Retracted: Effect of surface‐treated TiO2 on non‐isothermal crystallization behavior of poly trimethylene terephthalate nanocomposites

The study of the non‐isothermal crystallization behavior of poly(trimethylene terephthalate) (PTT)/TiO₂ nanocomposites using untreated and surface‐treated TiO₂ has been carried out with different theoretical models. The PTT/untreated TiO₂ and surface‐treated TiO₂ nanocomposites were prepared employing batch mixing technique with an aim to investigate the influence of the TiO₂ dispersion on the crystallization behavior. The nucleation efficiency of the TiO₂ nanoparticles has been demonstrated with the use of Avrami and Jeziorny models. Test results indicated that the PTT matrix with surface‐treated TiO₂ particles has higher crystallization temperature and melting point than those with untreated PTT/TiO₂ nanocomposites. Unlike untreated TiO₂, surface‐treated TiO₂ particles also showed less effect on the degree of crystallization of the PTT matrix. The TiO₂ nanoparticles act as a nucleating agent in the PTT matrix by reducing the t_½ of the crystallization time, thus making it easy to form crystals. © 2012 Society of Plastics Engineers     

Mechanical properties and nonisothermal crystallization kinetics of polyamide 6/functionalized TiO2 nanocomposites

Titanium dioxide (TiO₂) nanoparticles were pretreated with excessive toluene‐2,4‐diisocyanate (TDI) to synthesize TDI‐functionalized TiO₂ (TiO₂‐NCO), and then polymeric nanocomposites consisting of polyamide 6 (PA6) and functionalized‐TiO₂ nanoparticles were prepared via a melt compounding method. The interfacial interaction between TiO₂ nanoparticles and polymeric matrix has been greatly improved due to the isocyanate ( NCO) groups at the surface of the functionalized‐TiO₂ nanoparticles reacted with amino groups ( NH₂) or carboxyl ( COOH) groups of PA6 during the melt compounding and resulted in higher tensile and impact strength than that of pure PA6. The nonisothermal crystallization kinetics of PA6/functionalized TiO₂ nanocomposites was investigated by differential scanning calorimetry (DSC). The nonisothermal crystallization DSC data were analyzed by the modified‐Avrami (Jeziorny) methods. The results showed that the functionalized‐TiO₂ nanoparticles in the PA6 matrix acted as effective nucleation agents. The crystallization rate of the nanocomposites obtained was faster than that of the pure PA6. Thus, the presence of functionalized‐TiO₂ nanoparticles influenced the mechanism of nucleation and accelerated the growth of PA6 crystallites. POLYM. COMPOS., 35:294–300, 2014. © 2013 Society of Plastics Engineers     

Non-isothermal crystallization kinetics of TiO2 nanoparticle-filled poly(ethylene terephthalate) with structural and chemical properties

The present research work includes non-isothermal crystallization kinetics of poly(ethylene terephthalate) (PET)–titanium dioxide (TiO₂) nanocomposites as well as structural and chemical properties of these nanocomposites. The average grain size of chemically synthesized TiO₂ nanoparticles has been calculated 19.31 nm by TEM and XRD. The morphology and structural analysis of PET–TiO₂ nanocomposites, prepared via solution casting method, has been investigated using SEM and XRD, respectively. The nature of chemical bonds has been discussed on the basis of FTIR spectra. The effect of TiO₂ nanoparticles and cooling rates on non-isothermal crystallization kinetics of PET was examined by differential scanning calorimetry at various heating and cooling rates. It has been observed that TiO₂ nanoparticles accelerate the heterogeneous nucleation in PET matrix. The crystallization kinetics could be explained through Avrami–Ozawa combined theory. TiO₂ nanoparticles cause to make molecular chains of PET easier to crystallize and accelerate the crystallization rates during non-isothermal crystallization process; this conclusion has also been verified by Kissinger model for crystallization activation energy.     

Isothermal crystallization kinetics and melting behaviors of nanocomposites of poly(trimethylene terephthalate) filled with nano‐CaCO3

The isothermal crystallization and subsequent melting behavior of poly(trimethylene terephthalate) (PTT) composites filled with nano‐CaCO₃ were investigated at designated temperatures with differential scanning calorimetry. The Avrami equation was used to fit the isothermal crystallization. The Avrami exponents were determined to be 2–3 for the neat PTT and PTT/CaCO₃ composites. The particles of nano‐CaCO₃, acting as nucleating agents in the composites, accelerated the crystallization rate, with the half‐time of crystallization decreasing or the growth rate constant (involving both nucleation and growth rate parameters) increasing. The crystallization activation energy calculated from the Arrhenius formula was reduced as the nano‐CaCO₃ content increased from 0 to 2%, and this suggested that nano‐CaCO₃ made the molecular chains of PTT easier to crystallize during the isothermal crystallization process. Subsequent melting scans of the isothermally crystallized composites exhibited triple or double melting endotherms: the greater the content was of nano‐CaCO₃, the lower the temperature was of the melting peak. The degree of crystallization deduced from the melt enthalpy of composites with the proper concentration of nano‐CaCO₃ was higher than that of pure PTT, but it was lower when the nano‐CaCO₃ concentration was more than 2%. The transmission electron microscopy pictures suggested that the dispersion state of nano‐CaCO₃ particles in the polymer matrix was even when its concentration was no more than 2%, whereas some agglomeration occurred when its concentration was 4%. Polarized microscopy pictures showed that much smaller or less perfect crystals formed in the composites because of the interaction between the molecular chains and nano‐CaCO₃ particles. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Nonisothermal crystallization behavior and crystals morphology of poly(trimethylene terephthalate)/nano‐calcium carbonate composites

Nonisothermal crystallization behavior and crystal morphology of poly(trimethylene terephthalate) (PTT) composites filled with modified nano‐calcium carbonate (CaCO₃) had been investigated by using differential scanning calorimetry and polarized optical microscopy. The modified Avrami equation and Ozawa theory were used to investigate the nonisothermal crystallization, respectively. The particles of nano‐CaCO₃, acting as a nucleation agent in composites, accelerated the crystallization rate by decreasing the half‐time of crystallization or increasing the parameters of Z_c and K(T). Moreover, the nano‐composite with 2 wt% nano‐CaCO₃ exhibited the highest crystallization rate. The Avrami and the Ozawa exponents, n and m of the nano‐composites, were higher than those of neat PTT, suggesting more complicated interaction between molecular chains and the nanoparticles that cause the changes of the nucleation mode and the crystal growth dimension. The effective activation energy calculated from the Friedman formula was reduced as nano‐CaCO₃ content increased, suggesting that the nano‐CaCO₃ made the molecular chains of PTT easier to crystallize during the nonisothermal crystallization process. The optical micrographs showed that much smaller or less perfect crystals were formed in composites because of the presence of the nano‐CaCO₃ particles. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Anionic nylon 6/TiO2 composite materials: Effects of TiO2 filler on the thermal and mechanical behavior of the composites

The nylon 6‐based composite materials containing untreated and surface‐treated TiO₂ particles with 3‐aminopropyltriethoxysilane (APTEOS), as coupling agent were prepared by in situ anionic polymerization of ε‐caprolactam in the presence TiO₂ as a filler using the rotational molding technique. The thermal behavior and mechanical properties of the neat nylon 6 and its composites were investigated using various techniques such as differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), a tensile and flexural test and impact strength. Experimental results revealed that both untreated and surface‐modified TiO₂ had distinct influence on the melting temperature (T_m), crystallization temperature (T_c), and degree of crystallinity (α_DSC), thermal stability, storage modulus (E′), and loss factor (tan δ), and mechanical properties of nylon 6 matrix. Dynamical mechanical analysis indicated that addition of TiO₂ particles into nylon 6 matrix increased both the storage modulus and the glass transition temperature. The corresponding values of nylon 6 composites with modified filler were higher than that of nylon 6 composite with untreated TiO₂ particles. Tensile and flexural characteristics of the nylon 6 composites were found to increase while the elongation at break and impact strength with increase in TiO₂ concentration relative to neat nylon 6. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

New kinetic models for the crystallization of anatase nanoparticles from amorphous titania (TiO2)

In this article, amorphous Titania (TiO₂) nanoparticles were crystallized both in a solution environment and by a dry heat treatment using new kinetic models with the capabilities of more accurately predicting the polymorphic transformation behavior of TiO₂. In these models, both the nucleation and growth processes were simultaneously taken into account. The results were indicative of the Surface Nucleation (SN) of anatase occurring in a hydrothermal treatment process through the phase transformation. Also, both the surface and interface nucleation processes were found to play significant roles in the phase transformation kinetics when dealing with dry heat treatments at low temperatures. The proposed models were advantageous to any other published models, in which the nucleation mechanisms had been incorporated with suitable growth expressions. In other words, no experimental data of a particle size were required to investigate the phase transformation kinetics of TiO₂ nanoparticles in the models presented in this article.     

Effect of SiO2 and TiO2 nanoparticle on the properties of phenyl silicone rubber

Two types of nanoparticles TiO₂ and SiO₂ treated with silane coupling agents were incorporated into phenyl silicone rubber at a low concentration (≤1.0%) and cured by the room temperature vulcanized method. The results showed that treated TiO₂ or SiO₂ nanoparticles improved the ultraviolet (UV)‐shielding ability and enhanced the visible transmittance of the phenyl silicone rubber, compared with their respective untreated particles. Moreover, when comparing treated nanoparticles, TiO₂ was more responsible for augmenting the UV‐shielding ability of the phenyl silicone rubber, while SiO₂ played a more important role in increasing the transmittance of visible light. Low levels of nanoparticles reduced the dielectric constant of the nanocomposite; however, on reaching a critical concentration, increasing the nanoparticle content had the opposite effect. The thermal conductivity of nanocomposites increased linearly with the amount of treated nanoparticles, while SiO₂ nanocomposites exhibited better thermal conductivity than those of TiO₂. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42806.     

Crystallization kinetics of poly(trimethylene terephthalate)/poly(ether imide) blends

The crystallization kinetics of a melt‐miscible blend, consisting of poly(trimethylene terephthalate) (PTT) and poly(ether imide) (PEI) prepared by solution precipitation, has been investigated by means of optical polarized microscopy and differential scanning calorimeter. It was found that both the PTT spherulitic growth rate (G) and overall crystallization rate constant (k_n) were depressed, with increasing PEI composition or crystallization temperature (T_c). The kinetic retardation was attributed to the decrease in PTT molecular mobility, and the dilution of PTT concentration due to the addition of PEI, which has a higher glass transition temperature (T_g). According to the Lauritzen–Hoffman theory of secondary nucleation, the crystallization of PTT in blends was similar to that of neat PTT as regime III, n = 4 and regime II, n = 2 growth processes, while the transition point of regime III to II has been shifted from 194°C for neat PTT to 190°C for blends. POLYM. ENG. SCI. 46:89–96, 2006. © 2005 Society of Plastics Engineers     

Crystallization behavior of poly(ϵ‐caprolactone)/Tio2 nanocomposites obtained by in situ polymerization

Poly(?‐caprolactone) (PCL)/titanium dioxide (TiO₂) nanocomposites were prepared by in situ polymerization of ?‐caprolactone in the presence of modified‐TiO₂ nanoparticles as initiators. The molecular weight of PCL matrix was dependent on the amount of the TiO₂ fillers. The incorporation of TiO₂ did not significantly affect the crystalline structure of PCL. Moreover, a tendency of the nanoparticles to form aggregates was observed, especially at higher fillers contents. The analysis of the crystallization process showed that the addition of TiO₂ nanoparticles accelerated the crystallization rate of PCL, and the crystallization rates increased by increasing the filler content. The crystallization activation energy dependence on the filler content observed here is probably the consequence of the two competing factors. The tendency of activation energy obtained by nonisothermal crystallization is similar to that of isothermal crystallization. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Effects of carbon‐coated titanium dioxide nanoparticles as a photostabilizer on the photodegradation of rigid poly(vinyl chloride)

In this study, nanocomposites of rigid poly(vinyl chloride) (UPVC) using the synthesized carbon‐coated titanium dioxide (TiO₂) nanoparticles and commercial powder of titanium dioxide (with rutile structure) were prepared by melt blending. The presence of carbon‐coated TiO₂ nanoparticles with rutile structure in UPVC matrix led to an improvement in photo stability of UPVC nanocomposites in comparison with commercial UPVC. The photocatalytic degradation behavior of nanocomposites was investigated by measuring their structural changes, surface tension, and mechanical and morphological properties before and after UV exposure for 700 h. It was found that mechanical and physical properties of UPVC nanocomposites are not considerably reduced after UV exposure in the presence of carbon‐coated TiO₂ nanoparticles even in small percentage of nanoparticles in comparison with the presence of commercial TiO₂ particles. Therefore, it can be concluded that UPVC/TiO₂ nanocomposite with low content of carbon‐coated TiO₂ nanoparticles(0.25 wt %) illustrated high stability under light exposure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40228.     

Crystallization of poly(ethylene oxide) embedded with surface‐modified SiO2 nanoparticles

The crystallization of poly(ethylene oxide) (PEO) in the presence of silica nanoparticles (SiO₂ NPs) was investigated in terms of heterogeneous nucleation of SiO₂ NPs using polarizing optical microscopy and differential scanning calorimetry. The content and surface functionality of SiO₂ NPs were considered as the main factors affecting crystallization, and the effect of annealing time and temperature was also examined. The SiO₂ NPs acted as heterogeneous nucleates during the crystallization process, thereby enhancing the nucleation density and limiting the spherulitic growth rate. A kinetics study of non‐isothermal crystallization showed that the crystallization rate of 5 wt% SiO₂/PEO nanocomposite was ca 2.1 times higher than that of neat PEO. In addition, among various surface‐functionalized SiO₂ nanoparticles, alkyl‐chain‐functionalized SiO₂ NPs were favorable for achieving a higher crystallization rate due to the enhanced compatibility between the SiO₂ NPs and PEO chains. © 2012 Society of Chemical Industry     

Overall crystallization behavior of polypropylene–clay nanocomposites; Effect of clay content and polymer/clay compatibility on the bulk crystallization and spherulitic growth

The effect of clay nanoparticles on the overall crystallization (isothermal crystallization, spherulitic growth, and nonisothermal crystallization) behavior of polypropylene (PP) was studied by means of differential scanning calorimetry and polarized light optical microscopy. In addition, the changes produced by the compatibility between the filler and the matrix were analyzed by using more hydrophobic clays or incorporating PP grafted with maleic anhydride (PP‐g‐MA). Different models were used to predict the relative degree of crystallinity and several parameters were analyzed. A clear nucleating effect of clay nanoparticles was found on the experimental behavior (induction time, half‐crystallization time, and overall crystallization time) and also deducted from the models parameters (Avrami exponent, rate constant, nucleation activity, activation energy). The effect was also related with the matrix/clay compatibility. In addition, the polarized light optical microscopy showed that the number of spherulites increased and their size decreased when clay was incorporated, which is also an indication of the heterogeneous nucleating behavior of such particles. We also noted faster spherulitic growth and increasing K_g (the model parameter). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Crystallization and spherulitic growth kinetics of poly(trimethylene terephthalate)/polycarbonate blends

The macroscopic and microscopic melt‐crystallization kinetics of poly(trimethylene terphthalate) (PTT)/polycarbonate (PC) blends have been measured by differential scanning calorimetry (DSC), and optical microscopy (OM). The results are analyzed in terms of the Avrami equation and the Hoffman–Lauritzen crystallization theory (HL model). Blending with PC did not change the crystallization mechanism of PTT, but reduced the crystallization rate compared with that of neat PTT at the same crystallization temperature. The crystallization rate decreased with increasing crystallization temperature. The spherulitic morphology of PTT was influenced apparently by the crystallization temperature and by the addition of PC. X‐ray diffraction shows no change in the unit cell dimension of PTT was observed after blending. Through the HL theory, the classical regime II→III transition was detected for the neat PTT and the blends. The nucleation parameter (K_g), the fold‐surface free energy (σ_e), and the work of chain folding (q) were calculated. Blending with PC decreased all the aforementioned parameters compared with those of neat PTT. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Effective incorporation of TiO2 nanoparticles into polyamide thin‐film composite membranes

The effectiveness of TiO₂ nanoparticles in improving the performance of polyamide (PA) thin‐film composite (TFC) membranes has been investigated. PA TFC membranes were prepared by interfacial polymerization with m‐phenylenediamine (MPD) and 1,3,5‐benzene tricarbonyl trichloride (TMC) where TiO₂ particles were added during and after interfacial polymerization. To distribute the TiO₂ nanoparticles uniformly in the PA films, colloidally stable TiO₂ sols were synthesized and added to the aqueous MPD solution rather than to an organic TMC solution. Through the use of different incorporation methods, TiO₂ particles were located on the top surface, in PA film layer, and in both positions. In the case of dense PA layers, the hydrophilicity of the membranes was significantly improved due to the presence of TiO₂ particles, resulting in an increased water flux. On the other hand, the enhancement of water flux was less significant when TiO₂ particles were incorporated into a loose PA film that was prepared with additives. In addition, a BSA fouling test confirmed that TiO₂ nanoparticles effectively improve the antifouling properties of the membranes for both dense and loose PA films. This effect is possibly due to increased hydrophilicity, covering of the fouling space, and a reduction in surface roughness. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43383.     

Physical properties and enzymatic hydrolysis of poly(L‐lactide)–TiO2 composites

Amorphous poly(L ‐lactide) (PLLA) composite films with titanium dioxide (TiO₂) particles were prepared by solution‐casting using methylene chloride as a solvent, followed by quenching from the melt. The effects of surface treatment, volume fraction, size, and crystalline type of the TiO₂ particles on the mechanical properties and enzymatic hydrolysis of the composite films were investigated. The tensile strength of the PLLA composite films containing TiO₂ particles except for anatase‐type ones with a mean particle size of 0.3–0.5 μm was lowered and the Young's modulus became higher with increasing the content of TiO₂ particles. The tensile strength of the composite films containing anatase‐type TiO₂ with a mean particle size of 0.3–0.5 μm at contents of 20 wt % or less was almost the same as that of the pure PLLA film. The enzymatic hydrolysis of PLLA matrix was accelerated by the addition of the hydrophilic anatase‐type TiO₂ particles (nontreated or Al₂O₃ treated) with a mean particle size of 0.3–0.5 μm at relatively high contents such as 20 wt %. On the other hand, the enzymatic hydrolysis of PLLA matrix was inhibited by composite formation with the hydrophobic rutile‐type TiO₂ particles (Al₂O₃‐stearic acid treated, or ZrO₂‐Al₂O₃‐stearic acid treated). These results suggest that the mechanical properties and enzymatic hydrolyzability of the PLLA can be controlled by the kind and amount of the added TiO₂ particles. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 190–199, 2005     

Effect of Inorganic Filler on the Crystallization,Mechanical Properties and Rheological Behavior of Poly(trimethylene terephthalate)

Poly(trimethylene terephthalate) filled with nano-CaCO₃ and ultra-fine talc was prepared by melt blending using a co-rotating twin screw extruder. The effect of these two inorganic filler on the crystallization and melting behavior, mechanical properties and rheological behavior of PTT were characterized. The DSC results indicated that both nano-CaCO₃ and ultra-fine talc exhibited heterogeneous nucleation effect on the crystallization of PTT, and more significant nucleation effect were observed in PTT/nano-CaCO₃ composite due to the smaller size and better dispersion of nano-CaCO₃ in PTT matrix. Mechanical properties study suggested that the incorporation of nano-CaCO₃ and ultra-fine talc greatly improved the tensile and flexural properties of PTT. Ultra-fine talc tends to lower the impact properties, while nano-CaCO₃ tend to increase the impact strength of the PTT/nano-CaCO₃ composite. When 2 wt.% of nano-CaCO₃ was added, the impact strength increased by one time. Rheological behavior study indicated nano-CaCO₃ exhibited plasticization effect on PTT melt and decreased the viscosity of PTT, while ultra-fine talc increased the viscosity of PTT due to the hindrance of the layer structure of talc.     

Characterization and crystallization behavior of poly(ethylene‐co‐trimethylene terephthalate) copolymers

A series of poly(ethylene‐co‐trimethylene terephthalate) (PETT) copolymers were prepared by polycondensation. The synthesized PETT are block copolymers and the content of poly(trimethylene terephthalate) (PTT) units incorporated into the copolymers are always larger than that fed in the polymerization. The nonisothermal crystallization at the different cooling rates was studied by means of differential scanning calorimetry. The copolymers develop the crystallization later and show the lower melting temperature than the corresponding enriched homopolymers. The modified Avrami analysis fit well the nonisothermal crystallization of these polymers. The overall rate of crystallization of PTT is fastest and that of PET is slowest, whereas the copolymers are between them at the same cooling rate. The minor PET units incorporated into PTT polymer chains reduce the crystallization of PTT segments, but the present minor PTT units in the PET chains seem to accelerate the crystallization of PET segments. The Avrami exponent nvaries in the range of 3 – 4, indicating that the nonisothermal crystallization follows the homogeneous nucleation and two‐ to three‐dimensional growth mechanism. Wide angle X‐ray diffraction analysis explains that the PET and PTT units do not cocrystallize and it is considered as the enriched polymer segments to crystallize during crystallization. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

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     

Surface modification of a calcium fluoride filler and the effect on the nonisothermal crystallization behavior of poly(ethylene terephthalate)

Two different types of calcium fluoride particles (～325 nm), one of them surface modified using a long‐chain organophosphorous reagent, were incorporated into a poly(ethylene terephthalate) (PET) matrix. The CaF₂ particles were synthesized by a simple chemical precipitation method. To modify the particles surface, a heat treatment using Cyanex^® 921 [tri‐n‐octylphosphine oxide (TOPO)] dissolved in isopropanol, was carried out. Therefore, unlike the as‐synthesized particles, the modified particles contained an amount of TOPO. The composite materials were prepared by melt‐blending PET and particles at different filler loadings. The influence of the particles surface modification on the nonisothermal crystallization behavior of PET was investigated by using differential scanning calorimetry and field emission scanning electron microscopy. The Jeziorny‐modified Avrami equation was applied to describe the crystallization kinetics and several parameters were analyzed (half‐crystallization time, Avrami exponent, and rate constant). According to the results, the fluorite particles act as nucleating agents, accelerating the PET crystallization rate. However, the effect on the polymer crystallization rate was more noticeable with the addition of the nonmodified particles where the surface might play an important role for epitaxial crystallization, while the addition of the particles, with an organic coating layer on the surface, resulted in a crystallization behavior more similar to the observed for neat PET. POLYM. ENG. SCI., 54:2938–2946, 2014. © 2014 Society of Plastics Engineers