Bioinspired Tunable Sacrificial Bonds Endowing Tetra‐PEG Based PU Hydrogel with Tunable Mechanical Properties,Shape‐Memory,and Self‐Healing Functions

Development of hydrogels with excellent and tunable mechanical properties combining with multifunctions is an intriguing issue in material science and engineering. Herein, bioinspired tunable sacrificial bonds are introduced into the tetra‐poly(ethylene glycol) (PEG) based polyurethane (PU) (TP) network to afford a hydrogel with tunable mechanical properties, shape‐memory, and self‐healing functions. The mussel‐inspired compound of Lysine‐dopamine (LDA) is introduced into the network of TP hydrogel through polyurethane/polyurea chemistry to form LDA‐tetra‐PEG‐PU (LTP) hydrogel. As catechol groups in LDAs can intermolecularly interact with each other and can also coordinate with ferric ions with different coordination ratios, these physical interactions with different strengths in the afforded LTP hydrogel construct kinds of sequentially tuned sacrificial bonds. As a result, these sacrificial bonds preferentially rupture prior to the covalent network upon external loading, which dissipate the energy and endow the hydrogel with advanced and postadjustable mechanical properties. This mechanism is investigated in detail. Furthermore, the LTP hydrogel shows multifunctions such as shape‐memory and self‐healing abilities. In addition, the tetra‐PEG based hydrogel shows remarkable thermoresponsiveness that the hydrogel distinctly contracts with the increase of the temperature. The improved mechanical strength and multifunctions should enlarge the application areas of the tetra‐PEG based hydrogel in various fields.     

Detection of Foot‐and‐Mouth Disease Virus Using a Polydiacetylene Immunosensor on Solid‐Liquid Phase

The rapid detection of foot‐and‐mouth disease virus (FMDV) is vital for the prevention of foot‐and‐mouth disease outbreaks. In this study, a polyvinylidene difluoride (PVDF)‐supported polydiacetylene (PDA) immunosensor is developed to detect FMDV, in which a polyclonal antibody against the FMDV VP1 antigen is conjugated as a specific virus‐binding module without a linker. First, a liposome‐based immunosensor is generated for the FMDV VP1 protein in the form of photopolymerized PDA colloids. Then, the VP1‐specific PDA immunosensors are modified onto PVDF strip to enable the rapid and portable detection of FMDV. Detailed analyses are performed using ultraviolet‐visible spectroscopy, dynamic light scattering, transmission electron microscopy, and scanning electron microscopy. A blue‐to‐red color transition is observed in the presence of FMDV particles, indicating the potential applications of FMDV‐specific PDA immunosensors for use in solid‐phase detection as well as via liquid‐phase liposome platforms. Thus, this work provides a rapid and simple detection for FMDV.     

Core–Shell Structured Cellulose Nanofibers/Graphene@Polypyrrole Microfibers for All‐Solid‐State Wearable Supercapacitors with Enhanced Electrochemical Performance

Thanks to their considerable electrochemical and mechanical properties, fiber‐shaped supercapacitors have become the most potential energy storage devices for portable and wearable electronics in the future; however, challenges still exist in the pursuit of practical applications among them. In this work, ternary microfibers, which are composed of TEMPO‐oxidized cellulose nanofibers/reduced graphene oxide microfiber cores coated with polypyrrole shell layers, are successfully fabricated through industrializable and sustainable wet‐spinning and interfacial polymerization strategies. The prepared microfibers possess well‐defined microstructures and outstanding mechanical properties (559 MPa). When assembled into symmetrical all‐solid‐state fiber‐shaped supercapacitors (FSCs), they exhibit remarkable electrochemical properties (647 mF cm^?2, 14.37 µWh cm^?2 at 0.1 mA cm^?2), prominent cycling stability (92.5% capacitance retention and 92.6% coulomb efficiency after 10 000 cycles), and extraordinary flexibility (no significant decay in capacitance after 5000 bending cycles), which are superior to all the congeneric FSCs reported to date. The prominent performances are ascribed to the synergistic effect of the well‐designed ternary system and synergistic effects between interior components. The advantages in electrochemical, mechanical, and industrial properties of the ternary FSCs can provide reference and boost the development of flexible energy storage applications.     

Poly[(3‐hydroxybutyrate)‐co‐(3‐hydroxyvalerate)]/layered double hydroxide nanocomposites

BACKGROUND: The thermomechanical performance of poly[(3‐hydroxybutyrate)‐co‐(3‐hydroxyvalerate)] (PHBV) is associated with its crystallization. Enhanced nucleation using a stearate‐functionalized synthetic layered double hydroxide (LDH) presents a potential solution. RESULTS: PHBV crystallization varied with concentration of LDH. At lower LDH concentration, thermal history‐induced cold crystallization was present. The extent of this order–disorder transition decreased with increasing LDH concentration and was completely eliminated at 7 wt% LDH. PHBV did not have a melt recrystallization peak but the introduction of LDH resulted in an increasingly pronounced melt recrystallization with increasing LDH concentration. Polarized optical microscopy coupled with differential scanning calorimetry and wide angle X‐ray diffraction (WAXD) analysis indicated increased lamella thickness in the nanocomposites compared to pure PHBV. WAXD and transmission electron microscopy showed that the nanocomposites had an intercalated but aggregated dispersion. CONCLUSION: The concentration of nanofiller provides unique effects in PHBV. Mechanical performance was found to scale with composition as determined using dynamic mechanical analysis and tensile testing. Copyright © 2008 Society of Chemical Industry     

Crosslinkable fluorinated hyperbranched polyimide for thermo‐optic switches with high thermal stability

A series of fluorinated hyperbranched polyimides (FHBPIs) were synthesized by condensation of a triamine monomer, 1,3,5‐tris(2‐trifluoromethyl‐4‐minopheoxy) benzene (TFAPOB) and various aromatic dianhydride monomers with different linear length for application on integrated optical devices. Near infrared absorption measurement shows that it has high transparency in optical communication wavelength region. The glass transition temperature and thermal decomposition temperature were 189°C and 596°C, respectively. According to the atomic force microscopy analysis, the surface roughness of the FHBPI films is 0.208 nm. A classic Mach–Zehnder interferometer thermo‐optic switch with single mode waveguide fabricated by FHBPIs represents excellent switching characteristic. The rise time and fall time of this device are 530 µs for both. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Morphology,structure, and kinetic analysis of nonisothermal cold‐ and melt‐crystallization of syndiotactic polystyrene

Nonisothermal cold‐ and melt‐crystallization of syndiotactic polystyrene (sPS) were carefully carried out by Perkin–Elmer Diamond differential scanning calorimetry, polarized optical microcopy (POM), and wide angle X‐ray diffraction. The experimental data subjected to the two types of processing were thoroughly analyzed on the basis of Avrami, Tobin, Ziabicki, and combination of Avrami and Ozawa models. Avrami, Tobin, and Ziabicki analyses indicate that nonisothermal cold‐crystallization (A) characterizes smaller Avami and Tobin exponent and larger Ziabicki kinetic crystallizability index G than those obtained from nonisothermal melt‐crystallization (B) possibly due to the existence of partially ordered structures in the quenched samples. Kissinger and the differential isoconversional method (DICM) of Friedman's were utilized to obtain effective energy barrier of A, in good agreement with that obtained by using Arrhenius equation to analyze the isothermal cold‐crystallization, indicating that Kissinger and Friedman equations can be applied to obtain activation energy from A of sPS. X‐ray diffraction analysis indicates that cold‐crystallization mainly produces α‐type crystal but for melt‐crystallization the contents of α‐type and β‐type crystals depend on the cooling rates. The POM also indicates the difference of end morphology of the sample between A and B. At the same time, the DICM of Friedman's was applied to analyze experimental data of B, which were divided into two groups with 20 K/min as the threshold, and it was found that the formation of β‐type crystal possesses larger absolute value of effective activation barrier than the formation of α‐type crystal. © 2006Wiley Periodicals, Inc. J Appl Polym Sci 103: 1311–1324, 2007     

Influence of grafting on structural and optical properties of nylon‐6 fibers

This study throws light on the change of the optical properties and some structural properties due to graft copolymerization of polydiallyldimethyl ammonium chloride (PDADMAC) and polyacrylamide (PAA) of nylon‐6 fibers. Multiple‐beam interferometric technique in transmission was used to study the change of the diameter, refractive indices, and birefringence of nylon‐6 fibers at different graft yields. The results were utilized to investigate the isotropic refractive index, the mean polarizabilities per unit volume, dielectric constant, dielectric susceptibility, and surface reflectivity for nylon‐6 and grafted nylon‐6 fiber. The effect of grafted PAA onto modified nylon‐6 fibers containing PDADMAC on the crystallinity was studied by X‐ray diffraction. These results reflect good effect of grafting on the optical and structural properties of nylon‐6 fibers. The opto‐thermal properties of grafted PAA with different graft yields have been studied. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Highly Sensitive Detection of Fe3+ Ions Using Waterborne Polyurethane‐Carbon Dots Self‐Healable Fluorescence Film

In this study, nitrogen‐doped carbon dots (N‐C‐dots) are synthesized via a green and gentle electrochemical‐hydrothermal method. The N‐C‐dots are grafted into the backbone of waterborne polyurethane (WBPU) synthesized from hexamethylene diisocyanate and polycarbonate diol (PCDL). Due to the introduction of N‐C‐dots, the WBPU is functionalized including being able to self heal and specifically identified Fe³⁺. The self‐healing performance of the WBPU‐N‐C‐dots film is principally attributed to the hydrogen bonding effect of the WBPU and the N‐C‐dots. On the other hand, based on the quenching of fluorescent characteristics of the WBPU‐N‐C‐dots film, it is successfully used in the detection of Fe³⁺, showing a wide detection range, good selectivity, and high sensitivity. What's more, the tensile strength of the sample is enhanced from 3.50 to 7.12 MPa when the N‐C‐dots content is increased in the WBPU and the thermal stability is improved as a result of the formation of the more thermally‐stable network structures. Interestingly, compared to the traditional solution detection in WBPU‐N‐C‐dots emulsion with the limit of detection of 2.23 × 10^?6 m , the detection has the lower limit of detection of 2.19 × 10^?6 m in the WBPU‐N‐C‐dots film. These results show that the WBPU‐N‐C‐dots film exhibits great application as an intelligent response‐type material.     

Synthesis and characterization of novel photo‐crosslinkable fluorinated poly(phthalazinone ether)s for optical waveguides

A series of novel photo‐crosslinkable fluorinated poly(phthalazinone ether)s containing 1,1‐diphenylethylene segments in the polymer main chain, used for optical waveguide materials, were synthesized by polycondensation reaction of decafluorobiphenyl with a mixture of 4‐(4‐hydroxylphenyl)(2H)‐phthalazin‐1‐one (DHPZ), 4,4‐(hexafluoroisopropylidene)diphenol and 1,1‐bis(4‐hydroxyphenyl)ethylene (BHPE) as co‐reactant. The feed ratio of DHPZ to total bisphenols varied from 0 to 80 mol%, while that of BHPE remained at 20 mol% for all polymers. The obtained copolymers show good solubility in some common polar organic solvents. The resulting polymers were photo‐crosslinked after UV irradiation for 10 min in the presence of a photoinitiator. The cured polymers show good chemical resistance, high thermal stability (temperatures of 1% mass loss after curing of 472–496 °C under nitrogen) and high glass transition temperatures (160–249 °C) which could be further increased by about 10 °C after photochemical crosslinking. By adjusting the copolymerizing bisphenol content, the refractive indices of transverse electric and transverse magnetic modes (at 1550 nm) of films of the polymers were exactly tuned in the range 1.5029–1.5661 and 1.4950–1.5502, respectively. The propagation losses of the cured films were measured and found to be less than 0.3 dB cm^?1 at 1550 nm, indicating the promise of these materials for passive optical waveguide devices. Copyright © 2011 Society of Chemical Industry     

Decentralized Control System Design under Uncertainty Using Mixed‐Integer Optimization

Decentralized control system design comprises the selection of a suitable control structure and controller parameters. In this contribution, the optimal control structure and the optimal controller parameters are determined simultaneously using mixed‐integer dynamic optimization (MIDO) under uncertainty, to account for nonlinear process dynamics and various disturbance scenarios. Application of the sigma point method is proposed in order to approximate the expectation and the variance of a chosen performance index with a minimum number of points to solve the MIDO problem under uncertainty. The proposed methodology is demonstrated with a benchmark problem of an inferential control for a reactive distillation column. The results are compared with established heuristic design methods and with previous deterministic approaches.     

A study on hydrodynamic characteristics in a Φ38 pulsed extraction column by four‐sensor optical fiber probe

Accurate prediction of dispersed phase droplet behavior is crucial to the design and scaling‐up of an extraction column. In this article, the dispersed droplet velocity algorithm and the diameter algorithm in a liquid–liquid two‐phase flow have been developed based on the bubble velocity model in gas–liquid two‐phase flow of Lucas [Measurement Science & Technology. 749, 758(2005)] and Shen [International Journal of Multiphase Flow. 593, 617(2005)]. Hydrodynamic characteristics, including droplet diameter, holdup and droplet velocity, were measured using a self‐made four‐sensor optical fiber probe in a 38 mm‐diameter pulsed sieve‐plate extraction column. Water and kerosene were used as continuous and dispersed phases, respectively. The influences of the pulsed intensity, the continuous and dispersed phase superficial velocities on the hydrodynamic characteristics were investigated. The experimental results show that it is reliable to use a four‐sensor optical probe to measure the hydrodynamic characteristics of a pulsed extraction column. © 2016 American Institute of Chemical Engineers AIChE J, 63: 801–811, 2017     

The Development of Fibers That Mimic the Core–Sheath and Spindle‐Knot Morphology of Artificial Silk Using Microfluidic Devices

Spider and silkworm produce diverse silk fibers from spinning dopes through smart spinnerets. Spider's capture silk is composed of core thread and periodic spindle‐knots, while silkworm silk consists of fibroin core and sericin outer layer. To mimic the morphologies of natural heterostructured silks, artificial fibers are dry‐spun using a multichannel microfluidic chip, served with a highly viscous core solution of regenerated silk fibroin and low viscosity sheath solution of sericin. Silk fibers with core–sheath, groove, and spindle‐knot structures are obtained by controlling the flow rates and viscosities of the two microfluids depending on the laminar flow, Kelvin–Helmholtz instability, or Plateau–Rayleigh instability.     

Droplet velocity,size, and local holdup measurements in an extraction column by tri‐sensor optical probe

The tri‐sensor optical probe was applied to study the hydrodynamic characteristic in a pulsed sieve plate extraction column. Two immiscible liquids consisting of the dispersed phase (kerosene) and continuous phase (water) were introduced in countercurrent operation. Local parameters such as droplet velocity, drop size, and holdup of the dispersed phase were obtained. It was found that the tri‐sensor optical probe could be used as an efficient and convenient technique for measuring local hydrodynamic parameters inside the pulsed sieve plate extraction column. Furthermore, the results indicated that pulsation intensity imposed more influence on these hydrodynamic parameters than two‐phase superficial flow rates in the investigated ranges. Experimental results were found to be in good agreement with the empirical correlations reported in literature. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3958–3963, 2015     

Method for Direct Determination of Glassy Phase Dissolution in Hydrating Fly Ash‐Cement System Using X‐ray Diffraction

A method for quantitative X‐ray diffraction analysis is developed for direct determination of the glassy phase content of fly ash in a hydrating binary blend of cement and low‐calcium, siliceous fly ash. The intensity contributions of the unhydrated glassy phase of fly ash and the amorphous reaction products to the intensity pattern of the total amorphous phase in the hydrating binary blend are obtained by decomposition of the total intensity signature as a sum of component pseudo Voigt (PV) peaks. An experimental program involving binary blends with three different low calcium siliceous fly ashes and two different curing temperatures is reported. The centers of the component PV peaks of the fly ash glassy phase fitted to the overall intensity pattern are found to be invariant. The glassy phase content of hydrating binary blends determined from the XRD method were found to agree well with the values obtained from a selective dissolution method.     

Interaction Parameter Method for Investigating BTEX Extraction Using the Hollow‐Fiber Microporous Membrane Liquid/Liquid Extraction Technique

This work focused on the extraction of BTEX from aqueous solution by a hollow‐fiber microporous membrane liquid/liquid extraction (HF‐MMLLE) technique. A simple and rapid method based on the Hansen solubility parameters (HSP) theory was adopted to theoretically determine the interaction parameter (χ₁₂) between the extractants and BTEX. Experiments were carried out to establish the relationship between the interaction parameter and the extraction performance. Furthermore, the distribution coefficient and permeability coefficient related to the extraction performance were also discussed, which verified the relationship from a quantitative idea. It was observed that the liquid/liquid extraction was based on the strong affinities between the extractants and the target pollutants. This method should be paid more attention for its potential application in other solvent‐sensitive processes.     

Selective Removal of H2S from Gas Streams with High CO2 Concentration Using Hollow‐Fiber Membrane Contractors

Selective and simultaneous separation of H₂S and CO₂ from CH₄ was accomplished in a hollow‐fiber membrane contactor (HFMC). The absorption of both H₂S and CO₂ using an aqueous solution of methyldiethanolamine (MDEA) was almost complete and acid gases were totally removed. Despite the large difference between H₂S and CO₂ concentrations, the rate of H₂S absorption was not significantly influenced by CO₂ absorption. The independent effect and interactions of several process variables on the separation performance of H₂S and CO₂ were investigated. The results indicated that the membrane contactor could be a highly efficient choice for removal of almost all H₂S in the presence of a large CO₂ content even at high gas/liquid flow ratio. The selectivity of H₂S was about three times higher compared to the conventional absorption packed towers.     

One‐Pot Hydroxy Group Activation/Carbon‐Carbon Bond Forming Sequence Using a Brønsted Base/Brønsted Acid System

A new sequential two‐step multicatalytic strategy is presented consisting in the efficient DBU‐catalysed trichloroacetimidation of an alcohol followed by a ditriflylamine (Tf₂NH)‐catalysed intermolecular alkylation by silicon‐based nucleophiles and C H nucleophiles. The distinct feature of the trichloroacetimidate group allows use of weaker acid catalysts such as 1,1′‐bi‐2‐naphthol (BINOL)‐derived phosphoric acid, pointing out the possible development of an enantioselective variant. This unprecedented sequential one‐pot Brønsted base‐Brønsted acid catalysis further expands the synthetic scope of the trichloroacetimidate group.     

Control of a Batch Polymerization System Using Hybrid Neural Network ‐ First Principle Model

In this work, the utilization of neural network in hybrid with first principle models for modelling and control of a batch polymerization process was investigated. Following the steps of the methodology, hybrid neural network (HNN) forward models and HNN inverse model of the process were first developed and then the performance of the model in direct inverse control strategy and internal model control (IMC) strategy was investigated. For comparison purposes, the performance of conventional neural network and PID controller in control was compared with the proposed HNN. The results show that HNN is able to control perfectly for both set points tracking and disturbance rejection studies.     

Gel Point Investigation of a Chitosan System Using Fourier Transform Rheometry and Multi‐Frequency Excitation

In this study, the sol‐gel transition temperature of a thermosensitive chitosan system was measured using SAOS, in‐real time FTR and multi‐frequency SAOS excitation. From FT analysis, we found that the intensity of the harmonics stayed constant while the chitosan system remained in the solution state, while it increased passed the gelation point. Multi‐frequency SAOS excitation was also carried out using a summation function of sine waves that allowed performing the measurements in the LVR. This last technique could determine the unique (frequency independent) critical sol‐gel transition temperature, and was found to be less tedious than the application of the traditional Chambon and Winter's method.