An addition of Fe(2+) ions to solution, iron preoxidation in water, or an increase of temperature all result in an increasing decomposition rate. There is no single surface product that would inhibit the decomposition of orange. This information is crucial to perform efficient, clean and low cost waste water treatment. The findings presented here make the treatment of wastewater in the presence of metallic iron a very promising solution.     

Changes in surface composition of Fe-Si-Cr-K oxide alkylation catalyst: the marked role of potassium ferrites

The influence of gas-phase methylation of phenol on the state of the Fe-Si-Cr-K oxide catalyst surface was investigated by thermodesorption of K atoms and ions. Changes in potassium desorption energies, as determined from Arrhenius-like plots, varied from 3.07 eV to 1.21 eV for the atoms and from 2.59 eV to 2.89 eV for ion desorption from the active and deactivated samples, respectively. The results were discussed in terms of transformation of the catalyst surface and formation of β-ferrite.     

Changes in surface composition of Fe-Si-Cr-K oxide alkylation catalyst: the marked role of potassium ferrites

The influence of gas-phase methylation of phenol on the state of the Fe-Si-Cr-K oxide catalyst surface was investigated by thermodesorption of K atoms and ions. Changes in potassium desorption energies, as determined from Arrhenius-like plots, varied from 3.07 eV to 1.21 eV for the atoms and from 2.59 eV to 2.89 eV for ion desorption from the active and deactivated samples, respectively. The results were discussed in terms of transformation of the catalyst surface and formation of β-ferrite.     

Unexpected behavior of the surface composition of PtRh alloys during chemical reaction

The changes in the surface composition of a Pt(50)Rh(50)(100) alloy due to an ongoing 2H(2) + O(2)-->2H(2)O chemical reaction have been studied in situ. Exploiting the high-energy resolution and surface sensitivity of synchrotron radiation core-level spectroscopy it was possible to monitor the population of the two transitions metals atoms at the gas-surface interface. Sequences of fast high-resolution core-level spectra of the Rh3d(5/2), Pt4f(7/2), and O1s core levels showed a continuous exchange of atoms between the first and subsurface layers. An unexpected Pt surface enrichement was found under slightly oxidizing conditions, opposite to what found in a highly oxidizing atmosphere.     

Kinetics of lipid layer formation at interfaces

A formal kinetic model of lipid layer formation at an interface in contact with a liposomal suspension is developed and investigated. Neglecting diffusion (for sufficiently high bulk concentrations) the kinetic scheme consists of two consecutive processes: (I) irreversible transformation of ‘soluble’ intact vesicles from the ‘subsurface’ layer into ‘adsorbed’ ones (‘defected’ or ‘ruptured’ liposomes, ‘mesophases’); and (II) irreversible transformation of the ‘adsorbed’ vesicles into a lipid monolayer. The resulting set of two differential equations is analyzed making use of the ‘steady-state concentration’ approach (with ‘adsorbed’ vesicles as intermediate compound). Numerical results illustrate the predicted kinetic behavior which depends on the relative magnitude of the rates of the two consecutive processes. Approximate analytical solutions in the case of a much slower process I are obtained in some limiting cases. The model is used to estimate rate constants from previously established experimental kinetic data at the air/water interface.