Synthesis of diallyl‐containing polyimide and the effect of allyl groups on properties

A diallyl‐containing bisphenol, 1,1‐bis(3‐allyl‐4‐hydroxyphenyl)‐1‐(6‐oxido‐6H ‐dibenzo [c,e][1,2] oxaphosphorin‐6‐yl) ethane ( 1 ), was prepared by a two‐step procedure. Then, a diallyl‐containing diamine, 1,1‐bis(3‐allyl‐4‐(4‐aminophenoxy)‐phenyl)‐1‐(6‐oxido‐6H‐dibenzo [c,e][1,2] oxaphosphorin‐6‐yl)ethane ( 3 ), was prepared from the nucleophilic substitution of ( 1 ) with 4‐fluoronitrobenzene, followed by the reduction by Fe/HCl. A flexible polyimide ( 4 ) with curable diallyl linkages was prepared from the condensation of ( 3 ) and 4,4′‐oxydiphthalic anhydride in m‐cresol in the presence of isoquinoline. Curing polyimide ( 4 ) at 300 °C leads to thermosetting polyimide ( 5 ). We discussed the amounts of allyl group on T_g, coefficient of thermal expansion, and thermal stability of thermosetting polyimides, and found that thermal properties and dimensional stability of thermosetting polyimides increase with the amounts of cured allyl moieties. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 513–520     

High‐Tg and low‐dielectric epoxy thermosets based on a propargyl ether‐containing phosphinated benzoxazine

A propargyl ether‐containing benzoxazine (4) was prepared from a potassium carbonate‐catalyzed nucleophilic substitution of propargyl bromide and a phenolic OH‐containing benzoxazine (3) , which was prepared from 1‐(4‐hydroxyphenyl)‐1‐(4‐aminophenyl)‐1‐(6‐oxido‐6H ‐dibenz <c,e><1,2> oxaphosphorin‐6‐yl)ethane (1) by a three‐step procedure. The curing reactions of (4) were monitored by IR and DSC. A reaction mechanism was proposed based on the observation. Benzoxazines (3) and (4) were applied as epoxy curing agents. The microstructure and the structure‐property relationship of the resulting thermosets are discussed. The double‐strand structure in (4) ‐cured epoxy thermosets afforded higher crosslinking density, and led to higher thermal properties. In addition, the (4) ‐cured epoxy thermosets possess half the amount of highly polar hydroxyl groups than those of the (3) ‐cured epoxy thermosets, resulting in a lower dielectric constant, dissipation factor, and water absorption. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1359–1367     

On a piecewise-smooth map arising in ecology

In this paper, we study a two-dimensional piecewise smooth map arising in ecology. Such map, containing two parameters d and β, is derived from a model describing how masting of a mature forest happens and synchronizes. Here d is the energy depletion quantity and β   is the coupling strength. Our main results are the following. First, we obtain a “weak” Sharkovskii ordering for the map on its nondiagonal invariant region for a certain set of parameters. In particular, we show that its Sharkovskii ordering is the natural number (resp., the positive even number) for β>1$\beta >1$ (resp., 0<β<1$0<\beta <1$). Second, we obtain a region of parameter space for which its corresponding global dynamics can be completely characterized.     

Influence of annealing temperature on the structural, optical and mechanical properties of ALD-derived ZnO thin films

ZnO thin films grown on Si(1 1 1) substrates by using atomic layer deposition (ALD) were annealed at the temperatures ranging from 300 to 500 °C. The X-ray diffraction (XRD) results show that the annealed ZnO thin films are highly (0 0 2)-oriented, indicating a well ordered microstructure. The film surface examined by the atomic force microscopy (AFM), however, indicated that the roughness increases with increasing annealing temperature. The photoluminescence (PL) spectrum showed that the intensity of UV emission was strongest for films annealed at 500 °C. The mechanical properties of the resultant ZnO thin films investigated by nanoindentation reveal that the hardness decreases from 9.2 GPa to 7.2 GPa for films annealed at 300 °C and 500 °C, respectively. On the other hand, the Young's modulus for the former is 168.6 GPa as compared to a value of 139.5 GPa for the latter. Moreover, the relationship between the hardness and film grain size appear to follow closely with the Hall-Petch equation.     

Packaging of microfluidic chips via interstitial bonding technique.

In this paper, we describe an interstitial bonding technique for packaging of microfluidic chips. The cover plate is first placed on top of the microfluidic chip, followed by dispensing the UV-curable resin into the resin-loading reservoirs. With the interstitial space between the cover plate and the microfluidic chip connecting to the loading reservoirs, the UV-curable resin wicks through capillary force action and hydrostatic pressure generated by the liquid level in the resin-loading reservoirs. When reaching the microchannels, the UV-curable resin stops flowing into the microchannels due to the force balance between the surface tension and hydrostatic pressure. The assembly is then placed under the UV light, followed by further curing in the thermal oven. It is found that there is no leakage from the bonded microfluidic chips and a good DNA separation result was obtained by using the microfluidic chips as fabricated. This bonding technique is relatively simple and fast, which can be applied to the packaging of microfluidic chips made from hybrid materials with complicated designs as long as the interstitial space connects to the loading reservoirs.     

Extraction of surfactin from fermentation broth with n-hexane in microporous PVDF hollow fibers: Significance of membrane adsorption

In order to avoid foaming behavior and the formation of stable emulsions in traditional extraction, non-dispersive extraction of surfactin from the fermentation broth of Bacillus subtilis ATCC 21332 culture with n-hexane was studied in microporous polyvinylidene fluoride (PVDF, pore size 0.2 μm) hollow fiber module. In this work, the broth was pretreated by acid precipitation and the precipitate was then dissolved in NaOH solution, and the treated broth was passed through the lumen side of the module and n-hexane was flowed across the shell side. Experiments were performed at a fixed pH of 8.0 and a flow rate of both phases of 2.5 mL min⁻¹ but at different surfactin concentrations (300–3000 mg L⁻¹). Under the conditions studied, it was shown that surfactin was adsorbed onto the surface of the fibers, instead of being extracted by n-hexane and transported through the pores of the fibers into bulk n-hexane phase. The adsorption capacity was determined and the adsorption dynamics was analyzed. The purity of surfactin desorbed from the fibers with ethanol was found to be higher than that obtained after solvent extraction with n-hexane.     

Piecewise linear maps, Liapunov exponents and entropy

Let be a class of piecewise linear maps associated with a transition matrix A. In this paper, we prove that if fA,x∈LA, then the Liapunov exponent λ(x) of fA,x is equal to a measure theoretic entropy hmA,x of fA,x, where mA,x is a Markov measure associated with A and x. The Liapunov exponent and the entropy are computable by solving an eigenvalue problem and can be explicitly calculated when the transition matrix A is symmetric. Moreover, we also show that maxxλ(x)=maxxhmA,x=log(λ₁), where λ₁ is the maximal eigenvalue of A.     

Preparation of protein-silicate hybrids from polyamine intercalation of layered montmorillonite

Hybrids of the model BSA protein and layered silicate clay with d spacing of approximately 62 A were prepared from either direct or stepwise intercalation. The pristine montmorilloinite (Na+-MMT) was first modified by poly(oxyalkylene)-amine salts (POP- and POE-amine) of 2000 g/mol Mw to a gallery-expanded silicate (d spacing=53 and 18 A, respectively), which became accessible for BSA protein embedding. Subsequent BSA substitution allowed the embedding of the protein into the layered clay galleries in an uncompressed conformation. The stepwise process of embedding large molecules into the silicate gallery provides a new method for synthesizing biomaterial/clay hybrids potentially useful in drug delivery or biomedical design.     

Influence of Temperature on the Formation of Silver Nanoparticles by using a Seed‐Free Photochemical Method under Sodium‐Lamp Irradiation

Silver nanoparticles can be prepared by using a seed‐free photo‐assisted citrate reduction method under the irradiation of a sodium lamp. Under the same irradiation intensity, bath temperatures are crucial in influencing the reaction rate, morphologies of final products, and shape evolution of the silver nanostructures. For example, when the bath temperature is 80 °C, the product yields of silver nanoplates, nanorods, and nanodecahedra are 38±6 %, 35±10 %, and 12±8 %, respectively. However, when the bath temperature is 30 °C, the product yields of silver nanoplates, nanorods, and nanodecahedra are 6±3 %, 0 %, and 83±16 %, respectively. Time‐dependent UV/Vis spectra and TEM images show that silver nanoplates were formed at the earlier reaction stage and greatly decreased in amount at the later stage when the bath temperatures are less than or equal to 40 °C. This indicates that the silver nanoplates, which can be regarded as intermediates, are kinetically favored products. They are not thermodynamically favored products at these relatively low bath temperatures. The SERS spectra of crystal violet (CV) show that all the silver colloids synthesized at various temperatures exhibit good enhancement factors and that the colloids prepared at lower bath temperatures have a higher enhancement factor.     

Room-temperature ferromagnetism in amorphous In–Ga–Zn–O films fabricated by using pulsed-laser deposition

Room-temperature ferromagnetism (RTFM) was observed in pulsed-laser deposited amorphous In–Ga–Zn–O (a-IGZO) films undoped with impurities containing unpaired d or f electrons. The presence of oxygen vacancies in the prepared a-IGZO films was verified by X-ray photoelectron spectroscopy and suggested to be responsible for the observed RTFM. The electrical and optical properties of the a-IGZO films were also investigated.