Raman microprobe spectra of spin-oriented and drawn filaments of poly(ethylene terephthalate)

Polarized Raman spectra of single filaments of spin-oriented and drawn fibres of poly(ethylene terephthalate) were recorded. Various Raman bands and their intensities correlated with (1) conformation of the glycol linkage, (2) orientation of the chains, and (3) crystallinity. Because the degrees of crystallinity and orientation were known from X-ray diffraction, density and optical birefringence, it became possible to identify features of the Raman spectra which correlated with each of the effects noted above. The degree of orientation, as a function of take-up speed or draw ratio, was correlated with the intensity ratios of the various polarization components. The appearance and increases in intensity of bands due to trans glycol conformations and the disappearance of the gauche bands with increasing orientation could be followed readily. It appears that many of the Raman bands earlier assigned to crystallinity in PET actually represent the trans conformation of the glycol group as is also observed in i.r. spectra. This conclusion is based on the observation that in spinoriented amorphous materials the trans conformation bands increase in intensity with increasing birefringence. Also an amorphous highly oriented fibre shows these same transconformation bands with high intensity. On the other hand, the width of the carbonyl band, which is the classical indicator of the amorphous or crystalline character of PET, confirmed the amorphous nature of this sample. In conclusion, by monitoring appropriate features of the Raman spectra of spin-oriented and drawn fibres, we have been able to confirm that orientation can occur independently of crystallization in PET.     

Effect of liquid isothermal bath position in modified poly(ethylene terephthalate) PET melt spinning process on properties and structure of As-spun and annealed filaments

The ability to produce as-spun poly(ethylene terephthalate) (PET) filaments that possess previously unsurpassed levels of as-spun orientation and tensile properties was achieved through the implementation of a device described as a liquid isothermal bath (LIB). Although much has been published regarding the general effect of the LIB on various properties and structural features, the results of the present study further contribute to the continued development of this unique technology by investigating the positional dependence of the device, as well as the effect of a subsequent annealing process. Characterization methods employed in the present study included birefringence, percent crystallinity, tensile properties, loss tangent temperature dependence, DSC melting behavior, and wide-angle and small-angle X-ray scattering. Strong inferences drawn from the loss tangent temperature dependence indicate that all of the as-spun and annealed LIB filaments possess a more rigid amorphous phase than that present in either the as-spun or annealed no LIB filament and that the extent of rigidness appears to become more profound as the bath is operated at a position more distant from the spinneret. DSC melting endotherms of the as-spun LIB filaments consist of dual overlapping peaks, one component of which is believed to represent the presence of a novel extended chain type of crystalline structure. Application of a simple two phase model allowed for the quantitative evaluation of an amorphous orientation factor, which was found to range, depending on the bath position, from 1.7 to 3.9 times higher in the as-spun LIB filaments than that present in the as-spun no LIB filament. The annealing process was found to play an important role in facilitating the transformation from an as-spun highly oriented and predominantly amorphous structure to a well-defined semicrystalline fibrillar structure. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2051–2068, 1998     

Fine structure and physical properties of polyethylene/poly(ethylene terephthalate) bicomponent fibers in high‐speed spinning. I. Polyethylene sheath/poly(ethylene terephthalate) core fibers

The high‐speed melt spinning of sheath/core type bicomponent fibers was performed and the change of fiber structure with increasing take‐up velocity was investigated. Two kinds of polyethylene, high density and linear low density (HDPE, LLDPE) with melt flow rates (MFR) of 11 and 50, [HDPE(11), LLDPE(50)], and poly(ethylene terephthalate) (PET) were selected and two sets of sheath/core combinations [HDPE(11)/PET and LLDPE(50)/PET bicomponent fibers] were studied. The fiber structure formation and physical property effects on the take‐up velocities were investigated with birefringence, wide‐angle X‐ray diffraction, thermal analysis, tensile tests, and so forth. In the fiber structure formation of PE/PET, the PET component was developed but the PE components were suppressed in high‐speed spinning. The different kinds of PE had little affect on the fine structure formation of bicomponent fibers. The difference in the mechanical properties of the bicomponent fiber with the MFR was very small. The instability of the interface was shown above a take‐up velocity of 4 km/min, where the orientation‐induced crystallization of PET started. LLDPE(50)/PET has a larger difference in intrinsic viscosity and a higher stability of the interface compared to the HDPE(11)/PET bicomponent fibers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2254–2266, 2000     

卷绕速度对PTT初生纤维结构与性能的影响

PTT特性粘数0.935 dL/g,卷绕速度2 500-4 000m/min,熔融纺丝制备PTT初生纤维(PTT/POY),研究了卷绕速度对其结构和性能的影响。结果表明:提高卷绕速度,PTT/POY的玻璃化温度、结晶度和密度提高,冷结晶温度和过热度降低;晶面距和晶粒尺寸略有增加,双折射先逐渐增加,达到最大值后降低,声速取向因子则逐渐增加,但非晶区取向大分子链的取向度随之减小。随卷绕速度的提高,PTT/POY的断裂强度和初始模量增加,而断裂伸长率和断裂比功降低。热拉伸倍数与卷绕速度有关,2 500~4 000 m/min时,应取1.18~1.57。     

Effect of recycling on the properties of poly(ethylene terephthalate) films

Different proportions of recycled poly(ethylene terephthalate) (PET) films were blended with virgin PET and evaluated for physicomechanical, chemical, thermal, optical and barrier properties. The safety evaluation of the films for food contact applications has also been carried out. The variations in properties, such as tensile behaviour, impact strength, tear resistance, burst strength, gloss, haze, barrier properties, crystallization temperature and melting temperature, are reported. © 2000 Society of Chemical Industry     

Blends of poly(ethylene terephthalate) and poly(butylene terephthalate)

Commercial grade poly(ethylene terephthalate), (PET, intrinsic viscosity = 0.80 dL/g) and poly(butylene terephthalate), (PBT, intrinsic viscosity = 1.00 dL/g) were melt blended over the entire composition range using a counterrotating twin‐screw extruder. The mechanical, thermal, electrical, and rheological properties of the blends were studied. All of the blends showed higher impact properties than that of PET or PBT. The 50:50 blend composition exhibited the highest impact value. Other mechanical properties also showed similar trends for blends of this composition. The addition of PBT increased the processability of PET. Differential scanning calorimetry data showed the presence of both phases. For all blends, only a single glass‐transition temperature was observed. The melting characteristics of one phase were influenced by the presence of the other. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 75–82, 2005     

Synthesis and characterisation of copolyesters from poly(ethylene terephthalate) and poly(hexamethylene terephthalate)

Copolyesters containing poly(ethylene terephthalate) and poly(hexamethylene terephthalate) (PHT) were prepared by a melt condensation reaction. The copolymers were characterised by infrared spectroscopy and intrinsic viscosity measurements. The density of the copolyesters decreased with increasing percentage of PHT segments in the backbone. Glass transition temperatures (T_g). melting points (T_m) and crystallisation temperatures (T_c) were determined by differential scanning calorimetry. An increase in the percentage of PHT resulted in decrease in T_g, T_m and T_c. The as-prepared copolyesters were crystalline in nature and no exotherm indicative of cold crystallisation was observed. The relative thermal stability of the polymers was evaluated by dynamic thermogravimetry in a nitrogen atmosphere. An increase in percentage of PHT resulted in a decrease in initial decomposition temperature. The rate of crystallisation of the copolymers was studied by small angle light scattering. An increase in percentage of PHT resulted in an increase in the rate of crystallisation.     

Modeling of solid-state polymerization of poly(ethylene terephthalate)

A mathematical model for solid-state polymerization of poly(ethylene terephthalate) was developed. The effects of temperature and chain entanglement on chain mobility were considered to estimate the rate constants of chemical reactions. The diffusivities of volatile byproducts could be determined using the free volume theory.^13,14 The model predictions were validated with experimental data reported in the literature. In addition, assuming that the concentration profiles of volatile byproducts in spherical particles are described by a sinusoidal function, the mass transfer rate of the byproducts at a given time could be derived as an ordinary differential equation that can be easily treated. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:837–846, 1998     

Spinning and properties of poly(ethylene terephthalate)/organomontmorillonite nanocomposite fibers

By in situ polycondensation, a intercalated poly(ethylene terephthalate)/organomontmorillonite nanocomposite was prepared after montmorillonite (MMT) had been treated with a water‐soluble polymer. This nanocomposite was produced to fibers through melt spinning. The resulting nanocomposite fibers were characterized by X‐ray diffraction (XRD), differential scanning calorimeter (DSC), and transmission electron microscopy (TEM). The interlayer distance of MMT dispersed in the nanocomposite fibers was further enlarged because of strong shear stress during processing of melt spinning. This was confirmed by XRD test and TEM images. DSC test results showed that incorporation of MMT accelerated the crystallization of poly(ethylene terephthalate) (PET), but the crystallinity of the drawn fibers just had a little increasing compared with that of neat PET drawn fibers. Also compared with pure PET drawn fibers, tensile strength at 5% elongation and thermal stability of the nanocomposite fibers were improved. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1443–1447, 2005     

Effect of poly(ethylene glycol) on the solid‐state polymerization of poly(ethylene terephthalate)

Poly(ethylene glycol) (PEG) and end‐capped poly(ethylene glycol) (poly(ethylene glycol) dimethyl ether (PEGDME)) of number average molecular weight 1000 g mol^?1 was melt blended with poly(ethylene terephthalate) (PET) oligomer. NMR, DSC and WAXS techniques characterized the structure and morphology of the blends. Both these samples show reduction in T_g and similar crystallization behavior. Solid‐state polymerization (SSP) was performed on these blend samples using Sb₂O₃ as catalyst under reduced pressure at temperatures below the melting point of the samples. Inherent viscosity data indicate that for the blend sample with PEG there is enhancement of SSP rate, while for the sample with PEGDME the SSP rate is suppressed. NMR data showed that PEG is incorporated into the PET chain, while PEGDME does not react with PET. Copyright © 2005 Society of Chemical Industry     

Uniaxial orientation and tensile properties of poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) blends

Amorphous films of poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) (PET/PEN) blends with different blend ratios were uniaxially drawn by solid-state coextrusion and the structure development during solid state deformation was studied. As-prepared blends showed two T_gs. The lower T_g was ∼72 °C, independent of the blend ratio. In contrast, the higher T_g increased with increasing PEN content. Thus, the coextrusion was carried out around the higher T_g of the sample. At a given draw ratio of 5, which was close to the achievable maximum draw ratio, the tensile strength of the drawn samples from the initially amorphous state increased gradually with increasing PEN content. On the other hand, the tensile modulus was found to decrease initially, reaching a minimum at 40-60 wt% PEN, and then increased as the PEN content increased. The results indicate that we can get the drawn films with a moderate tensile modulus and a high tensile strength. The drawn samples from the blends containing 40-60 wt% of PEN showed a maximum elongation at break, and a maximum thermal shrinkage around 100 °C. Also, the degree of stress-induced crystallinity showed a broad minimum around the blend ratio of 50% of PEN. These morphological characteristics explained well the effects of blend ratio on the tensile modulus and strength of drawn PET/PEN blend films.     

Effects of pH and Neutral Salts on the Adsorption of the Poly(ethylene glycol terephthalate) Condensates Toward Poly(ethylene terephthalate) Fiber

This study deals with the effects of pH and neutral salts on the adsorption of PET fiber with four kinds of poly(ethylene glycol terephthalate) condensated from dimethyl terephthalate (DMT) and poly(ethylene glycol) (PEG). The surface properties of the aqueous solution, the contact angle of polyol‐treated PET fabrics, and its parameters were also discussed. The pH of the solution or the adding of neutral salt in the polyol solution largely affected the contact angle of polyol‐treated PET fabrics as well as the surface tension of the solution. A lower pH of the polyol solution or adding neutral salts in the solution showed a lower surface tension and a lower contact angle that resulted in a better adsorption between polyol and poly(ethylene terephthalate) fibers. The lower pH of the solutions and a higher valence of the added neutral salt in the solution showed a largely positive effect on the adsorption parameters, and the order of effectiveness is Al₂(SO₄)₃ > MgSO₄ > Na₂SO₄.     

Mechanical properties of poly(ethylene terephthalate) modified with functionalized polymers

This study examined the effect of blending poly(ethylene terephthalate) (PET) with 5% of a functionalized polymer. The blends were characterized by particle size and size distribution, unnotched tensile behavior, toughness, and notch sensitivity. The improved properties of blends that incorporated a functionalized elastomer were consistent with in situ formation of a graft copolymer by reaction with PET end groups. Triblock copolymers were examined that had styrene end blocks and an ethylene/butylene midblock (SEBS) with grafted maleic anhydride. The present study extended previous investigations that focused on level of grafting to examine the effects of component molecular weight and PET hydroxyl‐to‐carboxyl end‐group ratio. Increasing the molecular weight of the SEBS and decreasing the hydroxyl‐to‐carboxyl ratio of the PET increased the effectiveness of the SEBS. In addition, a mix of an unfunctionalized SEBS with a functionalized SEBS was more effective than a single SEBS with the same total anhydride content. The same elastomers were the most effective for modifying a lower molecular weight PET (intrinsic viscosity 0.73) and a higher molecular weight PET (intrinsic viscosity 0.95). Some functionalized polypropylenes included in the study did not enhance the properties of PET. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 203–219, 1999     

Acetaldehyde scavengers and their effects on thermal stability and physical properties of poly(ethylene terephthalate)

The acetaldehyde (AA) scavenging abilities of poly(ethylene terephthalate) (PET) blends containing various concentrations of anthranilamide, meta-xylenediamine (MXDA), or alpha-cyclodextrin have been evaluated. It was found that higher AA scavenger concentrations generally resulted in greater reductions in detectable AA in terms of both the AA generation rates and residual AA contents. As little as 100 ppm, by weight, of anthranilamide and MXDA were respectively shown to reduce residual AA detected in PET preforms by 46% and 36%. Melt-blending 500 ppm of alpha-cyclodextrin, into PET, reduced preform residual AA concentration by 42%. The scavengers acted as PET nucleating agents causing more rapid crystallization while heating the blends from the glassy state and when cooling from the melt; however, they caused no changes in the glass transitions, melting characteristics, or oxygen permeation behaviors of the blends. Addition of optimal scavenger concentrations had minimal effects on preform intrinsic viscosity and color changes. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of shearing on crystallization behavior of poly(ethylene terephthalate)

The shear‐induced crystallization behavior of PET was investigated by measuring the time‐dependent storage modulus (G′) and dynamic viscosity (η′) with a parallel‐plate rheometer at different temperatures and shear rate. The morphology of shear‐induced crystallized PET was measured by DSC, X‐ray, and polarizing optical microscopy. When a constant shear rate was added to the molten polymer, the shear stress increased with the time as a result of the orientation of molecular chains. The induction time of crystallization is decreased with frequency. Moreover, the rate of isothermal crystallization of PET was notably decreased with increasing temperature. The shape of spherulites is changed to ellipsoid in the direction of shear. In addition, aggregation of spherulites is increased with increasing frequency. Particularly, the row nucleation morphology could be observed under polarized light for ω = 1. From the results of DSC, the melting point and enthalpy have a tendency to decrease slightly with increasing frequency. The crystallite size and perfectness decreased with frequency, which was confirmed with X‐ray data. The unit length of the crystallographic unit cell of the PET increased and the (1 0 3) plane peak increased with increasing frequency. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2640–2646, 2001     

Microstructure and crystallization of melt‐mixed poly(ethylene terephthalate)/poly(ethylene isophthalate) blends

Physical blends of poly(ethylene terephthalate) (PET) and poly(ethylene isophthalate) (PEI), abbreviated PET/PEI (80/20) blends, and of PET and a random poly(ethylene terephthalate‐co‐isophthalate) copolymer containing 40% ethylene isophthalate (PET₆₀I₄₀), abbreviated PET/PET₆₀I₄₀ (50/50) blends, were melt‐mixed at 270°C for different reactive blending times to give a series of copolymers containing 20 mol % of ethylene isophthalic units with different degrees of randomness. ¹³C‐NMR spectroscopy precisely determined the microstructure of the blends. The thermal and mechanical properties of the blends were evaluated by DSC and tensile assays, and the obtained results were compared with those obtained for PET and a statistically random PETI copolymer with the same composition. The microstructure of the blends gradually changed from a physical blend into a block copolymer, and finally into a random copolymer with the advance of transreaction time. The melting temperature and enthalpy of the blends decreased with the progress of melt‐mixing. Isothermal crystallization studies carried out on molten samples revealed the same trend for the crystallization rate. The effect of reaction time on crystallizability was more pronounced in the case of the PET/PET₆₀I₄₀ (50/50) blends. The Young's modulus of the melt‐mixed blends was comparable to that of PET, whereas the maximum tensile stress decreased with respect to that of PET. All blend samples showed a noticeable brittleness. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3076–3086, 2003     

Morphology and crystallization of poly(ethylene terephthalate)

The melting behaviour and the morphology of poly(ethylene terephthalate) crystallized from the melt are reported. In general, dual or triple melting endotherms are seen, and single endotherms are seen when the samples are crystallized above 215°C for long times. The location of the uppermost endotherm was found to be constant below T_c = 230°C, and above that temperature the location depends on T_c. Therefore, we have shown that samples of PET which are crystallized above T_c = 230°C contain perfect crystals only; below T_c = 230°C, they contain perfect and imperfect crystals. Scanning electron microscopy showed that the perfect crystals are the dominant lamellae in the spherulitic structure, while the imperfect crystals are the subsidiary lamellae in the spherulitic structure, The amorphous regions are located between individual lamellae.     

Activity of substrates in the catalyzed nucleation of poly(ethylene terephthalate) melts

The activity, Φ of AgBr, AgI, PbF₂, Ag₂S, LiF, and CaF₂ in the catalyzed nucleation of poly(ethylene terephthalate) (PET) melts was determined using a nonisothermal differential scanning calorimetry (DSC) technique. A comparison with existing experimental data was made. It is established that the higher the melting temperature of the substrate the lower its activity as a crystallization core in the heterogeneous nucleation of PET. The lateral surface energy, σ, the end surface energy, σ_e, the adhesion energy, β, and the difference between the surface energies at the substrate/melt, σ_sf, substrate/deposit, σ^*, and the total energy of misfit dislocations, E_d [i.e., σ_sf - (σ^* - E_d)] were calculated. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 349–353, 1997     

Phase structure and properties of poly(ethylene terephthalate)/high‐density polyethylene based on recycled materials

Blends based on recycled high density polyethylene (R‐HDPE) and recycled poly(ethylene terephthalate) (R‐PET) were made through reactive extrusion. The effects of maleated polyethylene (PE‐g‐MA), triblock copolymer of styrene and ethylene/butylene (SEBS), and 4,4′‐methylenedi(phenyl isocyanate) (MDI) on blend properties were studied. The 2% PE‐g‐MA improved the compatibility of R‐HDPE and R‐PET in all blends toughened by SEBS. For the R‐HDPE/R‐PET (70/30 w/w) blend toughened by SEBS, the dispersed PET domain size was significantly reduced with use of 2% PE‐g‐MA, and the impact strength of the resultant blend doubled. For blends with R‐PET matrix, all strengths were improved by adding MDI through extending the PET molecular chains. The crystalline behaviors of R‐HDPE and R‐PET in one‐phase rich systems influenced each other. The addition of PE‐g‐MA and SEBS consistently reduced the crystalline level (χ_c) of either the R‐PET or the R‐HDPE phase and lowered the crystallization peak temperature (T_c) of R‐PET. Further addition of MDI did not influence R‐HDPE crystallization behavior but lowered the χ_c of R‐PET in R‐PET rich blends. The thermal stability of R‐HDPE/R‐PET 70/30 and 50/50 (w/w) blends were improved by chain‐extension when 0.5% MDI was added. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of annealing treatments on the essential work of fracture of biaxially drawn poly(ethylene terephthalate)

The biaxial sequential stretching process of poly(ethylene terephthalate) produces films with a fibrillar microstructure in which fibrils are parallel to the transverse extrusion direction. The mechanical properties of such films are strongly anisotropic due to both the orientation of crystallites and the properties of the intrafibrillar and interfibrillar amorphous phases. The idea is to modulate the properties of the amorphous phase without altering the fibrillar structure by annealing treatments. The morphology (crystallinity and orientation of the crystalline phase) of the annealed films is characterized and their mechanical properties (tensile tests and essential work of fracture) are tested in the longitudinal direction (parallel to the micro fibrils) and in the transverse direction (perpendicular to the micro fibrils). The crystalline phase orientation is the key parameter governing modulus anisotropy. Concerning crack propagation, annealing treatments lead to opposite evolution of the specific essential work of fracture parameter (w_e) in the longitudinal and transverse directions. Thus, it is possible to erase fracture propagation anisotropy through an adequate annealing treatment. Copyright © 2012 Society of Chemical Industry