Copolymers from methyl methacrylate and butyl acrylate with hyperbranched architecture

This is a first report of the synthesis and characterization of acrylic copolymers from methyl methacrylate (MMA) and butyl acrylate (BA) with hyperbranched architecture. The copolymers were synthesized using a free radical polymerization (Strathclyde method) in emulsion technique. Divinyl benzene was used as the brancher which acted as a comonomer and 1‐dodecanethiol was used as a chain terminating agent. A linear copolymer from MMA and BA was also synthesized for comparison. The hyperbranched architecture was established from spectroscopic and rheological measurements. The gel permeation chromatography showed all hyperbranched copolymers were low molecular weight with lower polydispersity index (PDI) ( 23,000, PDI ～ 2.00) compared to the linear grade ( 93,000, PDI ～ 2.20). They were more spherical and achieved lower viscosity (yet higher solubility, >90%) than the linear grade (<50%) which was mostly open ended. Lower viscosity at equivalent solid content made the hyperbranched polymers a potential binder for adhesive and coating application. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45356.     

Compressive shape memory behavior of spring‐shaped polylactic acid alloy type

This article presents an experimental study on the shape memory behavior of blends of thermoplastic polyurethane (TPU) and biodegradable polylactic acid (PLA) at the PLA/TPU weight ratios of 70/30 (PT7030) and 50/50 (PT5050). The manufactured springs were studied comprehensively based on their morphological and thermal properties. Scanning electron microscopy micrographs were captured, which verified that TPU was compatible with PLA. The wide‐angle X‐ray diffraction suggested that the crystallinity of PLA was enhanced in the presence of TPU. In order to determine the shape recovery properties [shape recovery ratio (R_r), shape fixing ratio (R_f), and shape recovery force (F_r)], the samples programmed at three different temperatures (T_p) of 70, 80, and 90 ° and at various recovery temperatures (T_r) over 40 to 90 ° , were studied. In general, the spring made with PT7030 showed higher R_r, R_f, and F_r values. The highest R_r (99%) was obtained at programmed temperature (T_p) of 70 ° and recovery temperature (T_r) of 90 ° . However, the R_r value for this spring programmed at 70 ° and recovered near body temperature was 50% with F_r of 1.4 N. Furthermore, the highest F_r (15.6 N) was observed in the spring made of PT7030 programmed at 80 ° and recovered at T_r of 78 ° . © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45115.     

Investigation and modelling of damping mechanisms of magnetorheological elastomers

Damping in MREs is considered to be ascribed to viscous flow of the rubber matrix, interfacial damping at the interface between the magnetic particles and the matrix and magnetism induced damping. In this study, individual components in MREs that contribute to material damping were investigated. A model was developed to include viscous flow of the rubber matrix, interfacial damping and magnetism induced damping to give the total damping capacity of MREs ( )It was found that depends on frequency, iron sand content, strain amplitude and is independent of the applied magnetic field over saturation magnetization. The proposed model was assessed experimentally using a series of isotropic and anisotropic MREs. Comparison between tan δ with showed that matched the experimental trends with average percentage difference of 8.1% and 21.8% for MREs with modified iron sand unmodified iron sand, respectively. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43247.     

Synthesis of aminated glycidyl methacrylate grafted rice husk and investigation of its anion‐adsorption properties

In this study, we focused on the synthesis, characterization, and adsorption capacity testing of aminated glycidyl methacrylate grafted rice husk (RH‐g‐GMA–Am). Our goal was to obtain a high‐performance surface for the adsorption of various anions. Glycidyl methacrylate grafted rice husk (RH‐g‐GMA) was prepared by the graft copolymerization of glycidyl methacrylate with rice husk; the product was further subjected to an amination reaction. The surface properties, sorption characteristic functional groups, isotherm and kinetic studies, pore diffusion models, and effects of the temperature and pH on the material properties were studied under batch conditions. The IR spectroscopy results show additional surface functional groups for RH‐g‐GMA–Am. The adsorptions of and on RH‐g‐GMA–Am were found to follow pseudo‐second‐order kinetics; this indicated a possible dominant role played by chemisorption. The rate‐limiting step for mass transfer was found to be boundary layer diffusion. Furthermore, the sorption isotherms for and fit the Langmuir model. The amination of RH‐g‐GMA drastically increased the removal efficiency from 3 to 82% and from 6 to 93% for and , respectively. Moreover, RH‐g‐GMA–Am exhibited a better removal efficiency in the pH range of 4–6.5. Regeneration studies revealed that the surface of RH‐g‐GMA–Am could be regenerated repetitively by simple acid washing with an insignificant decrease in the active surface for consecutive adsorptions. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43002.     

The role of wettability of nonideal nozzle plate: From drop‐on‐demand droplet jetting to impact on solid substrate

The dynamics of drop‐on‐demand (DoD) droplet formation and subsequently impact on the solid substrate are investigated using a three‐dimensional (3‐D) multirelaxation‐time (MRT) pseudopotential lattice Boltzmann (LB) model. The wettability of nonideal nozzle plate and solid substrate is modeled by a geometric scheme within the LB framework. The dynamics of droplet formation are explored in a range of the inverse of Ohnesorge number , , and , and the Reynolds number , , and . For , no satellite droplet is observed and the wettability of nozzle plate greatly influences the velocity and length of jetting fluids. For , the filament breakup and recombination are observed. The moment of filament breakup is delayed with advancing contact angle increasing. For with , the primary and satellite droplets could not be recombined with and which agree with the literature. Whereas with , the recombination occurs. The dynamics of subsequent oscillating droplet impact on the substrate are similar to that of equilibrium droplet which could obtain high‐resolution printed features. Consequently, considering with large and numbers, the printable range could be extended which could help increase the printing frequency and boost the production outputs of inkjet printing. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2837–2850, 2018     

Mass transfer coefficient of tubular ultrafiltration membranes under high‐flux conditions

The effect of suction flow on the mass transfer coefficient of tubular ultrafiltration membranes, in particular that under a high‐flux condition, was studied. We pointed out that is proportional to under turbulent conditions, and that the proportional constant, b, exceeds 0.023 when the effect of suction flow is not negligible. We conducted the velocity variation method using ultrafiltration membranes with MWCOs of 20k and 100k and dextrans having molecular weights of 40,000 and 70,000 at the conditions, where exceeded . We demonstrated that the effect of suction flow includes not only flux but also the diffusion coefficient of solute, and that the ratio of the flux to the diffusion coefficient, expressed as , is an important index. Finally, we concluded that , when is smaller than , giving the Deissler equation itself, and that , when exceeds . © 2017 American Institute of Chemical Engineers AIChE J, 64: 1778–1782, 2018     

Controlling micro‐ and nanofibrillar morphology of polymer blends in low‐speed melt spinning process. Part I. Profiles of PLA/PVA‐filament parameters along the spinline

The profiles of PLA/PVA filament parameters (e.g., temperature, velocity, tensile stress, and apparent elongational viscosity) along the spinline in the low‐speed melt spinning process under various spinning conditions were investigated. Owing to the combination of the filament velocity and filament temperature measurements using laser doppler velocimetry (LDV) and infrared thermography, respectively, the fiber formation zone was determined. The length of the fiber formation zone obtained from filament velocity profiles is always shorter than that obtained from the filament temperature profiles ( . Obviously, this unexpected phenomenon occurs for low spinning speeds due to the axial heat conduction effect of the filament along the spinline and the nonuniform radial temperature distribution through the cross‐sectional thick filament. Another remarkable finding is related to the Nusselt number which has been found as nearly constant along the spinline in the low‐speed melt spinning process. Thus, mathematical simulations of the filament temperature profiles will be simplified drastically. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44258.     

NMR spectroscopic study of chemical equilibria in solutions of formaldehyde,water, and butynediol

Liquid mixtures of formaldehyde, water, and butynediol are complex reacting multicomponent systems in which formaldehyde forms oligomers both with water and butynediol. ‐ and ‐NMR spectra of these mixtures are elucidated. The species distribution of the oligomers is quantitatively determined by ‐NMR spectroscopy. The measurements cover temperatures from 293 to 366 K, overall formaldehyde mass fractions from to , and overall butynediol mass fractions from to . A mole fraction‐based and an activity‐based model of the chemical equilibrium in the studied system are developed and chemical equilibrium constants are reported. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4442–4450, 2017     

Mechanism of internal and external electron donor effects on propylene polymerization with MgCl2‐supported Ziegler–Natta catalyst: New evidences based on active center counting

Two TiCl₄/Di/MgCl₂ type supported Ziegler–Natta catalysts were prepared by loading dibutylphthalate or dicyclopentyldimethoxysilane (DCPDMS) (internal donor, Di) and TiCl₄ on activated δ‐MgCl₂ in sequence, and a blank catalyst was prepared by loading TiCl₄ on the same δ‐MgCl₂ without adding Di. These catalysts have similar specific surface area and pore size distribution, thus form a suitable base for comparative studies. Propylene polymerization with the catalysts was conducted in n‐heptane slurry using triethylaluminum (TEA) as cocatalyst, and the effects of Di as well as De (external donor, in this work it was DCPDMS) on the number of active centers, the distribution of active centers among three polypropylene (PP) fractions (isotactic, medium isotactic, and atactic PP chains), and chain propagation rate constants of the PP fractions were studied by counting the number of active centers in the PP fractions using a method based on selective quench‐labeling of the propagation chains by 2‐thiophenecarbonyl chloride. When De was not added in the polymerization, introducing a phthalate type Di in the catalyst evidently changed the active center distribution by enhancing the proportion of active centers producing isotactic PP (iPP) ( ), but scarcely changed reactivities of the three groups of active centers forming the three fractions. When the De was added in the polymerization system with TiCl₄/phthalate/MgCl₂ catalyst, further shifting of active center distribution in favor of took place, meanwhile reactivities of the three groups of active centers also remarkably changed in favor of . Mutual effects of these changes led to overwhelming dominance of iPP production in the TiCl₄/Di/MgCl₂–TEA/De system (Di = phthalate, De = alkoxysilane). In contrast, though using alkoxysilane as Di also caused shifting of active center distribution in favor of when De was not added, addition of alkoxysilane De caused reverse shifting of active center distribution in favor of those producing PP of lower stereoregularity. This unfavorable change largely counteracted the reactivity changes in favor of caused by the De, rendering the catalytic system rather poor isospecificity. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46605.     

Counterion-Induced Cationic Flexible Nanoparticle Catalytic of Piperidinolysis of Phenyl Salicylate

The removal of PSa^? from bulk aqueous phase to the pseudo‐micellar phase by halobenzoate counterion X is responsible for the monotonic increase in k_obs (pseudo first‐order rate constants) with the increase in the values of [MX] where MX = sodium salts of 2‐, and 4‐halobenzoic acids. The values of ion exchange constants, or for X = 2‐ and 4‐halobenzoate ions in the presence of tetradecyltrimethylammonium bromide (TTABr) were calculated from the apparent catalytic rate constants, ^Xk_cat which represent the catalytic effect of CFN. Larger values of or were observed for X = 4‐halobenzoate ions than that for X = 2‐halobenzoate ions due to isomeric factors. The values of or determined in the presence of TTABr were compared with previously determined or values in the presence of cetyltrimethylammonium bromide (CTABr). The values of or are nearly 8 ~ 9‐fold larger for 4‐IBz^?, 4‐BrBz^? and 4‐ClBz^? compared to the respective values of X = 2‐IBz^?, 2‐BrBz^? and 2‐ClBz^?. The values of or for X = 4‐FBz^? is nearly 3‐fold larger than that for X = 2‐FBz^?. The values of or for X = 2‐ and 4‐halobenzoates are significantly smaller in the presence of TTABr than these in the presence of CTABr nanoparticles.     

Defect engineering on phase structure and temperature stability of KNN‐based ceramics sintered in different atmospheres

Lead‐free MnO‐doped 0.955K_0.5Na_0.5NbO₃‐0.045Bi_0.5Na_0.5ZrO₃ (Abbreviated as KNN‐0.045BNZ) ceramics have been prepared by the conventional solid‐state sintering method in reducing atmosphere ( = 1 × 10^?10 atm) and air. For ceramics sintered in reducing atmosphere, only Mn²⁺ ions exist in ceramics who preferentially occupy the cation vacancies in A‐site at x = 0.2‐0.4, whereas Mn²⁺ ions substitute for Zr⁴⁺ ions in B‐site to form defects () at x > 0.4. For ceramics sintered in air, mixed Mn²⁺, Mn³⁺, and Mn⁴⁺ ions coexist here. The Mn²⁺ ions preferentially occupy the cation vacancies in A‐site at x = 0.2‐0.4 and then Mn²⁺ ions substitute for Zr⁴⁺ ions in B‐site at x > 0.4. Meanwhile, the Mn³⁺ ions and Mn⁴⁺ ions substitute for Nb⁵⁺ ions in B‐site to form defects () at x = 0.2‐0.8. The (, , and ) dipolar defects show a positive dipolar defect contribution (DDC) to the , whereas the dipolar defects () show a negative DDC to the . The dipolar defects ( ‐ and ) can help improve the temperature stability of . The 0.4% MnO‐doped KNN‐0.045BNZ ceramics sintered in reducing atmosphere show excellent piezoelectric constant d₃₃ = 300 pC/N and 0.2% MnO‐doped KNN‐0.045BNZ ceramics sintered in air possess optimal piezoelectric constant d₃₃ = 290 pC/N.     

Pressure drop through platinized titanium porous electrodes for cerium‐based redox flow batteries

The pressure drop, , across a redox flow battery is linked to pumping costs and energy efficiency, making fluid properties of the electrolyte important in scale‐up operations. The at diverse platinized titanium electrodes in Ce‐based redox flow batteries is reported as a function of mean linear electrolyte velocity measured in a rectangular channel flow cell. Darcy's friction factor and permeability vs. Reynolds number are calculated. Average permeability values are: 7.10 × 10^?4 cm² for Pt/Ti mesh, 4.45 × 10^?4 cm² for Pt/Ti plate + turbulence promoters, 1.67 × 10^?5 cm² for Pt/Ti micromesh, and 1.31 × 10^?6 cm² for Pt/Ti felt. The electrochemical volumetric mass transport coefficient, , is provided as a function of . In the flow‐by configuration, Pt/Ti felt combines high values with a relatively high , followed by Pt/Ti micromesh. Pt/Ti mesh and Pt/Ti plate gave a lower but poorer electrochemical performance. Implications for cell design are discussed. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1135–1146, 2018     

Self‐synthesized epoxy terminated polydimethylsiloxane with various molecular weights toughening epoxy resin

Polydimethylsiloxane terminated by epoxy group (EP‐PDMS) with various molecular weight ( ) were synthesized by 1,3‐bis[3‐(2,3‐epoxypropoxy)‐propyl]‐1,1,3,3‐tetramethyldisiloxane (DOTMDS) and dimethylcyclosiloxane (D_n). The epoxy value measured by potentiometric titration, were 0.161, 0.092, 0.065, 0.044 mol/100 g, and the (calculated from epoxy value) 1,242, 2,174, 3,077, 4,545 g/mol, respectively (corresponding to EP‐PDMS1, 2, 3, 4). With the increasing ratio of D_n/DOTMDS, we can see the increase of and the decrease of epoxy group content according to FTIR result. Then these EP‐PDMS were used to improve the toughness of the epoxy resin (diglycidyl ether of bisphenol A, DGEBA). Mechanical tests showed that, the impact strength of the epoxy resin was improved by EP‐PDMS. The toughening effect was decreased when EP‐PDMS with relative higher was used. This was ascribed to that the EP‐PDMS with high was easier to agglomerate, and the active group was easier to be embedded which in turn resulted in lower toughening efficiency. This was also confirmed by scanning electron microscopy results. J. VINYL ADDIT. TECHNOL., 24:268–274, 2018. © 2016 Society of Plastics Engineers     

Preparation of nonwoven mats of electrospun poly(lactic acid)/polyaniline blend nanofibers: A new approach

The preparation of nonwoven mats of electrospun poly(lactic acid)/polyaniline (PANI) blend nanofibers faces some critical challenges that will be addressed in the present work. The challenges are in achieving high and adjustable content of PANI while keeping the spinnable solution nonagglomerated with no need to further filtration that might lead to wrong estimation of PANI content in the mat. We report an unprecedented content of 40% wt of PANI that is achieved using a new two‐step procedure. It is based on: (1) the preparation of the spinnable solution from a friable nonagglomerated and readily dispersible PANI: ‐TSA powder and (2) the use of an optimized mixture of ‐cresol/dichloromethane. The obtained nanofiber mats are characterized by FTIR and UV–vis spectroscopy. The morphology and the thermal stability of the nanofibers are investigated by scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). The amorphous structure of the nanofibers is verified using XRD measurements. The DC‐conductivity of these blend nanofibers is found to be far larger than the published DC‐conductivity values for blend nanofibers of PANI with PLLA or with other polymers. This is attributed to the high content of PANI in the blend and to the role played by ‐cresol as a secondary dopant. The investigation of the aging effect on the DC‐conductivity reveals an exponential decrease with a characteristic time of weeks. The electrical impedance spectroscopy (EIS) shows a pure ohmic behavior of the blend mat. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43687.     

Electric field‐assisted precipitation of lead selenide quantum dots in borosilicate glass

The influence of electric field on the precipitation and optical properties of PbSe quantum dots (QDs) in borosilicate glasses was investigated. Diameters of the PbSe QDs increased as was increased from 0.0 to 0.6 kV/mm even at the same subsequent heat treatment at 510°C for 2 hours. Increase in to 0.9 kV/mm caused red‐shift of the absorption and photoluminescence (PL) bands of QDs. Application of also led to decreases in viscosities that accelerated diffusion of ions; this phenomenon led to the formation of large QDs and resulted in the red‐shifts of the absorption and PL bands. Increase in the temperature due to Joule heating was ~38°C that led to an observed decrease in viscosities.     

Mixed‐Norm Spaces and Prediction of SαS Moving Averages

Suppose that is an i.i.d. symmetric α‐stable noise, 1 < α < 2, and consider the moving average process given by . Conditions are obtained for the convergence rate of the moving average series, as well as that of the inverted (autoregressive) representation . These conditions are expressed in terms of the associated function and its reciprocal belonging to certain mixed‐norm spaces of functions on the open unit disc. Properties of these spaces are explored. Criteria are also derived for the rate of mixing in a certain sense.     

Influence of 2,2′,6,6′‐tetramethyl biphenol‐based anion‐exchange membranes on the diffusion dialysis of hydrochloride acid

Quaternary ammonium functionalized poly(arylene ether) (QPAE‐Br) membranes based on 2,2′,6,6′‐tetramethyl biphenol for diffusion dialysis (DD) were designed and successfully fabricated via nucleophilic substitution polycondensation, bromination, film casting, and quaternization. The structures, thicknesses, ion‐exchange capacities (IECs), water uptakes, swelling ratios, ion conductivities, and mechanical properties of QPAE‐Br were used to characterize the membranes. The influence of the membrane structures on the DD performances was investigated by DD tests of simulated industrial pickling wastewater (1 mol/L HCl, 0.1 mol/L FeCl₂). The DD results show QPAE‐a (IEC = 1.51 mmol/g) as the best DD candidate. Predialysis treatments further improved the DD performances of QPAE‐Br. QPAE‐a exhibited an excellent proton diffusion coefficient ( ) of 0.033 m/h and a high separation factor (S) of 95.45 after the predialysis treatment at room temperature; these values were much higher than those of the commercial DF‐120B membrane (0.004 m/h for and 24.3 for S at 25 °C) and other reported DD membranes. QPAE‐a has great potential for acid recovery via DD. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45333.     

First‐Principles Study of Sc1−xTixF3 (x ≤ 0.375): Negative Thermal Expansion,Phase Transition,and Compressibility

We present the first‐principles investigation of (x ≤ 0.375). Controllable thermal expansion of is achieved by different Ti contents. The negative thermal expansion (NTE) behavior is weakened gradually with increasing Ti content, which is consistent with experimental measurements. The Jahn–Teller effect plays an important role in the cubic‐to‐rhombohedral phase transition, which stems from the enhanced energy stability when the 3d orbitals of cation split into triply degenerate and sets. The unusual thermal stiffening of is found, which is similar to that of and but contrary to other NTE materials.     

Cationic effect of charge compensation on the sulfide capacity of aluminosilicate slags

The effect of CaO on the sulfide capacity of CaO‐Al₂O₃‐SiO₂ slags was studied from the viewpoint of the ionic structure of alumina in slag. The aluminum coordination number was analyzed using ²⁷Al 500‐MHz solid nuclear magnetic resonance spectroscopy and the results were compared with those of the sulfide capacity analysis. The sulfide capacity of slag, in the peralkaline region (), exhibited a linear relationship with respect to basicity () as excess free Ca²⁺ formed a 4‐coordinated aluminum unit structure (^[IV]Al; ) and stabilized the sulfide ions (). However, sulfide capacity in the peraluminous region () exhibited a nonlinear relationship with respect to basicity () owing to the structure of higher‐coordinated aluminum units (^[V]Al, ^[VI]Al; Al³⁺) and the relative lack of Ca²⁺. Therefore, the sulfide capacity of high Al₂O₃‐bearing slags strongly depended on the basicity () and stability of sulfide ions (), which depended on the competitive behavior of Ca²⁺ owing to the structural changes in Al₂O₃. The effect of the aluminum coordination number on the sulfide capacity was discussed in detail using an analysis of the slag structure and thermodynamics model.     

A piezomicrobalance system for high‐temperature mass relaxation characterization of metal oxides: A case study of Pr‐doped ceria

A system for mass relaxation studies based on a gallium phosphate piezocrystal microbalance has been developed, built, and successfully used to characterize a representative mixed ionic and electronic conducting material. The apparatus is constructed to achieve reactor gas exchange times as short as 2 seconds and temporal resolution in mass measurement of 0.1 seconds. These characteristics enabled evaluation of mass relaxations that occurred on the 6 seconds time scale. Proof of concept for materials characterization capabilities of the system was carried out using 10% praseodymium‐doped cerium oxide (PCO), a material that undergoes, at selected temperatures and oxygen partial pressures, changes in mass but not in conductivity. Thin films were deposited on the piezocrystals via pulsed laser deposition (PLD). Mass relaxation curves were collected at 700°C upon application of a small step change in oxygen partial pressure, . Using two different films, the surface reaction constant, k_S, was obtained over the range from 10^?4 to 0.1 atm. Its value is found to vary between 9.7 × 10^?6 and 1.7 × 10^?4 cm/s, displaying a power law dependence on , with a law exponent of 0.67 ± 0.02, as averaged over the two sets of results. This steep dependence of k_S on is surprisingly independent of a change in dominant defect type within the range of measurement.