Dispersion polymerization of styrene using poly(4-vinylpyridine) macro-RAFT agent under UV radiation

The dispersion polymerization of styrene using a poly(4-vinylpyridine) (P4VP) macromolecular RAFT (macro-RAFT) agent as both a macro-initiator and a colloidal stabilizer under UV radiation was investigated for the first time. The P4VP macro-RAFT agent (M _n,GPC=49,000 g/mol, PDI=1.14) was prepared by the RAFT polymerization of 4-vinylpyridine using 2-cyanoprop-2-yl dithiobenzoate as a chain transfer agent. The resulting polystyrene (PSt) particles had hairy P4VP chains, which could successfully immobilize very small Au nanoparticles on the surface of the PSt particles. It was found that hairy polymeric particles could be produced by photo-initiated dispersion polymerizations of vinyl monomers using macro-RAFT agents that are susceptible to UV radiation as both macro-initiators and colloidal stabilizers.     

Size-controlled nanoparticles of poly(acrylonitrile-<Emphasis Type="Italic">co</Emphasis>-methyl methacrylate) for moisture-absorbing heat release applications

Hydrophilic and water-insoluble poly(acrylonitrile-co-methyl methacrylate) [P(AN-co-MMA)] nanoparticles were prepared to investigate their moisture-absorbing heat release effect. The nanoparticle size was controlled by varying the composition of AN and MMA. First, P(AN-co-MMA) nanoparticles were synthesized by emulsion polymerization, followed by cross-linking with hydrazine for water insolubility. Secondly, the hydrazine-cross-linked P(AN-co-MMA) nanoparticles were hydrolyzed in an aqueous NaOH solution to form hydrophilic groups. The hydrolyzed and cross-linked P(AN-co-MMA) [hc-P(AN-co-MMA)] nanoparticles had a more uniform and smaller particle size with increasing MMA content compared to the PAN nanoparticles, this is due to decreasing polar nitrile groups in the P(AN-co-MMA) with MMA content. A nanoparticle size less than 45 nm was obtained for P(AN-co-MMA) with a 20 mol% MMA content. The hc-P(AN-co-MMA) nanoparticles showed a temperature rise maximum of up to 12.9 °C in the moisture-absorbing heat release test. In addition, when the nanoparticles with 20 mol % MMA content were coated on cotton fabrics, the temperature of the fabrics increased by up to 7.8 °C at 90 % relative humidity. This demonstrates that the nanoparticles can be applied as a potential moisture-absorbing heat release material.     

Electrospinning and microwave absorption of polyaniline/polyacrylonitrile/multiwalled carbon nanotubes nanocomposite fibers

Electrical conductive nanocomposite fibers were prepared with polyaniline (PANI), polyacrylonitrile (PAN) and multi-walled carbon nanotubes (MWCNTs) via electrospinning. The morphology and electrical conductivity of the PANI/PAN/MWCNTs nanocomposite fibers were characterized by scanning electron microscope (SEM) and Van De Pauw method. Electrical conductivity of nanocomposite fibers increased from 1.79 S·m^?1 to 7.97 S·m^?1 with increasing the MWCNTs content from 3.0 wt% to 7.0 wt%. Compared with PANI/PAN membranes, the mechanical property of PANI/PAN/MWCNTs nanocomposites fiber membranes decreased. The microwave absorption performance of composite films was analyzed using waveguide tube, which indicated that with the thickness increasing the value of R_L reduced from ?4.6 to ?5.9 dB.     

Microwave-enhanced alkali treatment of Pinus yunnanensis: Physiochemical characterization of the dissolved lignins

Pinus yunnanensis was subjected to water-bath and microwave treatments in 1% NaOH aqueous solutions at 100 °C with various ratios of bath heating time to microwave heating time (0/120, 20/100, 40/80, 60/60, 80/40, 100/20 and 120/0 min). The lignins dissolved in the alkali liquors were separated and purified, and their physicochemical features were comparatively characterized by sugar analysis, GPC, FT-IR, ¹³C and HSQC NMR, as well as thermogravimetric analysis (TGA). The results showed that the lignin fractions extracted with microwave heating (20-120 min) had high molecular weights and polydispersities (M_w 3150-5710 g/mol, M_n 2130-3020 g/mol, M_w/M_n 1.48-2.00) as compared to those prepared without microwave heating (M_w 3080 g/mol, M_n 2080 g/mol, M_w/M_n 1.48). The most striking characteristic of all lignin fractions was the almost absence of associated sugars (0.16-3.25%). The TGA results indicated that the thermal stability of the lignin fraction increased with the increment of the molecular weight. FT-IR and NMR spectra suggested that the lignin fractions showed similar structures which were mainly composed of guaiacyl (G) and minor amounts of p-hydroxyphenyl (H) units. Moreover, HSQC NMR spectrum of a typical lignin fraction (prepared with microwave heating for 120 min) revealed that it contained dominant amounts of β-O-4′ linkages (64.6%) and phenylcoumaran (β-5′) substructures (25.8%) together with small amounts of resinol (β-β′) substructures (6.7%) and coniferyl alcohol end groups (2.9%).     

Properties of basic dyes on polyacrylonitrile treated m-aramid fabrics

Treatment of polyacrylonitrile (PAN) onto m-aramid fabric was carried out by pad-dry-cure method using dimethylformamide (DMF) dissolved acrylic fiber solution. The obtained PAN treated m-aramid fabric was dyed using exhaustion method with basic dyes. The effect of PAN treatment on fabric stiffness property was acceptable with acrylic fiber solutions ranging from 1 wt% to 4 wt%. Whilst, more than 4 wt% PAN treated fabrics exhibited undesirable stiffness. The dyeing results showed that PAN treated m-aramid fabrics exhibited a significant increase in color strength when compared to untreated fabric, arising from an increase in anionic dye sites (styrene SO₃ ^? group). Wash fastness was comparable to that of untreated fabric, indicating the strong interaction between dye molecules and the PAN. Rubbing fastness of treated fabrics was not affected by treatments with PAN concentrations lower than 4 wt%. Further increase in PAN concentration led to poorer rubbing fastness property due to the problem of surface dyeing. For light fastness, the PAN treatment failed to improve the light fastness property which is the main disadvantage of basic dyeing of aramid fabric. Finally, in case of PAN treatments with the range of 1 wt% to 4 wt%, the flame retardancy property of PAN treated m-aramid fabrics was found not affected by the percent add-on. However, above 4 wt% PAN treatment, the flame retardancy performance became deteriorated.     

Rheological and thermal properties of acrylonitrile-acrylamide copolymers: Influence of polymerization temperature

An attempt was made to correlate the polymerization temperature and rheological and thermal properties of acrylonitrile (AN)-acrylamide (AM) copolymers. The copolymers were synthesized at different polymerization temperature. The copolymer structure was characterized by gel permeation chromatography (GPC) and Infrared spectrum (IR). The rheological and thermal properties were investigated by a viscometer and differential scanning calorimeter-thermogrametric (DSCTG) analysis, respectively. When the polymerization temperature increased from 41 °C to 65 °C, the molecular weight ([`(M)] <sub>w</sub> )(\overline M _w ) of copolymers decreased from 1,090,000 to 250,000, while its conversion increased from 18% to 63%, and the polymer composition changed slightly. To meet the requirements of carbon fibers, the rheological and thermal properties of products were also investigated. It was found that the relationship between viscosity and [`(M)] _w\overline M _w was nonlinear and the viscosity index (n) decreased from 3.13 to 2.69, when the solution temperature increased from 30 °C to 65 °C. This suggests the dependence of viscosity upon [`(M)] _w\overline M _w is higher at lower solution temperature. According to the result of activation energy, the sensivity of viscosity to solution temperature is higher for AN-AM copolymers synthesized at higher polymerization temperature. The result of thermal analysis shows that the copolymers obtained at higher polymerization temperature are easier to cyclization evidenced from lower initiation temperature. The weight loss behavior changed irregularly with polymerization temperature due to irregular change of liberation heat.     

Effect of calcium carbonate nanoparticles on barrier properties and biodegradability of polylactic acid

In this study, the effect of calcium carbonate (CaCO₃) nanoparticles on the barrier properties and biodegradability of polylactic acid (PLA) was investigated. For this purpose, nanocomposite films with various CaCO₃ nanoparticle contents (0, 3, 5, 10, and 15 wt%) were prepared by solution casting method. The gas permeability of nitrogen (N₂), oxygen (O₂), and carbon dioxide (CO₂) was evaluated through a constant volume and variable pressure apparatus at different pressures and temperatures. According to results, barrier properties were improved by loading CaCO₃ nanoparticles up to 5 wt%, and the gas permeability of CO₂, O₂, and N₂ was decreased from 1.4, 0.31, and 0.07 Barrer to 0.48, 0.095, and 0.019 Barrer, respectively. In addition, it was also observed that the gas permeability of samples was decreased by increasing feeding pressure and increased by enhancing temperature. Furthermore, morphological results confirmed the formation of agglomerations and large clusters over 5 wt% CaCO₃ nanoparticles. Finally, the thermal properties and biodegradability of PLA were increased by employing CaCO₃ nanoparticles. These results suggested PLA nanocomposites as favorable candidates for food packaging applications.     

Polyacrylonitrile/electroconductive TiO<Subscript>2</Subscript> nanoparticles composite fibers <Emphasis Type="Italic">via</Emphasis> wet-spinning

For the first time, novel polyacrylonitrile (PAN)/electroconductive TiO₂ (EC-TiO₂) nanoparticles composite fibers have been successfully spun via wet-spinning. The composite fibers had uniform diameter and homogeneous surface. Moreover, at low content of EC-TiO₂ nanoparticles, the composite fibers realized a transition from an insulator to a conductor. This work has provided a simple and effective avenue for the production of PAN/EC-TiO₂ nanoparticles composite fibers that have great potential applications in the antistatic textiles.     

Highly porous polyacrylonitrile/polystyrene nanofibers by electrospinning

The concept of phase separation was coupled with electrospinning to induce polyacrylonitrile (PAN) and polystyrene (PS) bicomponent electrospun fibers that, upon removal of the phase-separated PS domains by solvent extraction, became nanoporous. Electrospinning of PAN (Mw 150 kDa) with 5 % w/w PS (Mw 250 kDa) at a 10 % w/w total concentration in N,N-dimethylformamide (DMF) produced fibers with stable morphology and average diameters from 1130±680 to 890±340 nm by FESEM. The nanoporous fibers made from a 95/5 w/w PAN/PS bicomponent precursor had internal pores of about 20∼110 nanometers. Pore sizes of the porous PAN fibers were decreased to approximately ∼25 nm after oxidation and carbonization thermal treatment because of fiber shrinkage during the thermal treatment. The fibers retained a high density of pores after the thermal treatment.     

Preparation of high molecular weight atactic poly(vinyl alcohol) by photo-induced bulk polymerization of vinyl acetate

Vinyl acetate was polymerized in ultraviolet-ray initiated bulk system at low temperatures using 2,2′-azobis(2,4-dimethylvaleronitrile) (ADMVN) or 2,2′-azobis(isobutyronitrile) (AIBN) as the photoinitiator, respectively. High molecular weight (HMW) poly(vinyl alcohol) (PVA) having number-average degree of polymerization (P _n ) of 3,900–7,800 and syndiotactic diad (S-diad) content of 52.5–54.0% could be prepared by complete saponification of synthesized linear poly(vinyl acetate) (PVAc) havingP _n of 5,900–9,400 obtained at conversion of below 30%.P _n of PVA using ADMVN was larger than that of PVA using AIBN. On the other hand, conversion of the former was smaller than that of the latter, and it was found that the initiation rate of the ADMVN was lower than that of AIBN. This could be explained by a fact that the rate of photolysis of AIBN is faster than that of ADMVN due to the higher quantum yield or dissociation rate constant of AIBN than that of ADMVN. TheP _n , syndiotacticity, and whiteness of PVA from PVAc polymerized at lower temperatures were superior to those of PVA from PVAc polymerized at higher temperatures.     

High Performance Poly(methyl methacrylate-acrylic acid-divinylbenzene) Microcapsule Encapsulated Heat Storage Material for Thermoregulating Textiles

The preparation of high performance poly(methyl methacrylate-acrylic acid-divinylbenzene) (P(MMA-AADVB)) microcapsule encapsulating octadecane (OD) having carboxyl groups on the surface for textile application was studied. The P(MMA-methyl acrylate (MA)-DVB) microcapsule was previously prepared by microsuspension iodine transfer polymerization prior to hydrolysis of MA segment to obtain AA in the P(MMA-AA-DVB) shell. Using 30 wt% of MA and 20 wt% of DVB, the latent heats of melting and crystallization of the encapsulated OD were close to those of original OD (245 and 251 J/g-OD, respectively). After hydrolysis, the zeta potential value of the obtained P(MMA-AADVB) microcapsule surface was -33 mV representing the formation of carboxyl groups of PAA derived from PMA. The influences of nucleating agent amount and type on the reduction of supercooling were then investigated. Using 1-octadecanol at 10 wt% of OD provided the best result. T_c of the encapsulated OD increased and reached to that of original OD while the latent heats were maintained. The hydrolyzed P(MMA-AA-DVB) presented higher efficiency than P(MMA-MA-DVB) microcapsules for fabric coating without external binder which may due to the interaction of microcapsule surface functional group with fabric.     

Surface modified ployacrylonitrile nanofibers and application for metal ions chelation

Ployacrylonitrile (PAN) nanofibers were formed by electrospinning. Amidoxime ployacrylonitrile (AOPAN) nanofibers were prepared by reaction with hydroxylamine hydrochloride, which were used as the matrix for metal ions chelation. FTIR spectra of the PAN nanofibers and AOPAN nanofibers were recorded for analysis of the surface chemical structures. The AOPAN conventional fibers were also prepared for comparison, and surface morphologies of the modified PAN conventional fibers and PAN nanofibers were observed by FESEM. Metal ions concentrations were calculated by AAS. The chelated isothermal process and kinetics parameters of the modified PAN nanofibers and PAN conventional fibers were studied in this work. Results indicated that the saturated coordinate capacity of AOPAN nanofibers to Cu²⁺, Cd²⁺ was 3.4482 and 4.5408 mmol/g (dry fiber) respectively, nearly two times higher than that of AOPAN conventional fibers. Besides, the desorption rate of Cu²⁺ and Cd²⁺ from metal chelated AOPAN nanofibers was 87 and 92 % respectively in 1 mol/l nitric acid solution for 60 min. The isothermal processes were found to be in conformity with Langmuir model.     

Spectroscopic Analyses on Chain Structure and Thermal Stabilization Behavior of Acrylonitrile/Methyl Acrylate/Itaconic Acid-based Copolymers Synthesized by Aqueous Suspension Polymerization

We have synthesized a series of copolymers with different compositions of acrylonitrile (AN, 80–100 wt%), methyl acrylate (MA, 4–20 wt%) and itaconic acid (IA, 0–3 wt%) by using an efficient aqueous suspension polymerization, and have investigated the molecular structure and thermal stabilization behavior of PAN homopolymer, AN/MA-based bipolymers, and AN/MA/IA-based terpolymers by adopting ¹H/¹³C-NMR and thermal FT-IR analyses. The viscosity-average molecular weight of the synthesized polymers were measured to be ~263,000 g/mol. The reactivity ratios of AN and MA for all the copolymers were evaluated to be 0.99 and 1.05, respectively. Accordingly, the output compositions of the synthesized copolymers were quite consistent with the input monomer compositions. The ¹³C NMR analysis revealed that all the synthesized polymers have an atactic chain configuration, regardless of the feed composition. The structural evolutions during the thermal stabilization process of the copolymers in air environment were characterized by monitoring the temperature-dependent changes of characteristic absorbance bands at 2240 cm^-1 (C≡N), 1595 cm^-1 (C=N) and 1660 cm^-1 (C=O) with aid of thermal FT-IR spectroscopy. It was found that the IA unit in the terpolymers accelerated the oxidation and cyclization reactions, unlike the retarding effect of MA unit, and that the onset temperatures of the oxidation reaction of the copolymers with IA unit was lower than that of the cyclization reaction.     

Synthesis of poly(norbornene ester)s by using (<Emphasis Type="Italic">η</Emphasis><Superscript>3</Superscript>-substituted allyl) palladium (NHC) complex as catalyst and investigation of their chemical structure - Glass transition temperature - Refractive index relationships

The synthesis of poly(norbornene ester)s by using a (η ³-substituted allyl) palladium (N-heterocyclic carbene (NHC)) complex as catalyst was performed and the relationship between chemical structure and glass transition temperature or refractive index of poly(norbornene ester)s was investigated. Norbornene ester monomers were synthesized via esterification of 5-norbornene-2-methyl alcohol and aromatic carboxylic acids. The polymerization catalyst, (η ³-substituted allyl) palladium (NHC) complex, was synthesized according to a published procedure. ¹H-NMR spectroscopy was performed to determine chemical structure of monomers and polymers. The molecular weight of the polymers was measured via gel permeation chromatography and the thermal properties were analyzed via thermogravimetric analysis and dynamic mechanical analysis. Refractive indices of polymer films were measured using a prism coupler. Polymers with the highest M _n (between 100 kg/mol and 300 kg/mol) were synthesized when the ratio of monomer to catalyst was 2000:1. The glass transition temperature of synthesized polymers was about 100 °C lower than that of conventional norbornene polymers. Among the six polymers of different chemical structures, four polymers exhibited a refractive index of 1.6 or more at a wavelength in the visible light region.     

Preparation of ZnO nanoparticles and nanofibers and their use in the degradation of rhodamine B dye under UV irradiation

ZnO nanoparticles (ZNPs) were obtained via a direct calcining method. ZnO nanofibers (ZNFs) were fabricated by electrospinning polyacrylonitrile (PAN) and zinc acetate (Zn(Ac)₂) solution and calcining PAN/Zn(Ac)₂ nanofibers. The samples were characterized by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), fourier transform infrared spectrum (FT-IR), X-ray diffraction (XRD), photoluminescence spectra (PL) and UV-vis spectroscopy. The results showed that the sizes of the ZNPs ranged from 90–275 nm with the average value 170 nm. The ZNFs were constructed by a series of nanoparticles along the fiber axis, and the sizes of the nanoparticles ranged from 50–250 nm with the average size 150 nm. The ZNPs and the ZNFs were both crystallized with hexagonal wurtzite structure. Although the nanoparticles in the ZNFs accumulated along the fiber axis and more surface oxygen vacancies were formed for the ZNPs, the distance of photocatalytic activities between these two kinds of catalyst was only 5 %. Besides, both the ZNPs and the ZNFs could be recycled and reused for their stable photocatalytic activities. Compared with the ZNPs, the ZNFs showed a wider application for their fibrious morphology.     

Preparation of aminated polyacrylonitrile porous fiber mat and its Application for Cr(VI) ion removal

Porous polyacrylonitrile (PAN) fiber mat was prepared by electrospinning PAN in N,N-dimethylformide solution with poly(methyl methacrylate) (PMMA) as pore-forming agent. Then, the porous PAN fiber mat was chemical modified by the tetraethylenepentamine to acquire aminated porous polyacrylonitrile (APPAN) fiber mat. Common aminated PAN fiber mat was also prepared for comparison. The surface morphologies of the APPAN and PAN fiber mat were characterized by scanning electron microscopy (SEM) and the corresponding specific surface areas were also measured. FT-IR/ATR spectra of the APPAN and PAN fiber mat were recorded for analysis of the surface chemical structures. The Cr(VI) absorption results demonstrated that the porous structure in the fiber could obviously increase the absorption capacity of the fiber mat.     

Synthesis and Characterization of Superabsorbent Polymer Based on Carboxymethyl Cellulose-<Emphasis Type="Italic">graft</Emphasis>-Itaconic Acid

Superabsorbent polymers of carboxymethyl cellulose-graft-itaconic acid were synthesized using potassium persulfate as a free radical initiator in the presence of N,N′-methylene bisacrylamide as a crosslinker using solution polymerization technique. The structures of the grafted copolymers were characterized by FT-IR spectroscopy and thermogravimetric analysis. The effect of reaction variables such as concentration of carboxymethyl cellulose, itaconic acid, initiator, crosslinker, and neutralizing agent were optimized to achieve a hydrogel with high swelling capacity of 74 g/g (DI water) and 18 g/g (0.9 wt% NaCl solution). The swelling kinetics of the prepared SAP were analyzed by applying the Fickian diffusion model and the Schott’s pseudo second order kinetics model. The diffusion exponents in the Fickian model, n, showed values of 0.73-0.93, indicating that chain relaxation behavior during absorption had a large effect on total absorbency.     

Compressive viscoelastic properties of softwood kraft lignin-based flexible polyurethane foams

Softwood kraft lignin (SKL)-based water-blown flexible polyurethane foams were prepared using SKL as a crosslinking agent and a hard segment polyol. Polyethylene glycol (PEG) as a soft segment diol and 2,4-toluene diisocyanate (TDI) were used. While increasing hard segment content caused the increase in crosslink density in foams, the foams became more and more viscous with increasing hard segment content due to the distinctive phase heterogeneity in foams. In this case, the contributiveness of the filler-like behaviors of separated hard segments always overtook the crosslinking effects derived from SKL in terms of overall viscoelasticity, thus the resultant viscometric properties such as tanδ _max and hysteresis loss increased as hard segment content increased. Furthermore, increasing M _n,PEG caused the severer microphase separation and intensified the filler effects in foams, thus the foams became more viscous with increasing M _n,PEG. The 25 % and 65 % CFD values and Young’s moduli of foams increased with increasing hard segment content due to the increase in crosslink density for foams, and the properties also increased with increasing foam density. Most of foams showed the support factors in the range of 2–3, which are suitable values for cushioning use. Even though the microscopic deformation behaviors in foams are irrelevant to foam density, the cyclic compressive tests showed that the higher foam density possess the better shape recovery performances.     

Biotic interactions affecting potato production

Pest/pathogen interactions affecting potato production are reviewed. Many reported interactions in potatoes and other crops are best termed associations or interrelationships. True synergistics interactions can be expressed as Y = b₁ x₁ + b₂ x₂ + b₃ (x₁ x₂) + - b_n x_n + e in which Y is a measure of plant growth, b₁, b₂, b_n are constants, x₁, x₂, x_n are independent variables and e is the error term. Examples of interactions including pathogen vectors, and various interactions involving different viruses and biotic taxa and among biotic taxa (e.g., virus-virus, virus-fungus, fungusbacteria, and nematode-fungus) in potatoes are cited. It is included that important interactions do occur in potato production systems and that additional research is needed to identify unknown interacting factors and to elucidate mechanisms of those previously described. Particular needs exist for holistic or synoptic studies to identify the role of interacting factors in total crop management.     

New Insights of Turmeric Extract-Loaded PLGA Nanoparticles: Development,Characterization and In Vitro Evaluation of Antioxidant Activity

Here, we presented new insights of the development of poly(lactic-co-glycolic acid) nanoparticles containing turmeric compounds (turmeric-PLGA-NPs) using emulsion-solvent evaporation method. The nanoparticulate system was characterized by size, zeta potential, morphology, release profile, partition parameter, stability and encapsulation efficiency (%EE). Antioxidant activity studies were also evaluated. The Korsmeyer-Peppas model (M_t/M_∞ vs. t) was used to determine the release mechanisms of the studied system. Our results demonstrated the emulsion-solvent evaporation method was shown advantageous for producing turmeric-PLGA-NPs in the range of 145 nm with high homogeneity in size distribution, zeta potential of ?21.8 mV and %EE about 72%. Nanoparticles were stable over a period of one month. In vitro study showed a release of curcumin governed by diffusion and relaxation of the polymeric matrix. The partition parameter of the extract in relation to blank-PLGA-NPs was 0.111?±?0.008 M^?1, indicating a low affinity of curcumin for the polymer matrix. Antioxidant ability of the turmeric-PLGA-NPs in scavenging the radical 2,2-azinobis (3-ethylbenzothiazoline- 6-sulfonic acid) (ABTS) was inferior to free turmeric extract and showed a concentration and time-dependent profile. The study concluded that PLGA nanoparticles are potential carriers for turmeric extract delivery.