Thermomechanical and cyclic behavior of biocomposites based on renewable thermoplastics from dimer fatty acids

Microbiocomposites based on renewable thermoplastic matrices such as thermoplastic polyurethane (TPU) and polyamide (DAPA), synthesized from dimer fatty acids, and high aspect ratio talc were prepared. TPU/DAPA blends and their corresponding biocomposites exhibited mechanical behavior, which is linked to those of the matrices and their relative contents, i.e., going from a typical semicrystalline behavior (DAPA) to an elastomeric one (TPU). The understanding of the thermomechanical and cyclic behavior of these advanced materials, particularly for TPU/DAPA with high TPU content, is detailed. Addition of particles of high aspect ratio natural talc (HAR) improved the storage modulus over the whole temperature range (almost five times with 5 wt % HAR). Under cyclic manipulation, the biocomposites displayed a stress softening related to the Mullins' effect. An increase of the hysteresis and the residual deformation with the HAR content has been shown. The hyperelastic models of Mooney–Rivlin and Ogden–Dorfmann, used to predict the loading and unloading behavior, fitted with experimental data. The present work also reports the experimental characterization of the deformation mechanisms of these renewable biocomposites through different microscopic techniques at different scales, such as atomic force, scanning electron and transmission electron microscopies. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44610.     

Ethylene vinyl acetate/nanoclay‐based pigment composites: Morphology,rheology, and mechanical,thermal, and colorimetric properties

In this study, a new type of nanopigment, obtained from a nanoclay (NC) and a dye, was synthesized in the laboratory, and these nanopigments were used to color an ethylene vinyl acetate (EVA) copolymer. Several of these nanoclay‐based pigments (NCPs) were obtained through variations in the cation exchange capacity (CEC) percentage of the NC exchanged with the dye and also including an ammonium salt. Composites of EVA and different amounts of the as‐synthesized nanopigments were prepared in a melt‐intercalation process. Then, the morphological, mechanical, thermal, rheological, and colorimetric properties of the samples were assessed. The EVA/NCP composites developed much better color properties than the samples containing only the dye, especially when both the dye and the ammonium salt were exchanged with NC. Their other properties were similar to those of more conventional EVA/NC composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2987–2994, 2013     

Synthesis and nonlinear optical properties of novel y‐type polyurethanes containing different concentrations of chromophore

A new series of Y‐type polyurethanes containing different concentrations of nonlinear optical (NLO) chromophore with aniline donor and tricyanofurane (TCF) acceptor have been successfully prepared, and characterized by FTIR, UV‐Vis, and ¹H‐NMR spectra. New polyurethanes were synthesized with different chromophore contents by introducing diol N, N‐dihydroxyethylaniline or 4‐[N, N‐(dihydroxyethyl)amino]benzaldehyde. These NLO polyurethanes exhibit good film forming property and high thermal stability up to 281°C. The highest electro‐optic coefficient (r₃₃) of polymers is up to 39 pm V^?1 measured by simple reflection technique at 1310 nm, and the temporal stability of the poling‐induced order at elevated temperature of 80°C was much improved through the introducing of hydrogen bonding interaction in this system. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Biobased blends of poly(propylene carbonate) and poly(hydroxybutyrate‐co‐hydroxyvalerate): Fabrication and characterization

Poly(propylene carbonate) (PPC), a CO₂‐based bioplastic and poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) were melt blended followed by injection molding. Fourier transform infrared spectroscopy detected an interaction between the macromolecules from the reduction in the OH peak and a shift in the C?O peak. The onset degradation temperature of the polymer blends was improved by 5% and 19% in comparison to PHBV and PPC, respectively. Blending PPC with PHBV reduced the melting and crystallization temperatures and crystallinity of the latter as observed through differential scanning calorimetry. The amorphous nature of PPC affected the thermal properties of PHBV by hindering the spherulitic growth and diluting the crystalline region. Scanning electron micrographs presented a uniform dispersion and morphology of the blends, which lead to balanced mechanical properties. Incorporating PHBV, a stiff semi‐crystalline polymer improved the dimensional stability of PPC by restricting the motion of its polymer chains. © 2016 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44420.     

Trehalose‐based thermosetting resins. I. Synthesis and thermal properties of trehalose vinylbenzyl ether

Trehalose vinylbenzyl ether was synthesized from trehalose and p‐chloromethylstyrene (CMS) in DMSO in the presence of powdered NaOH. The structure of the product was characterized by IR and ¹H NMR spectroscopy. Degree of substitution (DS) on a trehalose unit calculated from the ¹H NMR spectrum varied from 2.4 to 3.2 by changing the feed ratio of p‐chloromethylstyrene to trehalose. Thermal properties of the resin were analyzed by differential scanning calorimetry (DSC). DSC analysis revealed that the resin DS 2.4 has one exothermal peak at 132°C, whereas the resins DS 2.8 and 3.0 have two exothermal peaks. Furthermore, the resin DS 3.2 was found to have only one exothermal peak at 191°C. Dynamic mechanical analysis (DMA) and thermomechanical analysis (TMA) revealed that the cured resin has one transition, implying a glass transition. Biodegradability was assayed by the BOD method, and several percent of the cured resin was found to be degraded with activated sludge for 50 days. Further degradation, however, was not observed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 46–51, 2004     

Linear low‐density polyethylene colored with a nanoclay‐based pigment: Morphology and mechanical,thermal, and colorimetric properties

In this study, a novel kind of hybrid pigment based on nanoclays and dyes was synthesized and characterized. These nanoclay‐based pigments (NCPs) were prepared at the laboratory with sodium montmorillonite nanoclay (NC) and methylene blue (MB). The cation‐exchange capacity of NC exchanged with MB was varied to obtain a wide color gamut. The synthesized nanopigments were thoroughly characterized. The NCPs were melt‐mixed with linear low‐density polyethylene (PE) with an internal mixer. Furthermore, samples with conventional colorants were prepared in the same way. Then, the properties (mechanical, thermal, and colorimetric) of the mixtures were assessed. The PE–NCP samples developed better color properties than those containing conventional colorants and used as references, and their other properties were maintained or improved, even at lower contents of dye compared to that with the conventional colorants. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical and thermal properties of low density polyethylene composites filled with dye‐loaded shell powder

To achieve reinforcement and coloring in one combined process of polymer production, a dye‐loaded shell powder (DPSP) based on Congo red and pearl shell powder was prepared and used as a versatile bio‐filler in low‐density polyethylene (LDPE). The DPSP was characterized by means of X‐ray diffraction, Fourier transform infrared spectroscopy and thermogravimetric analysis. The mechanical, thermal, and colorimetric properties of prepared LDPE/DPSP composites were investigated as well. Adding DPSP could significantly increase the strength and stiffness of LDPE composites while giving an outstanding coloring performance. Moreover, the impact strength of LDPE composites was improved at lower filler loading rate, and the maximum incorporation content could reach 10 wt % with a good balance between toughness and stiffness of LDPE composites. The thermal performance studies confirmed an increase in thermal stability and heat resistance of LDPE composites with the incorporation of DPSP. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44118.     

Preparation and adsorption properties of diethylenetriamine‐modified chitosan beads for acid dyes

This work has demonstrated that the novel chitosan derivative, synthesized by phase transition and grafting diethylenetriamine, has a great potential for the adsorption of acid dyes from aqueous solutions. Four acid dyes with different molecular sizes and structures were used to investigate the adsorption performance of diethylenetriamine‐modified chitosan beads (CTSN‐beads). Results indicated that the adsorption of dyes on CTSN‐beads was largely dependent on the pH value and controlled by the electrostatic attraction. In addition, the adsorption rate (AO10 > AO7 > AR18 > AG25) and adsorption capacities (AO7 > AR18 > AO10 > AG25) were directly related to the molecular size of the dye and the amount of the sulfonate groups on the dye molecules. The equilibrium and kinetic data fitted well with the Langmuir–Freundlich and pseudo‐second‐order model. Furthermore, thermodynamic parameters indicated that the adsorption processes occurred spontaneously and higher temperature made the adsorption easier. The reuse tests indicated that the CTSN‐beads can be recovered for multiple uses. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4090–4098, 2013     

Colloidal properties of copolymer‐encapsulated and surface‐modified pigment dispersion and its application in inkjet printing inks

A styrene–maleic acid copolymer (PSMA)‐encapsulated 2‐[(2‐methoxy‐4‐nitrophenyl) azo]‐N‐(2‐methoxyphenyl)‐3‐oxobutyramide (PY74) dispersion was prepared by the phase‐separation technique. A surface‐modified PY74 dispersion was prepared with PSMA sodium as a dispersant by the milling method. Furthermore, the two dispersions were applied to formulate pigment inks. The colloidal properties of these two dispersions were compared. The printing and color performance of the prepared inks were also investigated. The results show that the PSMA‐encapsulated PY74 dispersion with a small particle size had higher stabilities of NaCl concentration, pH value, and temperature than the surface‐modified PY74 dispersion. The apparent viscosity of the PSMA‐encapsulated PY74 dispersion changed little, while it changed greatly in the surface‐modified PY74 dispersion with an increase of the shear rate from 10 to 100 s⁻¹. The ink printing and color performance of printed Fabrics indicated that the PSMA‐encapsulated PY74 dispersion was more suitable for the preparation of inkjet printing ink than the surface‐modified PY74 dispersion. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Phosphate ester groups‐containing ricinoleic acid‐based Ca/Zn: Preparation and application as novel thermal stabilizer for PVC

Phosphate ester groups containing ricinoleic acid‐based Ca/Zn (LPPRA‐Ca and LPPRA‐Zn) stabilizer was successfully synthesized from ricinoleic acid (RA) and used as thermal stabilizers for poly(vinyl chloride) (PVC). These thermal stabilizers were characterized by Fourier transform infrared spectrometry, ¹H nuclear magnetic resonance, and inductively‐coupled plasma atomic emission spectroscopy. The effects of LPPRA‐Ca/LPPRA‐Zn, CaSt₂/ZnSt₂, and other stabilizers on the thermal stability of PVC were studied through Congo Red test, discoloration tests, thermogravimetric analysis (TGA), TGA–infrared, and TGA–mass spectrometry. The thermal stability tests show that LPPRA‐Ca/LPPRA‐Zn displays the best initial color stability and long‐term thermal stability for PVC. The superior performance is attributed to the synergistic effect of LPPRA‐Ca and LPPRA‐Zn. Moreover, a lower Zinc content of LPPRA‐Zn in PVC helps to decrease the “zipper dehydrochlorination” of the product, which contributes to a better initial thermal stability. Except for the better stabilization performance, LPPRA‐Ca/LPPRA‐Zn also displays better plasticization performance for PVC compared with other stabilizers. A possible stabilizing mechanism of PVC/LPPRA‐Ca/LPPRA‐Zn system was presented. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45940.     

Synthesis,characterization, and application of a triazene‐based polysulfone as a dye adsorbent

Novel triazene‐based polysulfone, poly 4‐(4‐aminophenylsulfonyl)diazobenzene, was synthesized from 4‐[(4‐aminobenzene)sulfonyl]aniline (Dapsone) in the presence of sodium nitrite/silica sulfuric acid system, under solvent‐free conditions, and also in aqueous media to compare their polymerization process and the products. The structures of the obtained polymers under the two conditions were characterized for the first time in this investigation by several analytical and spectroscopic methods such as FT‐IR, ¹H‐NMR, UV–vis, thermogravimetric and differential thermal analyses, gel permeation chromatography, mass spectrometry, and CHN micro‐elemental analysis. The results showed that both polymerization processes had made the same product; nevertheless, the solvent‐free conditions afforded silica‐coated poly 4‐(4‐aminophenylsulfonyl)diazobenzene. In another study, the ability of the silica‐coated polymer, to remove some usual applied water‐soluble dyes by spectrophotometric detection, was measured in which cationic structure dyes such as Rhodamine B and Cationic blue 41 were preferably adsorbed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Approach in Macadamia integrifolia residue based low-density polyethylene composites on mechanical and thermal performance

Macadamia nutshell residues are generated in large quantities, around 70%–77% for each ton produced, and it is a waste material with high techno-economic potential. This work purpose a sustainable alternative to valorize macadamia nutshell residues (MN) as reinforcing in low-density polyethylene (LDPE) composites through melt mixing, using different fiber contents (0, 5, 10, and 20 wt%), and investigate the influence of fibers (residues) in composites by mechanical tests and thermal analysis. The fibers addition has significantly increased the composites' stiffness compared with neat LDPE, causing a reduction of toughness and resilience, leading to lower impact energy absorption. The LPDE/MN20% composite obtained the best tensile and flexural mechanical performance, resulting in a maximum modulus, which implies an increase of 36.9% and 77.6% compared with the neat LDPE. The addition of macadamia fibers on the composites acted as nucleation points of spherulites, which promoted an increase in the crystallization degree. Consequently, better performance of mechanical properties was observed in the green composites. Thus, the macadamia nutshell residues present a promising future as filler in LDPE for enhancing composites' thermal and mechanical properties.     

Coloration properties and chemo‐rheological characterization of a dioxazine pigment‐based monodispersed masterbatch

A dioxazine‐based color pigment was added to a commercial polyamide 6 (PA6) through an extrusion process, in order to prepare monoconcentrated violet masterbatches through different production set‐up. A detailed characterization of the resulting materials was carried out in order to find the best processing parameters combination to optimize pigment dispersion and to reduce the clogging power. The preparation of masterbatches with repeated extrusions markedly reduced the filter pressure value and increased the Relative Color Strength, while filtration did not significantly influence pigment dispersion. Rheological measurements and end‐groups analysis were conducted on the same materials with the aim to evaluate their thermal degradation resistance, and the thermal stability of the compounds was retained even upon three extrusions. Therefore, it can be concluded that a proper optimization of the process parameters could lead to an important reduction of the production waste, increasing the quality of the final product. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41452.     

Synthesis and characterization of hetarylazo disperse colorants: Preparation and properties of conventional and microemulsified inks for polyester ink‐jet printing

The synthesis and characterization of three hetarylazo disperse colorants are described. These compounds were used for the preparation of conventional inks and/or oil‐in‐water microemulsions (microemulsified dyes). The viscosity, conductivity, surface tension, and pH of these inks were studied over a period of time and discussed with respect to their structure. The particle size and particle size distribution of a representative microemulsion were compared to those of a corresponding conventional ink. The measured properties were compared to the properties of commercially available inks. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Development of water‐blown bio‐based thermoplastic polyurethane foams using bio‐derived chain extender

Water‐blown bio‐based thermoplastic polyurethane (TPU) formulations were developed to fulfill the requirements of the reactive rotational molding/foaming process. They were prepared using synthetic and bio‐based chain extenders. Foams were prepared by stirring polyether polyol (macrodiol), chain extender (diol), surfactant (silicone oil), chemical blowing agent (distilled water), catalyst, and diisocyanate. The concentration of chain extender, blowing agent, and surfactant were varied and their effects on foaming kinetics, physical, mechanical, and morphological properties of foams were investigated. Density, compressive strength, and modulus of foams decrease with increasing blowing agent concentration and increase with increasing chain extender concentration, but are not significantly affected by changes in surfactant concentration. The foam glass‐transition temperatures increase with increasing blowing agent and chain extender concentrations. The foam cell size slightly increases with increasing blowing agent content and decreases upon surfactant addition (without any dependence on concentration), whereas chain extender concentration has no effect on cell size. Bio‐based 1,3‐propanediol can be used successfully for the preparation TPU foams without sacrificing any properties. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermal degradation and combustion behavior of intumescent flame‐retardant polypropylene with novel phosphorus‐based flame retardants

The objective of this study was to develop an environmentally friendly fire‐retardant polypropylene (PP) with significantly improved fire‐retardancy performance with a novel flame‐retardant (FR) system. The system was composed of ammonium polyphosphate (APP), melamine (MEL), and novel phosphorus‐based FRs. Because of the synergistic FR effects among the three FRs, the FR PP composites achieved a V‐0 classification, and the limiting oxygen index reached as high as 36.5%. In the cone calorimeter test, both the peak heat‐release rate (pHRR) and total heat release (THR) of the FR PP composites were remarkably reduced by the incorporation of the novel FR system. The FR mechanism of the MEL–APP–FR–PP composites was investigated through thermogravimetric analysis and char residue characterization, and the results reveal that the addition of MEL–APP–FRs promoted the formation of stable intumescent char layers. This led to the reduction of pHRR and THR and resulted in the improvement of the fire retardancy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45962.     

Optimization of thermoelectric properties of metal‐oxide‐based polymer composites

Thermoelectric modules can be used for thermal energy harvesting. Common rigid thermoelectric stacks usually contain heavy metal alloys such as Bi₂Te₃. In order to substitute conventional materials and to reduce manufacturing costs, nontoxic, inexpensive and abundant materials using low‐cost processes are first choice. This study deals with polymer composites consisting of a polysiloxane matrix filled with thermoelectric Sn_0.85Sb_0.15O₂ particles in micrometer scale. Thin composite sheets have been prepared by doctor blade technique and the Seebeck coefficient, the electrical and thermal conductivity, and the porosity were measured. Platelet‐type particles, consisting of Sn_0.85Sb_0.15O₂‐coated insulating mica substrate and globular Sn_0.85Sb_0.15O₂ particles have been varied in size, coating thickness and were mixed with each other in different ratios. The filler content was varied in order to maximize the figure of merit, ZT, to 1.9 × 10^?5 ± 4 × 10^?6. Owing to their low raw material costs and the high degree of design freedom of polymer composites, one may use these materials in thermoelectric generators for remote low‐power demanding applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40038.     

Fluid biomulching based on poly(vinyl alcohol) and fillers from renewable resources

This article reports on the results obtained in an investigation on the application of biodegradable polymeric materials in the agricultural practice of mulching. Particular attention has been devoted to the effect of biobased mulching films generated in situ by low‐pressure spraying of polymeric water dispersions on the various cultivars. In a field trial, the effectiveness of the hydromulching (liquid‐mulching) technique was assessed by the monitoring of the growth and yield of lettuce and corn, which were used as reference plants. Conventional plastic films and straw mulching (SM) were compared with liquid‐mulching treatments based on poly(vinyl alcohol) and natural fillers derived from agroindustrial wastes (sugar cane bagasse, wheat flour, saw dust, and wheat straw). An improvement of the biomass yield of the two selected plants with respect to conventional polyethylene mulching was attained in various liquid‐mulching formulations with positive effects on the maintenance of soil structure. Alternative fluid‐mulching treatments based on biodegradable components were effective in preserving soil aggregates and improving some crop growth parameters. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Modification of melamine‐formaldehyde resins by substances from renewable resources

In the present contribution, investigations on the chemical modification of thermosetting melamine formaldehyde resins by natural polyol compounds are presented. As representative agents soluble starch, sucrose, and glycerol were chosen to cover three different classes of polyols. The major aim was to use substances produced from natural bio‐renewable feedstock that are available in large quantities and may serve as environmentally innocuous and bio‐renewable substitutes for petro‐chemically derived and potentially hazardous materials. Different reaction conditions lead to resins with varying technical performance. For soluble starch no reaction conditions could be found that allow the adoption of this substitute for the laminate industry due to insufficient technological performance. Sucrose and glycerol on the other hand yielded impregnation resins with suitable performance. Chemical linkage of the modifying agent into the chain propagation by poly‐condensation however, was only found with glycerol. The covalent incorporation of glycerol in the network was observed with addition of glycerol at different stages during synthesis. The technological performance of the various modified thermosetting resins was assessed by determining flow viscosity, molar mass distribution, the storage stability, and in a second step laminating impregnated paper to particle boards and testing the resulting surfaces according to standardized quality tests. Spectroscopic evidence of chemical incorporation of glycerol was found by applying by ¹H, ¹³C, ¹H/¹³C HSQC, ¹H/¹³C HMBC, and ¹H DOSY methods. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Lignocellulosic jute fiber as a bioadsorbent for the removal of azo dye from its aqueous solution: Batch and column studies

The feasibility of the use of jute fiber for the adsorption of azo dye from an aqueous solution was evaluated with batch and fixed‐bed column studies. The batch studies illustrated that dye uptake was highly dependent on different process variables, namely, the pH, initial dye concentration of the solution, adsorbent dosage, contact time, ionic strength, and temperature. The exothermic and spontaneous nature of adsorption was revealed from thermodynamic study. The equilibrium adsorption data were highly consistent with the Langmuir isotherm and yielded an R² value of 0.999. Kinetic studies divulged that the adsorption followed a pseudo‐second‐order model with regard to the intraparticle diffusion. In the column studies, the total amount of adsorbed dye and the adsorption capacity decreased with increasing flow rate and increased with increasing bed height and initial dye concentration. Also, the breakthrough time and exhaustion time increased with increasing bed depth but decreased with increasing flow rate and influent dye concentration. The column performances were predicted by the application of the bed‐depth service time model and Thomas model to the experimental data. The virgin and dye‐adsorbed jute fiber was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy analyses. The investigation suggested that jute fiber could be applied as a promising low‐cost adsorbent for dye removal. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013