An optical investigation of high‐tenacity polyester (H‐T PET) fibers annealed at different temperatures

A two‐beam “Interphako” interference microscope was used to study the effect of annealing on the physical properties of high‐tenacity poly(ethylene terephthalate) H‐T PET fibers. The PET fibers were annealed with free ends for 1 h at temperatures ranging from 100 to 200°C. The shrinkage, refractive indices, and orientation angle of the PET fibers were determined for different annealing temperatures. The measured birefringence and orientation function were found to have decreased with increasing temperature, whereas the degree of crystallinity and the onset temperature (DSC) increased. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

A study on multiple melting of isotactic polypropylene

Multiple melting characteristics of a highly isotactic polypropylene (iPP) were studied by means of differential scanning calorimetry (DSC). Double melting characteristics were observed on melting iPP crystallized isothermally at temperatures ranging from 110 to 140°C. iPP crystallized below and above 125°C exhibited different double melting characteristics from each other. For iPP crystallized below 125°C, the single melting peak split into two peaks during slow DSC heating scans without changing the total crystallinity in the polymer. On the other hand, the double melting endotherm of iPP crystallized above 125°C seemed to come from two preexisting crystal fractions having different T_m. There existed an optimum annealing temperature range where the five-minute annealing of iPP raised T_m of the polymer significantly. The treatment also increased the crystallinity of iPP crystallized isothermally at 110°C by 12%.     

Annealing‐induced structural rearrangement and its toughening effect in injection‐molded isotactic polypropylene

To improve the toughness of isotactic polypropylene (iPP), by blending modification or special processing techniques, is an ongoing pursuit in the polymer community. In this study, the toughness of injection‐molded iPP bars has been enhanced by about four times upon annealing at 140°C, in parallel with slight increasing of stiffness. Through various structural characterizations it has been confirmed that the remarkable toughening effect in the annealed iPP bars mostly results from the enhanced molecular mobility in the amorphous phase due to lamellar perfection, rather than from the change of molecular orientation, crystal modification, crystallinity, and so on. Moreover, it is deduced that the gain of mobile amorphous fraction in the hierarchical iPP bars upon annealing follows the order of skin > intermediate > core, same to that contributing to the toughness enhancement. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

The influence of annealing treatment on the molecular structure and the mechanical properties of isotactic polypropylene fibers

An investigation was carried out on the effects of annealing treatment on the molecular structure and the mechanical properties of isotactic polypropylene fibers annealed in an air heated environment at temperatures ranging from 60 to 140°C. Analysis of the equatorial X‐ray diffraction traces showed the presence of a three phase system of amorphous‐smectic‐monoclinic forms and revealed the transformation of the metastable smectic form to the highly stable monoclinic form as the annealing temperature is increased, resulting in an enhanced degree of crystallinity and the crystallite size. The improvements in the degree of crystallinity and the crystallite size became more remarkable above 120°C. Evaluation of the crystallinity was carried out using an analysis of density, infrared spectroscopy, and X‐ray diffraction methods whereas the state of the molecular orientation was evaluated using polarized infrared spectroscopy measurements only. Polarized infra‐red spectroscopy measurements after the curve fitting procedure showed a slight increase of the molecular orientation of the helical chain segments present in the crystalline phase represented by the IR bands at 841 and 998 cm^?1 whereas the amorphous structure represented by the IR band at 974 cm^?1 showed no significant change with increasing annealing temperature. The improvement in the molecular orientation of the crystalline phase became more remarkable above 120°C. Tensile strength of the annealed fibers increased with increasing annealing temperature but the elongation at break and the initial modulus were not affected as much as the tensile strength. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Quantification of the Young's modulus for polypropylene: Influence of initial crystallinity and service temperature

In this study, the mechanical properties of isotactic polypropylene (iPP) materials with different crystallinities at room and elevated temperatures were investigated. In order to obtain samples with a certain range of crystallinity, and to ensure a uniform microstructure of these samples, the iPP samples obtained by injection molding required melt compression molding and controlled annealing. In the macromechanical studies, the experimental results showed that the storage modulus and Young's modulus of polypropylene were sensitive to the service temperature. The crystallinity also had a great influence on this relationship. A function was proposed to evaluate the dependence of the Young's modulus of polypropylene on initial crystallinity and service temperature, and tested based on experimental data. The Young's modulus of iPP is reduced by about 90% when the service temperature rises from 25 to 125 °C. Moreover, the reduced value in Young's modulus between polypropylene having the highest and lowest crystallinity was reduced from 214.55 to 56.75 MPa. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48581.     

Structural evolution and mechanical properties of iPP melt spun fibers subjected to thermal treatment

An investigation of the structure and mechanical behavior of melt-spun isotactic polypropylene (iPP) fibers subjected to thermal treatment in an inert atmosphere is described. Two iPP formulations, Basell Pro-fax PH835 and ExxonMobil Achieve 3854, synthesized by the Ziegler-Natta and metallocene catalysts respectively, and spun at take-up velocities of 1000 to 3000 m/min are considered. The evolution of the structure is monitored with WAXS, SAXS, Raman spectroscopy and birefringence measurements. The fibers spun at 1000 m/min are predominantly mesomorphic, while those spun at 3000 m/min are semi-crystalline in the as-spun state. Thermal treatment for 20 min at 145 °C erases the processing history and increases the crystallinity of all samples. It is shown that thermal treatment leads to the formation of a secondary set of kebab lamellae which are thinner than the original ones, separated by thicker lamellae. The spatial variability of the lamellar thickness and of interlamellar spacings is estimated from the SAXS data and it is concluded that the variability is rather pronounced in all samples. Both annealed and non-annealed fibers are subjected to monotonic and cyclic mechanical testing. Large differences are seen in the behavior of non-annealed fibers processed in different conditions. The monotonic mechanical behavior of the annealed fibers is not very much different from that of the corresponding non-annealed fibers. The central difference between annealed and non-annealed samples is observed in the cyclic behavior; annealed samples containing lamellae with bimodal distribution of thickness exhibit bimodal hysteresis curves while this feature is not observed in non-annealed samples.     

In situ studies on the temperature‐related deformation behavior of isotactic polypropylene spherulites with uniaxial stretching: The effect of crystallization conditions

The deformation behavior of isotactic polypropylene (iPP) spherulites with uniaxial stretching was investigated at different drawing temperatures via in situ polarized optical microscope (POM) observation. The iPP spherulites were prepared by two procedures: cooled to the room temperature from melt and annealed at 135, 140, and 145°C for 3 h. It was found that the crystallization conditions dominate the crystalline morphology and even the tensile properties of iPP. For iPP which crystallized during cooling progress, the spherulites were imperfect and the boundaries of the spherulites were diffuse, displaying good toughness at various drawing temperatures. For iPP annealed at high temperatures displayed the brittle fracture‐modes and the crack happened between spherulites, which due to the large and perfective spherulites have thick lamellas and weak connection at interspherulitic boundary. The shape and size of the iPP spherulites formed at 140 and 145°C are affected with uniaxial stretching till to the fracture of the samples at different drawing temperatures. The spherulites obtained at 135°C are deformed along the drawing direction at 100°C but not affected at low drawing temperatures, indicating the toughness increased with the increase of the drawing temperatures. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Enhanced molecular orientation and strain hardening in melt‐spun isotactic polypropylene monofilaments through partial melting recrystallization

Achieving high molecular orientation, by increasing spinning velocity and/or postdrawing, is critical to improve the mechanical properties of isotactic polypropylene (iPP) fibers. In this study, we have demonstrated that upon annealing around melting point the molecular orientation of both amorphous and crystalline phases in melt‐spun iPP monofilaments is significantly enhanced, in parallel with the improved stability of crystals, because of partial melting and oriented recrystallization. As a result, high level stress and remarkable strain hardening are generated during stretching of annealed monofilaments. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Optothermal properties of fibers. XIII. Evaluation of the form birefringence and some other structural parameters due to thermal annealing for polyester (PET) fibers

In this work, changes in the structure of polyester [poly(ethylene-terephtalate) (PET)] fibers after annealing at constant temperature (120 and 140°C) and different times were studied interferometrically. The density of annealed PET fibers were measured by a system based on vibrating string. The Pluta polarizing interference microscope was used to determine the optical parameters of these fibers. The density and optical results were used to calculate the degree of crystallinity, the form birefringence, the number of monomeric units per unit volume, harmonic mean polarizability of the dielectric, harmonic mean specific refractivity, and the virtual refractive index. The behavior of fiber crystallinity at different annealing conditions were discussed with different optical parameters. Hermans optical orientation function have been compared with the generalized Lorentz–Loranz equation given by de Vries. Microinterferograms and curves are given for illustration. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:1955–1963, 1998     

Optothermal properties of fibers. IX. Study changes of optical parameters by multiple-beam technique due to thermal annealing for natural silk fibers

Multiple-beam Fizeau fringes were used for studying the effect of the annealing process on the refractive indices and birefringence of natural silk fibers (best yellow Italian silk, Ford & Co. Ltd). Silk fibers were annealed at a constant time of 2 h with different annealing temperatures ranging from 60 to 160 ± 1°C. A scanning electron microscope was used for measuring the cross-sectional shape and a longitudinal view of the natural silk fibers. The Becke-line method was used for measuring the skin refractive indices and the birefringence of the natural silk fibers. The thermal coefficient of the refractive index, Cauchy dispersion constants, dispersive power, dielectric constant at infinity, polarizability per unit volume, isotropic polarizability, and isotropic refractive index were determined interferometrically. Microinterferograms and curves are given for illustration. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1495–1504, 1998     

Effect of annealing on the structure and properties of polyvinylidene fluoride hollow fiber by melt‐spinning

Polyvinylidene fluoride hollow fibers were prepared by melt‐spinning technique under three spinning temperatures. The effects of annealing treatment on the structure and properties of hollow fiber were studied by differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), tensile test, and scanning electron microscopy (SEM) measurements. DSC and WAXD results indicated that the annealing not only produced secondary crystallization but also perfected primary crystallization, and spinning and annealing temperature influenced the crystallinity of hollow fiber: the crystallinity decreased with the increase of spinning temperature; 140°C annealing increased the crystallinity, and hardly influenced the orientation of hollow fiber; above 150°C annealing increased the crystallinity as well, and furthermore had a comparative effect on the orientation. The tensile tests showed that the annealed samples, which did not present the obvious yield point, exhibited characteristics of hard elasticity, and all the hollow fiber had no neck phenomenon. Compared with the annealed sample, the precursor presented a clear yield point. In addition, the annealed samples had a higher break strength and initial modulus by contrast with the precursor, and the 140°C annealed sample showed the smallest break elongation. SEM demonstrated the micro‐fiber structure appeared in surface of drawn sample. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 935–941, 2007     

Thermal annealing‐induced superior toughness in polypropylene/poly(ethylene glycol) blend and its structural origin

In this study, a water‐soluble crystallizable polymer, poly(ethylene glycol) (PEG), was compounded with isotactic polypropylene (iPP), and a subsequent thermo‐annealing process was added to improve the toughness of iPP/PEG blend. By adding a small amount of PEG (5 wt%) into iPP, only a mild increment of 40% in toughness was achieved. However, the toughness of iPP/PEG (95/5) blend could be improved remarkably when the postprocessing procedure, thermal annealing, was utilized. For example, the notched impact strength of iPP/PEG blend annealed under 120°C for 12 h was five times of that of neat iPP. In addition, the tensile strength of annealed blend was slightly changed, compared with neat iPP. To ascertain the origin of toughening, various crystallographic and morphological/structural characterizations, including X‐ray diffraction, electron microscopy, and calorimeter were employed. A specific structural change, in which more and more amounts of micrometer/sub‐micrometer voids, yielded within the amorphous iPP region during the annealing process, was responsible for the prominent toughening behavior. POLYM. ENG. SCI., 53:2053–2060, 2013. © 2013 Society of Plastics Engineers     

Optothermal properties of fibers: 12‐Interferometric investigation for thermally treated viscose fibers

The present article studies the structure of annealed viscose fibers interferometrically at a constant temperature of 100 ± 1°C at different times. The Pluta polarizing interference microscope has been used for determining the mean refractive indices and mean birefringence. The results were used to calculate the optical orientation function and the angle of orientation. The value (Δα/3α₀), which depends on the molecular structure of the polymer, remains constant. Relationships between the mean refractive indices, birefringence, isotopic refgractive index, and polarizabilities per unit volume with different times were given for these fibers. The samples were subjected to X‐ray diffraction to clarify the variation of crystallinity with the annealing conditions. Differential thermal analysis measurements were used to determine the glass transition temperature of viscose fiber. Measurements of the volume swelling parameter of the viscose fibers with different liquids were given. Also, determinations of Cauchy's constants, dispersive power, and dielectric constant at infinity were carried out. Illustrations are given using graphs and microinterferograms. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 361–369, 1999     

AC breakdown of melt-crystallized isotactic polypropylene

The effect of polymer morphology on the dielectric breakdown of isotactic polypropylene was investigated under the influence of a ramped ac voltage. Samples were prepared by melt-pressing polypropylene beads into plaques and subsequently quenching or isothermally cyrstallizing these plaques. Some of the quenched samples were annealed at different temperatures to induce further crystallinity. The plaques were then characterized by wide-angle X-ray diffraction, density measurements, and differential scanning calorimetry. The 60 Hz, ac breakdown voltages of the samples were determined at 7°C, 23°C, and 45°C in a specially designed test cell. There was a lack of any significant effect on the ac breakdown strength of isotactic polypropylene of either the overall crystallinity or the crystallite thickness. This result can be understood in light of previous studies relating the electrical breakdown of polymers to morphology. It is postulated that the degree of crystallinity would influence the breakdown characteristics only when the amorphous regions constitute a small fraction of the total volume, that is, at very high crystallinity values—values beyond the range of the present study.     

Mechanical properties and superstructure of isotactic polypropylene fibers prepared by continuous vibrating zone‐drawing

A continuous vibrating zone‐drawing (CVZD) was applied to study the effect of vibration on the mechanical properties and superstructure of isotactic polypropylene fibers. The CVZD treatment was a new drawing method by which the fiber was continuously drawn at a rate of 0.5 m/min under vibration using the specially designed apparatus. The CVZD treatment was carried out in five steps at a drawing temperature of 150°C and a frequency of 100 Hz, and applied tensions increased step by step with processing in the range of 14.8 to 207 MPa. The obtained fiber had a birefringence of 0.0373, crystallinity of 62.4%, tensile modulus of 17.6 GPa, and tensile strength of 1.11 GPa. These values are higher than those of the continuous zone‐drawn isotactic polypropylene fiber previous reported. The vibration added to the fibers during the zone‐drawing was effective in developing amorphous orientation and improving the mechanical properties. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 600–608, 2001     

Formation and behaviour of low‐temperature melting peak of quenched and annealed isotactic polypropylene

The process of low‐melting point (LMP) α‐phase formation in a quenched and annealed isotactic polypropylene (iPP) was studied by means of differential scanning calorimetry. The influence of preparation conditions (quenching and annealing temperatures, annealing times and sample thickness), together with the measurement parameters (heating and cooling rates), on the iPP melting behaviour are analysed. The results reveal a constant yield of LMP crystals over a wide range of quenching temperatures. This study also suggests that the LMP α‐crystals originate from the crystallization of polymer portions, which are somewhere between the amorphous and the smectic phase on the macromolecular scale of order. © 2001 Society of Chemical Industry     

Optothermal properties of fibers. V. Optical anisotropy in silk fibers as a function of annealing process

Silk fibers (Best Yellow Italian Silk, Ford & Co. Ltd) were annealed at constant temperatures of 100 and 150°C for different times ranging from 1 to 10 h and for different temperatures ranging from 60 to 160 ± 1°C for a constant time of 2 h. Refractive indices and birefringence were measured interferometrically. Two Independent techniques were used to study the optical anisotropy in these fibers. The first technique was to study the effect of annealing on the swelling properties of fibers from its diffraction pattern using a He Ne laser beam. The second is the application of a double-refracting interference microscope. The double-beam technique is considered the most favorable technique in determining the mean re-fractive indices and the double refraction of the annealed samples. The behavior of optical properties at different annealing temperatures and times are discussed. The results obtained clarify that the reorientations occurred due to annealing at different conditions. Microin-terferograms and curves are given for illustration. © 1996 John Wiley & Sons, Inc.     

Effect of polypropylene fiber processing conditions on fiber mechanical behavior

An investigation into the mechanical behavior of melt‐spun isotactic polypropylene (iPP) fibers is reported. Two different iPP formulations, PH835 and Exxon3854, synthesized using Ziegler–Natta and metallocene catalysts, respectively, and spun at take‐up velocities ranging from 1000 to 3000 m min^?1 were subjected to uniaxial tensile loading, cyclic loading and creep tests. The strain rate sensitivity was determined by performing strain rate jumps. Injection molded specimens from the same iPP formulations were tested under the same conditions. The fiber birefringence increases slightly with increasing take‐up velocity, while the crystallinity is approximately insensitive to this process parameter in this range of velocities. Fibers from the two iPP samples behave differently at large plastic strains despite having the same birefringence and crystallinity. Differences are also seen in creep. The behavior of fibers is significantly different from that of the injection molded samples of the same iPP and same crystallinity. These have lower strain hardening rate, smaller failure strains, close to zero strain rate sensitivity and exhibit a yield point phenomenon. The difference is associated with the different nature and spatial organization of the crystals and inter‐crystalline amorphous and mesomorphic phases. © 2014 Society of Chemical Industry     

The role of dry and wet isothermal annealing treatment on the structure and the mechanical properties of isotactic polypropylene fibers

Dry and wet annealing of isotactic polypropylene fibers was carried out under constant length at 120°C in air and in glycerine environments with annealing times ranging from 1 to 30 h. A detailed analysis of the infrared spectrum of samples annealed, especially in air, showed clear evidence of the surface oxidation as indicated by the appearance of oxygen containing functional groups. Annealing was found to lead to an improved structural organization as indicated by the crystallinity, crystallite size, and orientation measurements using X‐ray diffraction and infrared spectroscopy methods. Analysis of the X‐ray diffraction measurements showed a gradual transformation of metastable smectic phase to a more stable α‐monoclinic phase with increasing annealing time. Crystallinity, crystallite size, and orientation measurements performed for the samples annealed in air and in glycerine environments showed no distinct difference. Mechanical properties of the annealed samples were influenced by the annealing environment. Annealing in an air environment resulted in a continuous loss of tensile strength up to the annealing time of 12 h due to an oxidation related chain scission mechanism. On the other hand, annealing in glycerine environment resulted in a continuous and gradual increase of tensile strength without loss of physical form up to the annealing time of 30 h. It is suggested that wet annealing in glycerine environment should be used to obtain improved tensile strength values. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Drawing and annealing of polypropylene fibers: Structural changes and mechanical properties

A study has been carried out on the influence of cold drawing (25°C), hot drawing (140°C), and annealing (140°C) on the structure and mechanical properties of a series of four different well-characterized melt spun polypropylene filaments. The influence of the interaction between melt spinning and drawing variables was given special attention. Cold drawing increased the orientation in the samples, disrupts the initial monoclinic crystal structure and the morphology of the filaments, and it results in extensive fibrillation. Annealing restored the monoclinic structure but eliminated only a small part of the fibrillation. Hot drawing produced changes which were qualitatively similar to the combined effects of cold drawing and annealing. The orientation and morphology of the asspun filaments were found to have major effects on drawing behavior and the mechanical properties of the drawn fibers for a given draw ratio. It was found, however, that the mechanical properties (tensile strength, tangent elastic modulus, and elongation to break) of the melt spun, hot drawn and cold drawn, and annealed fibers could all be correlated with birefringence measurements.