Morphology,crystallization, and mechanical properties of poly(ethylene terephthalate)/multiwalled carbon nanotubes composites

Poly(ethylene terephthalate)/multiwalled carbon nanotubes (PET/MWCNTs) with different MWCNTs loadings have been prepared by in situ polymerization of ethylene glycol (EG) containing dispersed MWCNTs and terephthalic acid (TPA). From scanning electronic microscopy images of nanocomposites, it can be clearly seen that the PET/MWCNTs composites with low‐MWCNTs contents (0.2 and 0.4 wt %) get better MWCNTs dispersion than analogous with high‐tube loadings (0.6 and 0.8 wt %). The nonisothermal crystallization kinetics was analyzed by differential scanning calorimetry using Mo kinetics equation, and the results showed that the incorporation of MWCNTs accelerates the crystallization process obviously. Mechanical testing shows that, in comparison with neat PET, the Young's modulus and the yield strength of the PET nanocomposites with incorporating 0.4 wt % MWCNTs are effectively improved by about 25% and 15%, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

Preparation and crystallization of poly(ethylene terephthalate)/SiO2 nanocomposites by in‐situ polymerization

Poly(ethylene terephthalate) (PET)/SiO₂ nanocomposites were prepared by in situ polymerization. The dispersion and crystallization behaviors of PET/SiO₂ nanocomposites were characterized by means of transmission electron microscope (TEM), differential scanning calorimeter (DSC), and polarizing light microscope (PLM). TEM measurements show that SiO₂ nanoparticles were well dispersed in the PET matrix at a size of 10–20 nm. The results of DSC and PLM, such as melt‐crystalline temperature, half‐time of crystallization and crystallization kinetic constant, suggest that SiO₂ nanoparticles exhibited strong nucleating effects. It was found that SiO₂ nanoparticles could effectively promote the nucleation and crystallization of PET, which may be due to reducing the specific surface free energy for nuclei formation during crystallization and consequently increase the crystallization rate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 655–662, 2006     

Synthesis and properties of poly(ethylene terephthalate)/clay nanocomposites by in situ polymerization

Poly(ethylene terephthalate) (PET)/clay nanocomposites (PCNs) with N‐methyl diethanol amine (MDEA)‐based organoclays are synthesized by using in situ polymerization. Four kinds of MDEA‐based materials are prepared and used as organifiers of pristine montmorillonite. The clay treated with the organifiers has a d‐spacing range that is about 14–21 Å. The PCNs with these organoclays are characterized by using wide‐angle X‐ray diffraction, scanning and transmission electron microscopy, atomic force microscopy, capillary rheometry, and tensile and barrier testing. The PCNs form an intercalated and delaminated structure. The well‐stacked nanoclays are broken down into small pieces in the PET matrix and the thickness of the clay bundle decreases to 20 nm. The melt viscosity and tensile strength of these PCNs increases with only 0.5 wt % clay. In oxygen barrier testing, the PCN with 1 wt % well‐dispersed organoclay shows a twofold higher barrier property than pure PET. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1262–1271, 2007     

Poly(ethylene terephthalate) nanocomposite fibers with functionalized multiwalled carbon nanotubes via in-situ polymerization

Poly(ethylene terephthalate) (PET) hybrids with newly synthesized functionalized multiwalled carbon nanotubes (MWNTs) were obtained by carrying out the in situ polycondensation of ethylene glycol with dimethyl terephthalic acid. The PET hybrids were melt-spun to produce monofilaments with various functionalized MWNT contents and draw ratios (DRs). The thermomechanical properties and morphologies of the PET hybrid fibers were determined using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), wide angle X-ray diffraction (XRD), electron microscopy (SEM and TEM), and a universal tensile machine (UTM). The XRD analysis and TEM micrographs show that the levels of nanosize dispersion can be controlled by varying the MWNT content. It was found that the addition of only a small amount of functionalized MWNTs was sufficient to improve the properties of the PET hybrid fibers. The maximum enhancement in the ultimate tensile strength was found to arise at a functionalized MWNT content of 0.5 wt %. However, the initial modulus was found to increase linearly with increases in the functionalized MWNT loading from 0 to 1.5 wt %. The thermal properties and conductivities of the PET hybrid fibers were found to be better than those of pure PET fibers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and properties of poly(ethylene terephthalate)/ATO nanocomposites

Antimony doped tin oxide (ATO) nanoparticles modified poly(ethylene terephthalate) (PET) composites used for manufacturing antistatic PET fiber were synthesized by in situ polymerization. The crystallization and multiple melting behavior of the nanocomposites were systemically investigated by means of Differential Scanning Calorimeter (DSC), Fourier Transform Infrared (FTIR), X‐ray Diffraction (XRD) techniques. The degree of crystallinity in nanocomposites increased with increasing ATO content. Smaller and more incomplete crystals are presented in the crystalline regions of the nanocomposites with increasing the content of ATO, which could be attributed to heterogeneous nucleation effects of ATO nanoparticles. Dynamic Mechanical Analysis (DMA) measurements showed that the storage moduli of the nanocomposites increased with increasing the content of ATO, due to formation of immobilized layer between polymer and filler. The interactions between ATO and PET molecules result in high tan δ for the PET/ATO nanocomposites. Percolation threshold of PET/ATO hybrid fibers prepared by the nanocomposites at room temperature was as low as 1.05 wt %, much lower than that of the composites filled with conventional conductive particles. Adding ATO nanoparticles obviously improves the conductivity of PET. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Carbon nanotubes induced crystallization of poly(ethylene terephthalate)

We have investigated the crystallization characteristics of melt compounded nanocomposites of poly(ethylene terephthalate) (PET) and single walled carbon nanotubes (SWNTs). Differential scanning calorimetry studies showed that SWNTs at weight fractions as low as 0.03 wt% enhance the rate of crystallization in PET, as the cooling nanocomposite melt crystallizes at a temperature 10 °C higher as compared to neat PET. Isothermal crystallization studies also revealed that SWNTs significantly accelerate the crystallization process. WAXD showed oriented crystallization of PET induced by oriented SWNTs in a randomized PET melt, indicating the role of SWNTs as nucleating sites.     

Thermal and mechanical properties of poly(ethylene terephthalate)/lamellar zirconium phosphate nanocomposites

The preparation of nanocomposites of poly (ethylene terephthalate) (PET) and lamellar zirconium phosphorous compounds by melt extrusion was investigated. Two types of zirconium phosphorous compounds were synthesized by the direct precipitation reaction method: α‐zirconium bis(monohydrogen orthophosphate) monohydrate (ZrP) and organic–inorganic hybrid layered zirconium phenylphosphonate (ZrPP). Composites containing 2 and 5 wt % ZrP and ZrPP were prepared in a twin‐screw extruder and specimens were obtained by injection molding. The extent of dispersion of the layered filler in the composite matrix was investigated by X‐ray diffraction and transmission electron microscopy (TEM). The crystallization and thermal properties were analyzed by differential scanning calorimetry and thermogravimetry, and the mechanical properties were evaluated by tensile tests. Whereas ZrP‐containing composites showe characteristic diffraction peaks at 2θ 11.7° (d = 7.54 Å), indicative of no delamination, ZrPP showed practically no low‐angle diffraction peak at 2θ 5.5° (d = 15.24 Å), indicating loss of the layered order. TEM images of ZrPP particles indicated the formation of an intercalated/partially delaminated nanocomposite. The behavior was attributed to the higher affinity of the polyester with phenyl groups on the platelet surface of ZrPP. In both cases, the addition of the fillers increased the crystallization rate and the modulus. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3868–3876, 2006     

Morphology and electrical properties of carbon black/poly(ethylene terephthalate)/polypropylene composite

This work attempts to develop a carbon black (CB) filled conductive polymer composite based on poly(ethylene terephthalate) (PET) and polypropylene (PP). The process follows by localizing the CB particles in the minor phase (PET), and then the conductive masterbatch was elongated to form conductive microfibrils in PP matrix during melt extrusion process. After compression molding, a fine conductive three‐dimensional microfibrillar network is constructed. For comparison purpose, CB, PET, and PP are mixed using different pattern. The morphology and the volume resistivity of the obtained composites are evaluated. Electrical conductivity investigation shows that the percolation threshold and resistivity values are dependent on the CB concentration. The best morphological observation shows that the PET phases forms well‐defined microfibrils, and CB particles overwhelmingly localize in the surfaces of the PET microfibrils, which led to a very low percolation threshold, i.e., 4.5 phr, and a reasonable conductivity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

PEN/PET共混物结晶行为研究

用差示扫描量热法(DSC)研究了不同共混比例PEN/PET共混物的熔体结晶行为,并进行了等温结晶动力学测定。结果表明:随着两种组分向中间比例(50/50)靠近,共混物的熔融温度越低,结晶速率也越慢。     

Recycled poly(ethylene terephthalate)/layered silicate nanocomposites: morphology and tensile mechanical properties

Various amounts (1, 3 and 5 wt%) of a non-modified natural montmorillonite clay (Cloisite^® Na⁺) or of an ion-exchanged clay modified with quaternary ammonium salt (Cloisite^® 25A) were dispersed in a recycled poly(ethylene terephthalate) matrix (rPET) by a melt intercalation process. Microphotographs of composite fracture surfaces bring evidence that particles of Cloisite^® 25A are much better dispersed in the rPET matrix than those of Cloisite^® Na⁺. Moreover, WAXS measurements indicate that the lamellar periodicity of Cloisite^® 25A is increased in the composites, which evidences intercalation of rPET between silicate layers (lamellae) of the clay. In the case of Cloisite^® Na⁺, a very small thickening of lamellae due to mixing with rPET indicates only minute intercalation.Uniaxial tensile tests show that both clays increase the modulus of the rPET composites; more effective Cloisite^® 25A accounts for a 30% increase at loading of 5 wt%. Yield strength remains practically unaffected by the used fractions of the clays while tensile strength slightly decreases with the clay content; in parallel, strain at break dramatically drops. Tensile compliance of the composites is virtually independent of applied stress up to 26 MPa. Essential part of the compliance corresponds to the elastic time-independent component, while the viscoelastic component is low corresponding only to a few percent of the compliance even at relatively high stresses. The compliance of the composites is only slightly lower than that of the neat rPET, the reinforcing effect of Cloisite^® 25A being somewhat stronger. Both clays have beneficial effect on the dimensional stability of the composites since—in contrast to the neat rPET—the creep rate does not rise at long creep periods.     

Crystallization kinetics,structure, and rheological behavior of poly(ethylene terephthalate)/multilayer graphene oxide nanocomposites

This work aims to produce poly(ethylene terephthalate)/multilayer graphene oxide (mGO) nanocomposites via continuous melt mixing in twin-screw extrusion, and to study the changes in crystallization and melt flow behavior. Three mGO contents (0.05, 0.1, and 0.3 wt%) were used. Differential scanning calorimetry analyses showed that at 0.1 wt%, mGO acted best as nucleating agent, increasing the crystallization kinetics as well as the melt crystallization temperature (T_mc) by more than 20%. It was also observed that mGO increases the crystals perfection. The nucleating behavior was confirmed by X-ray diffraction and small angle X-ray scattering analyses, which showed a decrease in the composites' crystalline lamella thickness (l_c) and long period. X-ray microtomography data confirms that this behavior is significantly affected by the mGO agglomerates distribution and specific surface area inside the polymer matrix. The rheological behavior was studied under two different conditions. It was noticed that under lower shear stresses the mGO particles hinder the polymer flow, increasing the composites viscosity and the pseudo-solid character. However, under higher shear stresses, for example, when flowing through a die, the nanomaterial enters its “superlubricity state,” acting as a lubricant to the flow. This is industrially interesting, because it may allow the use of less severe processing parameters to produce the nanocomposites.     

Synthesis and characterization of poly(ethylene terephthalate)/attapulgite nanocomposites

A kind of clay with fibrous morphology, attapulgite (AT), was used to prepare poly (ethylene terephthalate) (PET)/AT nanocomposites via in situ polymerization. Attapulgite was modified with Hexadecyltriphenylphosphonium bromide and silane coupling agent (3‐glycidoxypropltrimethoxysilane) to increase the dispersion of clay particles in polymer matrix and the interaction between clay particles and polymer matrix. FTIR and TGA test of the organic‐AT particles investigated the thermal stability and the loading quantity of organic reagents. XRD patterns and SEM micrographs showed that the organic modification was processed on the surface of rod‐like crystals and did not shift the crystal structure of silicate. For PET/AT nanocomposites, it was revealed in TEM that the fibrous clay can be well dispersed in polymer matrix with the rod‐like crystals in the range of nanometer scale. The diameter of rod‐like crystal is about 20 nm and the length is near to 500 nm. The addition of the clay particles can enhance the thermal stability and crystallization rate of PET. With the addition of AT in PET matrix, the flexural modulus of those composites was also increased markedly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1279–1286, 2007     

Preparation and properties of deep dye fibers from poly(ethylene terephthalate)/SiO2 nanocomposites by in situ polymerization

In this study, poly(ethylene terephthalate) (PET)/SiO₂ nanocomposites were synthesized by in situ polymerization and melt‐spun to fibers. The superfine structure and properties of PET/SiO₂ fibers were studied in detail by means of TEM, DSC, SEM, and a universal tensile machine. According to the TEM, SiO₂ nanoparticles were well dispersed in the PET matrix at a size level of 10–20 nm. The DSC results indicated that the SiO₂ nanoparticles might act as a marked nucleating agent promoting the crystallization of the PET matrix from melt but which inhibited the crystallization from the glassy state, owing to the “crosslink” interaction between the PET and SiO₂ nanoparticles. The tensile strength of 5.73 MPa was obtained for the fiber from PET/0.1 wt % SiO₂, which was 17% higher than that of the pure PET. The fibers were treated with aqueous NaOH. SEM photographs showed that more and deeper pits were introduced onto PET fibers, which provided shortcuts for disperse dye and diffused the reflection to a great extent. According to the K/S values, the color strength of the dyeing increased with increasing SiO₂ content. It is found that the deep dyeability of PET fibers was improved greatly. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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 complicated influence of branching on crystallization behavior of poly(ethylene terephthalate)

The randomly branched poly(ethylene terephthalate) (BPET) was prepared by bulk polycondensation from dimethyl terephthalate (DMT) and ethylene glycol (EG), with 0.4–5.0 mol % (with respect to DMT) of glycerol (GL) as a branching agent. The glass transition and crystallization behavior was studied by differential scanning calorimetry (DSC). It was found that the glass transition temperature of BPET reduced with the increasing content of GL until 1.2 mol %, and then increases a little at high degrees of branching. When compared with a linear PET, the crystallization temperature of BPET from the melt shifted to higher temperature as GL content was smaller than 1.2 mol %, and then became lower while GL load was added. Nonisothermal crystallization kinetics was studied through the modified Avrami analysis. It was revealed that the overall crystallization rate parameter of BPET became larger when the GL content was less than 1.2 mol %, then turned to lower at higher branching degree. This indicated that low degree of branching could enhance the overall crystallization of poly(ethylene terephthalate) (PET), whereas high degree of branching in the range of 3.5–5.0 mol % would block the development of crystallization. On the basis of Hoffman's secondary crystallization theory, the product σσ_e of the free energy of formation per unit area of the lateral and folding surface was calculated. According to the change of the product σσ_e with the degree of branching, a possible explanation was presented to illuminate this diverse effect of different degrees of branching on crystallization. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of multiwall carbon nanotubes on thermomechanical and electrical properties of poly(trimethylene terephthalate)

Multiwalled carbon nanotubes (MWCNTs) were synthesized using chemical vapor deposition and poly(trimethylene terephthalate) (PTT)/MWCNT composites with varying amounts of MWCNTs were prepared by melt compounding using DSM micro‐compounder. Morphological characterization by SEM and TEM showed uniform dispersion of MWCNTs in PTT matrix upto 2% (w/w) MWCNT loading. Incorporation of MWCNTs showed no effect on percent crystallinity but affected the crystallite dimensions and increased the crystallization temperature. Dynamic mechanical characterization of composites showed an increase in storage modulus of PTT upon incorporation of MWCNTs above glass transition temperature. The electrical conductivity of PTT/MWCNT composites increased upon incorporation of MWCNTs and percolation threshold concentration was obtained at a loading of MWCNTs in the range of 1–1.5% (w/w). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Crystallization behavior of poly(ethylene terephthalate)/multiwalled carbon nanotubes composites

Crystallization behavior of poly(ethylene terephthalate)/multiwalled carbon nanotubes (PET/MWNTs) composites have been investigated under isothermal conditions and in comparison with the conventional nucleating agents, sodium benzoate, and micrometric carbon/glass fibers. In the PET/MWNTs composites, MWNTs promote the crystallization of PET as a heterogeneous nucleating agent, and the nucleation efficiency is greatly enhanced when MWNTs was homogeneously dispersed in PET matrix. In comparison with pure PET, spherulites size of PET/MWNTs composites is significantly reduced, and the shape becomes quite irregular. TEM images indicate that MWNTs bundles locate in the center of spherulites of PET and act as nuclei. Fold surface free energy during nucleation process for MWNTs nucleated PET is just half of pure PET, suggesting that MWNTs are efficient nucleating agents for PET. The sequence of nucleating ability of is given as follows: sodium benzoate>MWNTs>talc>carbon fibers≈glass fibers. The nucleation in the presence of sodium benzoate is a chemical nucleation process that may cause severe degradation of PET, but MWNTs nucleate PET through “particle effect,” which does not affect the molecular weight of PET. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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