Infrared spectroscopic investigation of the effects of titania photocatalyst on the degradation of linear low density polyethylene film for commercial applications

There is a need in industry for a commodity polyethylene film with controllable degradation properties that will degrade in an environmentally neutral way, for applications such as shopping bags and packaging film. Additives such as starch have been shown to accelerate the degradation of plastic films, however control of degradation is required so that the film will retain its mechanical properties during storage and use, and then degrade when no longer required. By the addition of a photocatalyst it is hoped that polymer film will breakdown with exposure to sunlight. Furthermore, it is desired that the polymer film will degrade in the dark, after a short initial exposure to sunlight. Research has been undertaken into the photo- and thermo-oxidative degradation processes of 25 ìm thick LLDPE (linear low density polyethylene) film containing titania from different manufacturers. Films were aged in a suntest or in an oven at 50 °C, and the oxidation product formation was followed using IR spectroscopy. Degussa P25, Kronos 1002, and various organic-modified and doped titanias of the types Satchleben Hombitan and Hunstsman Tioxide incorporated into LLDPE films were assessed for photoactivity. Degussa P25 was found to be the most photoactive with UVA and UVC exposure. Surface modification of titania was found to reduce photoactivity. Crystal phase is thought to be among the most important factors when assessing the photoactivity of titania as a photocatalyst for degradation. Pre-irradiation with UVA or UVC for 24 hours of the film containing 3% Degussa P25 titania prior to aging in an oven resulted in embrittlement in ca. 200 days. The multivariate data analysis technique PCA (principal component analysis) was used as an exploratory tool to investigate the IR spectral data. Oxidation products formed in similar relative concentrations across all samples, confirming that titania was catalysing the oxidation of the LLDPE film without changing the oxidation pathway. PCA was also employed to compare rates of degradation in different films. PCA enabled the discovery of water vapour trapped inside cavities formed by oxidation by titania particles. Imaging ATR/FTIR spectroscopy with high lateral resolution was used in a novel experiment to examine the heterogeneous nature of oxidation of a model polymer compound caused by the presence of titania particles. A model polymer containing Degussa P25 titania was solvent cast onto the internal reflection element of the imaging ATR/FTIR and the oxidation under UVC was examined over time. Sensitisation of 5 ìm domains by titania resulted in areas of relatively high oxidation product concentration. The suitability of transmission IR with a synchrotron light source to the study of polymer film oxidation was assessed as the Australian Synchrotron in Melbourne, Australia. Challenges such as interference fringes and poor signal-to-noise ratio need to be addressed before this can become a routine technique.

Low density polyethylene and grafted lignin polyblends using epoxy-functionalized compatibilizer: mechanical and thermal properties

Lignin was graft copolymerized with methyl methacrylate using manganic pyrophosphate as initiator. This modified lignin was then blended (up to 50 wt%) with low density polyethylene (LDPE) using a small quantity of poly[ethylene-co-(glycidyl methacrylate)] (PEGMA) compatibilizer. The mechanical properties of the blend were substantially improved by using modified lignin in contrast to untreated lignin. Differential scanning calorimetry studies showed loss of crystallinity of the LDPE phase owing to the interaction between the blend components. Thermogravimetric analysis showed higher thermal stability of modified lignin in the domain of blend processing. This suggested that there is scope for useful utilization of lignin, which could also lead to the development of eco-friendly products. (c) 2005 Society of Chemical Industry.

Effect of morphology on electrical treeing in low density polyethylene nanocomposites

Influence of polymer morphology on the inception and the growth of electrical trees in unfilled low density polyethylene (LDPE) as well as LDPE filled with 1, 3 and 5% by weight nanoalumina samples stressed with 50 Hz ac voltage has been studied. It is seen that there is a significant improvement in tree inception voltage with filler loading in LDPE filled with nanoparticles. Tree inception voltage increased with the filler loading up to 3% by weight nanoalumina loading and showed a reduction at 5% by weight loading. Change in tree growth patterns from branch to bush as well as a slower tree growth with increase in filler loading in LDPE alumina nanocomposites were observed. The degree of crystallinity and change in crystalline morphology induced by the presence of alumina nanoparticles in LDPE was studied using differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). DSC results show a similar melting behaviour for both unfilled LDPE and LDPE nanocomposites. However, there is a reduction in the degree of crystallinity for LDPE filled with 5% by weight nanoalumina. An increase in lamellae packing with increase in filler loadings and a highly disordered spherulitic structure for LDPE filled with 5% by weight nanoalumina was observed from the SEM images. The slow propagation of tree growth as well as reduction in tree inception voltage with increase in filler loadings were attributed to the morphological changes observed in the LDPE nanocomposites.

Preparation and properties of polyether pentaerythritol mono-maleate grafted linear low density polyethylene by reactive extrusion

A reactive type nonionic surfactant, polyether pentaerythritol mono-maleate (PPMM) was synthesized in our laboratory. PPMM was adopted as functionalizing monomer and grafted onto linear low density polyethylene (LLDPE) with a melt reactive extrusion procedure. FT-IR was used to characterize the formation of grafting copolymer and evaluate their degree of grafting. The effects of monomer concentration, reaction temperature and screw run speed on the degree of grafting were studied systematically. Isothermal crystallization kinetics of LLDPE and LLDPE-g-PPMM samples was carried out using DSC.

Preparation and Characterization of Melt Grafting 2-acrylamido-2-methyl-1-propanesulfonic Acid onto Pre-Irradiated Linear Low Density Polyethylene

Linear low density polyethylene (LLDPE) was functionalized with 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) by using -ray pre-irradiation in air in a twin-screw extruder. Fourier-transformed infrared spectroscopy (FT-IR) and electron spectroscopy for chemical analysis (ESCA) were used to characterize the formation of LLDPE-g-AMPS copolymers. The content of AMPS in LLDPE-g-AMPS was determined by using element analysis instrument. The effects of concentrations of monomer, reaction temperature and pre-irradiation dose on degree of grafting were investigated. The critical surface tension of LLDPE-g-AMPS was measured by using contact angle method. The influences of the degree of grafting on crystallization properties were studied by using DSC. Compared with neat LLDPE, the crystallization temperature increased about 4C, and crystallinity decreased with increasing degree of grafting. Crystallization rates of grafted LLDPE were faster than that of plain LLDPE at the same crystallization temperature.

Preparation and properties of a reactive type nonionic surfactant grafted linear low density polyethylene

A reactive type nonionic surfactant, monostearic acid monomaleic acid glycerol diester (MMGD) was synthesized in our laboratory. Grafting-copolymerization of linear low density polyethylene ( LLDPE) with MMGD was carried out by using beta ray irradiation in air in a twin-screw extruder. Evidence of the grafting of MMGD as well as its extent was determined by Fourier-transformed infrared (FT-IR) spectroscopy. The effects of monomer concentration, reaction temperature and screw run speed on degree of grafting were studied systematically. The thermal behavior of LLDPE-g-MMGD was investigated by using differential scanning calorimety ( DSC). Compared with neat LLDPE, the crystallization temperature ( Tc) of LLDPE-g-MMGD increased about 3 degrees C, and the melting enthalpy (Delta H-m) decreased with increase of MMGD content. It showed that the grafted MMGD monomer onto LLDPE acted as a nucleating agent. The tensile properties and light transmission of blown films were determined. Comparing with neat LLDPE film, no obvious changes could be found for the tensile strength, elongation at break and right angle tearing strength of LLDPE-g-MMGD film. The wettability is expressed by the water contact angle. With an increasing percentage of MMGD, the contact angles of water on film surface of LLDPE- g-MMGD decrease monotonically.

Preparation and properties of a novel nonionic surfactant grafted linear low density polyethylene

A novel nonionic surfactant, glycerol monostearic acid monomaleic acid diester (GMMD) was synthesized in our laboratory. Grafting-copolymerization of linear low density polyethylene (LLDPE) with GMMD was carried out by using P-ray irradiation in a twin-screw extruder. Evidence of the grafting of GMMD, as well as its extent, was determined by FT-IR. The effects of monomer concentration, reaction temperature and screw run speed on degree of grafting were studied systematically. The thermal behavior of LLDPE-g-GMMD was investigated by using differential scanning calorimety (DSC). Compared with neat LLDPE, the crystallization temperature (T,) of LLDPE-g-GMMD increased about 3 degrees C, and the melting enthalpy (Delta H-m) decreased with increase of GMMD content. It showed that the arafted GMMD monomer onto LLDPE acted as a nucleating agent. The tensile properties and light transmission of blown films were determined. Comparing with neat LLDPE film, no obvious changes could be found for the tensile strength, elongation at break and right angle tearing strength of LLDPE-g-GMMD film. Accelerated dripping property of film samples was investigated. The dripping duration of LLDPE-g-GMMD film and commercial anti-fog dripping film at 60 degrees C were 52 days and 17 days, respectively.

Low-density polyethylene superhydrophobic surface by control of its crystallization behavior

A simple and inexpensive method for forming a low-density polyethylene (LDPE) superhydrophobic surface by controlling the crystallization behavior of LDPE by adjusting the crystallization time and nucleation rate has been proposed. The resulting porous surface, with hierarchical micro- and nanostructures on the beautiful floral designs, has a water contact angle of 173.0degrees +/- 2.5degrees.

Effect of annealing on the viscoelastic and viscoplastic responses of low-density polyethylene

Two series of tensile tests with constant crosshead speeds (ranging from 5 to 200 mm/min) and tensile relaxation tests (at strains from 0.03 to 0.09) were performed on low-density polyethylene in the subyield region of deformations at room temperature. Mechanical tests were carried out on nonannealed specimens and on samples annealed for 24 h at the temperatures T = 50, 60, 70, 80, and 100 degreesC. Constitutive equations were derived for the time-dependent response of semicrystalline polymers at isothermal deformations with small strains. A polymer is treated as an equivalent heterogeneous network of chains bridged by temporary junctions (entanglements, physical crosslinks, and lamellar blocks). The network is thought of as an ensemble of mesoregions linked with each other. The viscoelastic behavior of a polymer is modeled as a thermally induced rearrangement of strands (separation of active strands from temporary junctions and merging of dangling strands with the network). The viscoplastic response reflects sliding of junctions in the network with respect to their reference positions driven by macrostrains. Stress-strain relations involve five material constants that were found by fitting the observations.

The viscoelastic and viscoplastic behavior of low-density polyethylene

Three series of tensile tests with constant cross-head speeds (ranging from 5 to 200 mm/min), tensile relaxation tests (at strains from 0.03 to 0.09) and tensile creep tests (at stresses from 2.0 to 6.0 MPa) are performed on low-density polyethylene at room temperature. Constitutive equations are derived for the time-dependent response of semicrystalline polymers at isothermal deformation with small strains. A polymer is treated as an equivalent heterogeneous network of chains bridged by temporary junctions (entanglements, physical cross-links and lamellar blocks). The network is thought of as an ensemble of meso-regions linked with each other. The viscoelastic behavior of a polymer is modelled as thermally-induced rearrangement of strands (separation of active strands from temporary junctions and merging of dangling strands with the network). The viscoplastic response reflects mutual displacement of meso-domains driven by macro-strains. Stress-strain relations for uniaxial deformation are developed by using the laws of thermodynamics. The governing equations involve five material constants that are found by fitting the observations. Fair agreement is demonstrated between the experimental data and the results of numerical simulation.

Electrically conductive, melt-processed ternary blends of polyaniline/dodecylbenzene sulfonic acid, ethylene/vinyl acetate, and low-density polyethylene

Although polyaniline (PANI) has high conductivity and relatively good environmental and thermal stability and is easily synthesized, the intractability of this intrinsically conducting polymer with a melting procedure prevents extensive applications. This work was designed to process PANI with a melting blend method with current thermoplastic polymers. PANI in an emeraldine base form was plasticized and doped with dodecylbenzene sulfonic acid (DBSA) to prepare a conductive complex (PANI-DBSA). PANI-DBSA, low-density polyethylene (LDPE), and an ethylene/vinyl acetate copolymer (EVA) were blended in a twin-rotor mixer. The blending procedure was monitored, including the changes in the temperature, torque moment, and work. As expected, the conductivity of ternary PANI-DBSA/LDPE/EVA was higher by one order of magnitude than that of binary PANI-DBSA/LDPE, and this was attributed to the PANI-DBSA phase being preferentially located in the EVA phase. An investigation of the morphology of the polymer blends with high-resolution optical microscopy indicated that PANI-DBSA formed a conducting network at a high concentration of PANI-DBSA. The thermal and crystalline properties of the polymer blends were measured with differential scanning calorimetry. The mechanical properties were also measured.

Graft chain propagation rate coefficients of acrylic acid in melt graft copolymerization with linear low density polyethylene

Graft chain propagation rate coefficients (k(p.g)) for grafting AA onto linear low density polyethylene (LLDPE) in the melt in ESR tubes have been measured via Fourier transform infrared (FTIR) spectroscopy and electron spin resonance (ESR) spectroscopy in the temperature range from 130 to 170 degrees C. To exclude the effect of homopolymerization on the grafting. the LLDPE was pre-irradiated in the air by electron beam to generate the peroxides and then treated with iodide solution to eliminating one kind of peroxides, hydroperoxide. The monomer conversion is determined by FTIR and the chain propagation free-radical concentration is deduced from the double integration of the well-resolved ESR spectra, consisting nine lines in the melt. The temperature dependence of k(p.g) is expressed:The magnitude of k(p.g) from FTIR and ESR analysis is in good agreement with the theoretical data deduced from ethylene-AA copolymerization, suggesting this method could reliably and directly provide the propagation rate coefficient. The comparison of k(p.g) with the data extrapolated from solution polymerization at modest temperature indicates that the extrapolated data might not be entirely fitting to discuss the kinetics behavior in the melt.

Morphology, structure, and properties of in situ compatibilized linear low-density polyethylene/polystyrene and linear low-density polyethylene/high-impact polystyrene blends

Blends of linear low-density polyethylene (LLDPE) with polystyrene (PS) and blends of LLDPE with high-impact polystyrene (HIPS) were prepared through a reactive extrusion method. For increased compatibility of the two blending components, a Lewis acid catalyst, aluminum chloride (AlCl3), was adopted to initiate the Friedel-Crafts alkylation reaction between the blending components. Spectra data from Raman spectra of the LLDPE/PS/AlCl3 blends extracted with tetrahydrofuran verified that LLDPE segments were grafted to the para position of the benzene rings of PS, and this confirmed the graft structure of the Friedel-Crafts reaction between the polyolefin and PS. Because the in situ generated LLDPE-g-PS and LLDPE-g-HIPS copolymers acted as compatibilizers in the relative blending systems, the mechanical properties of the LLDPE/PS and LLDPE/HIPS blending systems were greatly improved. For example, after compatibilization, the Izod impact strength of an LLDPE/PS blend (80/20 w/w) was increased from 88.5 to 401.6 J/m, and its elongation at break increased from 370 to 790%. For an LLDPE/HIPS (60/40 w/w) blend, its Charpy impact strength was increased from 284.2 to 495.8 kJ/m(2). Scanning electron microscopy micrographs showed that the size of the domains decreased from 4-5 to less than 1 mum, depending on the content of added AlCl3.

Thermal properties and morphology of noncrosslinking linear low-density polyethylene-grafted acrylic acid

Noncrosslinking linear low-density polyethylene-grafted acrylic acid (LLDPE-g-AA) was prepared by melt-reactive extrusion in our laboratory. The thermal behavior of LLDPE-g-AA was investigated by using differential scanning calorimetry (DSC). Compared with neat linear low-density polyethylene (LLDPE), melting temperature (T-m) of LLDPE-g-AA increased a little, the crystallization temperature (T-c) increased about 4degreesC, and the melting enthalpy (DeltaH(m) ) decreased with an increase in acrylic acid content. Isothermal crystallization kinetics of LLDPE and LLDPE-g-AA samples were carried out by using DSC. The overall crystallization rate of LLDPE was smaller than that of grafted samples. It showed that the grafted acrylic acid monomer onto LLDPE acted as a nucleating agent. Crystal morphologies of LLDPE-g-AA and LLDPE were examined by using SEM. Spherulite sizes of LLDPE-g-AA samples were lower than that of LLDPE.

Characterization and properties of the neutral and doped blends of poly(3-dodecylthiophene) with low-density polyethylene

In this paper, the structures and properties of the neutral and doped blends of poly(3-dodecylthiophene) (P3DDT) with low-density polyethylene (LDPE) were investigated. Wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), Fourier transform infrared spectra (FTIR), and scanning electron microscopy (SEM) were used to characterize the structures and morphologies of the blends, and conductivity was also measured. It was found that separate crystallizations occur between P3DDT and LDPE. When the amount of P3DDT is small in the blend, it has the effect of a nucleation reagent and has some influence on the crystal structure. After doping, the interaction force between the molecular chains increases, and leads to a more compact packing and a more uniform dispersion in morphology. Through blending, the thermal stability of pure component could be greatly improved, especially when the P3DDT content is 5 wt %. The conductivity measurements indicate that the conductivity increases with the increase of the P3DDT composition and doping time.