Photo-degradation and photo-oxidation of polyolefins: Importance of oxygen-polymer charge transfer complexes

The effect of prior irradiation (λ's > 300 nm) in an inert atmosphere on the subsequent photo-oxidative stabilities of polypropylene and low density polyethylene films has been examined using luminescence, infra-red and ultraviolet absorption techniques. Prior prolonged irradiation in an inert atmosphere of nitrogen was found to have no significant effect on the subsequent rates of photo-oxidation of the polymer films. The importance of oxygen-polymer charge transfer complexes in initiating photo-oxidation of the polymers is discussed in relation to the behaviour of other major photo-initiators such as carbonyl/unsaturated carbonyl and hydroperoxide groups.     

Vacuum Ultraviolet Irradiation of Polymers

The interest in incoherent sources for wavelength-selective photochemistry has increased lately, but little is still known about the behavior of polymers when exposed to far UV and vacuum UV (VUV) radiation. The same dearth of information exists regarding UV (VUV) radiation emitted by low-pressure plasmas during polymer treatment. In order to study VUV-UV effects on several polymers (polyethylene - PE, polystyrene - PS, hexatriacontane - HTC, and poly(methyl methacrylate) - PMMA), we have used the well-characterized emissions from hydrogen (broad-band emission) and hydrogen/argon mixture (near-monochromatic radiation) plasmas as light sources. During irradiation, samples were kept under vacuum or in a flow of pure oxygen at low pressure; in both cases the radiation fluxes at the sample position have been precisely determined by careful spectroscopic calibration experiments. We have employed a quartz crystal microbalance (QCM) to measure in-situ any possible mass change of the various polymers. Following irradiation, samples were analysed by ellipsometry (for thickness and refractive index), X-ray photoelectron spectroscopy (XPS, to evaluate the near-surface composition and content of various functional groups), and atomic force microscopy (AFM, for surface topography and roughness measurements).     

Light absorbing species in polyolefins: A fluorescence/derivative UV spectroscopy study

Further novel observations are reported on the nature of the hexane extractable fluorescent species in four polyolefins, namely low and high density polyethylene, polypropylene and poly (4-methylpent-1-ene). The concentration of fluorescent species extracted follows the order poly(4-methylpent-1-ene) > polypropylene > low density polyethylene ≡ high density polyethylene which follows closely the known photo-oxidation rates of the polymers. The total fluorescence spectrum is shown to be a complex mixture of several components and this is supported by second order derivative ultraviolet spectroscopy. Comparison of corrected fluorescence excitation spectra of the polymers with that of naphthalene shows several anomalies which suggest that the latter is not the major fluorescent species.     

Stress/strain analysis of polymeric materials by molecular dynamics simulations

Mechanical properties number themselves among the most important properties of any polymeric material used in engineering applications. The Molecular Mechanics approach has been used to calculate the mechanical moduli of various polymers, but this approach has the limitation of requiring experimental densities and neglecting both entropy contributions and local volume fluctuations which can be significant in condensed phase polymers such as glasses and melts. Although constant stress molecular mechanics can provide an estimate of the bulk density, constant stress molecular dynamics (CSMD) can overcome all these limitations. However, CSMD is limited by an inherently short simulation time scale. CSMD was used to calculate the bulk moduli, Young's moduli and density of various amorphous polymers, including: polyethylene, poly(propylene), polystyrene, poly(vinyl chloride), poly(ethylene terephthalate), poly(butylene terephthalate), nylon 6, poly(methyl methacrylate), polydimethylsiloxane, bisphenol-A polycarbonate, poly(phenylene sulfide). Results indicate that CSMD is a useful tool in characterizing mechanical properties of amorphous polymers despite this time scale limitation.     

ESCA study of polymer surfaces treated by plasma

Surfaces of polymers [polyethylene, polystyrene, poly(ethylene terephthalate), poly(oxymethylene), cellulose acetate, polyacrylonitrile, nylon 6, and polytetrafluoroethylene] treated with argon (inert) and nitrogen (reactive) plasma were examined by ESCA (electron spectroscopy for chemical analysis). Argon plasma treatment generally introduces oxygen functionalities into the polymer surface. Nitrogen treatment generally incorporates nitrogen and oxygen functionalities into the treated surface. The extent of oxygen incorporation is typically less than that produced by argon plasma. When nitrogen and oxygen functional groups are already in a polymer structure, the extent of additional incorporation of these two elements as a result of plasma treatment is very much less than with other polymers. Polymers which contain only one of the elements tend to incorporate the other element to much the same degree as polymers without either element initially present.     

Relation between free radicals and ultraviolet absorption in poly(methyl methacrylate)

A correlation between the radiation-induced nine-line electron spin resonance signal and the unstable component of the optical absorption in the near ultraviolet in poly(methyl methacrylate) is made on the basis of the radiation dose relationship, the dependence of production on irradiation temperature at a constant radiation dose, and on the fading of both signals on oxygen diffusion into the poly(methyl methacrylate) after irradiation. It is concluded that this correlation is applicable only immediately after irradiation and the stability of the initial radical is discussed with respect to the fading results. A process of radical decay and conversion is suggested to account for differences found in the fading characteristics of the two signals.     

Changes of surface chemical structure and composition of phenolphthalein poly(ether sulfone) in different radiations

To understand the different action mechanisms of space irradiation on polymers, phenolphthalein poly(ether sulfone) (PES‐C) blocks were irradiated by electrons and atomic oxygen. The changes in surface chemical structure and composition of PES‐C in different radiations were studied by attenuated total‐reflection FTIR (FTIR‐ATR) and XPS. It was found that PES‐C was prone to be influenced by space irradiation. Electron and atomic oxygen irradiation can destroy the molecular chain of PES‐C and result in changes of surface chemical composition of the polymer. But due to the different nature of the radiation sources, electron irradiation induced the carbonization of the polymer surface, while atomic oxygen irradiation resulted in the oxidation of the polymer surface. Besides this, the sulfone structure was reduced or oxidized depending on the nature of the radiation sources. So, different radiation sources might influence the surface chemical structure and composition of polymers differently. Copyright © 2008 John Wiley & Sons, Ltd.     

Dynamic evolution of gases in the γ‐ and helium‐ion radiolyses of solid polymers

The dynamic evolution of gaseous hydrogen, methane, and carbon dioxide in the γ‐ and ⁴He‐ion radiolyses of solid polymers was investigated. The polymers used include low‐density and high‐density polyethylene, polypropylene, polystyrene, poly(methyl methacrylate), Nylon 11, Nylon 6, and poly(dimer acid‐co‐alkyl polyamine). An inline quadrupole mass spectrometer was utilized to monitor the dynamic profiles of the gases produced in the radiolysis. One‐ and two‐dimensional numerical diffusion models were developed to simulate and extract optimum diffusion coefficients and gas yields from the experimental dynamic gas profiles. It was found that the dynamic evolution of molecular hydrogen from the bulk polymer is controlled by its diffusion in most cases, such as CO₂ in poly(methyl methacrylate). In the γ radiolysis of some polymers such as low‐density polyethylene and polypropylene, the dynamic evolution of methane is only partially controlled by the diffusion process, and some other postirradiation process is a factor. It is concluded that the simulation method developed in this article is helpful in understanding and predicting the mechanisms of gas evolution in the radiolysis of solid polymers. © 2001 John Wiley & Sons, Inc. J Polym Sci B Part B: Polym Phys 39: 1449–1459, 2001     

Infectious Behavior in Photo-oxidation of Polymers

When a polymer is used together with others,its aging process will be affected by the adjacent polymers.This infectious behavior between polymers makes the aging process more complex than that of an individual material.In this study,infectious behavior in photooxidation of polymers was investigated.Polypropylenes(PPs),an unstabilized PP and a commercial PP,were chosen as the infection sources.Six typical polymers,high density polyethylene(HDPE),low density polyethylene(LDPE),polystyrene(PS),polycarbonate(PC),poly(ethylene terephthalate)(PET),and polyamide 6(PA6),were used as the targets.The degree of oxidation of the targets was evaluated by attenuated total reflection-Fourier transform infrared spectroscopy(ATR-FTIR).An accelerating effect of two infection sources on the photo-oxidation of the target polymers was observed.Potential infectious agents from the infection sources were detected by pyrolysis-gas chromatography-mass spectrometry(Py-GC-MS)and gas chromatography(GC).The acceleration effect of two main infectious agents,i.e.acetone and acetic acid,on the photo-oxidation of the commercial PP was verified.The infectious effect of the infection source on the target polymer was considered to be a comprehensive result of the effects of a variety of infectious agents.     

The investigation on the effect of surface radiation oxidation of bamboo fiber‐filled PMMA composite

The aim of this investigation was to study the effect of surface thermal oxidation of bamboo/poly(methyl methacrylate) composite by irradiation. Thermal oxidative effects on the surface energy of bamboo fiber were measured by radiation as a function of exposure time and temperature. Oxidized bamboo/poly(methyl methacrylate), after exposure to air at temperatures of 100°C and 110°C, had a range of maximum surface energies from 38 to 41 mJ/m². Comparisons between Fourier transform infrared carbonyl peak growth and the surface energy showed that both methods detect oxidation, though the increase in surface energy was detected before the carbonyl peak growth was noticeable. The work of adhesion predicted by the surface free energies obtained in this work between a coated calcium carbonate and bamboo fiber changes by 10% due to the oxidation of the polymer at 110°C. The structural results were discussed in the oxidation chemistry of the macromolecule.     

Effective grafting of polymers onto ultrafine silica surface: Photopolymerization of vinyl monomers initiated by the system consisting of trichloroacetyl groups on the surface and Mn2(CO)10

The effective grafting of vinyl polymers onto an ultrafine silica surface was successfully achieved by the photopolymerization of vinyl monomers initiated by the system consisting of trichloroacetyl groups on the surface with Mn₂(CO)₁₀ under UV irradiation at 25 °C. The introduction of trichloroacetyl groups onto the surface of silica was achieved by the reaction of trichloroacetyl isocyanate with surface amino groups, which were introduced by the treatment of silica with 3‐aminopropyltriethoxysilane. During the polymerization, the corresponding polymers were effectively grafted onto the surface, based on the propagation of polymer from surface radicals formed by the interaction of trichloroacetyl groups and Mn₂(CO)₁₀. The percentage of poly(methyl methacrylate) grafting onto the silica reached 714.6% after 90 min. The grafting efficiency (proportion of grafted polymer to total polymer formed) in the polymerization of methyl methacrylate was very high, about 80%, indicating the depression of formation of ungrafted polymer. Polymer‐grafted silica gave a stable colloidal dispersion in good solvents for grafted polymer. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2157–2163, 2001     

Heat capacity of molten polymers

Heat capacities of molten polyethylene, polypropylene, poly-1-butene, polystyrene, and poly(methyl methacrylate) were measured over a wide range of temperature by using a differential scanning calorimeter. The upper limit of temperature was established for each polymer at about 10°K below the beginning of thermal decomposition. For poly-1-butene and poly(methyl methacrylate) the solid-state heat capacity was also measured starting from room temperature. Several samples of each polymer were used so that average values of heat capacities could be established (reported in 10°K intervals). The data revealed for all polymers a nearly linear increase of heat capacity with increasing temperature over the whole temperature range investigated.     

Thermal degradation of bromine-containing polymers: Part 11—Blends of poly(2,3-dibromopropyl methacrylate) and poly(2,3-dibromopropyl acrylate) with poly(methyl methacrylate) and poly(methyl acrylate)

The products of degradation of blends of poly(2,3-dibromopropyl methacrylate) and poly(2,3-dibromopropyl acrylate) with poly(methyl methacrylate) and poly(methyl acrylate) are predominantly those to be expected from the degradation of the individual polymers. However, the appearance of methyl bromide and methanol from all four blends indicates that some interaction does occur across the phase boundary between the two constituent polymers. This is presumed to consist of the reaction of hydrogen bromide, formed by decomposition of the brominated polymers with the methyl groups of the acrylate and methacrylate polymers.     

Photodegradation of poly(methyl methacrylate)

The vacuum photodegradation at 30°C. of poly(methyl methacrylate) and copolymers with acrylaldehyde, methacrylaldehyde, and methyl acrylate has been studied. The polymers were examined in the form of expanded films as produced by a freeze-drying technique. At least one molecule of carbon monoxide is evolved for each chain scission. It is concluded that chain scission in poly(methyl methacrylate) is primarily the result of photoinduced aldehyde groups.     

Grafting acrylic polymers from flat nickel and copper surfaces by surface-initiated atom transfer radical polymerization

Acrylic polymers, including poly(methyl methacrylate), poly(2,2,2-trifluoroethyl methacrylate), poly( N,N'-dimethyaminoethyl methacrylate), and poly(2-hydroxyethyl methacrylate) were grafted from flat nickel and copper surfaces through surface-initiated atom transfer radical polymerization (ATRP). For the nickel system, there was a linear relationship between polymer layer thickness and monomer conversion or molecular weight of "free" polymers. The thickness of the polymer brush films was greater than 80 nm after 6 h of reaction time. The grafting density was estimated to be 0.40 chains/nm2. The "living" chain ends of grafted polymers were still active and initiated the growth of a second block of polymer. Block copolymer brushes with different block sequences were successfully prepared. The experimental surface chemical compositions as measured by X-ray photoelectron spectroscopy agreed very well with their theoretical values. Water contact angle measurements further confirmed the successful grafting of polymers from nickel and copper surfaces. The surface morphologies of all samples were studied by atomic force microscopy. This study provided a novel approach to prepare stable functional polymer coatings on reactive metal surfaces.     

Improvement of wettability and detergency of polymeric materials by excimer UV treatment

The 172 nm ultraviolet (UV) excimer light was exposed to polyethylene (PE), polypropylene, poly(ethylene terephthalate) and nylon 6 surfaces in ambient air. Changes in the contact angle and particle deposition in liquid due to UV treatment were investigated from the viewpoints of wettability and detergency. For all polymers, the wettability and the acid-base component of the surface free energy evaluated by the contact angle measurements increased remarkably by UV treatment of 1 min. From surface analyses of the polymer surfaces by X-ray photoelectron spectroscopy and atomic force microscopy, oxygen concentration was found to increase after UV treatment, whereas little topographical change was observed. The deposition of PE and nylon 12 particles onto the polymer surface was examined, in situ, in water, water/ethanol mixture, ethanol and n-heptane. Although the number of deposited particles was largely dependent on the kinds of the particle, the substrate and the liquid, a significant decrease in the deposition due to UV treatment was confirmed in any system.     

Influence of thiobisphenols on the photo-oxidation of low density polyethylene

The influence of thiobisphenols, some products of their thermo-oxidative transformation and model compounds on the photo-oxidation of low density polyethylene (Ld PE) has been studied. Thiobisphenols are found to have a pro-oxidant effect in the early period of exposure, which increases with their concentration. On the other hand, the carbonyl build up was retarded in a later irradiation period. Similar effects have been observed with some thiobisphenol transformation products, bis(3,5-di-tert. butyl-4-hydroxybenzyl) sulphide and its oxidation products, sulphoxide and sulphone, respectively, and model 4,4′-methylenebis(2-methyl-6-tert. butylphenol). Dodecyl 3,3′-thiodipropionate retarded the carbonyl build up during the whole period of ultraviolet irradiation. Kinetic data show that a concentration of 0·1% by weight of thiobisphenols is the most effective in retarding the carbonyl build up in Ld PE films. The formation of non-alcoholic oxygenated structures seems to be a specific effect of the sulphur containing compounds under study.     

Effect of P(MMA-co-MAA) compatibilizer on the miscibility of nylon 6/PVDF blends

With the ultimate objective of enhancing the impact strength and weatherability of nylon 6 engineering plastic, blending with poly(vinylidene fluoride) (PVDF) was studied. In the absence of a compatibilizer the two polymers phase separate, resulting in a deterioration of the properties. Since poly(methyl methacrylate) is known to be miscible with PVDF, we evaluated poly(methyl methacrylate-co-methacrylic acid) (P(MMA-co-MAA)) of low methacrylic acid content as the compatibilizer. The carboxylic acid groups in the MAA units were expected to react with the end amino groups of nylon 6 forming block or graft copolymers, P(MMA-co-MAA)-g-nylon 6, in situ, which will function as the actual compatibilizer. The amount of P(MMA-co-MAA) added, the MMA/MAA composition and heat treatment time were varied to study their effects on the miscibility, morphology, and mechanical properties of nylon 6/PVDF blends. The enhancement of the compatibility of nylon 6 and PVDF by addition of P(MMA-co-MAA) and the partial miscibility of nylon 6 and PVDF has been confirmed through DSC, dynamic mechanical testing, SEM of fracture surfaces, and tensile testing. The decrease in the crystallization temperatures on addition of compatibilizer in DSC experiments suggests that the compatibilizer enhances the interaction between the two components and retards the crystallization. The dynamic mechanical thermal analysis experiments suggest that the compatibility in the amorphous regions of nylon 6 and PVDF in particular has been enhanced. The increase in the heat treatment time in the molten state resulted in further enhancement of the miscibility. The enhancement of compatibility by addition of a reactive compatibilizer and heat treatment resulted in a significant increase in the energy of rupture in tensile testing.     

用微模塑直接在聚合物曲面上制备微图形

用聚二甲基硅氧烷制备的,表面复制有微图形的"弹性印章"直接在聚乙烯,聚丙烯,聚苯乙烯和聚甲基丙烯酸甲酯等热塑性聚合物表面上进行热微模塑,无需复杂设备并可在普通实验室条件下,复制微图形,甚至在小试管外壁的曲面上或在用毛细管形成的微突起表面上也能制备出微曲面图形.讨论了不同聚合物对生成微图形的影响,认为结晶性聚合物以及在温度变化时有较大收缩率的聚合物在微模塑中难以获得清晰图形.无定形聚合物如聚苯乙烯和聚甲基丙烯酸甲酯等能够获得清晰的微结构.     

Photochemical Behavior in Copolymers of 2(2-Hydroxy-5-vinylphenyl)2H-benzotriazole and Methyl Methacrylate: Photochemical Processes in Polymeric Systems. 6

The photochemical behavior of poly[2(2-hydroxy-5-vinylphenyl)2H-benzotriazole)]-co-methyl methacrylate was studied by spectroscopic and analytical techniques; no degradation of this copolymer occurred when the bulk polymer was exposed for several thousand hours of accelerated aging by ultraviolet irradiation. However, by the end of the period, surface deterioration became noticeable. Picosecond flash photolysis on copolymer solutions demonstrated that the lowest energy excited singlet state undergoes rapid internal conversion with little or no triplet yield. The observed short singlet lifetime (～25 ps) is undoubtedly responsible for the photostability of this copolymer system. Analysis of the surface exposed to ultraviolet irradiation indicates some photooxidative degradation of the methyl methacrylate portion of the copolymer, but the surface 2(2-hydroxy-5-vinylphenyl)2H-benzotriazoles of the macromolecules remain unchanged.