New terpolymers from n-butyl acrylate,glycidyl methacrylate and tetrahydrofurfuryl acrylate: Synthesis,characterisation and estimation of reactivity ratios

Development and practical application of multicomponent copolymerisation systems, such as terpolymerisation, is an on-going process because even a small addition of a particular comonomer may have a significant impact on the desired property. Commonly, three separate pairs of binary polymerisation experiments are carried out to obtain monomer reactivity ratios (MRR) values that relates to the ternary polymerisation reactions. However, the reaction conditions in each binary system may not be representative of the whole ternary system. The error-in-variables model (EVM) method is a relatively recent statistical approach to solving multi-response parameter estimation problems, with the advantage that all MRR parameters can be directly estimated from terpolymerisation data. New ternary copolymers derived from n-butyl acrylate (nBA), glycidyl methacrylate (GMA) and tetrahydrofurfuryl acrylate (THFA) were synthesised in solution at 70±1 °C in the presence of benzoyl peroxide (BPO) as a free radical initiator. The terpolymers were characterised by ¹H NMR, ¹³C NMR and FTIR spectroscopic techniques. The terpolymer compositions were determined using ¹H NMR analysis. The polydispersities of the terpolymers with values between 1.66 and 1.85 suggest a strong tendency for chain termination by disproportionation. The glass transition temperatures of the terpolymers are found to be between those of the corresponding homopolymers and relative to their content. Increase in the nBA or THFA contents and decrease in the GMA content in terpolymers results in a decrease in the glass transition temperatures. The determination of MRR for the ternary system was obtained by employing the EVM model. Experimental terpolymerisation data agree well with calculations based on the Alfrey-Goldfinger equation and the unitary and binary azeotropes were calculated.     

Synthesis and characterization of new copolymers from glycidyl methacrylate and tetrahydrofurfuryl acrylate: Determination of reactivity ratios

The new copolymers from different feed compositions of glycidyl methacrylate (GMA) and tetrahydrofurfuryl acrylate (THFA) were synthesized using free radical polymerization in toluene at 70±1 °C using benzoyl peroxide (BPO) as initiator. The polymers were characterized by ¹H NMR, ¹³C NMR and FTIR spectroscopic techniques. The polydispersities of the copolymers suggest a strong tendency for chain termination by disproportionation. The glass transition temperature of the copolymers increases with increase in GMA content. The thermal stability of the copolymers increases with increase in THFA content. The copolymer compositions were determined using ¹H NMR analysis. Reactivity ratios for GMA and THFA as determined by the Mao-Huglin method were r₁=0.379 and r₂=0.266. The results showed that all these copolymerizations are strictly linear systems describable by the Mayo-Lewis equation based on the terminal model and that accurate reactivity ratio data can be obtained.     

Synthesis, film morphology, and performance of functional polysiloxane bearing polyether and benzophenone derivative side groups

A water-soluble polysiloxane (PE-PUVSi) bearing functional benzophenone derivative and hydrophilic polyether side groups was successfully synthesized by hydrosilylation of polyhydromethylsiloxane (PHMS) with 2-hydroxy-4-(β-allyloxy-γ-hydroxy)propyloxy benzophenone (MUV-O) and allyl polyoxyethylenepolyoxypropylene ether (F6). The chemical structure, film morphology, and performance of the synthesized polysiloxane were investigated and characterized by spectral analysis, atomic force microscope (AFM), Kawabata evaluation system (KES), and other instruments. Experiment results indicate that PE-PUVSi had an intensive UV-absorbing capacity at wavelengths of 243.6, 289.2, and 325.0 nm. It formed a hydrophilic polysiloxane film on both the fiber and the silicon wafer surface. On the wafer surface, PE-PUVSi actually showed non-homogeneous and phase-separated microscopic film morphology. In addition, PE-PUVSi could provide a bulky softness, good wettability, and antistatic property for the treated fabric and make the treated cotton fabric show a low UV transmittance at the wavelengths between 270 and 330 nm.     

Preparation and characterization of poly(methylmethacrylate-coglycidyl methacrylate)/n-hexadecane nanocapsules as a fiber additive for thermal energy storage

The interest to innovative products with high added values and processes in textile field has been rapidly increasing among the other industrial fields. One of innovations in this field is to produce of innovative textiles containing phase change material (PCMs) that have thermal storage and thermo-regulation properties. This study deals with preparation and characterization of poly(methylmethacrylate-co-glycidyl methacrylate)/n-hexadecane nanocapsules containing nhexadecane as phase change material for thermal energy storage. The chemical characterization of poly(methylmethacrylateco-glycidyl methacrylate)/n-hexadecane nanocapsules was made by fourier transform infrared (FT-IR) spectroscopy method as particle size and its distribution (PSD) were studied by scanning electron microscopy (SEM). Thermal properties of nanoencapsulated n-hexadecane were determined using differential scanning calorimetry (DSC). The melting and freezing temperatures of the nanoencapsulated n-hexadecane were 17.23 and 14.85 °C respectively as the latent heats of melting and crystallization were 148.05 and −147.63 J/g respectively. Produced nanocapsules were applied to polyacrylonitrile (PAN) by means of electrospinning and surface morphology of the fibers was investigated by SEM analysis. Based on the results, it can be considered that the nanoencapsulated n-hexadecane in poly(methylmethacrylate-co-glycidyl methacrylate) have good energy storage potential to be used in fibers.     

Responses of rice leaf thickness,SPAD readings and chlorophyll a/b ratios to different nitrogen supply rates in paddy field

The objective of this paper was to investigate the influence of different nitrogen (N) application rates to some morphological and physiological features of leaf blades, including leaf thickness, chlorophyll content at different leaf ages and chlorophyll a/b ratios. A paddy field and a cement tank experiments were conducted simultaneously. Rice leaf thickness was measured through a specially developed displacement sensor. Meanwhile, chlorophyll content was estimated using chlorophyll meter (SPAD) and spectrophotometer after ethanol extraction of leaf samples. With the increase of N application, leaf thickness became thinner and chlorophyll a/b ratios decreased. Moreover, the sensitivity of the SPAD readings of the same leaf at different leaf ages to N rates was assessed through coefficients of variation (CV). CV of SPAD readings increased from 8.8% to 21.6% during leaf lifetime, which indicates that SPAD readings became more and more sensitive to nitrogen rates as leaf aged. Therefore, SPAD readings of the lower leaves, which were physiologically older than the upper ones, were more sensitive to nitrogen rates.     

Kinetic, equilibrium and thermodynamic studies of ternary system dye removal using a biopolymer

In this paper, dye removal ability of sodium alginate (SA) as a biopolymer from ternary systems was investigated. Physical characteristics of SA were studied using Fourier transform infra-red (FTIR) and scanning electron microscopy (SEM). Three textile basic dyes were used as model compounds. The adsorption kinetics, isotherms and thermodynamics were studied. The effect of SA dosage, initial dye concentration and pH on dye removal was elucidated. It was found that adsorption kinetics of dyes followed with pseudo-second order kinetics. In addition, dyes followed with Langmuir, and extended Langmuir isotherm in single and ternary systems, respectively. The thermodynamic data showed that the dye adsorption onto SA was a spontaneous, endothermic and physisorption reaction. Based on the data of present investigation, one could conclude that the alginate being a biocompatible, eco-friendly and low-cost adsorbent might be a suitable alternative for elimination of dyes from colored aqueous solutions.     

Removal of methylene blue by amidoxime polyacrylonitrile-grafted cotton fabrics: Kinetic,equilibrium, and simulation studies

In this study, an amidoxime-grafted cotton fabric ion exchanger was developed for methylene blue (MB) removal from wastewater. The ability of the amidoxime-grafted cotton fabrics to remove MB ions from an aqueous solution was investigated in equilibrium, kinetics and thermodynamics studies. Equilibrium data agreed well with the Freundlich and Langmuir isotherm models. The result indicated that, based on the Langmuir coefficient, the maximum capacity (monolayer saturation at equilibrium) of the amidoxime-grafted cotton fabric was 22.27 mg/g. The kinetic data were found to follow the pseudo-second-order model, and intra-particle diffusion is the sole rate-controlling factor. Negative values of ΔG ⁰, ΔH ⁰, and ΔS ⁰ revealed the spontaneous, exothermic and entropy-driven nature of the process.     

Dual-mode adsorption of cochineal natural dye on wool fibers: Kinetic,equilibrium, and thermodynamic studies

The dual-mode adsorption model was used to investigate the adsorption behavior of cochineal natural dye on wool fibers. Kinetic, thermodynamic, and equilibrium characteristics were investigated in terms of the adsorption isotherm, affinity, enthalpy and entropy changes, dyeing rate, diffusion coefficient, and activation energy of dye diffusion. The results revealed the prominent role of dyeing pH in determination of dyeing mechanism and dye adsorption isotherm type. At pH 4, dual Langmuir-Nernst model with the highest correlation coefficient was found as the most appropriate isotherm model to describe the adsorption behavior of cochineal onto wool fibers while at pH 6, the adsorption isotherm was the Nernst type. Cochineal adsorption onto wool was exothermic which resulted in progressive fall in affinity and equilibrium dye up-take values with increasing temperature. Moreover, dyeing rate steadily increased with temperature. At pH 4, affinity, dyeing rate, and diffusion coefficient demonstrated higher values compared to pH 6 whereas enthalpy and entropy changes, and activation energy showed lower values. Additionally, negative value for activation energy was obtained at pH 6. The results are deliberated based on the different possible interactions between cochineal dye and wool fiber.     

Polylactic acid/carbon fiber composites: Effects of functionalized elastomers on mechanical properties,thermal behavior,surface compatibility,and electrical characteristics

In this study, the maleic anhydride grafted styrene-ethylene-butylene-styrene block copolymer (SEBS-g-MA) is used as the compatilizer for polylactic acid (PLA)/carbon fiber (CF) composites. The effects of SEBS-g-MA on the mechanical properties, thermal behavior, interfacial compatibility, and electrical characteristics of composites are then evaluated. The mechanical property tests indicate that when the amount of compatilizer increases, the tensile properties and flexural property of the composites decrease while their impact strength increases. The SEM results show that the compatilizer can decrease the interstices between PLA and CF, and thereby augments their interfacial compatibility. The differential scanning calorimetry (DSC) results confirm that the compatilizer results in a greater crystallization temperature and a greater crystallinity of the composites. The electrical characteristic results indicate that neither PLA nor SEBS-g-MA is not interfered with the conductive network that is constructed by CF, which is exemplified by an average electromagnetic shielding effect of above ?30 dB. This study confirms that SEBS-g-MA can improve interfacial compatibility and toughness, as well as attain good electrical characteristics of PLA/CF composites.     

Effects of functional groups and species richness on biomass constituents relevant for combustion: results from a grassland diversity experiment

Grassland biomass has been identified as a potential energy source. The combustion of mature and fibrous biomass, as occurs in extensive grasslands managed with low cutting frequencies, is one possible conversion technique. This study tested the relationship between plant diversity and biomass constituents relevant for combustion, as they determine energy content, energy yield and emission and corrosion risks. The biomass from a biodiversity experiment, with a species richness (SR) gradient of 1–60 species from Central European mesophilic grasslands divided into four functional groups (grasses, legumes, small and tall herbs), was harvested twice a year (in 2008 and 2009). The higher heating value (HHV) was estimated from carbon, hydrogen and oxygen contents to give insight into the energy potential of the species mixtures. The potential risk of emission and corrosion was assessed by analysing ash content, potassium, calcium, magnesium, nitrogen, sulphur and chloride content. HHV was independent of SR, and the overall mean was 18·13 MJ kg^?1 DM. Biomass and gross energy (GE) yield were positively affected by SR. The presence of legumes in a mixture resulted in increased HHV, biomass yield and GE, irrespective of the level of SR. Annual GE varied between 59 (average of monocultures) and 152 GJ ha^?1 year^?1 (mixture of sixty species). The concentration of ash‐forming elements was generally high, suggesting a pre‐treatment of the biomass prior to combustion. Emission‐ and corrosion‐related constituents were clearly affected by the different functional groups, and sulphur and nitrogen both declined with SR. The results of this study show that high SR in experimental grassland communities is beneficial for the energy output and that legumes play a key role for the energy potential. However, identifying a functional group as being solely beneficial or disadvantageous for fuel quality was difficult.     

An in depth study of crystallinity, crystallite size and orientation measurements of a selection of poly(ethylene terephthalate)fibers

A selection of commercially available poly(ethylene terephthalate) fibers with different degrees of molecular alignment and crystallinity have been investigated utilizing a wide range of techniques including optical microscopy, infrared spectroscopy together with thermal and wide-angle X-ray diffraction techniques. Annealing experiments showed increased molecular alignment and crystallinity as shown by the increased values of birefringence and melting enthalpies. Crystallinity values determined from thermal analysis, density, unpolarized infrared spectroscopy and X-ray diffraction are compared and discussed in terms of the inherent capabilities and limitations of each measurement technique. The birefringence and refractive index values obtained from optical microscopy are found to decrease with increasing wavelength of light used in the experiments. The wide-angle X-ray diffraction analysis shows that the samples with relatively low orientation possess oriented non-crystalline array of chains whereas those with high molecular orientation possess well defined and oriented crystalline array of chains along the fiber axis direction. X-ray analysis showed increasing crystallite size trend with increasing molecular orientation. SEM images showed micro-cracks on low oriented fiber surfaces becoming smooth on highly oriented fiber surfaces. Excellent bending characteristics were observed with knotted fibers implying relatively easy fabric formation.     

Extraction, identification and dyeing studies of Isosalipurposide, a natural chalcone dye from Acacia cyanophylla flowers on wool

A chalcone compound Isosalipurposide 1 was qualitatively isolated from Acacia cyanophylla yellow flowers. The dyeing of wool fabrics with this chalcone compound as a natural dye has been studied. The effect of dye bath pH and dyeing temperature were investigated. The obtained shades were bright with generally a good fastness. A post-mordanting method was used in the dyeing of wool with this chalcone dye. It was found that, generally, mordanting improved light fastness especially in the case of zinc sulphate.     

Responses of herbage P,Ca, K and Mg content and Ca/P and K/(Ca + Mg) ratios to long‐term continuous and discontinued cattle grazing on a rough fescue grassland

Herbage minerals affect performance of grazing cattle. We investigated the response of herbage P, K, Ca and Mg contents and Ca/P and K/(Ca + Mg) ratios to long‐term stocking rate, continuous vs. discontinued grazing practice, and sampling year. Cattle had been stocked at 2·4 and 4·8 animal unit months ha^?1 since 1949. Exclosures were installed in April 1998. Herbage samples were collected near peak herbage mass in 2001, 2003, 2008 and 2012 and analysed for mineral content. Mineral contents were similar between the two stocking rates, but were lower (P < 0·05) under discontinued than continuous stocking, with the exception of similar P contents. The content of P and K in herbage was higher and the content of Ca and Mg was lower (P < 0·05) in years with greater precipitation and lower temperatures. Herbage mineral content, with the exception of P, exceeded minimum recommended levels for cattle. Given the low P content in herbage (0·74–1·19 g kg^?1) and high Ca/P ratios during the dry and hot year (of 2001), a dietary P supplement should be considered for cattle grazing rough fescue grassland in drought years. The low K/(Ca + Mg) ratios (<2·2) suggest there is little risk of grass tetany in cattle grazing on this grassland.     

Rice crop duration and leaf appearance rate in a variable thermal environment.: I. Development of an empirically based model

Variable crop duration is a major constraint to rice double cropping in arid irrigated environments, such as the Sahel. Photoperiodism and low air and water temperatures during the cool season are the major causes of variability, and cultivars are needed whose photothermal response provides a more stable crop duration. A previous study analyzed cultivar photothermal constants on the basis of progress to flowering. The present study sought to identify, on the basis of leaf appearance rates, the phenological stages that are most sensitive photothermally, and to explore technical options to screen germplasm for stable crop duration. Three Oryza sativa, indica-type rice cultivars (Jaya, IKP, IR64) were sown in the field at 15-day intervals during the dry season of 1995 (11 sowing dates) and 1996 (5 sowing dates) in Ndiaye, Senegal, under full irrigation and wide spacing to reduce microclimate variability. Mean daily water temperature (T_w) varied from 13 to 35°C. After seed soaking, the rate at which the first leaf (L₁) appeared was linearly related with T_w, with a base temperature (T_base) of about 10°C. Appearance rates of the subsequent three leaves (L₂–L₄) had a similar T_base, and presented a distinct temperature optimum (T_opt) at about 23°C, beyond which development rates decreased. Errors were too large to determine differences among cultivars in thermal constants. No significant temperature response was observed for the leaf appearances between L₅ to the flag leaf (L₁₂ to L₂₀). Crop duration to flowering varied by 45 (IR64) and 63 days (Jaya). These variations were associated with highly variable leaf numbers in all cultivars, including photoperiod-insensitive IKP. One-third of the variable duration was hypothesized to be due to a variable basic vegetative phase (BVP), caused by variable germination and leaf appearance rates, and two-thirds to variable duration of panicle induction after BVP. Water temperature was the main determinant of both sources of variability. A simulation model, describing these temperature and photoperiod effects on leaf number, growth duration and leaf appearance rates, was developed using the 1995 data, and satisfactorily validated with the 1996 data. The model was used to identify phenological-stage and cultivar-specific causes of variable crop duration.     

The effects of treating low dry-matter, low digestibility grass with a bacterial inoculant on the intake and performance of beef cattle, and studies on its mode of action

This experiment evaluated a bacterial inoculant based on a single strain of Lactobacillus plantarum as a silage additive. Three silages were harvested on 8 September 1989 from the second regrowth of a perennial ryegrass sward, which had received 167 kg N, 28 kg P₂O₅ and 45 kg K₂O ha^?1. Mean dry matter (DM) and water soluble carbohydrate concentrations of the herbages at ensiling were 148 g kg^?1 and 78 g.(kg DM)^?1 respectively. Herbages were treated with either no additive (C), formic acid (3·0 1 t^?1) (F) or the inoculant (3·0 1 t^?1) (I) and were ensiled in three 80-t capacity silos. For silages C, F and I respectively, pH values were 4·70, 3·77 and 4·47, ammonia-N concentrations were 192, 111 and 182 g (kg total N)^?1 and butyrate concentrations were 6·8, 1·8 and 7·1 g (kg DM)^?1. The silages were offered ad libitum and supplemented with 2·0 kg concentrates per head daily to thirty-six heifers (mean initial live weight 442 kg). For silages C, F and I, silage DM intakes were 12·7, 14·4 and 14·1 (s.e. 0·42) g (kg live weight)^?1, metabolizable energy intakes were 155, 166 and 172 (s.e. 5·1) kJ (kg live weight)^?1, and estimated carcass gains were 456, 519 and 518 (s.e. 28·1) g d^?1 respectively. A further 18 similar cattle were used in studies on the digestibility of the silages, and rumen degradation of each was estimated with three mature cattle. Inoculant treatment significantly increased crude fibre (P <0·01), neutral detergent fibre (P <0·01), modified acid detergent fibre (P <0·01), hemicellulose (P <0·05) and N digestibilities (P <0·05) and tended to increase N retention from the total diet. It is concluded that although treatment of herbage that was difficult to ensile with the inoculant did not improve silage fermentation, it significantly increased digestibility, especially of the fibre fractions, and silage DM intake and tended to increase animal performance to levels similar to those achieved with a well preserved formic acid-treated silage. Increases in silage DM and metabolizable energy intakes are likely to have been attributable to the effects of the inoculant on digestibility, especially of the fibre fractions.     

Tobacco stems as a low cost adsorbent for the removal of Pb(II) from wastewater: Equilibrium and kinetic studies

Adsorption of Pb(II) ions from aqueous solution onto tobacco stems has been investigated to evaluate the effects of initial lead ion concentration, adsorbent dosage, contact time, pH and temperature on the removal of Pb(II) systematically. The optimal pH value for Pb(II) adsorption onto the tobacco stems was found to be 5.0. The removal of lead ions for concentrations 10, 30 and 50 mg L⁻¹ using 0.8 g adsorbent at contact time of 120 min and at temperature of 299 K were 94.37%, 92.10% and 90.43%, respectively. Thermodynamic parameters such as standard Gibbs free energy (ΔG°), standard enthalpy (ΔH°), and standard entropy (ΔS°) were evaluated by applying the Van’t Hoff equation, which describes the dependence of equilibrium constant on temperature. The thermodynamics of Pb(II) adsorption onto the tobacco stems indicated that the adsorption was spontaneous and endothermic. Langmuir and Freundlich isotherms were used to analyze the equilibrium data at different temperatures and the equilibrium data were found to fit Freundlich isotherm equation better than Langmuir isotherm. The adsorption was analyzed using pseudo-second-order kinetic equation.     

Analysis of quantitative trait loci for some starch properties of rice (Oryza sativa L.): thermal properties, gel texture and swelling volume

To understand the genetic basis of gelatinization temperature (GT), gel textural traits and flour swelling volume, quantitative trait loci (QTL) were mapped for these traits using a doubled haploid (DH) population derived from a cross between indica variety Zai-Ye-Qing 8 (ZYQ8) and japonica variety Jing-Xi 17 (JX17). The results indicated that the starch property parameters were continuously distributed among the DH lines, and some DH lines showed transgressive segregation for all the parameters. A total of 16 QTLs were identified for seven traits. A major QTL, the alk gene on chromosome 6 was significant for the three GT traits, onset temperature (T_o), peak temperature (T_p), and completion temperature (T_c). This locus could explain 49.4, 38.9, and 28.3% of the total variance, respectively, indicating that GT parameters were substantially controlled by the alk gene which has previously been identified for alkali spreading value (ASV). The additive effects of alk on T_o,T_p and T_c were from ZYQ8. Another two QTLs on chromosomes 1 and 7 were also identified for the three GT parameters, whose positive effects were contributed from JX17. Another QTL on chromosome 10 with the positive effects coming from ZYQ8 was significant only for T_c. However, the enthalpy (ΔH) of gelatinization was controlled by two minor QTLs on chromosomes 1 and 7. A major QTL, the Wx gene on chromosome 6 was identified for gel hardness and flour swelling volume which explained 58.8 and 36.6% of the total variances, respectively. Another two QTLs were also detected for flour swelling volume, one of which (qSV-7) could explain 21.4% of the total variance. However, gel cohesiveness was controlled by a major QTL located between alk and Wx on chromosome 6.     

Serratula tinctoria,a source of natural dye: Flavonoid pattern and histolocalization

In the context of new alternative crop development in Europe, flavonoids were investigated in saw-wort, Serratula tinctoria L., a perennial Asteraceae which was used as a yellow dye until the 19th century. The phytochemical study described in this report indicates that leaves rather than stems should be used, and harvested at the end of the plant growing cycle, when flavonoids are particularly concentrated. Microspectrofluorometry showed a specific distribution of the flavonoid aglycone, luteolin in stomatal cells whereas the corresponding glycoside (luteolin-7-O-glucoside) was observed in palisade parenchyma cells. The flavonoids luteolin-4′-O-glucoside and 3-methylquercetin were isolated for the first time in S. tinctoria leaves and identified by NMR spectroscopy. The role of these flavonoids is discussed in this paper. Using a rapid and simple method, i.e. flavonoid histolocalization associated with UV, it was demonstrated that saw-wort contains high concentrations of luteolin derivatives and could be considered for use again as a natural dye.     

Grazing legumes in Europe: a review of their status, management, benefits, research needs and future prospects

In many parts of Europe there has been a net decline in the use of forage legumes since the 1980s, despite the reputed value of legumes for low‐input livestock production systems. The political environment within which livestock farming in much of Europe operates (Common Agricultural Policy) is shifting the balance of economic advantage towards legumes and away from high usage of inorganic fertilizer. This has already been found for legume and grass–legume silages when compared with grass silages with a potential economic gain for farmers averaging 137 € ha^?1, corresponding to an annual benefit for the European livestock farming sector of as much as € 1300 million. Recent literature has shown that legume‐based grazing systems have the ability to reduce environmental problems by increasing the efficiency of N use and by avoiding a high transient surplus of soil mineral N. From the perspective of livestock nutrition, when forage legumes contain moderate levels of secondary compounds, such as condensed tannins and flavonoids, they offer considerable advantages including increased efficiency of N utilization within the digestive tract, reduced incidence of bloat hazard and higher resilience to parasites. Nevertheless, these benefits are partially counterbalanced in both temperate and Mediterranean regions by difficulties in establishment, maintenance and management under grazing. To gain knowledge on mixed grass–legume pastures, further research is required on: (i) the development of sustainable systems of livestock production which can maintain sward persistence and agricultural production under environmental stress; (ii) increasing knowledge of soil–plant–animal relations for a wide range of leguminous species, and under different soil types and climatic situations; and (iii) the benefits for consumers of food produced from low‐input livestock production systems.