Study of polystyrene/titanium dioxide nanocomposites via melt compounding for optical applications

This article presents the study of melt compounding of polystyrene (PS) with various types of titanium dioxide (TiO₂) nanoparticles and surfactants, using a corotating twin screw extruder with multiple screw element configurations. It was found that a properly designed high shear screw configuration and the copolymer of silicone, ethylene oxide, and propylene oxide‐based surfactant produced the greatest degree of nanoparticle dispersion in PS/TiO₂ nanocomposites, whereas a silane‐based surfactant and silicon dioxide (SiO₂) or aluminum oxide (Al₂O₃) coated TiO₂ nanoparticles yielded nanocomposites with the least photocatalytic degradation effects and the best retention of tensile and impact properties. POLYM. COMPOS., 28:241–250, 2007. © 2007 Society of Plastic Engineers     

Properties improvement of PMMA using nano TiO2

TiO₂ nanofillers (5 nm, 0–15% weight) have been introduced in the PMMA matrix using a twin screw extruder to increase the performance of PMMA. The twin screw extrusion process is optimized to disperse the particles into PMMA. Nanofiller infusion improves the thermal, mechanical, and UV absorption properties of PMMA. TiO₂‐PMMA nanocomposites exhibit the increase in tensile modulus (?90%), decomposition temperature (?31%), dimension stability (～ 60%) and UV absorption (～ 410%). Properties of the nanoTiO₂‐PMMA composites are depending on the dispersion of TiO₂ in the PMMA matrix. It is interrelated with loading. Formation and disappearance of the peaks in FTIR confirm the chemical interaction of PMMA with TiO₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Reactive extrusion processing of polypropylene/TiO2 nanocomposites by in situ synthesis of the nanofillers: Experiments and modeling

The effects of twin‐screw extrusion processing conditions upon the formation of polypropylene/titanium dioxide (PP/TiO₂) nanocomposites are investigated. To prepare PP/TiO₂ nanocomposites by limiting the problem of filler dispersion at the nanoscale, an original method was developed based on the creation of TiO₂ through hydrolysis–condensation reactions (sol–gel method) of titanium n‐butoxide precursor during PP extrusion. The feed rate, the screw speed, and the amount of inorganic precursor were varied independently. The conversion rate of precursor as a function of process parameters was quantified by gas chromatography and mass spectroscopy combined techniques through the assessment of the alcohol formed. The effects of processing conditions on the development of the sol–gel reaction have also been investigated by using numerical simulations. The comparison between experimental and theoretical results shows that this simulation approach is relevant to predict the conversion of the inorganic precursor to TiO₂ through hydrolysis–condensation reactions in molten PP. © 2011 American Institute of Chemical Engineers AIChE J, 2011     

Processing of polypropylene–clay nanocomposites: Single‐screw extrusion with in‐line supercritical carbon dioxide feed versus twin‐screw extrusion

This work investigates two different melt‐blending strategies for preparing compatibilized polypropylene‐clay nanocomposites, specifically: (1) conventional twin‐screw extrusion, and (2) single‐screw extrusion capable of direct supercritical carbon dioxide (scCO₂) feed to the extruder barrel. Proportional amounts (3 : 1) of maleic anhydride functionalized polypropylene compatibilizer and organically modified montmorillonite clay at clay loadings of 1, 3, and 5 wt % are melt‐blended with a polypropylene homopolymer using the two approaches. The basal spacing, degree of exfoliation, and dispersion of organoclay is assessed using X‐ray diffraction, transmission electron microscopy, and rheology. In terms of the latter, both steady shear and small‐amplitude oscillatory shear provide information about the apparent yield stress and solid‐like terminal behavior respectively. Finally, nanoindentation is performed to determine the room temperature modulus of each melt‐blended nanocomposite. The results reveal unequivocally that the high shear of the twin‐screw process is vastly superior to the single‐screw with in‐line scCO₂ addition in generating well‐exfoliated, percolated polypropylene‐clay nanocomposites. It is likely that increased contact time between clay and scCO₂ is necessary for scCO₂ to positively affect exfoliation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 884–892, 2007     

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.     

Balance of mechanical and electrical performance in polyimide/nano titanium dioxide prepared by an in‐sol method

Hybrid polyimide (PI)/titanium dioxide (TiO₂) films were prepared by in situ polymerization and sol–gel and in‐sol methods (where in‐sol method indicates that in situ polymerization and the sol–gel method were used in the same samples). The mechanical and electrical properties were found to be sensitive to the processing methods and the dispersion of nano titanium dioxide (nano‐TiO₂) in the PI matrix. For the PI/TiO₂ films prepared by the in situ polymerization method, their tensile strength increased with increasing TiO_{2‐in situ} (“TiO_{2‐in situ}” is “the TiO₂ nano‐particles prepared by in situ polymerization method”) concentration. However, the optimal corona lifetime of the PI/TiO₂ films was 15 min at 20 kHz and 2 kV because of poor dispersion. For the PI/TiO₂ films prepared by the sol–gel method, the corona lifetime reached 113 min because of superior dispersion and a tensile strength of about 19.63 MPa. A balance of mechanical and electrical performances was achieved with the in‐sol method. The corona‐resistant life of the PI/TiO₂ films was 43 min, which was about six times longer than that of the neat PI. Their tensile strength was 83.5 MPa; these films showed no decrease in this value compared with the pure PI films. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44666.     

Plasticized and nanofilled poly(lactic acid)‐based cast films: Effect of plasticizer and organoclay on processability and final properties

PLA‐based nanocomposites filled with the commercial organomodified montmorillonite Dellite 43B (D43B) and containing acetyl tri‐n‐butyl citrate (ATBC) as plasticizer were prepared by extrusion in a pilot‐scale twin‐screw extruder and melt casted into flexible films. A preliminary investigation was carried out in a laboratory batch mixer by varying blending conditions and addition procedures of the components. Indeed, the method of addition of ATBC and D43B considerably affected thermo‐mechanical properties and morphology of the resultant nanocomposites. The simultaneous introduction of both ATBC and D43B during the extrusion process allowed producing clearly exfoliated nanocomposite materials with modulated mechanical and thermal properties. Moreover, rheological results, obtained during melt extrusion, assessed the processability of nanofilled‐plasticized PLA, making this simple procedure interesting in view of the industrial production of nanostructured biomaterials based on plasticized PLA. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2013     

Surface modification of titanium dioxide nanoparticles by polyaniline via an in situ method

BACKGROUND: Nanoparticulate titanium dioxide (TiO₂) has the advantages of high chemical stability, high photocatalytic activity to oxidise pollutants in air and water, relatively low price and non‐toxicity. However, its high surface energy leads to the aggregation of nanoparticles. In addition, the wide band gap of TiO₂ (3.2 eV) only allows it to absorb ultraviolet (UV) light (<387 nm), which represents just a small fraction (3–5%) of the solar photons. These factors have limited its use in many fields. In this study, nanoparticulate TiO₂ was modified by polyaniline (PANI) in order to enhance its photoactivity under UV light and sunlight illumination. RESULTS: TiO₂ nanoparticles were modified by PANI via a chemical oxidative method. The introduction of small amounts of PANI enhanced the dispersion of TiO₂ nanoparticles and improved the photocatalytic activity under UV light. In addition, the band gap energies of all PANI/TiO₂ nanocomposites were lower than that of neat TiO₂ nanoparticles, so the PANI/TiO₂ nanocomposites can be excited to produce more electron–hole pairs under sunlight, which could result in higher photocatalytic activities. CONCLUSION: The modification of nanoparticulate TiO₂ by PANI can increase its photoactivity in the process of phenol degradation under UV light and sunlight illumination. Copyright © 2008 Society of Chemical Industry     

Mechanical,thermal, and morphological properties of injection molded poly(lactic acid)/SEBS‐g‐MAH/organo‐montmorillonite nanocomposites

Poly(lactic acid)/organo‐montmorillonite (PLA/OMMT) nanocomposites toughened with maleated styrene‐ethylene/butylene‐styrene (SEBS‐g‐MAH) were prepared by melt‐compounding using co‐rotating twin‐screw extruder followed by injection molding. The dispersibility and intercalation/exfoliation of OMMT in PLA was characterized using X‐ray diffraction and transmission electron microscopy (TEM). The mechanical properties of the PLA nanocomposites was investigated by tensile and Izod impact tests. Thermogravimetric analyzer and differential scanning calorimeter were used to study the thermal behaviors of the nanocomposite. The homogenous dispersion of the OMMT silicate layers and SEBS‐g‐MAH encapsulated OMMT layered silicate can be observed from TEM. Impact strength and elongation at break of the PLA nanocomposites was enhanced significantly by the addition of SEBS‐g‐MAH. Thermal stability of the PLA/OMMT nanocomposites was improved in the presence of SEBS‐g‐MAH. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Blown film extrusion of poly(lactic acid) without melt strength enhancers

Processing strategies were developed to manufacture poly(lactic acid) (PLA) blown films without melt strength enhancers (MSEs). The effects of processing temperature on PLA's melt properties (shear and elongational viscosities), PLA grades, and other processing conditions [ratio of take‐up roller to extruder's rotational screw speeds or processing speed ratio (PSR) and internal air pressures] on film's blow‐up ratio were examined. Experimental results indicate that extrusion‐blown amorphous and semicrystalline PLA films can be successfully manufactured without MSEs by controlling melt rheology through processing temperature and other extrusion processing conditions. PLA processed at lower extrusion temperature had higher melt viscosities, which favored the formation of stable films depending on the PSR and internal air pressure used. Inappropriate control of PSR and internal air pressure led to unstable films with various processing defects such as melt sag, bubble dancing, or draw resonance, irrespective of the lower extrusion processing temperature. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45212.     

Development of mesoporous titanium dioxide hybrid poly(vinylidene fluoride) ultrafiltration membranes with photocatalytic properties

A photocatalytic activity ultrafiltration membrane (UFM) was prepared by the blending of a poly(vinylidene fluoride) (PVDF) polymer with mesoporous titanium dioxide (M‐TiO₂) particles via the phase‐inversion method. The microstructure of the membrane and Ti element distribution were characterized by scanning electron microscopy and energy‐dispersive X‐ray spectroscopy. Their properties were also determined by thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, tensile stress tests, contact angle tests, bovine serum albumin retention, water flux, and permeation flux. When the M‐TiO₂ concentration reached 1 wt %, the thermal stability, mechanical properties, hydrophilicity, flux, and antifouling performance of the M‐TiO₂/PVDF UFM were improved to an optimal value with the M‐TiO₂ particles successfully entrapped and evenly distributed throughout the PVDF polymer matrix. Compared with the P25‐modified PVDF UFM (1 wt %), the M‐TiO₂‐modified PVDF UFM (1 wt %) exhibited better photocatalytic activity and wonderful stability in the UV photocatalytic degradation of the organic dye Rhodamine B. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43427.     

Enhanced electrical properties of polycarbonate/carbon nanotube nanocomposites prepared by a supercritical carbon dioxide aided melt blending method

Polycarbonate/carbon nanotube (CNT) nanocomposites were generated using a supercritical carbon dioxide (scCO₂) aided melt blending method, yielding nanocomposites with enhanced electrical properties and improved dispersion while maintaining the aspect ratio of the as-received CNTs. Baytubes^® C 150 P CNTs were benignly deagglomerated with scCO₂ resulting in 5 fold (5X), 10X and 15X decreases in bulk density from the as-received CNTs. This was followed by melt compounding with polycarbonate to generate the CNT nanocomposites. Electrical percolation thresholds were realized at CNT loading levels as low as 0.83 wt% for composites prepared with 15X CNT using the scCO₂ aided melt blending method. By comparison, a concentration of 1.5 wt% was required without scCO₂ processing. Optical microscopy, transmission electron microscopy, and rheology were used to investigate the dispersion and mechanical network of CNTs in the nanocomposites. The dispersion of CNTs generally improved with scCO₂ processing compared to direct melt blending, but was significantly worse than that of twin screw melt compounded nanocomposites reported in the literature. A rheologically percolated network was observed near the electrical percolation of the nanocomposites. The importance of maintaining longer carbon nanotubes during nanocomposite processing rather than focusing on dispersion alone is highlighted in the current efforts.     

Miscibility evolution of polycarbonate/polystyrene blends during compounding

The miscibility evolution of polycarbonate/polystyrene (PC/PS) blends during the compounding process in three blending methods of industrial relevance, namely melt blending, remelt blending in a twin‐screw extruder and third melt blending in an injection molding machine, was investigated by measuring their glass transition temperatures (T_g) and their specific heat increment (ΔC_p). Differential scanning calorimetry (DSC) was used to examine nine blend compositions. Shifts in glass transition temperature (T_g) of the two phases in melt‐mixed PC/PS blends suggest partial miscibility of one polymer in the other. The observed solubility strongly depends on blend composition and blending method. The T_g measurements showed maximum mutual solubility around 50/50 composition. The miscibility of PC/PS blended after the third stage (melt injection molding) was higher than that after the first stages (melt extrusion) and the second stages (remelt extrusion).     

Synthesis and dielectric properties of polyaniline/titanium dioxide nanocomposites

Two series of polyaniline–TiO₂ nanocomposite materials were prepared in base form by in situ polymerization of aniline with inorganic fillers using TiO₂ nanoparticles (P25) and TiO₂ colloids (Hombikat), respectively. The effect of particle sizes and contents of TiO₂ materials on their dielectric properties was evaluated. The as-synthesized polyaniline–TiO₂ nanocomposite materials were characterized by transmission electron microscopy (TEM), Fourier transform infrared (FTIR), thermal analysis (DTA/TGA), and X-ray diffraction (XRD). Dielectric properties of polyaniline–TiO₂ nanocomposites in the form of films were measured at 1 KHz–1 MHz and a temperature range of 35–150 °C. Higher dielectric constants and dielectric losses of polyaniline–TiO₂ nanocomposites than those of neat PANI were found. PANI–TiO₂ nanocomposites derived from P25 exhibited higher dielectric constants and losses than those from Hombikat TiO₂ colloids. Electrical conductivity measurements indicate that the conductivity of nanocomposites is increased with TiO₂ content. The dielectric properties and conductivities are considered to be enhanced due to the addition of TiO₂, which might induce the formation of a more efficient network for charge transport in the base polyaniline matrix.     

Conducting polyaniline‐titanium dioxide nanocomposites prepared by inverted emulsion polymerization

Conducting polyaniline (PAni)‐titanium dioxide (TiO₂) nanocomposites have been synthesized by the inverted emulsion polymerization method. Aqueous mixtures of aniline, a free‐radical oxidant, and/or TiO₂ nanoparticles (∼25 nm in diameter; mixture of anatase and rutile) are utilized to synthesize the hybrid nanocomposites. The polymerization is carried out in an organic solvent (chloroform, CHCl₃) in the presence of a protonic acid (hydrochloric acid, HCl) as a dopant and an emulsifier (cetyl trimethylammonium bromide). The resultant PAni‐TiO₂ nanocomposites are characterized with their structural, morphological, conducting, and optical properties. SEM and TEM images represent the PAni‐TiO₂ nanocomposites with the diameter range of 50–200 nm. Electrical conductivities are checked by standard four‐point probes method and found to be 0.38 S/cm for bulk PAni and 0.11 S/cm for PAni‐TiO₂ nanocomposites. UV–visible absorption shows two electronic bands at about 320 and 596 nm for bulk PAni and the blue‐shifted bands with the intensity changes due to the formation of PAni‐TiO₂ composites. Thermogravimetric analysis reveals that the composites have a higher degradation temperature than the PAni alone. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Supercritical CO2 as an exfoliating aid for nanocomposite preparation: Comparison of different processing methodologies

This article examines several new methods for compounding nanocomposite materials by twin screw extrusion that use supercritical CO₂ as a processing aid to produce more highly exfoliated polyolefin‐layered silicate nanocomposites than conventional melt intercalation. These methods varied the manner in which the plasticizing behavior of CO₂ influences the surfactant of an organoclay, the compatibilizer, and the matrix during preparation of a polyolefin nanocomposite. The results have shown that targeting CO₂ to the organoclay‐compatibilizer interface can improve the extent of intercalation. However, reduced performance was observed when CO₂ was introduced predominantly to the matrix or neat organoclay. In general, the different techniques of addition for CO₂ did bring about greater structural changes to the organoclay, but the stiffness of the resulting materials was lower than simply following a conventional melt intercalation approach. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Structure and properties of composite films prepared from cellulose and nanocrystalline titanium dioxide particles

Composite films were successfully prepared from cellulose and two kinds of nanocrystalline TiO₂ particles in a NaOH/urea aqueous solution (7.5 : 11 in wt %) by coagulation with H₂SO₄ solution. The structure, morphology, and properties of the films were characterized by transmission electron microscopy, scanning electron microscopy, X‐ray diffraction, TGA, tensile testing, UV–vis spectroscopy, and antibacterial test. The results indicated that TiO₂ particles in a cellulose matrix maintained the original nanocrystalline structure and properties. TiO₂(I) (anatase) and TiO₂(II) (the mixture of anatase and rutile) particles exhibited a certain miscibility with cellulose. The tensile strength of two kinds of composite films was higher than 70 and 75 MPa, when the content of TiO₂(I) and TiO₂(II) was 4 and 11 wt %, respectively. The cellulose composite films containing nanocrystalline TiO₂ particles displayed distinct antibacterial abilities and excellent UV absorption. This work provides a potential way for preparing functional composite materials from cellulose and inorganic nanoparticles in a NaOH/urea aqueous solution, without a destruction of the structure and properties of the particles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3600–3608, 2006     

Preparation and characterization of high melt strength polypropylene with long chain branched structure by the reactive extrusion process

The reactive extrusion of maleic anhydride grafted polypropylene (PP‐g‐MAH) with ethylenediamine (EDA) as coupling agent is carried out in a corotating twin‐screw extruder to produce long chain branched polypropylene (LCBPP). Part of PP‐g‐MAH is replaced by maleic anhydride grafted high‐density polyethylene (HDPE‐g‐MAH) or linear low‐density polyethylene (LLDPE‐g‐MAH) to obtain hybrid long chain branched (LCB) polyolefins. Compared with the PP‐g‐MAH, PE‐g‐MAH, and their blends, the LCB polyolefins exhibit excellent dynamic shear and transient extensional rheological characteristics such as increased dynamic modulus, higher low‐frequency complex viscosity, broader relaxation spectra, significantly enhanced melt strength and strain‐hardening behaviors. The LCB polyolefins also have higher tensile strength, tensile modulus, impact strength and lower elongation at break than their blends. Furthermore, supercritical carbon dioxide (scCO₂) is constructively introduced in the reactive extrusion process. In the presence of scCO₂, the motor current of the twin extruder is decreased and LCB polyolefins with lower melt flow rate (MFR), higher complex viscosity and increased tensile strength and modulus can be obtained. This indicates that the application of scCO₂ can reduce the viscosity of melt in extruder, enhance the diffusion of reactive species, and then facilitate the long chain branching reaction between anhydride group and primary amine group. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Rheological,mechanical, optical,and transport properties of blown films of polyamide 6/residual monomer/montmorillonite nanocomposites

Exfoliated nanocomposites of polyamide 6 (PA6) with residual monomer and an organically treated montmorillonite (3 and 5 wt %) were produced by twin‐screw extrusion. The composites had their steady state, dynamic, and transient rheological properties measured by parallel‐plates rheometry; their exfoliation level was characterized by wide angle X‐rays diffraction (WAXD) and transmission electron microscopy (TEM). The characterization showed as follows: (i) the nanoclay's lamellas were well dispersed and distributed thru the PA6, (ii) the postpolymerization of the residual monomer produced more branched chains than linear ones in the pure PA6, (iii) the nanoclay's lamellas acted as entanglement points in the nanocomposites, and (iv) the molecular weight of the PA6 in the nanocomposites decreased. Blown films of the nanocomposites were produced by single screw extrusion; the die pressure during the film blowing of the nanocomposites strongly decreased. The tensile mechanical properties of the blown films were also measured. Along the machine direction (MD), the best mechanical properties were obtained with the 5 wt % nanocomposite, whereas along the transverse direction (TD), the 3 wt % nanocomposite had the best behavior. The glass transition temperature (T_g) of the blown films was measured by dynamic mechanical thermal analyses (DMTA). The 5 wt % nanocomposite had the highest T_g of all the films. The optical properties were measured by spectrophotometry; the nanoclay decreased the films' haze, but the level of transmittance was not affected. The water vapor and oxygen permeability rates of the nanocomposites films were found to be lower than in the pure PA6 blown film as a result of a tortuosity effect. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Electrospun polyamide‐6 membranes containing titanium dioxide as photocatalyst

Electrospun polyamide‐6 membranes containing titanium dioxide (TiO₂) photocatalyst were prepared and characterized. By tailoring the electrospinning parameters it was possible to obtain membranes having two different thicknesses, namely 5 and 20 µm, in which TiO₂ particles were homogeneously dispersed. As a comparison, hybrid films made with polyamide‐6 matrix and TiO₂ filler were successfully produced, with inorganic/organic ratios of 10 and 20 wt%. The photocatalytic activity of both hybrid systems was evaluated by following the degradation of methylene blue as a target molecule as a function of UV irradiation time. A smoother degradation was recorded for the electrospun membranes with respect to the hybrid films probably due to a less exposed surface because of the highly porous structure. Even if a longer photodegradation time was necessary, the degradation of the dye was successfully achieved. Copyright © 2010 Society of Chemical Industry