Unveiling the self-assembly behavior of copolymers of AAc and DMAPMA in situ to form smart hydrogels displaying nanogels-within-macrogel hierarchical morphology

Stimulus responsive hydrogels are being considered as one of the most crucial biomaterials of current generation. A new technique has been established for developing hydrogels based on Acrylic acid (AAc) and N-[3-(Dimethylamino)propyl]-methacrylamide (DMAPMA), and relevant mechanism has been delineated. Aqueous redox copolymerization of different molar ratios of AAc and DMAPMA at 41 ± 1 °C, leading to the formation of interlocked nanogels of ∼300 nm diameter, which acted as the building blocks of a series of superabsorbent hydrogels having robust, honey-comb type three-dimensional architecture. Monomer composition, monomer feed ratio and water content in feed has been found to be important factors in the development of the stable poly(AAc-co-DMAPMA) hydrogel membranes (PADMAs) without any active crosslinking agent. At the cues of pH change from 7.0 to 3.5, pulsatile swelling-deswelling behavior varied, ranging from ∼5900% to ∼60% (mass) respectively, underlining smart hydrogel characteristics needed for specific biomedical applications. Elastic modulus of the gels, equilibrated at pH 7.0, is recorded to be >15 kPa under uniaxial compression. Underlying mechanism of the formation of such robust three-dimensional structures in poly(AAc-co-DMAPMA) hydrogel membranes, and the origin of hierarchical ‘nano-to-macro’ scale morphological features has been proposed.     

Modeling and experimental studies on single particle coal devolatilization and residual char combustion in fluidized bed

Single particle devolatilization followed by combustion of the residual coal char particle has been analyzed in a batch-fluidized bed. The kinetic scheme with distributed activation energy is used for coal devolatilization while multiple chemical reactions with volume reaction mechanism are considered for residual char combustion. Both the models couple kinetics with heat transfer. Finite Volume Method (FVM) is employed to solve fully transient partial differential equations coupled with reaction kinetics. The devolatilization model is used to predict the devolatilization time along with residual mass and particle temperature, while the combined devolatilization and char combustion model is used to predict the overall mass loss and temperature profile of coal. The computed results are compared with the experimental results of the present authors for combustion of Indian sub-bituminous coal (15% ash) in a fluidized bed combustor as well as with published experimental results for coal with low ash high volatile matter. The effects of various operating parameters like bed temperature, oxygen mole fraction in bulk phase on devolatilization time and burn-out time of coal particle in bubbling fluidized bed have been examined through simulation.     

Selective oxidation of olefins and aromatic alcohols with tert‐butylhydroperoxide catalyzed by polymer‐anchored transition‐metal complexes

Three polymer‐anchored metal complexes (Co, Cu, and Pd) were synthesized and characterized. The catalytic performance of these complexes was tested for the oxidation of olefins and aromatic alcohols. These complexes showed excellent catalytic activity and high selectivity. These complexes selectively gave epoxides and aldehydes from olefins and alcohols, respectively. Individually, the effect of various solvents, oxidants, substrate oxidant molar ratios, temperatures, and catalyst amounts for the oxidation of cyclohexene and benzyl alcohol were studied. Under optimized reaction conditions, 96, 81, and 71% conversions of cyclohexene and 86, 79, and 73% conversions of benzyl alcohol were obtained with Co(II), Cu(II), and Pd(II) catalysts, respectively. The catalytic results reveal that these complexes could be recycled more than five times without much loss in activity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Microstructure and mechanical performance examination of 3D printed acrylonitrile butadiene styrene thermoplastic parts

Fused filament fabrication (FFF) is a process where thermoplastic materials are heated to its melting point and then extruded, layer by layer, to create a three dimensional printed part. Printing occurs in a layered manner, which leads to creation of voids (air gaps) in the 3D printed parts. These voids act as centers for crack initiation, propagation and therefore resulting bulk mechanical properties are lower. This paper focuses on microstructural characterization and analysis of fused filament fabricated tensile test coupons made from acrylonitrile butadiene styrene polymer, at various design conditions. Comparable tensile modulus with injection molded specimens was obtained for FFF design condition that is, slice height (0.1778 mm), raster width (0.4064 mm), raster to raster air gap (−0.0015 mm), contour to raster air gap (−0.0508 mm) and raster angle (0°). Scanning electron microscope studies provided an understanding as to why FFF processed specimens yielded lower failure strain and an insight into the presence of intralayer voids in specimens having lower tensile modulus. The study confirmed that though bulk mechanicals were affected by the combined effect of inter, intra and interfacial voids, intravoids had a predominant influence.     

Multicomponent bulk metal nitride (Nb1/3Ta1/3Ti1/3)N1−δ synthesis via reaction flash sintering and characterizations

In this research, near fully dense single phase bulk multicomponent transition metal nitride (Nb_1/3Ta_1/3Ti_1/3)N_1−δ has been successfully synthesized from mixed commercial powders of NbN, TaN and TiN via reaction flash sintering technique. This was performed with an applied pressure of ~ 35 MPa at 25°C under a constant DC electric field (~24-32 V/cm). The flash event, which is the abrupt increase in current (up to ~ 25.2 A/mm²) and temperature, occurred without preheating. The threshold power dissipation on the sample right before the flash is ~ 0.7 W/mm³. The formation of single phase (Nb_1/3Ta_1/3Ti_1/3)N_1−δ random solid solution and its compositional uniformity were confirmed by XRD and EDS, respectively. The effects of ball milling duration and limiting current density on phase formation were studied. Simulation based on Joule heating provides an estimate of the ultimate sample temperature of ~ 1850°C. Vickers hardness of the obtained (Nb_1/3Ta_1/3Ti_1/3)N_1−δ is 17.6 ± 0.6 GPa, which is comparable to similarly flash sintered ingredient binary nitrides of TaN and NbN. TGA in air shows that the oxidation resistance of (Nb_1/3Ta_1/3Ti_1/3)N_1−δ is better than that of TaN and NbN but inferior to TiN. The study demonstrates that reaction flash sintering can be a highly efficient technique for synthesizing bulk multicomponent ceramics for both material fundamental investigations and application development.     

Guayule natural rubber composites: impact of fillers on their cure characteristics,dynamic and mechanical behavior

Guayule natural rubber (GNR) is an alternative resource of Hevea natural rubber (HNR) with 99.9% cis content in its 1,4-polyisoprene chemical backbone. In this study, compounds were formulated independently with four different reinforcing fillers such as carbon black (HAF), precipitated silica (VN3), fume silica (FUM) and nanofly ash (NFA) for the advancement of GNR based products. The cure characteristic, dynamic-mechanical performance and mechanical properties of GNR composite were studied with the reinforcing effect of different fillers on GNR. The cure characteristic results demonstrated that HAF and FUM silica filled compounds had more processing safety than VN3 and NFA filled compounds. Viscoelastic parameters of the vulcanizates were studied by dynamic mechanical analysis to estimate the glass transition characteristics and dynamic behavior. The higher storage modulus of FUM silica vulcanizate was an indication of superior filler reinforcing nature and improved rolling resistance than other filled systems. Additionally, HRTEM analysis also proved the better filler dispersion ability of FUM silica in GNR matrix. The mechanical properties were studied with a variation of each filler loading of 8, 16, and 32 phr in GNR vulcanizates. The tensile strength of each filled system increased with an increase of filler content from 8 to 32 phr. In comparison, FUM silica GNR vulcanizates exhibited better mechanical properties, therefore, it was considered as a better structure-performance composite than those of HAF, VN3 and NFA filled composites.

     

Influence of thermal and morphological characteristics on mechanical responses of polypropylene/γ‐irradiated elastomer blends

The approach of this paper is to examine the mechanical responses of polypropylene (PP)/γ‐irradiated ethylene acrylic elastomer blends and subsequently compare them with the PP/unirradiated ethylene acrylic elastomer blends. Thorough correlations were drawn between the mechanical characteristics of blends and their morphological, thermal, thermomechanical, and fractured surface morphological aspects. The idea of carrying out γ‐irradiation was to introduce crosslinking points in the elastomer phase. For better understanding, correlations between the impact test results and the fractured surface morphologies were analyzed. The limited tensile properties of PP/γ‐irradiated elastomer blends were attributed not only to the poor interfacial adhesion, obtained by fitting with several theoretical mechanical models, but also to the substantially higher elastomer particle size in the blends than in the PP/unirradiated elastomer blends. The higher loss modulus and tan δ values for PP/unirradiated elastomer blends along with the attainment of much smaller particles of elastomers were responsible for the phenomenal increase in impact properties, which was actually attributed to the formation of crazes inside the dispersed phase during applied impact stress. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46597.     

Isolation of High Oleate Recombinants in Peanut by Near Infra‐Red Spectroscopy and Confirmation With Allele Specific Polymerase Chain Reaction Marker

Near infrared (NIR) spectrophotometer offers rapid, noninvasive, nondestructive, and high‐throughput phenotyping of seed samples for use in agriculture and industry. In this study, a reflectance‐based NIR spectrophotometer was calibrated and used for the isolation of desirable higher‐oleic‐acid peanut recombinants from single‐seed‐derived segregating populations at F₇ and F₈ generations. A calibration model was developed through partial least‐square regression using wet chemistry data from 158 peanut genotypes. Desirable prediction for oil, palmitic acid, oleic acid, and linoleic acid in intact seed was obtained based on this calibration. It detected significant high correlations (r) and coefficient of determination (R²) between the actual gas chromatography values and NIR predicted values of fatty acid profile in another 123 peanut genotypes that were generated from crosses involving a high‐oleate mutant and Spanish bunch varieties with early maturity. From this recombinant single‐seed‐derived progenies, 15 higher‐oleate recombinants were isolated and later genotyped through an in‐house developed polymerase chain reaction‐based allele specific marker. The present study has generated high‐oleate peanut recombinants with early maturity in Spanish bunch background. The breeding materials generated here will be evaluated for yield attributing traits at different locations in future.     

CO2‐induced crystallization of polylactide and its self‐templating ‘stack of coins’ crystalline microstructure

Can we learn from biomineralization process of natural materials to fabricate a three‐dimensional (3D) thick laminate microstructure by stacking of two‐dimensional (2D) crystalline structure? By adopting this self‐organization principle of biomineralization process, a polymer is crystallized two‐dimensionally into a multi‐layered architecture. Herein, we demonstrate a 2D crystallization method of polylactide and its principle of self‐organization to develop the discontinuous laminate microstructures. We find that instead of building a multilayered morphology layer‐by‐layer, the lamellar microstructures can be built in one step by using self‐organization principle of 2D crystallization. The biopolymer PLA is compression molded, and the molded samples are crystallized by using supercritical CO₂ in a high pressure vessel_. The CO₂‐induced crystallization has a unique diffusion‐controlled crystallization mechanism, which tends to produce a disc‐shape spherultic structure. From microscopy analysis, we observe that these 2D spherulites are self‐organizing in nature and form 3D thick laminate structures with integrated amorphous phase in between. The obtained discontinuous laminate microstructure is comparable to “stack of coins” structure and we report the biomimetic approach of crystallization process. Thus, our study shows an innovative approach to engineer the crystalline microstructure of PLA. POLYM. ENG. SCI., 57:365–373, 2017. © 2016 Society of Plastics Engineers     

CO2‐induced crystal engineering of polylactide and the development of a polymeric nacreous microstructure

Nacre's biomineralization process and its self‐organizing brick‐and‐mortar crystalline microstructure have inspired many researchers to develop new materials derived from the natural world. In our study, we took a novel approach to two‐dimensional (2‐D) crystallization. That is, we applied the biomineralization self‐organizational principle that exists in natural materials to a biopolymer (polylactide). The CO₂‐induced crystallization of poly(d ‐lactide), with its unique diffusion‐controlled crystallization mechanism, tends to produce distinct 2‐D spherulitic structures. We found that these 2‐D spherulites were self‐organizing in nature, and that they created a stack of 2‐D spherulitic structures. These crystalline microstructures, with their intervening amorphous phase, were foamed in situ due to the CO₂‐induced crystallization self‐exclusion phenomenon. We compared the resultant crystalline structure with nacre's brick‐and‐mortar crystalline microstructure to confirm the biomimetic principle of self‐organization. To the best of our knowledge, this is the first time that a biopolymer has been crystallized in a 2‐D manner in a way that resembles nature's biomineralization process. The hierarchical crystalline microstructure is morphologically similar to that of nacre biomaterials. This novel crystallization technique is simple, absolutely non‐toxic and works swiftly to produce a brick‐and‐mortar crystalline microstructure with a high degree of order. © 2017 Society of Chemical Industry