Antioxidant Activity of Sesamin in Canola Oil

The present study presents the antioxidant activity of sesamin in canola oil compared with that of butylated hydroxytoluene (BHT) by monitoring the oxygen consumption and the decrease in linoleic acid and α-linolenic acid. The oxidation of canola oil was conducted at 35, 60, 90, 120 and 180 °C with addition of 50–400 ppm sesamin. Results from the oxygen consumption test showed that sesamin dose-dependently inhibited the oxidation of canola oil at concentrations of 50–200 ppm at temperatures of 60–180 °C, however, sesamin lost its antioxidant activity at a low temperature of 35 °C. The fatty acid analysis also demonstrated that sesamin at 50, 100 and 200 ppm dose-dependently prevented the oxidation of linoleic acid and α-linolenic acid in canola oil. Both the oxygen consumption and the fatty acid analysis demonstrated sesamin was less effective than BHT as an antioxidant at temperatures of 60–180 °C. It was therefore concluded that sesamin could prevent the lipid oxidation of frying fats and oil, however, its antioxidant activity was not as potent as that of BHT.     

Synthesis of polyglactin by melt/solid polycondensation of glycolic/L‐lactic acids

Polyglactin was successfully synthesized by the melt/solid polycondensation of a mixture of glycolic acid (GA) and L ‐lactic acid (LA) mostly at a GA to LA monomer ratio of 90/10. In the polymerization procedure, a solid polycondensate was first prepared by melt‐polycondensation at 150–190 °C, mechanically crushed into particles of various sizes (150–180, 180–210, 210–250, 250–300 and 300–355 µm), and subjected to solid‐state post‐polycondensation at 170 °C for 10–20 h. The polyglactin finally obtained was a colourless solid. Catalyst screening revealed that the single use of methanesulfonic acid gave the highest molecular weight of the product. Starting from the crushed melt‐polycondensate with a diameter range of 180–250 µm, the highest number‐average molecular weight of attained was 80 000 Da. This process can afford a facile route to large‐scale synthesis of polyglactin with high molecular weight. Copyright © 2004 Society of Chemical Industry     

A thermoanalytical study of chemical reactions of durable press and acrylic soil release textile finishing agents

Chemical reactions in systems with durable press reagents and acrylic soil release polymers are analyzed using differential scanning calorimetry. Self-condensation of N-methylol compound is the preponderant chemical reaction when a film with 70% methacrylic acid/30% ethyl acrylate copolymer and dimethylolethylene urea (DMEU) or dimethyloldihydroxyethylene urea (DMDHEU) is heated. This reaction proceeds through formation of transitory methylene ether bridges with methylene bridges as the thermodynamically favored product. An exotherm is observed under certain circumstances in DSC thermograms of films containing DMEU or DMDHEU and is attributed to a rapid shift of methylene either to methylene bridges. Appreciable anhydride formation occurs in the polymer only above about 160–170°C. Esterification of polymer by methylol reagent probably also occurs to a limited extent, especially above about 160–170°C. Soil release of fabrics treated in a one-bath process is often unsatisfactory because polymer is embedded in a matrix of condensed N-methylol compound which restricts swelling of polymer and, therefore, its utility as a soil release agent. The limited extent of reaction between polymer and methylol compound is of minor importance compared with this adverse morphology. However, in some cases, ester formation may be responsible for significantly inferior soil release of fabrics cured at higher temperatures, for example 210°C/30 sec rather than 160°C/3 min. In such cases, polymer may be trapped chemically as well as physically in the resin matrix.     

Thermal Oxidation Kinetics of Refined Hazelnut Oil

In this study, oxidation kinetics of refined hazelnut oil heated at the temperature range from 80 to 180 °C was evaluated. The changes in peroxide value, p‐anisidine value, polymer triglyceride content, α‐tocopherol content, and color values during oxidation were best fitted to zero‐order kinetic model. The rate constants for the p‐anisidine value, polymer triglyceride content, and degradation of α‐tocopherol of hazelnut oil increased at the temperatures between 80 and 160 °C, while the rate constant for peroxide value decreased at the temperatures between 80 and 140 °C. The activation energies for the formation of peroxides (at 80–140 °C), secondary oxidation products such as alkenals, the polymer triglycerides, and degradation of α‐tocopherol were found as 47.49, 29.95, 52.65, and 14.22 kJ mol^?1, respectively. The induction period of hazelnut oil was observed to reduce with increasing oxidation times. The increase in the b* value with the oxidation time and temperature was attributed to the fact that the heating process intensified the yellow color of the oil.     

The Role of Water in Protection Against Thermal Deterioration of Liquid Margarine

The thermal stability of liquid margarine and vegetable oils was investigated by measuring the oxidative stability index (OSI) at temperatures ranging from 90 to 180 °C, whereas total polar compounds (TPC) and tocopherols (vitamin E) were measured during heating at 180 °C in frying trays. Results showed that the OSI of liquid margarine was in the same range as the OSI of vegetable oils at lower temperatures, but at 160 and 180 °C, liquid margarine had significantly higher thermal stability, close to that observed for hard margarine and butter. The increased stability was confirmed by lower levels of TPC and a smaller relative reduction in vitamin E content during heating. Variations between different vegetable oils could partly be explained by differences in degree of saturation and level of vitamin E, with high oleic sunflower oil being the most stable oil at all temperatures. The water in liquid margarine vaporized within 1.5 min at 160 °C, and it is hypothesized that volatile pro‐oxidants are removed with the water, inducing a delay in deterioration. The results indicate a role for water in preventing lipid oxidation and decomposition in fat emulsion products at 160–180 °C, suggesting that liquid margarine, low in saturated fat, may be the healthier and preferable alternative for pan‐frying compared to other liquid vegetable oils.     

Change of orientation by thermal contraction of polyacrylonitrile fiber

Polyacrylonitrile polymer powder was dissolved in 70% nitric acid and spun into isotropic filament through a glass nozzle of 0.5 mm. diameter in a coagulating bath of 30% nitric acid. Stretching was carried out in two stages: the first stretching was done in water at 20°C. followed by drying, and the second stretching was done in a boiling saturated solution of ammonium sulfate. The total stretching ratio was 23. These filaments were shrunk freely in water at 70–180°C. The change in orientation factors was traced by x-ray, infrared dichroism, visible dichroism, and sonic modulus methods. The relation between the reciprocal absolute temperature of thermal contraction and the logarithm of fiber length is a straight line which has two inflection points at 93 and 175°C. The orientation factors by x-ray and infrared dichroism remain unchanged up to 175°C. On the contrary, the orientation factors by visible dichroism and sonic modulus drop suddenly at about 90°C. This indicates the occurrence of relaxation of the amorphous chain at the glass transition temperature and shows the polymer is not perfect single-phase material. Orientation of crystalline and amorphous phases is stable from 100 to 170°C. in spite of considerable thermal contraction. The stability of orientation can be explained by the growth of a folded structure in the polymer.     

The effect of oxygen concentration on oxidative deterioration in heated high-oleic safflower oil

High-oleic safflower oil was heated at 180°C in atmospheres with four levels of oxygen concentration (2, 4, 10, and 20%) modified with nitrogen gas, to assess the effects of atmospheric oxygen concentration on the oxidative deterioration of deep-frying oils. Acid value, carbonyl value, polar materials, linoleic acid, tocopherol contents, and oxidative stability were measured to evaluate the quality of heated oils. These values were found to be correlated with both heating time and oxygen concentration. Acid and carbonyl values and polar material content of oils heated at oxygen concentrations of 2 and 4% were lower than those at 10 or 20%. On the other hand, linoleic acid and tocopherols were hardly reduced in oils after heating for 30 h at 2% O₂, whereas they were decomposed according to the oxygen concentration and heating time. Oxidative stability was well maintained in oils heated at 2 and 4% O₂. These results suggest that the oxidative deterioration of heated higholeic safflower oil depends on oxygen concentration.     

The influence of thermal history on the properties of poly(3-hydroxybutyrate-co-12%-3-hydroxyvalerate)

The influence of thermal history on the properties of commercial P(3HB-co-12%-3HV) was studied. Thermogravimetric analysis and differential scanning calorimetry revealed that the plasticizer evaporated at 140°C or higher. The loss of plasticizer during thermal treatment at 170 and 180°C resulted in a slight increase of the melting temperature of the polymer. The processing time and temperature, as well as the cooling procedure influenced the thermal behaviour of the material. A decrease in molecular weight with time was found at the temperatures investigated and this significantly affected the mechanical properties of the polymer prepared at 180 and 200°C. The rate constant k_d of thermal degradation was slightly higher for samples during a shape-forming process in a Minimax apparatus than during a quiescent heating process (DSC) and its value increased with temperature. Limiting the processing at 170°C to 2 min gave a material with useful properties but increasing the residence time resulted in a decrease in strength, elongation at break, molecular weight and viscosity although it did not significantly influence the modulus of elasticity. Materials prepared at 180 or 200°C were more brittle and longer residence times resulted in a deterioration of the mechanical properties. © 1996 John Wiley & Sons, Inc.     

A simple and quick determination of aldehydes in autoxidized vegetable and fish oils

A simple and quick method for the quantitative determination of aldehydes in oxidized oils was established. The analysis was based on the reaction of N,N-dimethyl-p-phenylenediamine (DPPD) with aldehydes in the presence of acetic acid. Reaction products were determined by visible absorption at wavelengths of 400, 460 and 500 nm. The errors of the DPPD method in the analyses of total aldehydes in authentic mixtures of various aldehydes were less than 5%, and this method could be used successfully to determine aldehyde contents in oxidized vegetable and fish oils. The reaction time of the DPPD method (10 min at 30°C) is much shorter than that of the conventional method that uses 2,4-dinitrophenylhydrazine as a reagent (30 min at 60°C). The simplicity of the procedure enables a quick determination of aldehyde contents in oxidized oil samples.     

ACCELERATION OF THE WET OXIDATION REACTION OF PIPERAZINE BY HETEROGENEOUS Ru/TiO2 CATALYST

Wet air oxidation is a candidate technique for the effective treatment of wastewater contaminated by nitrogenous organic pollutants. Piperazine (PZ) is a cyclic diamine representing this class of compounds. In the present work, the wet oxidation reaction of PZ was studied for the first time. It was found that, in the studied range of temperatures of 180°–230°C and O₂ partial pressures of 0.69–2.07 MPa, the oxidation process was slow. Total organic carbon (TOC) conversion at 230°C and 0.69 MPa O₂ partial pressure was just 52% after 2 h. The investigated reaction was accelerated by a heterogeneous Ru/TiO₂ catalyst. Maximum TOC conversion (91%) was achieved during catalytic wet oxidation at 210°C and 1.38 MPa O₂ pressure. Kinetic data were collected over the range of temperatures 180°–210°C, O₂ partial pressures 0.34–1.38 MPa, and catalyst loading 0.11–0.66 kg/m³. The lumped TOC concentration decay was a two-step first-order process.     

Frying stability of canola oil in presence of pumpkin seed and olive oils

Frying performance of canola oil (CO) was investigated in the presence of 5, 10, and 15% levels of virgin olive oil (VOO) and pumpkin seed oil (PSO) during frying of potatoes at 180°C. Acid value, carbonyl value, total polar compounds content, and total tocopherols content of the oil samples were determined during the frying process. VOO and PSO addition improved the frying stability of the CO. Frying performance of the CO increased more in the presence of PSO than in the presence of the VOO. The PSO levels higher than 5% exerted pro‐oxidant effects, indicating the necessity of investigation at lower levels. The better antioxidative effect of PSO was attributed to its probably different phenolic composition.     

Studies on the improvement of cured two-stage phenolics performance. III. Relation between conditions of heat treatment and properties of wood-flour-filled phenolics

The effect of heat treatment on the properties of cured two-stage phenolics was studied. Samples were compression-molded from the compound that was prepared from novolac, wood flour (100 phr), and hexamethylenetetramine (15 phr). Samples were heat-treated in conditions of four levels for temperature (150°C, 170°C, 190°C, and 210°C) and time (4, 8, 16, and 24 h). The properties of samples heat-treated, such as weight loss, dimensional stability, water absorption after boiling, and flexural properties were measured. The relation between the properties and the conditions of heat treatment was examined statistically. From the results, it was decided that the optimum conditions of heat treatment for practical use were: (i) to decrease water absorption and to heighten electrical resistance, 210°C, 24 h; (ii) to improve flexural properties at room temperature and at 160°C; 170°C, 8 h, and 170–190°C, 24 h, respectively. It was concluded that the decrease of water absorption of moldings was due to the increase of hydrophobic nature of wood flour included in moldings by heat treatment and that the improvement of flexural property of moldings at 160°C was due to an increase of crosslinking density by heat treatment. The reasons for the improvement of the electrical properties by heat treatment were also discussed.     

Refining of rice bran oil by neutralization with calcium hydroxide

The applicability of calcium hydroxide (lime) in the neutralization of rice bran oil (RBO) was investigated. Crude RBO samples of three different free fatty acids (FFAs) (3.5–8.4 wt%) were degummed, dewaxed, bleached, and neutralized with lime and deodorized. The oils obtained thus were characterized by determining the color, peroxide value (PV), content of unsaponifiable matter (UM), and FFA. Conventionally practiced caustic soda neutralization (at 80–90°C) of FFA has in the present investigation been replaced by a high temperature (150–210°C) low pressure (2–4 mm Hg) reaction with lime. It was observed that neutralization with Ca(OH)₂ at high temperature (210°C) and under low pressure (2–4 mm Hg pressure) may substantially reduce the FFA content (0.8 wt%, after 2 h). The deodorized oil was found to be of acceptable color, PV, and content of UM and FFA. Neutralization of oil was also carried out by using NaHCO₃ and Na₂CO₃, nonconventional alkalies for neutralization, and the results were compared with NaOH and Ca(OH)₂. Overall recovery of oil in Ca(OH)₂ refining process (88.5 ± 0.6 wt%, for Sample 1 containing 8.4%‐wt FFA) was found to be more than other competitive processes studied.     

Use of NIR spectroscopy for estimation of FA composition of soy flour

The feasibility of NIR spectroscopy for the determination of FA composition in soy flour was examined. NIR spectra were obtained for a small amount of soybean powder (about 8 mg) in a modified single-grain cup using an NIR instrument by scanning the wavelengths from 1100 to 2500 nm at 2-nm intervals. The relationship between the NIR spectral patterns of soybean powder and the FA compositions was examined: As the linoleic acid ratio increased, the NIR absorbance at 1708 nm, where the linoleic acid moiety has an absorption band, became stronger downward in the second-derivative NIR spectra. The correlation coefficients between the standardized NIR readings at 1708 nm and the linoleic acid ratio or the oleic acid ratio in the FA composition of soy flour were −0.853 and 0.877, respectively. A rough estimation of the linoleic acid moiety or oleic acid moiety in soy flour could be successfully carried out with even a very small amount of soy flour according to the NIR spectral pattern due to the wavelength assignments of moieties.     

Polyamides and polyimides prepared from diaminomaleonitrile and their cross-linking to thermally stable resins

Unsaturated cyano-substituted polyamide and polyimides were prepared from the reactions of diaminomaleonitrile with terephthaloyl dichloride and tetracarboxylic dianhydrides such as pyromellitic dianhydride and benzophenone tetracarboxylic dianhydride. The polymers were characterized by inherent viscosity measurements, by FTIR and ¹H-NMR spectroscopy, as well as by DTA and TGA. They were soluble in polar aprotic solvents and certain strong inorganic and organic acids. Upon curing at 300°C for 70 h, cross-linked polymers were obtained that were stable up to 397–426°C in N₂ or air and afforded anaerobic char yield of 56–61% at 800°C. Their glass transition temperatures as determined by the thermal mechanical analysis (TMA) method were 210–249°C. © 1994 John Wiley & Sons, Inc.     

Chemical structure of poly(β‐cyclodextrin‐co‐citric acid)

We synthesized water‐insoluble polymers, poly(β‐cyclodextrin‐co‐citric acid)s, by heating a mixture of citric acid, cyclodextrin (CD), and Na₂HPO₄ as a catalyst with a 6 : 1 : 2 molar ratio at 160, 170, and 180°C for 10 and 20 min. The chemical composition of the polyesters was determined by high pressure liquid chromatography (HPLC) analysis of the polymer hydrolysates. The crosslinking mechanisms and thermal degradation of the polymers were also investigated. The polyesters contained 30–35% citric acid, 1–4% unsaturated carboxylic acids (i.e., itaconic, cis‐aconitic, trans‐aconitic, and mesaconic acids), and 60–70% CD, whereas about 40% of them were able to form inclusion complexes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Deodorization of vegetable oils. Part I: Modelling the geometrical isomerization of polyunsaturated fatty acids

Laboratory-scale treatments of canola oils similar to deodorization were carried out by applying the following conditions: reduced pressure with nitrogen or steam stripping at different temperatures ranging from 210 to 270°C for 2–65 h. The formation of the group of trans linolenic acid isomers follows a first-order reaction and the kinetic constant varies according to the Arrhenius’ law. Similar results were observed for the trans isomerization of linoleic acid. Based on these experiments, a mathematical model was developed to describe the isomerization reaction steps occurring in linoleic and linolenic acids during deodorization. The calculated degrees of isomerization are independent of the composition of the oil but related to both time and temperature of deodorization. The degree of isomerization of linolenic acid is unaffected by the decrease of this acid content observed during the deodorization. Deodorization at about 220–230°C appears to be a critical limit beyond which the linolenic isomerization increases very strongly. The newly established model can be a tool for manufacturers to reduce the total trans isomer content of refined oils, and was applied to produce a special selectively isomerized oil for a European Nutritional Project.     

Effect of fruit storage conditions on olive oil quality

"Koroneiki" olive fruit from trees grown in Crete were stored under five different conditions (0°C, air; 5°C, air; 5°C, 2% O₂+5% CO₂; 7.5°C, air; 7.5°C, 2% O₂+5% CO₂). Oil was obtained from fruit immediately after harvest and after fruit storage for 30 and 60 d. Olive oil quality was evaluated by determining acidity, peroxide value, absorption coefficients (K₂₃₂, K₂₇₀), phenol and chlorophyll content, fatty acid composition, and the resistance to oxidation by oven test. Olives stored at 7.5°C, even for 30 d, deteriorated from fungus development, and the obtained oil was of inferior quality with high acidity, peroxide value, and absorption coefficients. The same oil had high chlorophyll and phenol content, resulting in good oil resistance to oxidation. Olive oil from fruit stored at 0 or 5°C for 30 d had acceptable acidity, peroxide value, and absorption coefficients, but showed low resistance to oxidation, which was attributed to low chlorophyll and phenol content. This condition is further attributed to chilling injury caused by low storage temperatures. During storage, all treatments resulted in an increase of oleic acid, partly as a result of linoleic acid oxidation.     

Heat‐sealing properties of soy protein isolate/polyvinyl alcohol film made compatible by glycerol

Heat‐sealing properties are necessary for packaging materials. Soy protein isolate/polyvinyl alcohol (SPI/PVA) blend film is a biodegradable potential packaging material. We analyzed the effects of PVA content (0–20%), glycerol content (1–3%), and sealing temperature (180–230°C) on the heat‐sealing properties of SPI/PVA blend film. Results showed that SPI/PVA film obtained the desired sealing properties when the PVA content exceeded 15%. The sealing strength increased with the PVA content, reaching a maximum upon blending with 20% PVA and 1% glycerol at 220°C. The temperature at sealing strength was approximately twice that at 180°C. However, glycerol migrated to the surface and hindered the entanglement of macromolecular chains in the sealing interface, thereby resulting in reduction of seal strength. Glycerol vaporization at 204°C led to aesthetically unacceptable blistering in the sealing area. Therefore, the optimum sealing temperature of the blended film was ～200°C. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40308.     

Long-term-durable anti-icing superhydrophobic composite coatings

We prepared carbon-based superhydrophobic composite coatings through a quick technique, merging multiwalled carbon nanotubes (MWCNTs) and carbon nanofibers (CNFs) to obtain hierarchical nanostructures on fiber-reinforced polymer (FRP) sheets; this was followed by supercritical fluid (SCF) processing and physical mixing (PM). The prepared SCF–MWCNT–CNF and PM–MWCNT–CNF composite coatings showed high water contact angles of 171.6 and 160°. The surface morphologies of the composite coatings revealed a lot of even nanostructures and folding at high magnifications. A high number of CNFs were added to the MWCNTs to initiate different nanoroughnesses in the composite coatings. The as-prepared superhydrophobic composite coatings showed excellent anti-icing properties, as indicated by the supercooled water droplet (-20°C) test under environmental conditions. Also, the surface of the SCF–MWCNT–CNF superhydrophobic composite coating showed excellent antifouling properties. We studied the surface wettability increasing different temperatures (30–180°C) in the SCF–MWCNT–CNF composite; this exposed the fact that the FRP sheets were thermally stable up to 100°C, and a while later, they changed from a superhydrophobic state to a superhydrophilic state at 180°C. This study revealed an economically workable method for the preparation of MWCNT–CNF composites with SCF techniques. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47059.