Mechanical and thermal properties of potassium salts of poly(ethylene‐co‐ethylacrylate): Polyolefin ionomers in the absence of acid groups

The thermal and mechanical properties of ionomers prepared by partial saponification of poly(ethylene‐co‐ethylacrylate) (EEA) with potassium were investigated by using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The Vicat softening temperature (VST) and bending modulus were also evaluated. Molecular design of the present EEA‐based ionomers eliminates acid groups, which affect ionic aggregates for conventional ionomers. The DSC results showed that the melting enthalpy and main crystallization temperature decreased as the ion content increased, whereas on the other hand, the crystal melting temperature at about 360 K did not depend on the ion content, and a secondary exothermal peak was observed in the cooling process. The variance of the VST increased as the crystallinity decreased. The temperature‐dependent curves of DMA data of the EEA‐based potassium ionomers with a higher ion content showed elastic plateau even at temperatures above their crystal melting points. Our results indicate the existence of strong cross‐linking mediated by ion aggregates. The quadratic increase of stiffness as a function of ion content, increasing VST with decreasing crystallinity, and elastic plateau of temperature‐dependent moduli above crystal melting temperature are significant characteristics of the EEA‐based potassium ionomers, which contain ionic aggregations without acid group presence. POLYM. ENG. SCI., 55:1843–1848, 2015. © 2014 Society of Plastics Engineers     

Influence of annealing temperature on the lamellar and connecting bridge structure of stretched polypropylene microporous membrane

The influence of annealing temperature on the lamellar and connecting bridge structure of stretched polypropylene microporous membrane was investigated using small‐angle X‐ray scattering, temperature‐modulated differential scanning calorimetry and scanning electron microscopy. It is found that with increasing annealing temperature from 105 to 145 °C, the main lamella melting peak combines with that from connecting bridges and a uniform pore arrangement is obtained in the microporous membrane. The annealed lamella thickness is increased and lamellar structure is improved, due to the occurrence of melting and recrystallization during annealing. At the same time, more secondary crystals are formed. The melting and recrystallization and secondary crystals contribute to the appearance of an annealing peak in the differential scanning calorimetry curve of annealed film. During the following cold and hot stretching, the secondary crystals disappear and convert to initial connecting bridges. The improved lamellar structure can support the scaffold of pore structure, resulting in a uniform connecting bridge arrangement. But further increasing the temperature to 150 °C degrades the initial lamellar structure, leading to a decrease of pore arrangement in the stretched microporous membrane. Annealing leads to the difference of lamellar structure: the initial lamellar structure is improved and some weak secondary crystals are formed in the amorphous region. © 2014 Society of Chemical Industry     

Morphological study of chain-extended growth in polyethylene: 2. Annealed bulk polymer

The morphology of initially spherulitic, chain-folded polyethylene has been observed after specimens had been annealed at temperatures up to and including the melting point at 5.3₅ kbar. The pattern of the various phenomena corresponds to a transition from orthorhombic to hexagonal structures prior to melting in accordance with other recent work. Certain errors in the literature are corrected and additional evidence is provided for the view that the molecular mechanism of annealing in polyethylene is little different from local melting followed by recrystallization provided the effect of constraints is recognized.     

Effects of annealing on the hierarchical crystalline structures and mechanical properties of injection‐molded bars of high‐density polyethylene

The effect of annealing on the microstructural evolution and mechanical properties of high‐density polyethylene parts molded via gas‐assisted injection molding was investigated using scanning electron microscopy, differential scanning calorimetry, two‐dimensional wide‐angle X‐ray diffraction and tensile testing. The results indicated that a variety of annealing temperatures could induce considerable variations in the hierarchical structures, crystallinity, lamellar thickness and yield stress of the molded bars. According to these results, the annealing temperatures could be divided into three regions. In the low‐temperature region of annealing at 80 °C, the spatial variation of the superstructure developed along the thickness direction and mechanical properties of the annealed sample were mainly unchanged and similar to those of the original specimen. At 100 and 120 °C, the intermediate temperature region of annealing, the thickness of the crystals, degree of orientation and yield stress of annealed samples were greatly improved. Finally, at 127 °C, the degree of orientation decreased and yield stress slightly improved, an indication of the high‐temperature annealing region being characterized by increasing melting/recrystallization and causing relaxation of oriented molecular chains. A model is proposed to interpret the mechanism of the annealing treatment of the samples at various temperatures. © 2013 Society of Chemical Industry     

Lamellar thickening behaviour of nylon-6,6 crystal by annealing

Nylon-6,6 — a typical polyamide — was annealed in the swollen state in glycerol to promote the partial melting of the polymer crystal. The recrystallization or lamellar thickening of nylon-6,6 crystal following partial melting was easily induced by this annealing, and the lamellar thickness of the crystal increased stepwise by $\text{1}\text{2}$ monomer unit length with increasing annealing temperature or annealing time. In addition, another distinct layer-thickening mechanism was observed which led to approximately doubling (and frequently quadrupling) the straight stem length of the lamellar crystal for all samples annealed under adequate conditions. New melting endotherms corresponding to these layer thicknesses (range of long spacings 140–180Å) were obtained by differential scanning calorimetry (d.s.c.) at temperatures ranging from 270° to 282°C. The mechanism of lamellar thickening is discussed with reference to the experimental results.     

Effect of high‐temperature annealing on the microstructure and mechanical properties of polypropylene with shish kebab or spherulite structure

Various annealing temperatures below, near, or above the melting temperature were used to anneal polypropylene with oriented shish kebab and isolated spherulite structures in this work. The results showed that a high annealing temperature decreases the time needed to achieve the ideal material property. When the annealing temperature is near or above the melting temperature, the impact strength would be 1.6 times improved by partial melting and recrystallization. The crystal structure of the oriented shish kebab or isolated spherulite structures was improved when annealed at 150 °C, whereas annealing at 165 or 170 °C recombined the crystal lamellae of the structure. Moreover, the high crystallinity and thick lamellae improved the impact and yield strength values of the spherulite structure. However, excessively high crystallinity and thick lamellae in the oriented shish kebab structure did not result in good mechanical performance. Therefore, the prediction of mechanical properties for the shish kebab structure based on crystallinity and lamellar thickness is not feasible. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46465.     

Effect of crystallinity on enthalpy recovery peaks and cold‐crystallization peaks in PET via TMDSC and DMA studies

Poly(ethylene terephthalate) (PET) sheets of different crystallinity were obtained by annealing the amorphous PET (aPET) sheets at 110°C for various times. The peaks of enthalpy recovery and double cold‐crystallization in the annealed aPET samples with different crystallinity were investigated by a temperature‐modulated differential scanning calorimeter (TMDSC) and a dynamic mechanical analyzer (DMA). The enthalpy recovery peak around the glass transition temperature was pronounced in TMDSC nonreversing heat flow curves and was found to shift to higher temperatures with higher degrees of crystallinity. The magnitudes of the enthalpy recovery peaks were found to increase with annealing times for samples annealed ≤30 min but to decrease with annealing times for samples annealed ≥40 min. The nonreversing curves also found that the samples annealed short times (≤40 min) having low crystallinity exhibited double cold‐crystallization peaks (or a major peak with a shoulder) in the region of 108–130°C. For samples annealed long times (≥50 min), the cold‐crystallization peaks were reduced to one small peak or disappeared because of high crystallinity in these samples. The double cold‐crystallization exotherms in samples of low crystallinity could be attributed to the superposition of the melting of crystals, formed by the annealing pretreatments, and the cold‐crystallizations occurring during TMDSC heating. The ongoing crystallization after the cold crystallization was clearly seen in the TMDSC nonreversing heat flow curves. DMA data agreed with TMDSC data on the origin of the double cold‐crystallization peaks. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Morphology and melting behaviour of poly(ethylene terephthalate) crystallized from the glassy state

The influence of annealing conditions on the morphology and melting behaviour of poly(ethylene terephthalate) (PET) was studied. PET annealed under isothermal conditions often shows double melting endotherms depending on the annealing temperature (T_a) and the heating rate of the calorimeter. It was found that the morphological structure and the lower melting peak depend strongly on the annealing temperature, T_a. The increase of the lower melting peak temperature with T_a is due to an increase of the lamellar thickness within the spherulitic structure and to a higher crystallite perfection.     

The link between rigid amorphous fraction and crystal perfection in cold-crystallized poly(ethylene terephthalate)

The rigid-amorphous fraction (RAF) in cold-crystallized and subsequently annealed poly(ethylene terephthalate) (PET) was investigated as a function of crystallinity and crystal perfection. During cold-crystallization, the amount of RAF increases non-linearly with crystallinity to a maximum of 44% at a crystallinity of 24%. Vitrification of the RAF is almost complete at the cold-crystallization temperature. Increasing the crystallinity from 24% after cold-crystallization to 44% by subsequent annealing at higher temperatures decreases the RAF. The specific RAF, i.e. the ratio of RAF to crystallinity at the glass transition temperature, T_g, of the mobile-amorphous fraction decreases from almost 2.0 after cold-crystallization to 0.75 after the subsequent annealing. The decrease in the specific RAF is attributed to crystal perfection which decreases the strain transmitted to the amorphous phase. Analysis of the reversing specific heat capacity of the annealed samples on cooling leads to the conclusion that the remaining RAF at the temperature of annealing is still glassy up to at least 490 K. An observed excess heat capacity above 490 K is due to reversible melting and is discussed within the frame of the concept of the specific reversibility of melting.     

Morphology, reorganization and stability of mesomorphic nanocrystals in isotactic polypropylene

The morphology and thermodynamic stability of crystals of isotactic polypropylene (iPP) were analyzed as a function of the path of crystallization by atomic force microscopy (AFM) and differential scanning calorimetry (DSC). Samples were melt-crystallized at different rates of cooling using a “controlled rapid cooling technique”, and subsequently annealed at elevated temperature. Mesomorphic equi-axed domains with a size less than 20 nm were obtained by fast cooling from the melt at a rate larger about 100 K s⁻¹. These domains stabilize on heating by growing in chain direction and cross-chain direction, to reach a maximum size of about 40-50 nm at a temperature of 433 K, with the quasi-globular shape preserved. Annealing at 433 K additionally triggers formation of different types of lamellae. It is suggested that these lamellae either develop by coalescence of nodules, or by recrystallization from the melt. The transition from the disordered mesomorphic structure, evident at ambient temperature after fast crystallization, to monoclinic structure on heating at about 340 K occurs at local scale within existing crystals, and cannot be linked to complete melting of mesomorphic domains and recrystallization of the melt. The temperature of melting of initial mesomorphic domains, after reorganization at elevated temperature, is identical to the temperature of melting of rather perfect lamellae, obtained by initial slow melt-crystallization, followed by annealing. The close-to-identical temperatures of melting of these crystals of largely different shapes are confirmed by model calculations, using the Gibbs-Thomson equation. Modeling of the melting temperature reveals that nodular crystals, stabilized by annealing at high temperature, exhibit a similar fold-surface as lamellar crystals.     

Investigation of melting behaviors and crystallinity of linear polyamide with high‐aliphatic content

The melting behaviors and crystal structures of a long alkyl chain polyamide and nylon 18 18, were investigated under annealing and isothermal crystallization conditions. Nylon 18 18 showed multiple melting peaks in differential scanning calorimetry (DSC) thermograms depending on thermal history of the samples. The origin of the multiple melting peaks may be a result of a melting and recrystallization mechanism during DSC scans. Wide‐angle X‐ray diffraction patterns showed two new diffraction peaks, which appeared at 0.44 and 0.37 nm, and are characteristic peaks of α‐form (triclinic structure) of even–even nylons with increasing annealing temperature. The intensities of these peaks increased, and they split further apart, with elevated annealing temperatures. The solid‐state ¹⁵N CP/MAS NMR spectra of the nylon 18 18 samples that had been quenched and annealed also confirmed the α‐crystalline form. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Annealing of commercial block polypropylene. II. Behavior of poly(ethylene-co-propylene) component

Moldings of ethylene–propylene block copolymer (block PP) are improved by annealing in their tensile impact strength (TIS) and brittle temperature (Tb). To elucidate the mechanism, the role of the poly(ethylene-co-propylene) (PEP) component was studied, and the component extracted with n-heptane from annealed test pieces was subjected to characterization by a fractionation technique. It is found that recrystallization takes place by annealing in the PP matrix and results in segregation of atactic PP and high molecular weight amorphous PEP from the crystal region to the amorphous region. Furthermore, crystalline PEP also undergoes recrystallization by annealing, increasing the miscibility in the interface of PP and PEP. These phenomena in the solid phase are discussed in connection with the annealing effect related to impact strength. © 1992 John Wiley & Sons, Inc.     

Annealing effects in poly(phenylene sulfide) as observed by dynamic mechanical analysis

Poly(phenylene sulfide) (PPS) is a semicrystalline engineering resin with exceptional solvent resistance and thermal performance. Properties such as these are directly related to the high crystallinity of PPS. In order to exploit its crystalline nature, PPS should be molded at a high tool temperature (hot oil tool) to allow for the highest crystallization rate, and therefore the highest percent crystallinity. Alternately, if a low mold temperature is used, the molded parts should be annealed. This latter process has been studied for injection molded neat PPS resin for various annealing temperatures. Two different grades of PPS were studied that represent cured and linear types. Samples were studied as-molded, and annealed at 160, 180, 200 and 220°C. Increases in glass transition temperature were noted upon annealing. An increase in storage modulus was also noted for annealed samples. This increase persisted up to approximately the annealing temperature. Differential scanning calorimetry has been used to show that annealing PPS allows for a secondary crystallization to occur whereby an endotherm appears that corresponds to the secondary crystalline phase melting near the annealing temperature. As the annealing temperature is increased, the area of the endotherm increases. The secondary crystallization explains the higher storage modulus that persists up to the annealing temperature. These results are discussed in terms of crystallinity and overall effect on heat distortion temperature.     

Annealing of commercial block polypropylene. I. Thermal and physical properties

Investigations were carried out regarding the effect of annealing of ethylene–propylene block copolymer (block PP) moldings on their tensile impact strength (TIS), brittle temperature (Tb), and other mechanical properties. Annealing near the melting point improves TIS and Tb as the result of recrystallization. With a system in which a minute amount of talc is added as a nucleating agent, the degree of improving TIS through annealing is considerably less than that with a nonnucleated system. The effect of annealing on the impact strength is due to changes of fine texture and morphology of crystallites and is explicable by recrystallization and polymer diffusion. © 1992 John Wiley & Sons, Inc.     

Morphological study of chain-extended growth in polyethylene: 3. Annealing of solution-grown lamellae

Solution-grown lamellae of three commercial polyethylenes of differing molecular weight ranges have been annealed on substrates at high pressures. The polymers transform to the new high-pressure phase before melting but the new lamellar thicknesses reached remain much below those found for the bulk material. Electron diffraction patterns support the identification of the new phase as hexagonal and it is concluded that the effects of annealing polyethylene in an unusual context are close to those which would have been produced by local melting followed by rapid recrystallization.     

Thermomechanical properties of nylon-6,6 annealed in glycerol

The high temperature properties of samples annealed in glycerol at 195°C for various periods of time and those of variously treated samples were examined by thermomechanical analysis (t.m.a.) and thermal stress/strain analysis (t.s.a.). The sample annealed under much more severe conditions preserves its shape and load strength at temperatures high above the melting point. As the crosslinked sample shows properties resembling those of the severaly annealed sample, while the hydrolysed samples show more deteriorated properties than those of the annealed sample, we can conclude that the severely annealed sample is easily set to a gel accompanying thermal degradation or oxidation during the annealing, which was also indicated by elementary analyses.     

Annealing effect on the microstructure of poly(vinyl chloride)

The effect of annealing on the microstructure of commercial grade poly(vinyl chloride) was investigated by calorimetric, X-ray and viscoelastic measurements. The degree of crystallinity increases with increasing annealing temperature from above the glass transition temperature up to 130°C, at which point the degree of crystallinity takes on a maximum value. Also, the crystal melting temperature increases with increasing annealing temperature. Thermal analysis and X-ray study suggest that the crystallite of poly (vinyl chloride) decomposes by thermal degradation when annealed, above 170°C. The isothermal crystallization process is analyzed using Avrami's equation employing the degree of crystallinity as a function of annealing time at various annealing temperatures. The crystallization rate has a maximum value at around 140°C. It is expected that the crystalline texture grows in the shape of a lineal-like habit, judging from the magnitude of Avrami's constant and from a study of the X-ray intensity distribution. The α_f-transition was observed to occur at temperatures 5 to 10°C lower than the crystalline melting temperatures for annealed specimens of poly(vinyl chloride) using a dynamic spring analysis. The α_f-transition may be attributed to thermal molecular motions with a long time scale, resulting from the cross-link points introduced by the small crystallites.     

Effects of curing temperature on poly(ethylene terephthalate)

The effect on poly(ethylene terephthalate) (PET) of thermal curing in a particular temperature range (T max =280-350C) in air have been studied. The changes in the structure were monitored using various characterization techniques such as differential scanning calorimetry, thermogravimetric analysis, optical microscopy equiped with hot-stage, and scanning electron microscopy. It was observed that when (PET) is cured at very high temperature above its original melting point, cross-linking of the (PET) samples occurs. The cross-linking takes place in the melt in this case. With increasing the curing temperature, the area of the higher melting peak temperature decreases due to the increase in cross-linking of (PET). In terms of spherulitic texture, it was found that with increasing the curing temperature more inter-lamellar intra-spherulitic inclusions are observed in the material.     

Influence of syndiotacticity and annealing temperature on the double melting peak behaviour of syndiotactic polypropylene

Fractionated syndiotactic polypropylene (sPP) samples with homogeneous tacticity were annealed at different temperatures. The influence of syndiotacticity and annealing temperature on the double melting peak phenomena were investigated. It is found that all fractions show double melting peaks at 75°C annealing temperature, while the low peak disappears when the fractions with higher syndiotacticity are annealed at 85°C and above. The fraction with the lowest syndiotacticity remains the same at any annealing temperature. In combination with wide-angle X-ray diffraction experiments, the double peaks are believed to correspond to the melting of cell II and III. The results indicate that higher temperature and syndiotacticity are the external conditions and internal structural factor that permit cell II to transform into cell III. © 1999 Society of Chemical Industry     

The effects of annealing (solid and melt) on the time evolution of the polymorphic structure of polyamide 6

To understand whether and how the thermal history, especially the melting annealing, affects the polymorphism and thermal property of polyamide 6 (PA6), the temperature‐modulated differential scanning calorimetry technology was used to investigate the effects of thermal histories, including annealing temperature, annealing time, and cooling rate, on the polymorphic behavior and thermal property of PA6. It was found that longer annealing time and faster cooling rate favored the formation of α crystal when PA6 samples were annealed in the solid‐state at 175°C. As the annealing temperature was elevated to 195°C, faster cooling rate also favored the formation of α crystal, whereas longer annealing time was more favorable for the formation of γ‐form crystals. When PA6 samples were annealed in the melt‐state (245°C), however, although the α crystal was dominating crystalline phase, the formation of γ crystal was greatly enhanced with increasing annealing time and cooling rate. Moreover, a small endothermic peak was observed in the low‐temperature region in PA6 samples annealed at 175°C and 195°C, which might be related to the melting of microcrystals formed in the amorphous regions during annealing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010