Deterioration of polyethylene pipes exposed to water containing chlorine dioxide

Chlorine species used as disinfectants in tap water have a deteriorating effect on many materials including polyethylene. There are only very few scientific reports on the effect on polyethylene pipes of water containing chlorine dioxide. Medium-density polyethylene pipes stabilized with hindered phenol and phosphite antioxidants were pressure tested with water containing 4 ppm chlorine dioxide at 90 °C and pH = 6.8 as internal medium. The stabilizers were rapidly consumed towards the inner pipe wall; the rate of consumption was four times greater than in chlorinated water (4 ppm, pH = 6.8) at the same temperature. The depletion of stabilizer occurred far into the pipe wall. A supplementary study on a polymer analogue (squalane) containing the same stabilizer package showed that the consumption of the phenolic antioxidant was 2.5 times faster when exposed water containing chlorine dioxide than on exposure to chlorinated water. The subsequent polymer degradation was an immediate surface reaction. It was confirmed by differential scanning calorimetry, infrared spectroscopy and size exclusion chromatography that in the surface layer which came into contact with the oxidising medium, the amorphous component of the polymer was heavily oxidized leaving a highly crystalline powder with many carboxylic acid chain ends in extended and once-folded chains. Scanning electron microscopy showed that propagation of cracks through the pipe wall was assisted by polymer degradation.     

Radiation effects on dihydroxypropyl-chitosan

Dihydroxypropyl-chitosan (DHP-chitosan), a derivative of chitosan used in practical applications, is hardly soluble in water because of the strong intermolecular hydrogen bonding. In order to improve its even more advanced practical applications, some further modifications of the polymer using electron beam radiation technique were carried out. In the current work, diluted lactic acid was used to improve the solubility of DHP-chitosan as a subversive of hydrogen bonding. The effects of electron beam radiation on the DHP-chitosan in solid state and solution state were investigated. It was found that solid state and low concentrated solution state result in degradation and high concentrated solution state is favorable for crosslinking. And a simple, effective strategy to achieve a novel DHP-chitosan hydrogel without any crosslinking agents was developed in a high concentrated polymer solution system under irradiation.     

Kinetics of chlorine-induced polyethylene degradation in water pipes

The presence of chlorine in drinking water supplies in many countries creates the undesirable side effect of causing a relatively under investigated degree of polymer degradation in the polyethylene pipes used for transport. In order to predict pipe lifetimes and ensure safe water supplies, a kinetic model using data for the degradation rates of polyethylenes immersed in chlorine solutions, was developed. In order to replicate phenomena that normally occur very slowly at low concentrations of chlorine, accelerated ageing studies were necessary. These were carried out at high chlorine concentrations under well-defined experimental conditions (70, 400 and 4000 ppm). Results showed that, for the chlorine concentrations studied, a chain scission process associated with carbonyl formation is occurring. It was also shown that the rate of this degradation does not depend on the presence of stabilizer. A kinetic model, taking into account the chlorine concentration, is proposed in order to simulate the molar mass changes occurring. This will facilitate the prediction of the degree of polyethylene embrittlement and ultimately the lifetime.     

Long-term behavior of GFRP pipes: Optimizing the distribution of failure points during testing

The certification of glass-fiber reinforced plastic (GFRP) piping systems is regulated by normative standards in which test series of 10,000 h are needed to predict the residual property of the expected life (normally, 50 years). In this paper, optimization of statistical distribution of the test is proposed. This system involves using orthogonal design and test schemes lasting under 10,000 h. Experimental results for long-term ring-bending strain (S_b) of GFRP pipes from the standard test procedure indicated that this system is practical and effective. The estimation error when using the proposed method was consistently less than 8% if compared to the standard method.     

Partially resorbable composite bone plate with controlled degradation rate, desired mechanical properties and bioactivity

Rate of polymer degradation is very important for implantable biomaterials since controlling the degradation rate may complement the biological response and affected mechanical property requirements. In spite of numerous publications on the potential use of combinations of poly lactic acid/bioactive glass fillers for degradable bone plate, little information exists on the controlling degradation rate and its effects on the other aspects such as biomechanical compatibility, bioactivity, etc. Our previous study revealed that a composite bone plate consist of poly l-lactic acid/braided bioactive glass fibers has the initial mechanical properties near to cortical bone. In this study, degradation rate and mechanical behavior of the composite bone plate were assessed, and also degradation rate was controlled by using proper manufacturing process and improving bonding between matrix and reinforcement. Moreover, bioactivity of the composite was considered before and after controlling degradation rate, because of the important role of bioactivity and ion release in healing acceleration. Results showed that degradation process of the composite could be controlled properly. Strength of the treated composite decreased only about 5% through 2 weeks and about 35% after 8 weeks while, the strength loss for the untreated composites was about 50 and 70 percent after 2 weeks and 8 weeks of degradation respectively. Although calcium-phosphate formation on the surface of the composite was postponed in the treated samples, the bioactivity of the composite remained unchanged and bone-like apatite was formed on the composite surface which is important for the application of the composite in bone tissue environment.     

The effects of γ-radiation on the thermal, mechanical, and segmental dynamics of a silica filled, room temperature vulcanized polysiloxane rubber

RTV-5370 is a filled polydimethylsilxoane–polymethylphenylsiloxane copolymer system originally developed by Dow Corning and now supplied by Rhone Poulenc. There is a desire to develop lifetime assessments of this material for certification programs and as a model system for understanding other filled siloxane polymer systems. We have initiated aging studies on these materials by employing accelerated aging tests with exposure to Co-60 γ-radiation. The effects of radiation exposure have been investigated by thermal (differential scanning calorimetry), mechanical (dynamic mechanical analysis), chemical (solvent swelling), and segmental dynamics (nuclear magnetic resonance) methods. The data show that RTV-5370 undergoes predominately radiation-induced crosslinking reactions over the dose range investigated. These reactions reduce the molecular weight between crosslinks, thereby hardening the composite and reducing the motional dynamics of segmental motion. DSC studies show dose dependent crystallization phenomena.     

Thermal properties of solvolysis lignin-derived polyurethanes

Thermal properties of polyurethane (PU) films prepared from solvolysis lignin (SL), polyethylene glycol (PEG) and diphenylmethane diisocyanate (MDI) were examined by differential scanning calorimetry and thermogravimetry. In the SL—PEG—MDI system, the SL content, the molecular weight (M_n) of PEG and the NCO/OH ratio were changed in order to control the thermal properties. Glass transition temperatures (T_g's) of the prepared PU's were dependent on the SL content, the M_n of PEG and the NCO/OH ratio. However, the T_g of PU was significantly influenced by the SL content: the increment of T_g was ca. 150 K when the SL content in PEG increased from 0 to ca. 50%. The decomposition of the PU's was markedly dependent on the content of SL. Other factors, such as the NCO/OH ratio and the M_n of PEG, are less dominant compared with the SL content. This fact suggests that the dissociation between the isocyanate groups and the phenolic OH groups in SL may be the major factor in the whole process of the thermal decomposition of the PU containing SL     

Structural effects on thermal properties and morphology in XLPE

This study investigated the morphological, thermal and mechanical changes with increasing crosslink density for two low density polyethylenes (LDPE). A reference LDPE was compared with an LDPE containing a higher number of vinyl groups that was introduced via a copolymerisation with a diene. During crosslinking, two reactions simultaneously occur in the copolymer, i.e. a reaction of the vinyl groups and combination crosslinking. After crosslinking with a low amount of peroxide, the majority of the crosslinks originate from reacted vinyl groups in the LDPE containing the higher number of vinyl groups, whereas the crosslinks in the reference LDPE originate from combination crosslinking, thus leading to different crosslinked structures for the two polymers. The melt temperature, crystallisation temperature, and degree of crystallinity were measured using a Differential Scanning Calorimeter. Thermal fractionation studies and morphology studies were also made. The Differential Scanning Calorimetry results show a decrease in those properties for both materials along with a concurrent change in the morphology when the crosslink density increased. The results deviate slightly between the materials.     

Influence of electron beam irradiation on physicochemical properties of poly(trimethylene carbonate)

Electron beam (EB) irradiation of poly(trimethylene carbonate) (PTMC), an amorphous, biodegradable polymer used in the field of biomaterials, results in predominant cross-linking and finally in the formation of gel fraction, thus enabling modification of physicochemical properties of this material without significant changes in its chemical structure. PTMC films (M_w: 167-553 kg mol⁻¹) were irradiated with different doses using an electron accelerator. Irradiation with a standard sterilization dose of 25 kGy caused neither significant changes in the chemical composition of the polymer nor significant deterioration of its mechanical properties. Changes in viscosity-, number-, weight-, and z-average molecular weights of PTMC for doses lower than the gelation dose (D_g) as well as gel-sol analysis and swelling tests for doses above D_g indicate domination of cross-linking over degradation. EB irradiation can be considered as an effective tool for increasing the average molecular weight of PTMC and sterilization of PTMC-based biomaterials.     

CI Reactive Black 5 dye as a visible crosslinker to improve physical properties of lyocell fabrics

Bi-functional reactive dyes have been used for reducing the fibrillation of lyocell fibres. The sole influence of CI Reactive Black 5 dye on the fibrillation tendency of lyocell single jersey knitted fabrics was investigated by dyeing with different concentrations (35 g/L for medium shade and 70 g/L for dark shade), dyeing without dyestuff and by decolouration process after each dyeing. The fibrillation tendency of lyocell fibres was accessed by means of fibre wet abrasion resistance and fibrillation number. Nitrogen content was used as indication of the amount of reactive dye in fabrics during dyeing and decolouration processes. The correlation between fibre fibrillation tendency and colour values of fabrics was found. Due to the fibrillation reduction, pilling formation in dyed lyocell fabrics was improved. As colour values can estimate the dye fixation and reduction in fabrics, reactive dye can be used as a visible marker for crosslinking effect on lyocell fabrics.     

Long term degradation of poly(?-caprolactone) films in biologically related fluids

The aim of this work was to study the long term degradation behaviour of poly(?-caprolactone) (PCL) films, potentially useful as substrates for tissue engineering, obtained by two different methods (compression moulding or casting in chloroform) in two biologically related media: phosphate buffered solution (PBS) and Dulbecco's modified Eagle's medium (DMEM). The films were characterized at different degradation times by differential scanning calorimetry (DSC), Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR). The molecular weight was determined by Gel Permeation Chromatography (GPC). Chemiluminescence (CL) was used to assess physical or chemical changes from the early stage of the degradation. A different behaviour is observed in samples immersed in PBS when compared with those treated in DMEM. In this medium, the degradation after one year and a half (18 months) shows that although the chemical structure has been modified, the layers become more fragile but maintain their consistency. A higher degradation rate is obtained for membranes obtained by casting with respect to those obtained by compression moulding.     

Study on composite membranes with high selective permeance properties

Flavonoids are natural products having several biological and physiological properties depending upon their molecular configurations. Flavonoids with similar configuration cannot be separated by traditional separation method and membrane separation technology whose selectivity is lower. This work investigates composite membranes with structural and functional molecular recognition properties prepared according to molecular imprinted technology. Functional silica sol was synthesized by taking luteolin as the template (or imprinting) molecule, γ-aminopropyltriethoxysilane (γ-APTS) as the functional monomer, and tetraethoxysilane (TEOS) as the cross-linker. The resultant functional silica sol was coated on Al₂O₃ microporous substrate followed by the removal of the template molecule. Scanning electron microscope micrographs showed a 5 μm thickness composite membrane with uniformly distributed porosity. Steady state flux was reached at ∼70 min at 215 L m⁻² h⁻¹ for the composite membrane, while a lower value of 168 L m⁻² h⁻¹ was measured for the blank membrane (i.e. non-templated). Further, in an aqueous mixture containing similar template molecules, the selectivity factor of luteolin to rutin was 14.1, thus suggesting that the imprinting process allowed for preferential permeance and affinity selectivity to the template molecule (i.e. luteolin). These results strongly suggest the formation of cavities, which are joined by channels to deliver the percolative effect for the permeation of luteolin. In addition to structural formation, further site recognition properties were accomplished by the functional silica sol in the composite matrix by electrovalent bonds. Considering the percolative effect in tandem with electrovalent bonds and under the influence of a concentration gradient (i.e. driving force), a mechanism of molecular recognition was proposed based on the molecular bond, followed by bond cutting and jumping to another site to form another molecular bond. The preparation method of the composite membrane was applied to other template molecules, and the template molecules can selectively permeate the membrane. So the method was universal for other substance. So it made it possible for the separation of the natural products exactly and efficiently. At the same time, it had great potential for the resolution of the chiral drugs and the preparation of the new membrane reactor.     

Effect of stress on the fire reaction properties of polymer composite laminates

A small-scale loading frame was used to apply tensile and compressive stresses to glass vinyl ester and glass polyester laminates in a cone calorimeter under a heat flux of 75 kW m⁻². It was found, for the first time, that stress has a small but significant effect on the fire reaction properties. Increasing tensile stress increased heat release rate and smoke production while shortening the time-to-ignition. Compressive stress had the reverse effect. This was attributed to the fact that tensile stress promotes the formation of matrix microcracks, facilitating the evolution of flammable volatiles. This hypothesis is further supported by the observation that stress has the greatest effect on the early heat and smoke release peaks, with a lower effect on the final ‘run-out’ values.Stress rupture (time-to-failure) curves were produced for tension and compression. In tension, the behaviour was fibre dominated, with times-to-failure being roughly 10 times those in compression. Compressive failure involved resin dominated local fibre kinking, initiated near to the rear face of the specimen. The failure time was determined by a significant proportion of the specimen reaching its glass transition temperature.     

Effect of preparation conditions on the optical and physical properties of an epoxy-functional inorganic-organic hybrid material system

A hybrid material system consisting of (3-glycidyloxypropyl)trimethoxysilane, dimethyldimethoxysilane and zirconium(IV) n-propoxide was prepared. The influence of processing parameters including Zr content, UV irradiation and sol ageing on the properties of the resultant thin films was discussed. Refractive index, at 633 nm, and reflectance measurements were performed and near-field waveguide images of the samples were taken. Optical propagation loss measurements, at 633 nm, were studied. Film thickness and cross-sectional scanning electron microscopy images were obtained as a function of process conditions. FT-IR spectroscopy was used to monitor chemical reaction pathways in the system during processing. It was demonstrated that the crosslinking of epoxy groups in the structure, along with inorganic network formation as a result of sol-gel reactions, was the primary reason for the changes in the optical and physical properties of the system. As Zr containing species and/or UV irradiation may be employed to crosslink the epoxy groups in the structure, the optical and physical properties of the system can be tuned by optimal combination of these two crosslinking methods, as well as sol ageing process.     

Gas transport properties of polypropylene/clay composite membranes

Polypropylene membranes modified with natural and organically modified montmorillonite clays were prepared. The permeability, diffusivity and solubility of helium, oxygen and nitrogen were determined for the unfilled and filled membranes over the temperature range 25-65 °C. Physical properties of polypropylene membranes were investigated using X-ray diffraction, thermogravimetric analyser, tensile testing and differential scanning calorimetry. The results showed that the filled membranes exhibit lower gas permeability compared to the unfilled polypropylene membrane. For helium, a reduced diffusivity is mainly responsible for the reduction in the permeability, in contrast, for nitrogen and oxygen, both diffusivity and solubility were reduced by the presence of fillers. The X-ray diffraction spectra showed that the incorporation of the unmodified and modified clay did not affect the crystallographic nature of polypropylene.     

Proton irradiation effects on the structural and tribological properties of polytetrafluoroethylene

Polytetrafluoroethylene (PTFE) was irradiated with protons in a ground-based simulation facility to study the effects of proton irradiation on the structural and tribological properties of PTFE. The structural changes were characterized by X-ray photoelectron spectroscopy (XPS) and attenuated total-reflection FTIR (ATR-FTIR), while the tribological properties were evaluated by friction and wear tests. It was found that proton irradiation induced the degradation of PTFE molecular chains, resulting in the increase of C concentration and the decrease in F concentration on the sample surfaces, and the surface chemical structure and morphology of the samples changed, which affected the friction coefficient and decreased the wear rate of the specimens as the friction and wear tests revealed.     

Controllable preparation and properties of composite materials based on ceria nanoparticles and carbon nanotubes

We report a method to prepare composites based on carbon nanotubes (CNTs) and CeO₂ nanoparticles (NPs). The CeO₂ NPs were attached to CNTs by hydrothermal treatment of Ce(OH)₄/CNT mixture in NaOH solution at 180 °C. It was found that larger CeO₂ NPs were formed in the presence of CNTs. Grain size of CeO₂ NPs in the composites can be reduced when NaNO₃ was added in the hydrothermal process. Electrochemical characterizations have shown that the composites possess a specific capacity between those of CNTs and CNTs mechanically mixed with CeO₂. These CeO₂/CNT composites could serve as promising anode materials for Li-ion batteries.     

Cyclodextrin effects on physical–chemical properties of novocaine

The UV-vis absorption and the fluorescence emission spectra of novocaine were analysed in aqueous cyclodextrin (CD) solutions. Either the absorbance read at λ_max 290 nm or the fluorescence emission intensity at λ_ems 346 nm increase in the presence of both α- and β-CD due to the formation of 1:1 inclusion complexes. The lower polarity of the CD-cavity sensed by the included drug enhances the emitted fluorescence; in fact, the same effect was observed in aqueous mixtures of acetonitrile, dioxane, or dimethylsulfoxide. The inclusion complex formation between the monocation of novocaine and CDs diminishes the electrical conductance of aqueous solutions of novocaine hydrochloride (NoHCl). Both the nitrosation reaction in aqueous acid medium and the ester hydrolysis in alkaline medium are retarded in the presence of CDs. The strongest effect was observed with β-CD as a consequence of the higher stability inclusion complex.     

Influence of monofunctional reactants on the physical properties of dimer acid‐based polyamides

Dimer acid‐based polyamides were synthesized by condensation polymerization in the absence and presence of monofunctional reactants. Acetic acid, oleic acid and propyl amine were used as monofunctional reactants. The influences of the equivalent percentage (E%) and type of monofunctional reactant on the physical properties of dimer acid‐based polyamides such as glass transition temperature (T_g), melting point (T_m), heat of fusion (ΔH), degree of polymerization (DP), number average molecular weight (M_n), and kinematic viscosity were investigated. The molecular weight and viscosity of dimer acid‐based polyamides decreased with the increase in equivalent percentage of monofunctional reactant. Differential scanning calorimetry (DSC) studies showed that acetic acid and propyl amine had higher effect on the thermal properties of polyamides than that of oleic acid. In the case of polyamides prepared in the presence of acetic acid, the values of T_g, T_m, and ΔH of the polyamides increased remarkably with the increase in acetic acid content. On the contrary, propyl amine had a decreasing effect on the values of T_g, T_m, and ΔH of the polyamides. Incorporation of oleic acid into the polymer structure had no significant effect on the values of T_g and T_m of the dimer acid‐based polyamides. Copyright © 2006 John Wiley & Sons, Ltd.     

Preparation and photochromic properties of pyrazolones/polyvinyl alcohol composite films

Novel photochromic composite films have been successfully fabricated by dispersing pyrazolone derivative:1,3-Diphenyl-4-(3-chlorobenzal)-5-hydroxypyrazole 4-phenylsemicarbazone (1a) into hydrosol of polyvinyl alcohol (PVA). The microstructure, photochromic behaviors and thermal bleaching properties were investigated by Raman spectroscopy, X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and ultraviolet-visible absorption spectroscopy (UV-vis). The results showed that 1a was not only blended but also well dispersed in the PVA polymer films with a suitable content of chromophore. Upon UV light irradiation, the composite films gradually changed from colorless to yellow and recovered fully to the initial state upon thermal bleaching. The time constants of photochromic reactions were almost the same as those of 1a observed in their crystalline state, indicating that the photochromic phenomenon is barely disturbed by the polymer matrix.