Epoxy composite reinforced with three‐dimensional polyimide fiber felt: Fabrication and tribological properties investigation

Novel epoxy (EP) composite reinforced with three‐dimensional (3D) polyimide (PI) fiber felt (PI_3D/EP) is first fabricated by vacuum assisted resin transfer molding. The tribological behaviors of pure EP and PI_3D/EP composite under dry sliding and water lubricated condition are comparatively studied. Results indicate that both wear rates and friction coefficients of PI_3D/EP composite are lower than those of pure EP. The wear resistance of PI_3D/EP composite is 9.8 times higher than that of pure EP under dry sliding of 1.5 MPa and 0.76 m s^?1 while a 27‐fold increase is achieved under water lubricated condition. The wear mechanisms of PI_3D/EP composite are investigated based on tribological testing results and scanning electron microscopy observations. The PI fiber felt provides strong 3D structure supports to sustain most of the loads on the composite, improving the mechanical and tribological properties significantly. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44160.     

Half order plus time delay (HOPTD) models to tune PI controllers

Methods based on the first‐order plus time delay (FOPTD) model are very popular for tuning proportional‐integral (PI) controllers. The FOPTD model‐based methods are simple and their utility has been proved with many successful applications to a wide range of processes in practice. However, even for some overdamped processes where the FOPTD model seems to be applied successfully, these empirical FOPTD model‐based methods can fail to provide stable tuning results. To remove these drawbacks, a PI controller tuning method based on half‐order plus time delay (HOPTD) model is proposed. Because FOPTD model‐based methods can be applied to higher order processes, the proposed HOPTD model‐based method can be applied to higher order processes as well. It does not require any additional process information compared to the FOPTD model‐based method and hence can be used for overdamped processes in practice, complementing the traditional FOPTD model‐based methods. © 2016 American Institute of Chemical Engineers AIChE J, 63: 601–609, 2017     

OPTIMALITY CHARACTERISTICS OF PI/PID CONTROLLERS: A COMBINED MIN-MAX/ISE INTERPRETATION

This communication addresses the tuning of PI and PID controllers on the basis of the IMC approach. The tuning is based upon a first order plus time delay (FOPTD) model and aims to achieve a step response specification. Through analysis it has been found that by using the IMC approach we get a PI or a PID depending on the rational approximation used for the time delay term. This article raises the question that the use of a PID instead of a PI controller should be based on another reason more related to the control objectives rather than the use of a better approximation for the time delay. An alternative tuning is presented here, from within the IMC formulation, based on a min-max optimization. From the tuning rule provided by this approach the optimum settings from an integral squared error criterion point of view are derived. The optimal controller results in being a PI controller. From this optimal controller as the starting point, the introduction of the derivative action can be seen as a detuning procedure that can increase the robustness of the controller. This approach provides further insight into the tuning of PI and PID controllers giving the (alternative) parameters a precise engineering meaning.     

Frequency domain tuning approach for adaptive feedforward control using lead–lag compensators

The tuning of lead–lag compensators to be used as feedforward controllers for measured disturbances is performed in the frequency domain. The identification of process G_u and disturbance dynamics G_d uses extended recursive least squares, and the frequency responses are calculated from the least squares coefficients. A lead–lag compensator G_ll is designed which minimises the function $G_{{\rm ll}} (j\omega ) + (G_{{\rm d}} (j\omega ))/(G_{{\rm u}} (j\omega ))$ over a finite number of frequencies, using the Nelder–Mead simplex method. The effectiveness of the frequency domain tuning strategy is compared by simulation to established tuning rules for first‐order plus delay processes. The tuning method is experimentally verified on a pilot scale methanol–water distillation column. © 2011 Canadian Society for Chemical Engineering     

Synthesis and in vitro biological evaluation as antitumour drug carriers of folate‐targeted N‐isopropylacrylamide‐based nanohydrogels

Copolymeric nanohydrogels based on N‐isopropylacrylamide, N‐(pyridin‐4‐ylmethyl)acrylamide and tert‐butyl‐2‐acrylamidoethyl carbamate, synthesized by microemulsion polymerization, were characterized using Fourier transform infrared spectroscopy and their size (38–52 nm) determined using quasielastic light scattering. Folic acid was covalently attached to the nanohydrogels (1.40 ± 0.07 mmol g^?1). Tamoxifen (6.7 ± 0.2–7.3 ± 1.2 µg TMX mg^?1 nanohydrogel), a hydrophobic anticancer drug, and 5‐fluorouracil (7.7 ± 0.7–10.14 ± 1.75 µg 5‐FU mg^?1 nanohydrogel), a hydrophilic anticancer drug, were loaded into the nanohydrogels. Maximum in vitro TMX release (77–84% of loaded drug) depended on interactions of the drug with hydrophobic clusters of the nanogels; however, no nanogel/5‐FU interactions allowed total release of the loaded drug. The cytotoxicity of unloaded nanohydrogels in MCF7, T47D and HeLa cells was low. Cell uptake of nanogels without bound folic acid took place in the three cell types by unspecific internalization in a time‐dependent process. Cell uptake increased for folic acid‐targeted nanohydrogels in T47D and HeLa cells, which have folate receptors. The administration of 10 and 30 µmol L^?1 TMX by TMX‐loaded nanogels and 10 µmol L^?1 5‐FU by 5‐FU‐loaded nanogels was effective on the three cell types, and the best results were obtained for folic acid‐targeted nanohydrogels. Copyright © 2012 Society of Chemical Industry     

The Voidage Function for the Drag Force Ratio in a Liquid‐Fluidized Bed

Di Felice (1994) has shown that the ratio of the drag coefficient, C_D, on a sphere in a liquid‐fluidized bed of uniform spheres to the drag coefficient, C_DS, on the same sphere in isolation and subjected to the same superficial liquid velocity, u, is given by a function ?^?β, where β was expressed as an empirical function of the particle Reynolds number, Re = duρ/µ. Here it is shown that C_D/C_DS is well approximated by ?^?mm, where the Richardson‐Zaki index n is a function of the terminal free‐settling Reynolds number, Re_t = du_tρ/µ, and m is 2 plus the slope of the standard log C_DS vs. log Re plot at plot at Re = Re_t. The present model, using the best experimentally confirmed equation for n and a new simple equation for and a new simple equation for m, is compared with that of Di Felice in their respective abilities to predict liquid‐fluidized bed expansion.     

1,2‐propanediol–cellulose–acrylamide graft copolymers

1,2‐Propanediol–cellulose–acrylamide graft copolymers (PCACs) were developed for enhanced oil recovery. They were prepared with acrylamide and 1,2‐propanediol (PDO)–cellulose, which was formed through the addition of glycols to cellulose by the Shotten–Baumann reaction between 3‐chloro‐1,2‐propanediol and cellulose. The graft copolymerization was initiated with a redox system between Ce⁴⁺ and glycols in cellulose. The infrared spectrum of PDO–cellulose had some characteristic absorption bands around 2960 (νC? H) and 1050 cm^?1 (νC? O) that also appeared for the PDO group and pyranose ring of cellulose, respectively. The rate of Ce⁴⁺ consumption by PDO–cellulose was investigated through the calculation of the overall kinetic constant from the slopes of ln(D ? D_R) versus time (where D is the absorbance and D_R is the absorbance of the original polysaccharide solution) The results showed that PDO–cellulose had high reactivity and that there were two mechanisms of oxidation by Ce⁴⁺ with PDO–cellulose. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3022–3029, 2004     

Membrane‐Supported Multichannel Microfluidic Solvent Extraction System

Although microfluidic solvent extraction (µSX) is a recent field in separation, its application is still limited to single‐channel microfluidic devices. However, the industrial application of microheat exchangers has already proven that parallelization of microchannels is an important tool to increase the specific device efficiency. Hence, in this study, a multichannel system for µSX is introduced. As a model process, D,L‐5‐phenylhydantoin was extracted from ethyl acetate into aqueous buffer. By means of different experimental setups, the potential and limitations of membrane‐supported multichannel µSX were investigated. The reactor dimensions perpendicular to flow and transmembrane mass transport are the most challenging factors for the introduced device.     

A conductive foam: Based on novel poly(styrene‐b‐butadiene‐co‐styrene‐b‐styrene) tri‐block copolymer filled by carbon black

In this article, a conductive foam based on a novel styrene‐based thermoplastic elastomer called poly(styrene‐b‐butadiene‐co‐styrene‐b‐styrene) tri‐block copolymer S(BS)S was prepared and introduced. S(BS)S was particularly designed for chemical foaming with uniform fine cells, which overcame the shortcomings of traditional poly(styrene‐b‐butadiene‐b‐styrene) tri‐block copolymer (SBS). The preparation of conductive foams filled by the carbon black was studied. After the detail investigation of cross‐linking and foaming behaviors using moving die rheometer, the optimal foaming temperature was determined at 180°C with a complex accelerator for foaming agent. Scanning electron microscopy (SEM) images shown that the cell bubbles of conductive foam were around 30–50 µm. The conductivity of foams was tested using a megger and a semiconductor performance tester. SEM images also indicated that the conductivity of foams was mainly affected by the distribution of carbon black in the cell walls. The formation of the network of the carbon black aggregates had a contribution to perfect conductive paths. It also found that the conductivity of foams declined obviously with the foaming agent content increasing. The more foaming agent led to a sharp increasing of the number of cells (from 2.93 × 10⁶ to 6.20 × 10⁷ cells/cm³) and a rapid thinning of the cell walls (from 45.3 to 1.4 µm), resulting in an effective conductive path of the carbon black no forming. The conductive soft foams with the density of 0.48–0.09 g/cm³ and the volume resistivity of 3.1 × 10³?2.5 × 10⁵ Ω cm can be easily prepared in this study. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41644.     

Interaction of crosslinked ethylene–propylene–diene terpolymer blends with chlorinated organic penetrants

The sorption and diffusion of halogenated hydrocarbon penetrants through different ethylene–propylene–diene terpolymer (EPDM) blends, such as EPDM/natural rubber, EPDM/bromobutyl rubber, and EPDM/styrene butadiene rubber (50/50 w/w), were studied. The diffusion coefficient of halogenated penetrants fell in the range 1.5–14.52 × 10^?7 cm²/s in the temperature range of 25–60°C. Transport data were affected by the nature of the interacting solvent molecule rather than its size and also by the structural variations of the EPDM blends. 1,2‐Dichloroethane showed a lower mass uptake compared to other penetrants. The temperature dependence of the transport coefficient was used to estimate the activation parameters, such as the activation energy of diffusion (E_D) and the activation energy of permeation (E_p) from Arrhenius plots. The activation parameters for E_D of aliphatic chlorinated organic penetrants was in the range 7.27–15.58 kJ/mol. These values fell in the expected range for rubbery polymers, well above their glass‐transition temperature. Also, the thermodynamic parameters, such as enthalpy and entropy, were calculated and fell in the range 2–15 kJ/mol and 3–54 J/mol/K, respectively. Both first‐ and second‐order transport kinetics models were used to investigate the transport kinetics, and first‐order kinetics were followed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1366–1375, 2003     

Towards a new strategy of a chitosan‐based molecularly imprinted membrane for removal of 4‐nitrophenol in real water samples

The issue of water contaminants, which affects human and environmental health, is not trivial. It is thus paramount to find new cheap and user friendly ways to detect and remove them from the environment. Here, the synthesis of a green chitosan (CS ) based molecularly imprinted membrane for the detection and quantification of 4‐nitrophenol (4‐NO₂Ph ) in aqueous media is proposed. The concentration of 4‐NO₂Ph in a water solution was measured by HPLC analysis. CS as a functional polymer, 4‐NO₂Ph as template, 4‐[(4‐hydroxy)phenylazo]benzenesulfonic acid as ligand, and glutaraldehyde as crosslinker in the presence of polyethylene glycol as porogen were used. The membrane was characterized by SEM and Fourier transform IR analyses, which confirmed the CS and polyethylene glycol backbone of the membrane. Kinetic studies of the detection system were performed by using pseudo‐first‐order and pseudo‐second‐order models. Then, the binding efficiency between 195.33 µmol L^?1 and 9235.55 µmol L^?1 of 4‐NO₂Ph was evaluated, finding a maximum adsorption of 723.25 µmol 4‐NO₂Ph per gram of membrane consistent with the Q _max calculated from the Langmuir isotherm. The selectivity of the membrane versus three phenolic competitor molecules, sharing very similar molecular structure to 4‐NO₂Ph , was demonstrated. Finally, the applicability of the membrane to real‐world samples was evaluated, by using drinking water spiked with 7.19 µmol L^?1 of 4‐NO₂Ph , obtaining a removal efficiency of 70.6%. © 2017 Society of Chemical Industry     

Synthesis of PID controller for unstable and integrating processes

Properly designed controllers provide stable closed-loop response for open-loop unstable processes. Internal model controller equivalent PID tuning rules for low order unstable plus dead time systems are synthesized in this work. The controller is approximated near the vicinity of zero (origin). Controller parameters are derived by equating the closed-loop response to a control-signature (desired closed-loop response) involving a user defined tuning parameter, λ. Simulations are carried out to show the performance of the proposed tuning scheme for both set point and disturbance rejection cases.     

Aryl acrylate porous functional polymer supports from water‐in‐oil‐in‐water multiple emulsions

Porous functional polymer supports are a class of material of wide interest due to the possibility of immobilising reactive species. A simplified procedure was applied for the preparation of porous polymer supports using a water‐in‐oil‐in‐water multiple emulsion. The primary emulsion was a high internal phase emulsion, having a volume fraction of water phase up to 95%. Two reactive acrylates, namely 4‐nitrophenyl acrylate and 2,4,6‐trichlorophenyl acrylate, were (separately) incorporated in the oil phase in order to obtain porous reactive polymer supports. Both acrylates were crosslinked with either divinylbenzene or ethylene glycol dimethacrylate, and beads of size ca 60 µm were obtained after the polymerisation of droplets suspended into the secondary aqueous phase. In the case of 4‐nitrophenyl acrylate and divinylbenzene as a crosslinker, particles with a star shape, the core being ca 60 µm in diameter and the arms ca 180 µm in length, were obtained. The polymers were functionalised with morpholine, tris(2‐aminoethyl)amine, piperidine or piperazine yielding supports with loadings of reactive groups of between 2.6 and 6.6 mmol g^?1. The results show that multiple emulsions can be precursors for porous polymer preparation. Copyright © 2007 Society of Chemical Industry     

Economic model predictive control of nonlinear time‐delay systems: Closed‐loop stability and delay compensation

Closed‐loop stability of nonlinear time‐delay systems under Lyapunov‐based economic model predictive control (LEMPC) is considered. LEMPC is initially formulated with an ordinary differential equation model and is designed on the basis of an explicit stabilizing control law. To address closed‐loop stability under LEMPC, first, we consider the stability properties of the sampled‐data system resulting from the nonlinear continuous‐time delay system with state and input delay under a sample‐and‐hold implementation of the explicit controller. The steady‐state of this sampled‐data closed‐loop system is shown to be practically stable. Second, conditions such that closed‐loop stability, in the sense of boundedness of the closed‐loop state, under LEMPC are derived. A chemical process example is used to demonstrate that indeed closed‐loop stability is maintained under LEMPC for sufficiently small time‐delays. To cope with performance degradation owing to the effect of input delay, a predictor feedback LEMPC methodology is also proposed. The predictor feedback LEMPC design employs a predictor to compute a prediction of the state after the input delay period and an LEMPC scheme that is formulated with a differential difference equation (DDE) model, which describes the time‐delay system, initialized with the predicted state. The predictor feedback LEMPC is also applied to the chemical process example and yields improved closed‐loop stability and economic performance properties. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4152–4165, 2015     

Kinetics of the anionic ring‐opening polymerization of octamethylcyclotetrasiloxane initiated by potassium isopropoxide

Kinetics of the anionic ring‐opening polymerization of octamethylcyclotetrasiloxane (D₄) in bulk initiated by potassium isopropoxide was studied. Several promoters including N‐methyl‐2‐pyrrolidinone (NMP), N,N‐dimethylformamide (DMF), and diglyme were used. It is indicated that the reactions are first‐order in D₄ during the initial stage of polymerization. The polymerization rate of D₄ is influenced by a number of factors, such as the nature of promoters, the molar ratio of promoter to initiator (C_p/C_i ratio), and the reaction temperatures. With the use of NMP as promoter, the polymerization rate constant at 30°C is 10.482 h^?1 with the C_p/C_i ratio equal to 3.0. As the C_p/C_i ratio increases, the polymerization rate constant increases sharply and the cyclic oligomers content in polymer decreases evidently. The back‐biting reaction that leads to the formation of decamethylcyclopentasiloxane (D₅) occurred in the polymerization of D₄. The rate of the D₅ formation relatively to the rate of D₄ conversion increases with the conversion of D₄. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3510–3516, 2006     

Nanometer‐thick patterned conductive films prepared through the self‐synthesis of polythiophene derivatives

The development of flexible electronics requires the patterning of conductive and active semiconductor films. Although inorganic materials such as indium tin oxide and metal nanoparticles have high conductivity and transparency, their poor interfacial adhesion with organic layers, lack of flexibility, high weight and high capital costs are drawbacks. In contrast, organic conducting polymers have great potential for use in commercial flexible electronic applications because of their low production costs, environmental stability and acceptable conductivities. A UV‐curable photoresist containing hydroxyl groups was prepared from a mixture of a photoinitiator, epoxy‐acrylate resin, hydroxyethyl methacrylate and tripropylene glycol diacrylate. Patterns having line widths/spaces of 100/100 µm and 10/5 µm were fabricated on a poly(ethylene terephthalate) (PET) substrate using lithography techniques. (3‐Methyl‐3,4‐dihydro‐2H‐thieno[3,4‐b]dioxepin‐3‐yl)methanol (ProDOT‐OH) was self‐synthesized through urethane linkages onto the surface of the patterned photoresist on the PET film, which was then dipped into a solution of another monomer, 3‐thienylethoxybutanesulfonate (TEBS), and initiator and polymerized in situ to form conductive poly(ProDOT‐OH‐co‐TEBS) films covering the surface of the patterned resist. The optimal conductivity of the poly(ProDOT‐OH‐co‐TEBS) films was ca 90 S cm^?1 with an optical transparency of ca 70%. A new bottom‐up technique has been developed for the preparation of patterned organic transparent conductive films: self‐synthesis of the monomer using urethane‐forming reactions and subsequent in situ polymerization. The conductivity of the films can be controlled by the polymerization reaction time and the resolution of the pattern. These conductive patterned films might be applicable to the manufacture of industrial touch panels or chemical/biological sensors. Copyright © 2009 Society of Chemical Industry     

Analytic Expressions of Ultimate Gains and Ultimate Periods with Phase‐Optimal Approximations of Time Delays

Ultimate gains and ultimate periods have long been used to tune PI/PID controllers since the Ziegler‐Nichols tuning. Recently, very simple analytic equations for ultimate gains and ultimate periods by approximating the arctangent function have been presented, which can be used to obtain simple tuning rules. Here, by applying the Routh stability method and phase‐optimal approximations of the time delay term, we present analytic expressions of ultimate parameters that are as simple as the existing ones, showing better accuracy.     

Synthesis and properties of novel crosslinkable second‐order nonlinear optical polymers based on 2,3,4,5,6‐pentafluorostyrene

Two crosslinkable second‐order nonlinear optical polymers were prepared by copolymerization of 2,3,4,5,6‐pentafluorostyrene, styrene (St), glycidyl methacrylate (GMA) and 1‐(4‐nitrophenyl)‐2‐(4‐{[2‐(methacryloyloxy) ethyl] ethylamino}‐phenyl) diazene (DR1M) via the sealed‐tube reaction technique. These polymers were characterized using ¹H, ¹³C and ¹⁹F NMR spectroscopy, gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The crosslinkable polymers have high molecular weights, good organosolubility, excellent film‐forming properties and high glass transition (106–110 °C) and thermal decomposition temperatures (290–350 °C) after being crosslinked. Furthermore, the polymer films possess not only high values (12–16 pm V^?1) of electro‐optical coefficient (r₃₃) at 1.3 µm wavelength but also low optical loss (1.7 dB cm^?1) at 1.55 µm wavelength, which is of interest for applications in electro‐optical devices. Copyright © 2004 Society of Chemical Industry     

Thiocompounds as simulants of sulphur mustard for testing of protective barriers

The protective potential of protective devices such as respirators, suits, gloves, and overboots is widely evaluated using the standard colorimetric test (spot disc breakthrough time test, also called SD BTT) involving sulfur mustard (SM) as the challenge chemical. The vesicant nature of SM makes the test inconvenient and poses stringent safety demands. Moreover, such tests are allowed only at a limited number of facilities, causing delay in product development and supply. This prompted the present study on the search for suitable SM simulant responsive to SD BTT test. The diffusivities at BTT (D_BTT) of 10 commercially available thiocompounds through butyl rubber (IIR) were compared vis‐a‐vis D_BTT of SM. For three representative thiocompounds, namely methyl (phenyl thio)acetate, 2‐chloroethyl phenyl sulfide (2‐CEPS) and phenyl‐n‐propyl sulfide (PNPS), the transport parameters through IIR were obtained. PNPS and 2‐CEPS were further compared with respect to D_BTT in elastomers such as IIR, ethylene–propylene–diene methylene rubber, polydimethylsiloxane, nitrile rubber, polybutadiene, and natural rubber. 2‐CEPS showed generally same order of D_BTT as SM implying its potential use as a simulant. The transport parameters for various 2‐CEPS/elastomer systems were also determined. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Controlling the photoluminescence of water‐soluble conjugated poly[2‐(3‐thienyl)ethyloxy‐4‐butylsulfonate)] for biosensor applications

The photoluminescence of poly[2‐(3‐thienyl)ethyloxy‐4‐butylsulfonate)] (PTE‐BS) in aqueous solution increases threefold on addition of the surfactant tetrabutylammonium perchlorate (TBA). Furthermore, the luminescence of the PTE‐BS/TBA system is reduced by more than five times by the addition of small amounts of the cationic electron acceptor methyl viologen (MV²⁺). The Stern–Volmer constant K_SV = 1.4 × 10⁴ L mol^?1 for the quenching of the polymer–surfactant complex by MV²⁺ is approximately 60 times smaller than the K_SV = 8.4 × 10⁵ L mol^?1 obtained in water polymer solutions without surfactant. Thus, the luminescence of PTE‐BS in aqueous solution can be modulated by complexing the polymer either with a surfactant or with a quencher. In this contribution we show that the surfactant/quencher tuning effect found in polymers of the phenylenevinylene family, such as poly(2,5‐methoxy‐propyloxysulfonate phenylenevinylene), also appears in polymers of the thiophene family such as PTE‐BS. Copyright © 2007 Society of Chemical Industry