Physical properties of PLGA films during polymer degradation

The rates of change of polymer properties (glass transition temperature, weight fraction sorbed water, and polymer molecular weight) were determined in poly (DL ‐lactide‐co‐glycolide) films under accelerated storage conditions. Films were stored at 70°C and 95%, 75%, 60%, 45%, or 28% relative humidity. Weight fraction sorbed water was determined by thermogravimetric analysis, the glass transition temperature (Tg_mix) of the polymer/water mixture by modulated temperature differential scanning calorimetry, and PLGA number‐average molecular weight (M_n) by size exclusion chromatography (SEC). Rates of moisture increase and Tg_mix decrease were related to the decrease in PLGA M_n through a modification of the Gordon‐Taylor equation. Understanding the relative rates of polymer physical and chemical degradation will allow for improved design of PLGA formulations that control rates of drug delivery and preserve drug stability. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Modification of phenol–formaldehyde resol resins by lignin,starch, and urea

Lignin‐based chemicals, starch, and urea were used as modifiers for phenol–formaldehyde resol resins. The effects of the addition stage of the modifiers used in the synthesis of the resins and the type of modification reagent on the structures of the resins and their molar masses and reactivities were investigated. The modifications with corn starch and lignin promoted condensation; this was verified by increased molar masses and high ratios of methylene bridges to the sum of free ortho and para aromatic groups with respect to the corresponding reference resin without a modification reagent. The later the modifier was added to the resin condensation mixture, the more methylene bridges were formed with respect to the amounts of free ortho and para aromatic groups. In addition, when urea or wheat starch was added in the later condensation stage, the final condensation also reached high stages. The modifications with lignosulfonate and starch, as well as the early addition of urea, enhanced p–p′ bridge structures. The lowest condensation stage and, therefore, the highest reactivity were found when wheat starch was added with the starting reagents. The curing heat of the wheat‐starch‐modified resins decreased according to the deferred addition point of starch. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 582–588, 2003     

Synthesis and properties of cardanol‐based epoxidized novolac resins modified with carboxyl‐terminated butadiene–acrylonitrile copolymer

Cardanol‐based, novolac‐type phenolic resins were synthesized with a cardanol‐to‐formaldehyde molar ratio of 1 : 0.7 with different dicarboxylic acid catalysts, including oxalic and succinic acids. These novolac resins were epoxidized with a molar excess of epichlorohydrin at 120°C in a basic medium. The epoxidized novolac resins were separately blended with different weight ratios of carboxyl‐terminated butadiene–acrylonitrile copolymer (CTBN) ranging between 0 and 20 wt % with an interval of 5 wt %. All of the blends were cured at 120°C with a stoichiometric amount of polyamine. The formation of various products during the synthesis of the cardanol‐based novolac resin and epoxidized novolac resin and the blending of the epoxidized novolac resin with CTBN was studied by Fourier transform infrared spectroscopy analysis. Furthermore, the products were also confirmed by proton nuclear magnetic resonance and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectroscopy analysis. The molecular weights of the prepared novolacs and their epoxidized novolac resins were determined by gel permeation chromatography analysis. The blend samples, in both cases, with 15 wt % CTBN concentrations showed the minimum cure times. These blend samples were also the most thermally stable systems. The blend morphology, studied by scanning electron microscopy analysis, was, finally, correlated with the structural and property changes in the blends. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of biodegradable block copolymers of poly(propylene fumarate‐co‐sebacate)‐co‐poly(ethylene glycol) and poly(ethylene fumarate‐co‐sebacate)‐co‐poly(ethylene glycol)

The synthesis of two low molecular weight linear unsaturated oligoester precursors, poly(propylene fumarate‐co‐sebacate) (PPFS) and poly(ethylene fumarate‐co‐sebacate) (PEFS), are described. PPFS, PEFS, and poly(ethylene glycol) are then used to prepare poly(propylene fumarate‐co‐sebacate)‐co‐poly(ethylene glycol) (PPFS‐co‐PEG) and poly(ethylene fumarate‐co‐sebacate)‐co‐poly(ethylene glycol) (PEFS‐co‐PEG) block copolymers. The products thus obtained are investigated in terms of the molecular weight, composition, structure, thermal properties, and solubility behavior. A number of design parameters including the molecular weights of PPFS, PEFS, and PEG, the reaction time in the polymer synthesis, and the weight ratio of PEG to PPFS or to PEFS are varied to assess their effects on the product yield and properties. The hydrolytic degradation of PPFS‐co‐PEG and PEFS‐co‐PEG in an isotonic buffer (pH 7.4, 37°C) is investigated, and it is found that the fumarate ester bond cleaves faster than does the sebacate ester bond. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 295–300, 2004     

Thermal and nondestructive analysis of high density polyethylene filled with milled salago fiber

Fillers are utilized for different purposes. In plastic industry, fillers are mainly used to extend the bulk of the compound; however, they can also improve physical properties, materials processing, and reduce cycle time of plastics. In this article, high-density polyethylene was filled with untreated and 5% alkaline-treated salago fiber, and thereafter the thermal and nondestructive properties of the composites were investigated. It was found that the chemical treatment of fiber increased the thermal stability and the mean coefficient value of linear thermal expansion of the treated composites as compared to the untreated ones. Moreover, the increase of fiber content in composites increased the crystallinity level while decreased the thermal capacity and melting temperature of the composites. The zinc, calcium, and phosphorus contents were found to be within the industry-acceptable range for elemental contents in polyolefins. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47873.     

Characterization of an alkali‐treated grass fiber by thermogravimetric and X‐ray crystallographic analysis

The thermal behavior of grass fiber was characterized by means of thermogravimetric analysis and differential scanning calorimetry analysis. The results proved that the removal of water‐soluble matter improved the thermal behavior of grass fiber over that of unleached fiber, and this was further enhanced by an alkali treatment of the grass fiber. The isothermal weight loss of the grass‐fiber specimens was analyzed at 100, 200, and 300°C for different time periods. Accelerated aging of the grass‐fiber samples was carried out to determine the effect of aging on the tensile strength. Partially delignified grass fiber showed maximum thermal stability. X‐ray diffraction analysis was also performed to verify the composition and to correlate the change in the tensile strength due to the water leaching and alkali treatment. The processing of grass fiber with NaOH and NaClO₂ reduced the amorphous fraction in the fiber sample. This may have been a result of the loss of the amorphous noncellulosic components of the fibers and the degradation of the unordered regions of the grass fiber. However, mercerization of the grass fiber revealed an increase in the amorphous fraction after a certain time exposure, confirming the decrease in the crystallinity. The morphology of the water‐leached and alkali‐treated grass fiber was studied with scanning electron microscopy © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The effect of formaldehyde/phenol (F/P) molar ratios on function and curing kinetics of high‐solid resol phenolic resins

A series of high‐solid resol phenolic resins (HSRPRs) were synthesized with different molar ratios (1.6, 1.8, 2.0, 2.2, and 2.4) of formaldehyde to phenol using calcium oxide and sodium hydroxide as catalyst. The effects of F/P molar ratios on physical properties, free formaldehyde and phenol, activity, structure, and thermally resistant properties of HSRPRs were fully investigated by chemical assays, liquid and solid ¹³C‐NMR, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The curing kinetics of different F/P molar ratios were explored with differential scanning calorimeter at four different heating rates (5, 10, 15, 20°C/min) from 35 to 200°C. Overall, HSRPRs with F/P = 2.0 had excellent comprehensive properties. The study was significant in solving the wastewater problem during the process of industry‐scale preparation of HSRPRs. We believed that the experimental findings would provide a new avenue for further study and application of HSRPRs. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Evolution of interactions between water and native corn starch as a function of moisture content

Thermostimulated current spectroscopy, thermogravimetric analysis, and differential scanning calorimetry (DSC) were used to study starch–water systems with moisture contents of 0–50% (on a total weight basis). DSC enabled the calculation of the amounts of bound and free water. The maximum quantity of bound water was detected for a 30% humidity sample. The existence of interactions between water and starch was proved and found to be weakened for samples containing more than 30% water. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2860–2865, 2002     

Thermal stability of modified end‐capped poly(lactic acid)

The influence of functional end groups on the thermal stability of poly(lactic acid) (PLA) in nitrogen‐ and oxygen‐enriched atmospheres has been investigated in this article using differential scanning calorimetry, thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA). Functional end groups of PLA were modified by succinic anhydride and l ‐cysteine by the addition–elimination reaction. PLA was synthesized by azeotropic condensation of l ‐lactic acid in xylene and characterized by nuclear magnetic resonance. The values of the activation energies determined by TGA in nitrogen and oxygen atmospheres revealed that the character of functional end groups has remarkable influence on the thermal stability of PLA. Moreover, DMA confirmed the strong influence of functional end groups of PLA on polymer chains motion. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41105.     

Morphology and thermal properties of poly(L‐lactic acid)/organoclay nanocomposites

A modified clay was used to prepare poly(L ‐lactic acid)/clay nanocomposite dispersions. X‐ray diffraction and transmission electron microscopy experiments revealed that poly(L ‐lactic acid) was able to intercalate the clay galleries. IR spectra of the poly(L ‐lactic acid)/clay nanocomposites showed the presence of interactions between the exfoliated clay platelets and the poly(L ‐lactic acid). Thermogravimetric analysis and differential scanning calorimetry were performed to study the thermal behavior of the prepared composites. The properties of the poly(L ‐lactic acid)/clay nanocomposites were also examined as functions of the organoclay content. The exfoliated organoclay layers acted as nucleating agents, and as the organoclay content increased, the crystallization temperature increased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of the carbonyl content on the properties of composite films based on oxidized starch and gelatin

To improve the properties of gelatin, oxidized starch (OS) with different carbonyl content was introduced into the gelatin. In this study, we researched the influence of the carbonyl content of OS on the rheological characteristics, swelling behavior, thermal properties, and wettability of the modified gelatin film (MGF). The MGF samples were prepared by the casting of a 10% w/w solution of gelatin and OS with 18.9, 38.7, and 49.3% carbonyl content, respectively. The results of the dynamic viscosity demonstrated that the influence of the temperature on the rheological characteristics of native gelatin film (NGF) was more obvious than that of MGF. Meanwhile, the viscosity of the samples decreased with increasing carbonyl content in OS. Both the differential scanning calorimetry and thermogravimetry curves indicated that the denaturation and pyrogenic decomposition temperatures of the MGF samples were higher than those of NGF; this meant that the crosslinking between NGF and OS improved the physicochemical properties of gelatin. Compared with the NGF sample, MGF was less hydrophilic because the hydrophilic groups of gelatin could be shielded by OS. Meanwhile, the acid–base and salt sensitivity of the MGF samples were very obvious; therefore, the MGF samples could potentially be used as biomedical materials. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3809–3815, 2013     

Improved mechanical and antibacterial properties of thermoplastic polyurethanes by efficient double functionalization of silver nanoparticles

When making nanocomposites, there is a big challenge to obtain both functional and mechanical enhancement. In this study, a new in situ polymerization methodology for the incorporation of surface modified silver nanoparticles (AgNPs) in a thermoplastic polyurethane matrix was developed. AgNPs with contents ranging from 0 to 1.5 wt % were used. A double functionalization of the nanoparticles with oleic acid was performed, which lead to a reaction of carboxylic acid groups in the nanoparticle's surface with isocyanate groups of the 4,4′‐methylene diphenyl diisocyanate monomer as corroborated from the Raman results. The successful incorporation of the nanoparticles was verified with EDS, TGA, and Raman measurements. Thermal properties of nanocomposites were investigated by DSC. AgNPs made positive impact in two ways: first, increased more than twice the elastic modulus, as studied via nanoindentation measurements and second, based on the inhibition zone method, great bactericidal effectiveness for nanocomposites containing 1.5 wt % AgNPs was observed for Escherichia coli. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46180.     

Coextrusion and biaxial orientation of multi-microlayer films

In this study, the multi-microlayer films (MMFs) prepared by the coextrusion of the corresponding polymers using a feed block design are reported. The alternating layers of the linear low-density poly(ethylene) and ethylene vinyl alcohol polymers are used to produce the 3-layered and 100-layered MMFs with the total thickness of around 640 μm. The MMFs are going through biaxial orientation and heat treatment which can change the morphologies and physical properties and reduce the thickness of the films to several micrometers. The differences in crystallinity, melting temperature, interface physical properties, tensile strength, and water vapor transmission rate of the MMFs are fully investigated. The intermolecular interaction of the 100-layered MMFs is much higher than that of the 3-layered MMFs possibly due to the tightly bonded layers which lead to the disappearance of the interface layers following by orientation. The MMFs are successfully prepared by coextrusion following by biaxial orientation and heat treatment of two or more different kinds of polymers with very different intrinsic properties. This MMFs exhibit excellent compatibility, mechanical property and water resistance characteristics which have potential uses in the composite materials for food and electronic packaging applications.     

Effects of two antioxidants with different degrees of steric hindrance on the thermal-oxidative aging properties of ABS resin

ABS resin is easily oxidized and deteriorated during use or processing. The addition of antioxidants is an effective method for improving ABS oxidation. The hindered phenol antioxidant DBHMIE and the asymmetrically hindered 245 were added separately or together to ABS; the oxidation induction temperature of ABS increased by 10.6, 12.1 and 14°C, with the addition of DBHMIE, 245 and their combination, respectively, and the initial decomposition temperature T3% increased by 29.7, 16.2 and 51.3°C, respectively. The addition of these two antioxidants to ABS did not greatly affect the mechanical properties of the material, but the impact strength increased by 2.24 kJ/m² when both antioxidants were added together. During the thermal aging test, the decomposition temperature of the ABS splines prepared with the combined antioxidants increased during the first few cycles. The impact strength of the splines prepared with the combined antioxidants was the highest, with the smallest decrease of only 5.18%. The yellow index of the spline prepared with the combined antioxidants was between those of splines prepared with the antioxidants added alone. The combination of DBHMIE and 245 induced synergistic effects, improved thermal-oxidative aging resistance, and improved and protected the toughness of ABS resin.     

Improvements in the thermal conductivity and mechanical properties of phase‐change microcapsules with oxygen‐plasma‐modified multiwalled carbon nanotubes

The thermal properties and mechanical properties are the key factors of phase‐change microcapsules (microPCMs) in energy‐storage applications. In this study, microPCMs based on an n‐octadecane (C18) core and a melamine–urea–formaldehyde (MUF) shell supplemented with O₂‐plasma‐modified multiwalled carbon nanotubes (CNTs) were synthesized through in situ polymerization. Meanwhile, two different addition methods, the addition of modified CNTs into the emulsion system or into the polymer system, were compared and examined. Scanning electron microscopy micrographs showed that the microPCMs were spherical and had a broadened size distribution. Fourier transform infrared testing demonstrated that the modified CNTs did not affect C18 coated by MUF resin. The results indicate that the thermal conductivity and mechanical properties of the microPCMs were remarkably improved by the addition of a moderate amount of modified CNTs, but the heat enthalpy and encapsulated efficiency decreased slightly. Moreover, the thermal conductivity and mechanical properties of microPCMs modified with CNTs directly added to the polymer system were superior to those with CNTs added to emulsion system. In particular, when 0.2 g of modified CNTs were added to the polymer system, the thermal conductivity of the microPCMs was improved by 225%, and the breakage rates of the microPCMs at 4000 rpm for 5, 10, and 20 min decreased by 74, 72, and 60%, respectively, compared with that of the microPCMs without modified CNTs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45269.     

Synthesis and performance of phenolic polybutadiene‐bound stabilizers

An antioxidant derivative, 6‐sulfanylhexyl 3‐(3,5‐di‐tert‐butyl‐4‐hydroxyphenyl)propanoate, was synthesized and examined. With a radical initiator, the addition of this compound to pending vinyls of OH‐telechelic, low molecular weight liquid polybutadiene (LBH) was performed to various degrees of conversion to form polymeric antioxidants (PAOs) in which the phenolic moiety was separated from the main chain by a spacer [? CH₂CH₂? S? (CH₂)₆? O? CO? ]. Pure, unstabilized LBH was mixed in several ratios with PAOs, Irganox 1520, and Irganox 1076, and the oxidation stabilities of these mixtures, determined by thermogravimetric analysis and differential scanning calorimetry, were compared. Probably because of their good compatibility with LBH, PAOs exhibited equal or better effectiveness than commercial antioxidants of the Irganox type. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 885–889, 2003     

Synthesis,characterization, and thermal properties of copolymers of behenyl acrylate and behenyl fumarate

Radical copolymerization of behenyl (systematic IUPAC nomenclature: n‐docosyl) acrylate and behenyl fumarate has been carried out in toluene at 70°C using benzoyl peroxide as initiator. Gel permeation chromatography was used to determine molecular weights (MW) and molecular weight distribution (MWD) of behenyl acrylate–behenyl fumarate (BA‐BF) copolymers. ¹H NMR and carbon analysis was used to determine the composition of BA‐BF copolymers. Monomer reactivity ratios for high conversion polymerization were calculated by conversion‐extended Kelen‐Tudos plot. Differential scanning calorimetric (DSC) measurements shows sharp melting peaks at about 64°C. Thermal stability studies were performed with thermogravimetric analyzer (TGA). By using these DSC and TGA data in several nonisothermal methods, the activation energies were calculated. X‐ray diffraction studies show the linearity of the copolymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2721–2726, 2003     

Thermal properties of extruded/injection‐molded poly(lactic acid) and biobased composites

To determine the degree of compatibility between poly(lactic acid) and different biomaterials (fibers), poly(lactic acid) was compounded with sugar beet pulp and apple fibers. The fibers were added in 85 : 15 and 70 : 30 poly(lactic acid)/fiber ratios. The composites were blended by extrusion followed by injection molding. Differential scanning calorimetry and thermogravimetric analysis were used to analyze the extruded and extruded/injection‐molded composites. After melting in sealed differential scanning calorimetry pans, the composites were cooled through immersion in liquid nitrogen and aged (stored) at room temperature for 0, 7, 15, and 30 days. After storage, the samples were heated from 25 to 180°C at 10°C/min. The neat poly(lactic acid) showed a glass‐transition transition at 59°C with a change in heat capacity (ΔC_p) value of 0.464. The glass transition was followed by crystallization and melting transitions. The enthalpic relaxation of the poly(lactic acid) and composites steadily increased as a function of the storage time. Although the presence of fibers had little effect on the enthalpic relaxation, injection molding reduced the enthalpic relaxation. The crystallinity percentage of the unprocessed neat poly(lactic acid) dropped by 95% after extrusion and by 80% for the extruded/injection‐molded composites. The degradation was performed in air and nitrogen environments. The degradation activation energy of neat poly(lactic acid) exhibited a significant drop in the nitrogen environment, although it increased in air. This meant that the poly(lactic acid) was more resistant to degradation in the presence of oxygen. Overall, injection molding appeared to reduce the activation energy for all the composites. Sugar beet pulp significantly reduced the activation energy in a nitrogen environment. In an air environment, both sugar beet pulp and apple fibers increased the activation energy. The enzymatic degradation of the composites showed a higher degradation rate for the extruded samples versus the extruded/injection‐molded composites, whereas the apple composites exhibited higher weight loss. The thermogravimetric analysis data showed that the degradation of unprocessed and extruded neat poly(lactic acid) followed a one‐step mechanism, whereas extruded/injection‐molded composites showed two‐step degradation. A higher fiber content resulted in up to three‐step degradation mechanisms. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Recovery of heavy metals from aqueous solution by using radiation crosslinked poly(vinyl alcohol)

Crosslinked poly(vinyl alcohol) (PVA) and PVA/acrylic acid hydrogels, prepared by γ‐irradiation, were used in the removal of heavy metals from aqueous solution. Comparative studies of the properties of the two hydrogels were made. The application of the prepared hydrogels as adsorbent materials for Cu²⁺, Co²⁺, and Ni²⁺ from aqueous solution was studied. The chemical and physical properties of the hydrogels, before and after adsorption of the heavy metal ions, were investigated by means of thermogravimetric analysis, differential scanning calorimetry, and scanning electron microscopy. The efficiency of such hydrogels for the recovery of metal ions was determined by atomic absorption and UV spectroscopic analysis. The effect of changing pH on the metal uptake was also studied. It was found that the prepared hydrogels have a substantial ability to adsorb metal ions from their solution. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1649–1656, 2004     

Studies on polyacrylates containing pendant ligand with carbonyl and hydroxyl functions and their divalent metal complexes

A series of monomers were prepared by reacting (meth)acryloyl chloride with 2,4‐dihydroxybenzophenone, 2,4‐dihydroxybenzaldehyde, and 2,4‐dihydroxyacetophenone, respectively. The monomers were polymerized in dimethylformamide (DMF) at 70°C using benzoyl peroxide as an initiator. Polymer–metal complexes were obtained from DMF solutions of polymers with an aqueous solution of metal ions. The polymers and polymer–metal complexes were characterized by elemental analysis and spectral studies. The IR spectra of these complexes suggest that the metals are coordinated through the oxygen of the carbonyl group and the oxygen of the phenolic–OH group. The electronic spectra, electron paramagnetic resonance (EPR) spectra, and magnetic moments of polychelates showed an octahedral and square planar structure for Ni(II) and Cu(II) complexes, respectively. X‐ray diffraction studies revealed that polychelates are highly crystalline. The thermal and electrical properties, catalytic activity, and structure–property relationships are discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2083–2090, 2003