Preparation of polyacrylate/paraffin microcapsules and its application in prolonged release of fragrance

The purpose of the present work was to develop a fragrance encapsulation system using polyacrylate/paraffin microcapsules. The Polyacrylate/paraffin microcapsules were fabricated by the method of suspension polymerization in Pickering emulsion. Morphology, size distribution, and thermal resistance of polyacrylate/paraffin microcapsules were investigated by scanning electron microscopy, light scattering particle size analyzer, and thermogravimetric analyzer. Results indicated that the crosslinked PMMA/paraffin microcapsules and P(MMA‐co‐BMA)/paraffin microcapsules prepared under optimal conditions presented regular spherical shape and similar size distribution. The crosslinked P(MMA‐co‐BMA)/paraffin microcapsules exhibited better thermal stability, with a thermal resistance temperature up to 184 °C. Fragrance microcapsules were prepared by encapsulating fragrance into crosslinked P(MMA‐co‐BMA)/paraffin microcapsules. The prolonged release performance of fragrance microcapsules was measured by ultraviolet‐visible near‐infrared spectrophotometer. 63.9% fragrance was retained after exposing fragrance microcapsules in air for 3 months, and the fragrance continued to release over 96 h in surfactant solution (sodium lauryl sulfonate, 20 wt %). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44136.     

Silica‐based self‐healing microcapsules for self‐repair in concrete

New self‐healing material for concrete repair has been fabricated through microencapsulation of silica sol via interfacial polymerization of poly(urea‐urethane). Smooth, uniform, and spherical capsules of 60–120 µm sizes were synthesized and optimized by studying the emulsification and polymerization steps of its synthesis. A hydrophile–lyophile balance (HLB) value of 3.0–5.0 and a rotational speed of 500 rpm were necessary to produce a stable emulsion system of silica sol in surfactants. The polymerization speed of 900 rpm and the methylene diisocyanate (MDI) monomer content of 15 wt % were both significant in getting the right size and smoothness of the microcapsules. With this method and cheap healing agents, industrial scale‐up is highly possible. The viscoelastic properties of the microcapsules were examined, and further characterizations were carried out through scanning electron microscopy, energy dispersive X‐ray spectroscopy, and Fourier transform infrared spectroscopy. After healing the microcracks in concrete, the results showed that the significant increase of compressive and bending strengths manifested the self‐healing ability of the microcapsules in concrete. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43090.     

Properties and application of polyimide‐based composites by blending surface functionalized boron nitride nanoplates

Ball milling was used to decrease the particle size of boron nitride (BN) nanoplates and to form more silylated functionalization of their surface. Such functionalized BN nanoplates enhanced their homogeneous dispersion in polyimide (PI) matrix. Thermal conductivities, thermal stabilities, and dielectric properties were characterized to investigate the particular effects on the performance of PI‐based composites with functionalized BN nanoplates. When the concentration of functionalized BN nanoplates increased to 50 wt %, thermal conductivity of the composite increased up to 1.583 W m^?1 K^?1, and the temperature of final thermal decomposition was improved to 600°C. An increasing trend was found in the dielectric constant of the composites while the dielectric loss decreased with the increase in the fraction. An appropriate fraction of functionalized BN nanoplates in PI‐based composites were necessary to meet the requirement of withstanding drilling forces for the interconnecting through holes of flexible circuits. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41889.     

Preparation and properties of a form‐stable phase‐change hydrogel for thermal energy storage

In this study, we aimed to fabricate a form‐stable phase‐change hydrogel (PCH) with excellent mechanical properties and heat‐storage properties. Sodium alginate (SA) and polyacrylamide (PAAm) composite hydrogels were prepared with ionically crosslinked SA in a PAAm hydrogel network. Glauber's salt [i.e., sodium sulfate decahydrate (Na₂SO₄·10H₂O)] was incorporated within the hydrogel network as a phase‐change material. Scanning electron microscopy micrographs revealed that Na₂SO₄·10H₂O was confined in the micropores of the hydrogel inner spaces, and differential scanning calorimetry curves showed that the composite hydrogel possessed a considerable storage potential. Mechanical properties tests, such as tensile and compressive measurements, presented a decreasing trend with increasing Na₂SO₄·10H₂O dosage. We concluded that the prepared composite PCH could be used to design hydrogel materials with thermal‐energy‐storage applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43836.     

Elaboration of small‐diameter vascular prostheses—Selection of appropriate sterilisation method

The aim of study is the elaboration of semi‐biodegradable, multilayered tubular structures as substitutes for the reconstruction of small diameter vascular prostheses (<6 mm). The inert external layer of the prostheses will be fabricated via the melt electrospinning of poly (l ‐lactide‐co‐glycolide) (PLGA). The middle layer will be constructed from polypropylene (PP); the first prototype will be produced via melt electrospinning and the second using the melt blowing technique. The general aim of this stage of the research is the selection of a sterilisation technique that is appropriate for semi‐biodegradable, multilayered tubular structures. For this purpose, single tubular structures created via the melt electrospinning of PLGA or PP and melt blown tubular structures of PP were elaborated. The influence of steam, ethylene‐oxide (EO), and radiation sterilisation techniques on the elaborated microstructure of tubular structures was analyzed during this study. The effect of each sterilisation technique was evaluated using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy/energy‐dispersive X‐ray spectroscopy analysis (SEM/EDS). The changes in average molecular weight (M_w) and crystallinity index (CI) of the PLGA tubular structures after EO and steam sterilisation were evaluated. The EO and steam sterilisation resulted in the complete destruction of PLGA tubular structures. Only the radiation sterilisation (accelerated electrons) did not influence on PLGA tubular structures morphology as well as thermal and chemical properties. FTIR and SEM/EDS analysis indicated that no changes in the chemical properties of PP tubular structures after each sterilisation occurred. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40812.     

Dithieno[2,3‐d:2′,3′‐d′]naphtho[2,1‐b:3,4‐b′]dithiophene based medium bandgap conjugated polymers for photovoltaic applications

Three novel medium band gap (MBG) conjugated polymers (CPs) (named as P1, P2, and P3, respectively) were developed by copolymerizing 2,7‐dibromo‐10,11‐di(2‐hexyldecyloxy)dithieno[2,3‐d:2′,3′‐d′]naphtho[2,1‐b:3,4‐b′]dithiophene (NDT‐Br) with three different units: 2,5‐bis(tributylstannyl)thiophene, 2,5‐bis(trimethylstannyl)thieno[3,2‐b]thiophene and trans?1,2‐bis(tributylstannyl)ethene, respectively. The thermal, optical, and electrochemical properties of the polymers were investigated. All of the polymers have good thermal stability and medium band gap (～ 1.9 eV). Prototype bulk heterojunction photovoltaic cells based on the blend P1/P2/P3 and [6, 6] phenyl‐C61 butyric acid methyl ester (PC₆₁BM) were assembled and the photovoltaic properties were assessed. Power conversion efficiencies (PCEs) of 1.61% ～ 2.43% have been obtained under 100 mW cm^?2 illumination (AM1.5). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43288.     

In vitro hydrolysis and magnesium release of poly(d,l‐lactide‐co‐glycolide)‐based composites containing bioresorbable glasses and magnesium hydroxide

Magnesium is important for both bone growth and cartilage formation. However, the postoperative intake of antibiotics such as quinolones may cause a reduction in magnesium levels in tissue. The addition of magnesium to scaffolds may therefore be beneficial for the regeneration of osteochondral defects. In this study, porous composite scaffolds were produced by gas foaming of poly(d ,l ‐lactide‐co‐glycolide) (PLGA) rods with magnesium‐containing bioresorbable glasses and magnesium hydroxide as fillers. The in vitro hydrolytical degradation of the composite scaffolds in Tris buffer was followed over a 10‐week period. Mg²⁺ was released in a controlled manner from the scaffolds with varying release profiles between the different materials. Higher glass content resulted in a reduced mass loss compared to scaffolds with lower glass content. As a result of the foaming method, the scaffolds shrank initially, without evidence that the addition of hydrophilic fillers would decrease the initial shrinkage. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42646.     

pH‐sensitive keratin‐based polymer hydrogel and its controllable drug‐release behavior

Using feather keratin as biocompatible and inexpensive natural biopolymer and methacrylic acid as a functional monomer, we prepared a pH‐sensitive feather‐keratin‐based polymer hydrogel (FKPGel) with grafted copolymerization. The obtained FKPGel was characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy. The swelling behavior and pH sensitivity of the FKPGel were investigated. When the small molecule (rhodamine B) and macromolecule (bovine serum albumin) were used as model drug molecules, the FKPGel exhibited controllable release behavior in vitro, and the hydrogels had pH sensitivity. For a small molecular drug, the cumulative release rate was 97% in 24 h at pH 8.4. For macromolecular drug, the cumulative release rate reached 89% at pH 7.4. Its release behavior could be controlled by the pH value. In summary, a simple method was found to reuse disused feathers. It is a kind of pH‐sensitive hydrogels to be applied in drug‐delivery systems. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41572.     

Industrial melt index prediction with the ensemble anti‐outlier just‐in‐time Gaussian process regression modeling method

Several data‐driven soft sensors have been applied for online quality prediction in polymerization processes. However, industrial data samples often follow a non‐Gaussian distribution and contain some outliers. Additionally, a single model is insufficient to capture all of the characteristics in multiple grades. In this study, the support vector clustering (SVC)‐based outlier detection method was first used to better handle the nonlinearity and non‐Gaussianity in data samples. Then, SVC was integrated into the just‐in‐time Gaussian process regression (JGPR) modeling method to enhance the prediction reliability. A similar data set with fewer outliers was constructed to build a more reliable local SVC–JGPR prediction model. Moreover, an ensemble strategy was proposed to combine several local SVC–JGPR models with the prediction uncertainty. Finally, the historical data set was updated repetitively in a reasonable way. The prediction results in the industrial polymerization process show the superiority of the proposed method in terms of prediction accuracy and reliability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41958.     

PCEC hydrogel used on sustained‐release hyaluronic acid delivery with lubrication effect

Injection of bionic synovial fluid (BSF) is a conventional method to improve the lubricity of artificial joints, but BSF cannot maintain long due to the dilution and degradation of BSF in human body. To prolong the effectiveness of hyaluronic acid (HA), which is the major component of BSF, this study applies a temperature‐sensitive poly(?‐caprolactone)–poly(ethylene glycol)–poly(?‐caprolactone) (PCEC) hydrogel loaded with HA to achieve long‐term lubrication. In addition, Fourier transform infrared, nuclear magnetic resonance analysis, X‐ray diffraction, scanning electron microscopy (SEM), and gel permeation chromatography spectra were used to analyze the structure of the synthetic hydrogel. Rheological test and test tube inverting method were used to characterize the thermosensitivity. The lubrication properties of the released solution were characterized by UV–vis, tribological tests, SEM, and 3D laser confocal scanning microscope. The experimental results reveal that the triblock PCEC hydrogel contains both hydrophilic block and hydrophobic block, and both PCEC and PCEC/HA hydrogels have phase‐changed effect when the temperature increases from room temperature to body temperature. Moreover, the friction coefficient of the released solution from PCEC/HA hydrogel is approximatively 38% lower than that of phosphate buffer saline. And the ability of shear resistance and creep recovery of PCEC/HA hydrogel are better than that of PCEC hydrogel. This study provides an effective approach to achieve long‐time lubrication effect for artificial joints. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46228.     

Biodegradation of in situ‐forming gel of poly(DLLA‐co‐CL) in vivo

Poly(dl ‐lactide‐co‐caprolactone) was dissolved in N‐methyl‐2‐pyrolidone (NMP) for preparing blank group formulation, and drug group was prepared by dissolving testosterone undecanoate (TU) as model drug in blank group. These formulations rapidly gelled by solvent diffusion effect after subcutaneous injection. The in vivo degradation of copolymer gel in rabbits was investigated after injection. The GPC and ¹H NMR results showed that no matter the gel contained drug or not, it had no effect on degradation rate for the P(DLLA‐co‐CL) carrier. Degradation products of copolymer were absorbed or excreted based on metabolism. Copolymer molar composition changed slightly in 3 months. The structures and characteristic of copolymers were characterized via DSC, TGA, and SEM, respectively. Experimental results showed that the copolymer had excellent heat resistance. Crystallinity increased gradually during degradation process. A dense cross‐sectional structure formed after 90 days. In addition, it can be obviously found that the degradation process of the copolymer proceeded in two steps. Mechanism of copolymer biodegradation in vivo was bulk degradation. The gel could well administrate the release of TU in a sustained way without significant burst features. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3800–3808, 2013     

Mathematical modeling of the extractables release from multi‐layered plastic films used in drug product containers

The release of extractables from multi‐layered plastic films such as those used in containers for liquid drug products has been investigated. Targeted extractables were chosen from the film's extractable profile, as elucidated by a controlled extraction study. The total available pool of targeted extractables was ascertained via exhaustive sequential extraction of the film and the film layer responsible for the target extractables was established. This information, along with the film's structure, was used to produce a mathematical migration model for each of these targets. The film was fashioned into pouches, filled with a simulating solvent and the release of the targeted extractables to the pouches' contents was measured. The measured and modeled concentrations were found to be very similar, establishing the model's ability to effectively mimic the experimental system. This result suggests that mathematical modeling, which is widely used in the food industry to assess the safety of food packaging, may be applicable to packaged pharmaceutical products. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41223.     

Preparation and properties of phase‐change heat‐storage UV curable polyurethane acrylate coating

Phase‐change heat‐storage UV curable polyurethane acrylate (PUA) coating was prepared by applying microencapsulated phase change materials (microPCMs) to PUA coating. MicroPCMs containing paraffin core with melamine‐formaldehyde shell were synthesized by in situ polymerization. The effect of stirring speed, emulsification time, emulsifier amount, and core/shell mass ratio on particle size, morphology, and phase change properties of the microPCMs was studied by using laser particle size analyzer, Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopic analysis, scanning electron microscopy, and differential scanning calorimetry. The results showed that the diameter of the microcapsules decreased with the increase of stirring speed, emulsification time, and emulsifier amount. When the mass ratio of emulsifier to paraffin is 6%, microcapsules fabricated with a core/shell ratio of 75/25 have a compact surface and a mean particle size of 30 μm. The sample made under the above conditions has a higher efficiency of microencapsulation than other samples and was applied to PUA coating. The dispersion of microPCMs in coating and heat‐storage properties of the coating were investigated. The results illustrated that the phase‐change heat‐storage UV curable PUA coating can store energy and insulate heat. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41266.     

Soluble‐eggshell‐membrane‐protein‐modified porous silk fibroin scaffolds with enhanced cell adhesion and proliferation properties

In this study, a porous silk fibroin (SF) scaffold was modified with soluble eggshell membrane protein (SEP) with the aim of improving the cell affinity properties of the scaffold for tissue regeneration. The pore size and porosity of the prepared scaffold were in the ranges 200–300 μm and 85–90%, respectively. The existence of SEP on the scaffold surface and the structural and thermal stability were confirmed by energy‐dispersive X‐ray spectroscopy, X‐ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. The cell culture study indicated a significant improvement in the cell adhesion and proliferation of mesenchymal stem cells (MSCs) on the SF scaffold modified with SEP. The cytocompatibility of the SEP‐conjugated SF scaffold was confirmed by a 3‐(4,5‐dimethyltriazol‐2‐y1)‐2,5‐diphenyl tetrazolium assay. Thus, this study demonstrated that the biomimic properties of the scaffold could be enhanced by surface modification with SEP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40138.     

Production of hyaluronic‐acid‐based cell‐enclosing microparticles and microcapsules via enzymatic reaction using a microfluidic system

This article describes the preparation of cell‐enclosing hyaluronic acid (HA) microparticles with solid core and microcapsules with liquid core through cell‐friendly horseradish peroxidase (HRP)‐catalyzed hydrogelation. The spherical vehicles were made from HA derivative possessing phenolic hydroxyl moieties (HA‐Ph) cross‐linkable through the enzymatic reaction by extruding cell‐suspending HA‐Ph aqueous solution containing HRP from a needle of 180 μm in inner diameter into the ambient coaxial flow of liquid paraffin containing H₂O₂ in a microtubule of 600 μm in diameter. By altering the flow rate of liquid paraffin, the diameters of gelatin and HA‐Ph microparticles were varied in the range of 120–220 μm and 100–300 μm, respectively. The viability of the enclosed human hepatoma HepG2 cells in the HA‐Ph microparticles of 180 μm in diameter was 94.2 ± 2.3%. The growth of the enclosed HepG2 cells was enhanced by decreasing the HRP concentration. The microcapsules of 200 μm in diameter were obtained by extruding HA‐Ph aqueous solution containing thermally liquefiable cell‐enclosing gelatin microparticles of 150 μm in diameter using the same microfluidic system. The enclosed cells grew and filled the cavity within 10 days. Spherical tissues covered with a heterogeneous cell layer were obtained by degrading the microcapsule membrane using hyaluronidase after covering the surface with a heterogeneous cell layer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43107.     

Syntheses,characterization, and hydrolytic degradation of P(ε‐caprolactone‐co‐δ‐valerolactone) copolymers: Influence of molecular weight

Biodegradable poly(ε‐caprolactone‐co‐δ‐valerolactone) copolymers were synthesized and investigated to study their behavior in aqueous medium. The copolyesters were produced by ring opening polymerization between ε‐caprolactone (CL) and δ‐valerolactone (VL) in bulk at 140°C using tin(II) octoate as catalyst. They were characterized by using ¹H NMR, size exclusion chromatography, differential scanning calorimetry, and MALDI TOF mass spectrometry. Reactivity ratio determination gave an insight on their microstructure. Hydration, hydrolytic degradation, and biocide release of P(CL‐VL) films with different molecular weights values were studied. A one‐order kinetic whose rate constant decreases with copolymer macromolecular weight was observed. Although the molecular weight decrease remained relatively weak after 8 months of immersion, a correlation between molecular weight and hydrolysis rate was shown by high performance liquid chromatography‐mass spectrometry. The ability of the P(CL‐VL) films to release active compounds dispersed in the films was studied by atomic absorption spectroscopy. The release behavior of all copolymers was identical with a zero‐order kinetic. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43007.     

Fabrication of thermally expandable core–shell microcapsules using organic and inorganic stabilizers and their application

Thermally expandable core–shell microcapsules (TEM) were fabricated with an organic steric stabilizer and an inorganic Pickering emulsifier. In order to fabricate a TEM, acrylonitrile (AN) and metacrylonitrile (MAN) were used as monomers. Halloysite nanotubes (HNTs) and poly(vinylpyrrolidone) (PVP) were used as the inorganic Pickering emulsifier and the organic stabilizer, respectively. The liquid hydrocarbon content in the core, and the thermal and expansion properties, of TEMs with two different emulsifiers were compared. The mechanical properties of polypropylene (PP) foams containing TEMs prepared with two types of stabilizers were analyzed. The TEMs polymerized with PVP showed a finer expanded cell, while those fabricated with HNTs resulted in a larger expanded cell in the PP matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44247.     

Prediction of the gas solubility in polymers by a radial basis function neural network based on chaotic self‐adaptive particle swarm optimization and a clustering method

A novel model based on a radial basis function neural network (RBF NN), chaos theory, self‐adaptive particle swarm optimization (PSO), and a clustering method is proposed to predict the gas solubility in polymers; this model is hereafter called CSPSO‐C RBF NN. To develop the CSPSO‐C RBF NN, the conventional PSO was modified with chaos theory and a self‐adaptive inertia weight factor to overcome its premature convergence problem. The classical k‐means clustering method was used to tune the hidden centers and radial basis function spreads, and the modified PSO algorithm was used to optimize the RBF NN connection weights. Then, the CSPSO‐C RBF NN was used to investigate the solubility of N₂ in polystyrene (PS) and CO₂ in PS, polypropylene, poly(butylene succinate), and poly(butylene succinate‐co‐adipate). The results obtained in this study indicate that the CSPSO‐C RBF NN was an effective method for predicting the gas solubility in polymers. In addition, compared with conventional RBF NN and PSO neural network, the CSPSO‐C RBF NN showed better performance. The values of the average relative deviation, squared correlation coefficient, and standard deviation were 0.1282, 0.9970, and 0.0115, respectively. The statistical data demonstrated that the CSPSO‐C RBF NN had excellent prediction capabilities with a high accuracy and a good correlation between the predicted values and the experimental data. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3825–3832, 2013     

Biopolyester‐based nanocomposites: Structural,thermo‐mechanical and biocompatibility characteristics of poly(3‐hydroxybutyrate)/montmorillonite clay nanohybrids

In this work, the structural, thermal, mechanical, and biocompatibility characteristics of biopolyester‐based nanocomposites with phyllosilicate clays, namely those of poly(3‐hydroxybutyrate) (PHB) with octadecylamine‐modified montmorillonite (C₁₈MMT), are reported. PHB/clay nanocomposites with various loadings were prepared by melt mixing. X‐ray diffraction measurements and transmission electron microscopy images revealed the coexistence of intercalated and exfoliated states in the produced nanocomposites. Atomic force microscopy imaging also shed light to the morphological characteristics of the pure PHB and the prepared nanocomposites. The thermal stability of the nanohybrid materials was improved with the 5 wt % loading nanocomposite to show the best improvement. In addition, the nanohybrids have lower melting point compared to pure PHB and enhanced storage modulus (E′). Finally, the biocompatibility of pristine PHB and the 5 wt % nanocomposite was assessed by studying the morphology and proliferation of osteoblast cells attached on their surfaces. The results after 3 and 7 days of cell culturing indicate the incorporation of nanoclays does not change the cell adhesion and spreading as compared to those on pure PHB. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41628.     

Effects of hydrosilyl monomers on the performance of polysiloxane encapsulant/phosphor blend based hybrid white‐light‐emitting diodes

Polysiloxane‐based encapsulants were prepared by a hydrosilylation reaction of methacryl polyhedral oligomeric silsesquioxane and different hydrosilyl monomers. With the wavelength conversion method, white‐light‐emitting diodes (WLEDs) were produced by the application of a thermally cured polysiloxane encapsulant/phosphor composite as a wavelength converter on blue‐light‐emitting InGaN diodes. The color rendering index, the Commission Internationale de l'Éclairage coordinates, correlated the color temperature, and the luminous efficacy of the WLEDs with different encapsulants were evaluated. The effects of the chemical structures of hydrosilyl monomers on the optical, mechanical, and thermal resistance properties of the encapsulants, together with the performance of the WLEDs, were investigated. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44524.