Structural changes of polylactic‐acid (PLA) microspheres under hydrolytic degradation

Low molecular‐weight polylactic acid (PLA) was obtained by direct polycondensation of a mixture of 95% l and 5% d ‐lactic acid isomers, without catalyst, at 195°C. This polymer was used for the synthesis of microspheres by emulsion–solvent evaporation method. Gel Permeation Chromatography (GPC), X‐ray Scattering (XRD), Differential Scanning Calorimetry (DSC), and Scanning Electron Microscopy (SEM) techniques were applied to follow morphological and structural changes of particles along in vitro degradation at 37°C. The original microspheres were amorphous but could crystallize partially upon heating. Samples stored in a humid environment exhibited an increase in the crystallization capability upon heating. Initial smooth‐surface microspheres were transformed to porous particles at the time of degradation at pH = 7 (37°C). The shape of mass loss vs. time curve supports the presence of a heterogeneous bulk degradation process. After hydrolytic degradation the residual particles showed a molecular weight decrease and a crystallinity increase. After 90 days the crystallinity attained a value of 53%. The X‐ray diffraction spectrum indicated the formation of a crystalline oligomeric structure. Crystallization of low molecular weight species will not enable the desired PLA absorption in drug delivery systems. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1223–1230, 1999     

Polypropylene nanocomposites with oxo‐degradable pro‐oxidant: Mechanical,thermal, rheological,and photo‐degradation performance

The objective of the study was to generate degradable polypropylene nanocomposites by incorporation of pro‐oxidant and different fillers like silica, silicate, and thermally reduced graphene. Graphene‐based composites exhibited higher crystallinity attributed to better dispersion and high aspect ratio platelets. Graphene composites with 2.5% additive content significantly enhanced the peak degradation temperature to 464°C as compared to 448°C for pure polymer. The processing conditions used for the nanocomposite generation were optimum as a uniform distribution of filler particles (or platelets) was observed in the PP matrix. The tensile modulus of the graphene composite with 2.5% additive content was 80% higher than pure PP, as compared to 60 and 30% for silicate and silica composites, respectively. Similarly, the storage modulus of the graphene nanocomposite with 1% additive content had 30% increment at 40°C as compared to pure PP. PP‐additive blends as well as PP nanocomposites with silica and silicate were observed to attain 100% degree of embrittlement within 6 months of UV exposure at 30°C. Graphene composites, though, had delayed photo‐degradation due to UV absorption by the platelets and high aspect ratio platelets acting as oxygen barrier for PP matrix, but the pro‐oxidant was successful in attaining controlled degradation. POLYM. ENG. SCI., 56:1229–1239, 2016. © 2016 Society of Plastics Engineers     

Effect of temperature on polyethylene teraphthalate coated ECCS plates in acetic‐acetate medium

Electrolytic chromium‐coated steel plates with a polyethylene teraphthalate (PET) polymer coating, used in the manufacturing of both flat and rippled wall cans and containers, were submitted to 40, 60, and 80°C heating in an acetic‐acetate medium and to electrochemical polarization tests, to study the PET coating degradation and the structural changes leading to a loss of the protection capacity of the steel, as well as to determine the detachment at the interface level. The samples were analyzed by Raman vibrational spectroscopy, micro‐Raman, and attenuated total reflection to evaluate changes in the composition and structure of the coatings. Also, the PET surface was characterized by scanning electron microscopy (SEM) to establish the coating degradation. Spectroscopy analyses showed small changes of crystallinity in the PET thickness at 80°C and a reduced effect of the mechanical forming of plates on crystallinity. The SEM characterization evidenced the presence of surface defects and failures on the coating caused by the acetic‐acetate medium. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Evaluation of heat treatment regimes and their influences on the properties of powder‐printed high‐density polyethylene bone implant

A two‐step heat treatment was utilized as a means to improve the mechanical properties of a high‐density polyethylene structure which was fabricated using the three‐dimensional printing technique. It was found that the relationship between structure and properties was strongly influenced by heat treatment conditions including treatment times (15–60 min) and treatment temperatures (140–180 °C) of both primary and secondary steps. The use of primary heating at 180 °C for 15 min and secondary heating at 160 °C for 60 min resulted in the highest tensile modulus and strength, 0.7 GPa and 14.8 MPa, respectively. The changes in both shrinkage and tensile properties were governed by the level of residual porosity and quality of polyethylene interface in samples which were both influenced by the degree of thermally induced densification and binder degradation. Empirical correlations between porosity and shrinkage or tensile properties were found to be power functions. Copyright © 2010 Society of Chemical Industry     

Regulation of trans‐1,4‐polyisoprene crystallinity and mechanical properties of styrene‐butadiene rubber/trans‐1,4‐polyisoprene vulcanizate

The effects of processing temperature and bis‐[γ‐(triethoxysilyl)‐propyl]‐tetrasulfide (Si69) on crystallization, morphology, and mechanical properties of styrene‐butadiene rubber (SBR)/trans‐1,4‐polyisoprene (TPI) vulcanizate are investigated. The crystallinity and crystalline melting temperature (T_m) of TPI in the vulcanizates with TPI/silica/(Si69) pre‐mixed at 150 °C are much lower than that pre‐mixed at 80 °C. At the same pre‐mixing temperature, the presence of 1 phr Si69 leads to a decreased crystallinity and T_m. The TPI domains with phase size of about 1 μm and silica are well dispersed in the vulcanizate, and TPI crystals get smaller in size and less in amount by pre‐mixing TPI, silica and Si69 at 150 °C. The vulcanizates with TPI/silica/(Si69) pre‐mixed at 150 °C have decreased tensile strength and modulus at a given extension than that pre‐mixed at 80 °C. At the same pre‐mixing temperature, the tensile strength and modulus of the vulcanizate increase with the addition of 1 phr Si69. The crystallinity of TPI component in SBR/TPI vulcanizate is effectively controlled by changing processing temperature and adding Si69, which is important for theoretical research and practical application of TPI. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44395.     

Effect of short chain‐branching distribution on crystallinity and modulus of metallocene‐based ethylene–butene copolymers

In this article, the short chain‐branching distribution (SCBD) of some metallocene‐based ethylene–butene copolymers was evaluated by DSC, and some conventional ethylene copolymers were also studied for the purpose of comparison. It is found that metallocene‐based ethylene copolymers have a relative narrower SCBD. These copolymers were crystallized under different modes, and the crystallinity and initial modulus of them were examined. The metallocene‐based ethylene copolymers contain less interfacial regions, and the melting temperatures of them decrease more rapidly with the decrease of density than those of conventional ethylene copolymers. Moreover, the metallocene‐based and conventional ethylene copolymers of similar density have close initial modulus when they are quenched or annealed at 100°C, but conventional ethylene copolymers show higher initial modulus when stepwise crystallized from 120°C. These differences in crystallinity and initial modulus were explained based on their differences in short‐chain branching distributions. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1709–1715, 2000     

High‐tensile‐strength polyvinyl alcohol films prepared from freeze/thaw cycled gels

The mechanical properties and molecular structure of a poly(vinyl alcohol) (PVA) film, which was obtained by eliminating water from a PVA hydrogel using repeated freeze/thaw cycles, were investigated by tensile tests, thermal analysis, and X‐ray diffraction measurements. The mechanical properties of PVA with 99.9% saponification were measured as a function of the number of freeze/thaw cycles performed. The tensile strength and Young's modulus increased and the elongation at break decreased with increasing freeze/thaw cycles. The tensile strength and Young's modulus of PVA films obtained after seven freeze/thaw cycles were as high as 255 MPa and 13.5 GPa after annealing at 130°C. Thermal analysis and X‐ray diffraction measurements revealed that this is because of a high crystallinity and a large crystallite size. A good relationship between the tensile strength and the glass transition temperature was obtained, regardless of the degree of saponification and annealing conditions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40578.     

Synthesis and characterization of high‐molecular weight aliphatic polyesters from monomers derived from renewable resources

A series of high‐molecular weight aliphatic polyesters have been synthesized, at temperatures of < 200°C, through a polycondensation reaction between 1,4‐butanediol and three diacids of different chain length (succinic acid, azelaic acid, and sebacic acid). All the polyesters obtained have a bio‐based content of 100% and number average molecular weight in the range of 28,000–116,000 Da. These average molecular weights are about 5–10 times higher than those of most reported aliphatic polyesters synthesized through similar reaction routes but at temperatures > 230°C. The over‐heating phenomenon, i.e., the observation of thermal degradation behavior of these polyesters at 230°C is reported. The crystallization behavior, mechanical properties, and enzymatic hydrolysis rate of the polyesters obtained are characterized. Poly(butylene succinate) (PBSu) shows the highest crystallinity and melting temperature, but the lowest thermal stability and slowest potential rate of enzymatic biodegradation rate compared with poly(butylene azelate) and poly(butylene sebacate). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40579.     

Structural changes of injection molded starch during heat treatment in water atmosphere: Simultaneous wide and small‐angle X‐ray scattering study

Native starches with wide varying amylose content were processed by injection molding. The injection‐molded materials were conditioned in water for 20 days and sealed in glass capillaries. Simultaneous wide‐ and small‐angle X‐ray scattering (WAXS and SAXS, respectively) were recorded during thermal heating using a synchrotron source. Crystallinity, SAXS invariant, Q, and long period, L, were measured as a function of heating temperature. The injection‐molding process provokes a destruction of the crystal forms A (cereal starch) and B (tubercle starch) but favors a development of the crystal form V_h. After wet conditioning, WAXS of the injection‐molded samples shows again the appearance of the crystal forms A or B, and crystallinity reaches values similar or larger than those of native starch. A constant heating rate (5°C/min) was particularly used for a comparison of potato and corn starch with a similar amylose content. While the crystallinity associated to forms A and B slowly decreases below 55°C and then rapidly decreases until its disappearance at 85–90°C, the invariant shows a maximum around 40°C and rapidly decreases thereafter. The total nanostructure disappearance occurs at temperatures about 10°C higher for the case of potato starch. In addition, a recovery of the WAXS and SAXS maxima during the subsequent cooling process before reaching room temperature was observed only for potato starch. Analysis of WAXS and SAXS for the rest of the starch materials reveals clear differences in the structural parameters of the samples that cannot be easily explained solely on the basis of the amylose content. Thus, for Cerestar and Roquette, it is noteworthy that there was a continuous decrease of L until its total disappearance as well as the persistence of crystallinity (form B), presumably stabilized by the presence of the V_h structure (12–15%). Real‐time crystallization experiments on two amorphous injection molded samples, waxy maize (free amylose starch) and potato starch, are also discussed. It is shown that the absence of amylose delays the recrystallization of amylopectine during the experiment. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 301–309, 2004     

Young's Modulus of Elasticity of Carbon‐Bonded Alumina Materials up to 1450°C

Investigating Young's modulus at elevated temperatures supports the understanding of microstructural changes as a function of application temperature. A sintered alumina and three carbon‐bonded alumina materials with carbon contents of 20 and 30 wt% and alumina grain size of 0.6–3 mm were investigated. Young's modulus was measured in a temperature range from 25°C to 1450°C by the impulse excitation technique. The Young's modulus of carbon‐bonded materials increases up to 140% at 1450°C. After one cycle, a decrease of the Young's modulus up to 50% is registered at room temperature. There is a strong hysteresis behavior during one cycle. Thermal expansion measurements show highest expansion for the highest graphite content material. The expansion of alumina grains and graphite flakes, resulting in microcrack generation during cooling and microcrack healing during heating, is reflected in the registered values of the Young's modulus as a function of the temperature. It is assumed, that higher graphite amounts as well as coarse grains lead to lower sintering effects of the microstructure at elevated temperatures and as a result lower values of the Young's modulus have been registered.     

Performance and structure changes of the aromatic co‐polysulfonamide fibers during thermal‐oxidative aging process

The changes in performance during thermal‐oxidative aging process of the aromatic co‐polysulfonamide (co‐PSA) fibers over a broad temperature range from 250 °C to 320 °C have been investigated. In addition, the mechanism of thermal‐oxidative aging process has been studied by using structural information obtained from the fibers at varying length scales. The results showed that a significant reduction in tensile strength was observed compared with that of initial modulus during aging process. Macroscopically, thermal‐oxidative aging mainly causes color changes of fibers and thermally induced macro defects begin to appear only at 320 °C for 100 h. On a micro level, the crystal structure of fibers remained stable and did not show significant changes expect that aging at 320 °C. In addition, thermo‐degradation as well as crosslinking has been observed primarily in amorphous region. With the increase of temperature and time duration, the crosslinking became more dominant and crosslinking density increases. Correspondingly, the fibril length decreases due to degradation and then increases due to the formation of crosslinked structures within the fibers. The results suggest that molecular degradation is the main cause of strength loss and the formation of crosslinking structure within the fibers contributes to the retention of modulus and improvement of creep resistance. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44078.     

High‐resolution thermogravimetry of poly(2,6‐dimethyl‐1,4‐phenylene oxide)

The thermal degradation and kinetics of poly(2,6‐dimethylphenylene oxide) (PPO) were studied by high‐resolution thermogravimetry. The thermogravimetry measurements were conducted at an initial heating rate of 50°C min⁻¹, resolution 4.0, and sensitivity 1.0 in both nitrogen and air from room temperature to 900°C. A two‐step degradation process was clearly revealed in air at the temperatures of 430°C and 521°C. The thermal degradation temperatures and kinetic parameters of the PPO appear to be higher in air than in nitrogen, indicative of a higher thermostability in air. The temperature, activation energy, order, and frequency factor of the thermal degradation of the PPO in nitrogen are 419°C, 100–120 kJ mol⁻¹, 0.5, and 13–17 min⁻¹, respectively. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1887–1892, 1999     

Structure and high‐resolution thermogravimetry of liquid‐crystalline copoly(p‐oxybenzoate‐ethylene terephthalate‐p‐benzamide)

Thermotropic liquid‐crystalline copoly(ester‐amide)s consisting of three units of p‐oxybenzoate (B), ethylene terephthalate (E) and p‐benzamide (A) were studied by proton nuclear magnetic resonance at 200 and 400 MHz, wide‐angle X‐ray diffraction, and high‐resolution thermogravimetry to ascertain their molecular and supermolecular structures, thermostability and kinetics parameters of thermal decomposition in both nitrogen and air. The assignments of all resonance peaks of [¹H]NMR spectra for the copoly(ester‐amide)s are given and the characteristics of X‐ray equatorial and meridional scans are discussed. Overall activation energy data of the first major decomposition have been evaluated through three calculating techniques. The thermal degradation occurs in three steps in nitrogen and air. The degradation temperatures are higher than 447 °C in nitrogen and 440 °C in air and increase with increasing B‐unit content at a fixed A‐unit content of 5 mol%. The temperatures at the first maximum weight‐loss rate are higher than 455 °C in nitrogen and 445 °C in air and also increase with an increase in B‐unit content. The first maximum weight‐loss rates range between 11.1 and 14.5%min⁻¹ in nitrogen and between 11.9 and 13.5%min⁻¹ in air. The char yields at 500 °C in both nitrogen and air range from 45.8 to 54.3 wt% and increase with increasing B‐unit content. But the char yields at 800 °C in nitrogen and air are quite irregular with the variation of copolymer composition and testing atmosphere. The activation energy and Ln (pre‐exponential factor) for the first major decomposition are usually higher in nitrogen than in air and increase slightly with an increase in B‐unit content at a given A‐unit content of 5 mol%. The activation energy, decomposition order, and Ln (pre‐exponential factor) of the thermal degradation for the copoly(ester‐amide)s in two testing atmospheres, are situated in the ranges of 210–292 kJmol⁻¹, 2.0–2.8, 33–46 min⁻¹, respectively. The three kinetic parameters of the thermal degradation for the aromatic copoly(ester‐amide)s obtained by high‐resolution thermogravimetry at a variable heating rate are almost the same as those by traditional thermogravimetry at constant heating rate, suggesting good applicability of kinetic methods developed for constant heating rate to the variable heating‐rate method. These results indicate that the copoly(ester‐amide)s exhibit high thermostability. The isothermal decomposition kinetics of the copoly(ester‐amide)s at 450 and 420 °C are also discussed and compared with the results obtained based on non‐isothermal high‐resolution thermogravimetry. © 1999 Society of Chemical Industry     

The crystallization behavior and mechanical properties of polylactic acid in the presence of a crystal nucleating agent

The crystallization behavior of polylactic acid (PLA) was studied in the presence of a crystal nucleating agent, ethylenebishydroxystearamide (EBH). The crystallization rate and crystallinity were significantly increased with addition of EBH. The isothermal crystallization half-time at 105°C was decreased from 18.8 minutes for neat PLA to 2.8 minutes for PLA with 1.0 wt % of EBH. The crystallinity of PLA with 1.0 wt % EBH was about 35% after 5-minute annealing at 105°C. Like neat PLA, the double melting peaks were also observed for nucleated PLA. The changes of the double melt peaks were investigated with various crystallization temperatures, heating rates, and annealing times. The heat deflection temperature (HDT) of nucleated PLA was up to 93°C after annealing. The correlation between crystallinity and HDT was demonstrated. A percolation threshold of crystallinity was found corresponding to HDT. The crystal size of nucleated PLA was significantly decreased with addition of EBH. The mechanical properties of annealed PLA blends simultaneously; showed improved modulus and impact strength. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Facile preparation of ferroelectric poly(vinylidene fluoride‐co‐trifluoroethylene) thick films by solution casting

We investigated the effects of annealing temperature and vacuum treatment on the crystallinity and ferroelectric properties of solution‐casted poly(vinylidenefluoride‐co‐trifluoroethylene), P(VDF‐TrFE), thick films. We varied the annealing temperature from 70°C to 150°C and achieved high‐quality ferroelectric thick films annealed at 130°C. Ferroelectric domains and their properties were confirmed using X‐ray diffraction, Fourier transform infrared spectroscopy with attenuated total reflection mode and ferroelectric/piezoelectric measurement systems. Drying and/or annealing in the vacuum allowed for the improvement of crystallinity and ferroelectric/piezoelectric properties. Importantly, the piezoelectric coefficient, d₃₃, of our optimal P(VDF‐TrFE) films after sufficient poling treatment was 36 pC/N and our P(VDF‐TrFE) power generator produced an output voltage of ～6 V under periodic bending and unbending motions. POLYM. ENG. SCI., 54:466–471, 2014. © 2013 Society of Plastics Engineers     

Thermal degradation of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) in drying treatment

This study examines the isothermal treatment of poly(3‐hydroxybutyrate) (PHB) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) powders and films. The PHB and PHBV crystallinities were determined using X‐ray diffractometry, and shown to increase with temperature (130–150°C) and then decreased from 55% to 45% at 180°C. The crystal morphology of crystal planes (101) and (111) became sharp at a high temperature. The weight average molecular weight (M_w) of PHB decreased from 1,028,000 to 41,800 g/mol when heated at 180°C for 30 min. The molecular weight of PHB decreased more rapidly than that of PHBV with time. No peak signal was observed in gel permeation chromatography after heating at 150°C because the solubility of PHB changed with crystallinity. The thermal behaviors of PHB and PHBV were analyzed by differential scanning calorimetry and thermogravimetric analysis. The roughness, contact angle, and surface morphology of PHB and PHBV films were also measured to determine the surface properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3659–3667, 2013     

Synthesis,characterization and thermal degradation of poly[2‐(3‐p‐bromophenyl‐3‐methylcyclobutyl)‐2‐hydroxyethylmethacrylate]

In this work, 2‐(3‐p‐bromophenyl‐3‐methylcyclobutyl)‐2‐hydroxyethylmethacrylate (BPHEMA) [monomer] was synthesized by the addition of methacrylic acid to 1‐epoxyethyl‐3‐bromophenyl‐3‐methyl cyclobutane. The monomer and poly(BPHEMA) were characterized by FT‐IR and [¹H] and [¹³C]NMR. Average molecular weight, glass transition temperature, solubility parameter, and density of the polymer were also determined. Thermal degradation of poly[BPHEMA] was studied by thermogravimetry (TG), FT‐IR. Programmed heating was carried out at 10 °C min⁻¹ from room temperature to 500 °C. The partially degraded polymer was examined by FT‐IR spectroscopy. The degradation products were identified by using FT‐IR, [¹H] and [¹³C]NMR and GC‐MS techniques. Depolymerization is the main reaction in thermal degradation of the polymer up to about 300 °C. Percentage of the monomer in CRF (Cold Ring Fraction) was estimated at 33% in the peak area of the GC curve. Intramolecular cyclization and cyclic anhydride type structures were observed at temperatures above 300 °C. The liquid products of the degradation, formation of anhydride ring structures and mechanism of degradation are discussed. © 1999 Society of Chemical Industry     

Formation of 4‐Hydroxy‐2‐Trans‐Nonenal,a Toxic Aldehyde,in Thermally Treated Olive and Sunflower Oils

4‐Hydroxy‐2‐trans‐nonenal (HNE) is a toxic aldehyde produced mostly in oils containing polyunsaturated fatty acid due to heat‐induced lipid peroxidation. The present study examined the effects of the heating time, the degree of unsaturation, and the antioxidant potential on the formation of HNE in two light olive oils (LOO) and two sunflower oils (one high oleic and one regular) at frying temperature. HNE concentrations in these oil samples heated for 0, 1, 3, and 5 hours at 185 °C were measured using high‐performance liquid chromatography. The fatty‐acid distribution and the antioxidant capacity of these four oils were also analyzed. The results showed that all oils had very low HNE concentrations (<0.5 μg g^?1 oil) before heating. After 5 hours of heating at 185 °C, HNE concentrations were increased to 17.98, 25.00, 12.51, and 40.00 μg g^?1 in the two LOO, high‐oleic sunflower oil (HOSO), and regular sunflower oil (RSO), respectively. Extending the heating time increased HNE formation in all oils tested. It is related to their fatty‐acid distributions and antioxidant capacities. RSO, which contained high levels of linoleic acid (59.60%), a precursor for HNE, was more susceptible to degradation and HNE formation than HOSO and LOO, which contained only 6–8% linoleic acid.     

High‐Temperature Compression Deformation Behavior of Fine‐Grained Carbon‐Bonded Alumina

Carbon‐bonded alumina with 33 wt% residual carbon was tested in compression at room temperature and at temperatures between 700°C and 1500°C in quasi‐static tests, creep tests, and stress relaxation tests. Therefore, a new high‐temperature test set up with inert gas chamber and inductive heating was used. The tests were accomplished by investigations of microstructure and Young's modulus. At room temperature, the results exhibit a pronounced hysteresis for the first loading cycle, which almost completely disappeared in subsequent cycles. The creep tests showed characteristic curves for compression whereas primary and secondary (stationary) creep occurred. Above 1000°C, a strong increase in creep rate was detected, whereas almost no creep was observed below this temperature. All creep curves were approximated with the models of logarithmic and Andrade creep. The activation energy for creep was found to be 263 kJ/mol above 1150°C. The resistance against stress relaxation showed an anomaly with a minimum between 1000°C to 1200°C and a maximum between 1300°C and 1400°C.     

Preparation of supramolecular thermally repairable elastomer by crosslinking of maleated polyethylene‐octene elastomer with 3‐amino‐1,2,4‐triazole

A supramolecular thermally repairable elastomer was prepared by crosslinking of semicrystalline maleated polyethylene‐octene elastomer (mPOE) with 3‐amino‐1,2,4‐triazole (ATA) via melt mixing method. Crosslinking of mPOE with ATA induced supramolecular hydrogen bonding networks; the nature of the networks was affected by the amount of ATA, which was confirmed by Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy. In addition, at 3 phr ATA content or above, a small number of ionic domains were observed in the tan δ curves of dynamic mechanical analysis. Dynamic mechanical analysis also showed that the storage modulus increased with increasing ATA content along with increase in the relaxation transition temperature which revealed strengthening of the network structures. Differential scanning calorimetry showed a reduction in melting temperature and degree of crystallinity of the mPOE with increasing ATA content which is attributed to hydrogen bonding networks. The shape memory property of the mPOE matrix imparted a thermal healing capability which was greatly enhanced in the presence of hydrogen bonding networks. The scratch marked on the polymer surface healed within 20 s after being heated at around 80 °C. © 2014 Society of Chemical Industry