Compressive moduli and network parameters of N‐isopropylacrylamide hydrogels copolymerized by monoesters of itaconic acid and crosslinked with tetraallylammonium bromide

The present study focuses on the mechanical properties of hydrophilically or hydrophobically modified poly(N‐isopropylacrylamide) (PNIPAAm) hydrogels, and all discussions on their improved mechanical strengths are based on the conformational effects of hydrophobic side chains attached to the comonomers and the structural differences between the crosslinkers. Three different types of monoalkyl itaconates, bearing octyl (Oc), cetyl (Ce), and cyclohexyl (CH) groups as comonomers, were used to prepare the copolymeric PNIPAAm hydrogels crosslinked with N,N′‐methylenebisacrylamide (BIS) and tetraallylammonium bromide (TAB) as neutral tetrafunctional and ionic octafunctional crosslinkers, respectively. The most striking result is the compressive E modulus of TAB‐crosslinked PNIPAAm hydrogel containing 10 mol % of mOcI. It reaches nearly 1.0 MPa and is independent of the temperature and pH of the swelling/shrinking medium. The result was discussed in terms of the inter/intramolecular interactions between hydrophobic octyl groups adopting a rod‐like conformation in the case of 25 °C/distilled deionized water (DDW) and 37 °C/DDW combinations. Further, it was observed that the electrostatic repulsive forces between the carboxylate groups on mOcI units could be suppressed even at 37 °C and pH 9 due to the rod‐like conformations of C₈H₁₇ groups. Its micrographs under bright‐field and polarized light supported the presence of an ordered anisotropic phase and multiple associations of extended, hydrophobic side chains. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45039.     

The electrochemical synthesis of poly(aniline-co-o-anisidine) on copper and their corrosion performances

The copolymer films PANI-co-POA and poly(aniline-co-o-anisidine) were carried out on copper (Cu) electrode, by applying two different scan rates (20 and 50 mV s⁻¹) and using two different thicknesses at high scan rate. Synthesizes were achieved under cyclic voltammetric conditions from 0.075 M aniline and 0.075 M o-anisidine containing sodium oxalate solutions. The synthesized copolymer films were strongly adherent and homogeneous in both cases. AC impedance spectroscopy (EIS), anodic polarization plots and open circuit potential–time curves were used to evaluate the corrosion performance of copolymer coated and uncoated electrodes in 3.5% NaCl. It was shown that the copolymer film coated at low scan rate exhibited a better property initially when compared with the copolymer film produced at high scan rate. However, it could not resist the attack of corrosion products, in longer time and meanwhile its barrier property significantly diminished. It was found that the thin copolymer film produced at high scan rate by its catalysing effect led to the formation of highly protective copper oxides on the surface whereby providing a better protection for long exposure times. It also emerged that the corrosion resistances of thin copolymer film produced at high scan rate and copolymer film synthesized at low scan rate were almost same and relatively higher for much longer periods when compared with the one observed for bare copper electrode.     

Surface-free energy analysis of hydrolyzed ethylene-vinyl acetate copolymers

Ethylene-vinyl acetate (E-VA) copolymers containing 12, 28, and 40 wt% of vinyl acetate, ethylene-vinyl acetate-vinyl alcohol terpolymers obtained by partial hydrolysis of (E-VA) copolymers and ethylene-vinyl alcohol (E-VOH) copolymers obtained by complete hydrolysis of (E-VA) copolymers were investigated by one-liquid contact-angle method. The polar force component of surface-free energy (γ) of copolymers drastically increased by the substitution of the acetate groups with hydroxyl groups. The dispersion force component (γ) of copolymers increased only slightly with the hydrolysis degree and deviated largely from the additivity law in regards of the surface area functions. The surface-free energy analysis of the cross-linked ethylene-vinyl alcohol and surface-hydrolyzed ethylene-vinyl acetate copolymers was also carried out.     

The discrete fractional Fourier transform

We propose and consolidate a definition of the discrete fractional Fourier transform that generalizes the discrete Fourier transform (DFT) in the same sense that the continuous fractional Fourier transform generalizes the continuous ordinary Fourier transform. This definition is based on a particular set of eigenvectors of the DFT matrix, which constitutes the discrete counterpart of the set of Hermite-Gaussian functions. The definition is exactly unitary, index additive, and reduces to the DFT for unit order. The fact that this definition satisfies all the desirable properties expected of the discrete fractional Fourier transform supports our confidence that it will be accepted as the definitive definition of this transform     

Quality factor in trench-refilled polysilicon beam resonators

In this paper, thermoelastic damping (TED) in trench-refilled (TR) polysilicon microelectromechanical beam resonators is studied as a mechanism for limiting quality factor (Q) at low frequencies. An approximate model based on Zener's theory is developed and verified by numerical simulations in FEMLAB. According to the proposed model a double-dip characteristic is expected for the quality factor versus frequency curve of TR beam resonators. To verify the model experimentally, equal-width TR micro-resonators are fabricated in different length to cover a broad range of frequencies. Frequency response of these devices agrees well with our model. By using the theoretical and numerical models developed in this paper, an upper bound for the quality factor in TR beam resonators or any similar structure such as TR polysilicon gyros can be predicted.     

Reconfigurable Dual Peptide Tethered Polymer System Offers a Synergistic Solution for Next Generation Dental Adhesives

Resin-based composite materials have been widely used in restorative dental materials due to their aesthetic, mechanical, and physical properties. However, they still encounter clinical shortcomings mainly due to recurrent decay that develops at the composite-tooth interface. The low-viscosity adhesive that bonds the composite to the tooth is intended to seal this interface, but the adhesive seal is inherently defective and readily damaged by acids, enzymes, and oral fluids. Bacteria infiltrate the resulting gaps at the composite-tooth interface and bacterial by-products demineralize the tooth and erode the adhesive. These activities lead to wider and deeper gaps that provide an ideal environment for bacteria to proliferate. This complex degradation process mediated by several biological and environmental factors damages the tooth, destroys the adhesive seal, and ultimately, leads to failure of the composite restoration. This paper describes a co-tethered dual peptide-polymer system to address composite-tooth interface vulnerability. The adhesive system incorporates an antimicrobial peptide to inhibit bacterial attack and a hydroxyapatite-binding peptide to promote remineralization of damaged tooth structure. A designer spacer sequence was incorporated into each peptide sequence to not only provide a conjugation site for methacrylate (MA) monomer but also to retain active peptide conformations and enhance the display of the peptides in the material. The resulting MA-antimicrobial peptides and MA-remineralization peptides were copolymerized into dental adhesives formulations. The results on the adhesive system composed of co-tethered peptides demonstrated both strong metabolic inhibition of S. mutans and localized calcium phosphate remineralization. Overall, the result offers a reconfigurable and tunable peptide-polymer hybrid system as next-generation adhesives to address composite-tooth interface vulnerability.     

Multi-Criteria Query Optimization in the Presence of Result Size and Quality Tradeoffs

In this paper, we present novel multi-criteria query optimization techniques for performing query optimization in databases, such as multimedia and web databases, which rely on imperfect access mechanisms and top-k predicates. We present an optimization model that (1) takes into account different binding patterns associated with query predicates, (2) considers the variations in the expected query result sizes as a function of query execution plans, and (3) considers the expected result qualities of the execution orders. We address the complexity and the well-known NP-complete nature of the query optimization problem by adaptively reducing the granularity of the search space. For this purpose, unlike the data histograms which capture the data distribution, we propose opt-histograms that capture the distribution of sub-query-plan values over many optimization tasks.     

Synthesis and characterization of poly(N‐isopropylacrylamide)s initiated with siloxane oligomer–(NH4)2Ce(NO3)6 redox pair

Poly(N‐isopropylacrylamide)s (PNIPAAM)s were synthesized via free‐radical polymerization using a ceric ammonium nitrate, Ce(IV)–α‐ω‐dihydroxy(polydimethylsiloxane) (Tegomer H‐Si 2111, PDMS) redox pair in hexane at 30°C in a nitrogen atmosphere. The dependence of the initiation and termination steps on the [NIPAAM]/[Ce(IV)] and [NIPAAM]/[PDMS] ratios were studied using gravimetry and FTIR, ¹H‐NMR, UV‐vis, and GFAA spectroscopy techniques. Gravimetric results indicated that, in the case of high concentrations of PDMS, the percentage of the solid portions of the products decreased while the amount of the oligomeric NIPAAM chains increased, that is, as the amount of PDMS in hexane was increased, the number of the short NIPAAM chains having PDMS segments at the two ends, also increased. UV‐vis results showed that the LCST of PNIPAAM initiated with Ce(IV) alone was higher than those of the ones that were synthesized using common initiator systems such as an ammonium persulfate–N,N,N′,N′‐tetramethylethylenediamine redox pair and azobis(isobutyronitrile). Further, it was observed that both siloxane blocks and ? NH? groups forming coordination bonds with free Ce(IV) ions and/or metal–ligand complexes had an important effect on the aggregation process of the chains. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1248–1254, 2003     

The use of polyindole for mild steel protection

Synthesis of polyindole was achieved on mild steel electrode previously coated with a very thin polypyrrole layer (PPy). Cyclic voltammetry technique was used for both syntheses; oxalic acid solution was used for synthesis of primer PPy coating and polyindole film (PI) was obtained from LiClO₄ containing acetonitrile medium. The corrosion performance of this PPy/PI coating was investigated properly in 3.5% NaCl solution by using anodic polarization and open circuit potential (E_ocp)–time curves and electrochemical impedance spectroscopy (EIS). This coating exhibited excellent barrier efficiency for a long time (about 190 h) and it was also able to provide a certain anodic protection. After 240 h of immersion time in corrosive test solution, the protection efficiency value was determined to be 98.9%.     

Semicontinuous emulsion polymerization of vinyl acetate: Effect of ethoxylation degree of nonionic emulsifiers

Poly(vinyl acetate) latices were prepared in the presence of an ammonium persulfate initiator, 10–50 mol of an ethoxylated nonylphenol nonionic emulsifier, and a poly(vinyl alcohol) colloid stabilizer by applying semicontinuous emulsion polymerization (delayed monomer and initiator addition process) in a laboratory scale similar to industrial practice. Two approaches were applied: the molar concentration of the nonionic emulsifier was kept constant and the weight ratios in the polymerization recipe varied or the weight ratios were kept constant. The effects of the change in the ethoxylation degree of the emulsifier to the final latex viscosity, average polymer molecular weight, polymer grafting degree, surface tension of the latex, and the surface free energy of the dried films were investigated. It was determined that the resultant latex viscosity decreases and the viscosity‐average polymer molecular weight increases with increase of the nonionic emulsifier ethoxylation degree. The increase of the ethoxylation degree does not seriously affect the surface tension of the resultant latex or the surface free energy of the dried poly(vinyl acetate) films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 844–851, 2002