UV stability of HMS-PP (high melt strength polypropylene) obtained by radiation process

HMS-PP in grains was synthesized by the gamma irradiation of PP under a crosslinking atmosphere of acetylene, followed by thermal treatment for radical recombination and thermal treatment for annihilation of the remaining radicals. The UV stability of the material was evaluated in pellet form. The accelerated weathering test of HMS-PP samples were performed under artificial ultra-violet light and in a condensation chamber Comexim (C-UV type) apparatus with UV exposure for 120 and 240 h. The results were compared to those from ageing caused by sunlight and dew under natural exposition. This work investigated changes in mechanical proprieties (elongation and rupture strength), Fourier transform infrared spectroscopy (FTIR), optical microscopy (MO), scanning electron microscopy (SEM) and rheological properties of HMS-PP after the UV ageing. We find that the HMS-PP has more degradation than regular PP and undergoes predominate chain scission in aggressive UV ageing conditions.     

Accelerated ageing due to moisture absorption of thermally cured epoxy resin/polyethersulphone blends. Thermal, mechanical and morphological behaviour

A model epoxy resin/anhydride system, modified with a polyethersulfone (PES) engineering thermoplastic toughening agent, has been studied under hydrothermal ageing in order to investigate the modification of the thermal, morphological and mechanical behaviour through dynamical mechanical thermal analysis, SEM microscopy and fracture toughness test respectively. Two different concentrations of the toughening agent were used in the blends and two ageing conditions have been considered, consisting of the immersion of the samples in distilled water at constant temperature of 70 °C for 1 week and for 1 month. Dynamical mechanical thermal analysis results on hydrothermally aged materials indicated the occurrence of progressive segregation effects with the formation of regions with different cross-linking degrees.Fracture toughness tests showed an increase of the K_IC value with the increase of the toughening agent concentration, revealing both a dramatic decrease of the same parameter after 1 week ageing for all the materials and the tendency to reach an almost constant value after 1 month ageing for all the formulations, with a slight increase with respect to 1 week ageing. These results have been interpreted on the basis of the SEM analysis, showing the presence of a well defined micrometric PES particles distribution in the epoxy/anhydride matrix, and discussed in the light of different water absorption mechanisms at short and long ageing times.     

SEM/EDX and vis spectrophotometry study of the stability of resin-bound mortars used for casting replicas and filling missing parts of historic stone fountains

A study by SEM/EDX and spectrophotometry in the visible region attempting to assess the stability of new resin-bound mortars used for casting replicas of marble historic fountains is presented in this paper. Different accelerating tests such as thermal ageing, UV light ageing, ageing in an SO(2) pollutant chamber, freezing cycles ageing, salt crystallisation ageing, natural ageing and biological attack have been applied to a series of test specimens prepared with polyester-, epoxy- and gel-coat-bound mortars. Examination of morphology, measurement of chemical composition and chromatic coordinates before and after ageing treatments establish the higher stability and resistance properties of these resin-bound mortars by comparison to those from the natural marbles.     

Application of cooling curve analysis in solidification pattern and structure control of grey cast irons

In this article, the composites based on long glass fibre reinforced polypropylene/intumescent flame retardant (LGFPP/IFR) were prepared by melt blending. The influence of thermal oxidative ageing on the LGFPP/IFR composites with different thermal oxidative ageing time at 140 °C was studied by means of oven heating. The thermal stability and flammability of the composites were respectively investigated by thermal gravimetric analysis (TG), limiting oxygen index (LOI), UL-94 test, cone calorimeter test (CCT), scanning electronic microscopy (SEM), mechanical properties test and energy-dispersive X-ray analysis (EDAX). A trend of increase first and then decrease in LOI values was shown in 0–50 days ageing, with the same trend as thermal stability obtained from TG in nitrogen condition. The CCT results indicated that the LGFPP/IFR composites after ageing achieved a higher heat release rate, which means a higher fire risk. The mechanical properties showed a global decrease in just 10 days ageing. Morphologies obtained from SEM showed that both the rupture of PP matrix and fibre interface debonding led to the decrease in mechanical properties. The EDAX proved that IFR particles could emerge and gather on the surface of sample in ageing procedure, which had great effects on the thermal stability and flame retardancy of the composites.     

Assessment of the ageing of triterpenoid paint varnishes using fluorescence,Raman and FTIR spectroscopy

The assessment of the influence of natural and artificial ageing on the spectrofluorescence of triterpenoid varnishes dammar and mastic is the focus of this work. Both Fourier transform infrared (FTIR) microscopy using attenuated total reflectance and Raman spectroscopy have been employed for complementary molecular analysis of samples. Synchronous fluorescence spectroscopy, excitation emission spectroscopy, and statistical analysis of data have been used to monitor changes in the optical properties of varnish samples. Assessment of naturally and artificially aged samples using excitation emission spectroscopy suggests that extensive exposure to visible light does not lead to easily appreciable differences in the fluorescence of mastic and dammar; cluster analysis has been used to assess changes, which occur with artificial ageing under visible light, indicating that differences in the fluorescence spectra of aged triterpenoids may be insufficient for their discrimination. The results highlight significant differences between the initial fluorescence of films of dammar and mastic and the fluorescence, which develops with ageing and oxidation, and specific markers, which change with ageing in FTIR and Raman spectra, have been identified.     

Seawater ageing of flax/poly(lactic acid) biocomposites

Natural fibre reinforced biopolymer composites, or biocomposites, are an alternative to the glass fibre reinforced thermoset composites widely used today in marine applications. Biocomposites offer good mechanical properties and total biodegradability, but if they are to be adopted for marine structures their durability in a seawater environment must be demonstrated. In the present study unreinforced PLLA (Poly(l-Lactic acid)), injected and film stacked flax composites with the same PLLA matrix have been examined. All the samples were aged in natural seawater at different temperatures in order to accelerate hygrothermal ageing. Changes to physico-chemical and mechanical behaviour have been followed by weight measurements, thermal and gel permeation chromatography (GPC) analyses, and tensile testing, completed by acoustic emission recording and scanning electron microscopy (SEM) examination. The matrix tensile stiffness is hardly affected by seawater at temperatures to 40 °C but the composite loses stiffness and strength. Fibre/matrix interface weakening is the main damage mechanism induced by wet ageing, but both matrix and fibre cracks also appear at longer periods.     

Gamma radiation for preservation of biologically damaged paper

Samples of nine different papers in use in the library, including two mould-contaminated papers, were irradiated with 14.4 kGy in a Co-60 facility. Five of the samples were subsequently subjected to an accelerated UV-ageing process. mechanical (tensile energy absorption and stretch) and optical properties were measured on control and irradiated samples, before and after ageing.

For most samples, the effect of ageing on mechanical properties turned out to be larger than that of irradiation. Irradiated and control samples were similarly affected by the accelerated ageing. Mould contaminated samples were still in acceptable conditions of use after irradiation. No discoloration effect was observed after irradiation and/or ageing.     

Process Induced Micro Structure Evolution in Polyester Polyurethane and Mechanical Properties Relationship

Summary: MDI-HQEE-Capa based thermoplastic polyurethane (TPU) with Shore hardness of 94 A was injection molded. In order to study the influence of melt conditions on the material structure evolution and resulting mechanical properties a systematical variation in processing temperatures in the range between 195 °C and 250 °C was applied. The mold temperature was kept constant at 60 °C. Process induced samples morphologies were investigated by means of light microscope (LM), scanning electron microscope (SEM) and differential scanning calorimeter (DSC). Mechanical visco-elastic properties were determined by means of cyclic tensile experiment and were correlated with results of structural investigations. The evaluation of morphology micrographs of raw TPU material and specimens molded at different temperatures shows a reduction in visual crystalline fraction. This gains a distinct change in the deformation behavior of injection molded TPU with increasing melt processing temperature.     

Contributions to the Characterization of Chlorinated Polyisoprene Surfaces

Summary: The present work is focused on the characterization of the surface properties and the mechanical properties of chlorinated polyisoprene films. Cross-linked polyisoprene films were treated with acidified hypochlorite solution and the influence of the chlorination time on the surface properties was determined by spectroscopic techniques including FT-IR spectroscopy and X-ray photoelectron spectroscopy (XPS). The surface morphology was investigated by scanning electron microscopy (SEM), optical microscopy and contact angle measurements. In addition, the effect of the chlorination time on the tensile strength and ageing stability of natural rubber latex gloves was investigated.     

Green chemicals and process to graft cellulose fibers

The treatment of additive-free hand sheet paper samples with cold plasma was carried out and showed that cellulose can be chemically linked with reactive natural products, namely myrcene (My) and limonene (LM). Contact-angle measurement and X-ray photoelectron spectroscopy (XPS) were used to ascertain the occurrence of the grafting. Indeed, the contact-angle value of a drop of water deposited at the surface of paper increased from 30° for unmodified substrate to about 105 and 107°, for LM- and My-treated samples, respectively. In fact, LM- and My-treated surfaces were rendered totally apolar. Indeed, the polar contribution to the surface energy decreased from about 23 mJ/m² for pristine samples to practically zero for treated ones. The treated surfaces displayed water-barrier properties; the penetration of the liquid was reduced significantly after LM and My treatments. The XPS spectra showed that the modification with LM and My gave rise to very significant change in the O/C ratio, as well as in the intensity of the C1 peak assigned to aliphatic carbon sequences.     

Effects of solar irradiation on the properties of ethylene-norbornene composites containing solvent dyes

This study investigates the effects of irradiation with artificial solar light on the resistance to aging of ethylene-norbornene (EN) copolymer with different solvent dyes and commercial stabilizers. The mechanical properties of the samples were measured before and after ageing using tensile tests. FTIR spectroscopy was used to evaluate the carbonyl index as a measure of photooxidation after irradiation. It was found that the carbonyl index of the samples depended on the type of additive in the composite. Secondary ion mass spectrometry (TOF-SIMS) was used to analyze the chemical composition of the sample surfaces. The degree of oxidative aging was evaluated by measuring the intensities of secondary C_xH_yO_z⁺ type ions. Samples containing anthraquinone solvent dyes, such as Solvent Blue 97 or Solvent Green 28, showed the most significant improvements in durability in an aging test. Some of the applied solvent dyes showed much greater ability than the studied stabilizers to protect EN films exposed to the full solar spectrum.     

Effect of the nanosilica content in the shell of coextruded wood‐plastic composites to enhance the ultraviolet aging resistance

Weathering durability of wood‐plastic composites (WPCs) is a significant issue for outdoor applications. Nanosilica is widely used to enhance the ultraviolet (UV) aging resistance of composites. In this study, the effects of nanosilica (0%, 1%, 2%, 5%, and 10%) added into the shell of coextruded WPCs were investigated after 2500‐hour UV exposure. Discoloration, durability, degradation, and photooxidation of the composites were studied by colorimetry, mechanical testing, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and X‐ray photoelectron spectroscopy (XPS). The samples with 2% nanosilica addition (the N2 samples) provided optimal color protection, showing the lowest ΔE* (color difference) and ΔL* (lightness) values in all samples. The surface of N2 samples was less oxidized after UV exposure as revealed by FTIR and XPS analysis, and showed fewer cracks in SEM images compared with controls and other samples. In addition, N2 samples provided best flexural properties. In summary, the addition of 2% nanosilica was most effective in protecting WPCs from UV degradation. Moreover, obtained results provide a theoretical development for adopting the nanosilica as a reinforcing agent in WPCs and applying coextruded WPCs in outdoors.     

Three-dimensional morphological characterization of optic nerve fibers by atomic force microscopy and by scanning electron microscopy.

A comparative study of scanning electron microscopy (SEM) and atomic force microscopy (AFM) imaging of the healthy human optic nerve was carried out to determine the similarities and the differences. In this study we compared the fine optic nerve structures as observed by SEM and AFM. The fibers of the right optic nerve of a 61-year-old man show different arrangements in transverse sections taken from the same individual 5 mm central to the optic canal and 5 mm peripheral to the optic chiasma; this difference can be recognized by light microscopy (LM), SEM, and AFM. AFM revealed such typical optic nerve fibers (taken from a point 5 mm central to the optic canal) with annular and longitudinal orientations, which were not visible by SEM in this form. By contrast, LM and SEM visualized other structures, such as pia mater and optic nerve fibers loosely arranged in bundles, none of which was visualized by AFM. The images, however, taken 5 mm peripheral from the optic chiasma show shapeless nerve fibers having a wavy course. Our results reveal that more detailed information on optic nerve morphology is obtained by exploiting the advantages of both SEM and AFM. These are the first SEM and AFM images of healthy human optic nerve fibers, containing clear representations of the three dimensions of the optic nerve.     

Coalescence of polystyrene nodules in soft poly(butyl acrylate)-based films

A two-stage emulsion polymerization procedure was used in order to obtain core–shell polymer particles having a core of polystyrene (PS), covered by a shell of either pure poly(butyl acrylate) (PBA) or a methacrylic acid-functionalized PBA. Films were then cast from these latexes, and their properties were studied without further treatments (“as-dried” films), as well as after a 3 hr heat treatment intended to provoke the coalescence of PS domains (“annealed” films). “As-dried” and “annealed” film samples were studied by dynamic mechanical analysis (DMA), scanning electron microscopy (SEM) and small angle neutron scattering (SANS). DMA and SEM results, as described in previous works, showed that for unfunctionalized films, the percolated PS domains coalesced under the annealing treatment, while for the functionalized films, they did not. On the other hand, SANS results presented here showed that even in the case of functionalized films, the presence of coalescence could be detected. It was concluded that while DMA and SEM reveal large-scale modifications provoked by the heat treatment, SANS is capable of detecting very smallscale changes which do not have a direct effect on the bulk physical properties of the samples.     

Microscopic aspects of autoschizic cell death in human ovarian carcinoma (2774) cells following vitamin C, vitamin K3 or vitamin C:K3 treatment.

Human ovarian carcinoma cells (MDAH 2774) were treated with sodium ascorbate (VC), menadione (VK3), or with a VC:VK3 combination for 1 h and then studied using light microscopy (LM) and scanning (SEM) and transmission electron (TEM) microscopy. Plasma membrane damage (blisters and blebs, hairy aspect) results from vitamin C (VC) treatment, while cytoskeletal damage and self-morsellation are caused by vitamin K3 (VK3) treatment. VC:VK3-treated cells exhibit exacerbated injuries characteristic of both VC and VK3 treatment as well as a significant decrease in cell diameters from 20-35 microm for control cells to 7-12 microm for VC:VK3 treatment. Moreover, after a 1-h exposure to the vitamin combination, autoschizis (43%), apoptosis (3%), and oncosis (1.9%) are observed at the percentages indicated. All cellular changes associated with autoschizis observed with SEM were confirmed by LM and TEM observations and are consistent with cell death by autoschizis: decrease in cell size, cytoplasmic self-excisions, degradation of the nucleus and nucleolus without formation of apoptotic bodies and, ultimately, karyorrhexis and karyolysis. These results also suggest that the vitamin combination may find clinical use in the treatment of ovarian cancer.     

Mass deacidification of papers and books. IV - A study of papers treated with aminoalkylalkoxysilanes and their resistance to ageing

In libraries and archives some of the time-acidified items are so brittle that they cannot be handled without risking loss of material. Currently used deacidification processes do not impart improved mechanical properties to the paper. The use of alcoholic solutions of three different types of aminoalkylalkoxysilanes was studied for the deacidification of paper-based items. It was shown that in addition to deacidifying and improving the stability of papers by providing an alkaline buffer the treatment also significantly improved their mechanical resistance, as measured by the folding endurance and tensile breaking resistance. Essential for the appraisal of the deacidification process, the behaviour upon ageing of the materials treated was investigated. Accelerated ageing methods involving heat/humidity and nitrogen dioxide atmosphere were used separately. It was shown that the reinforcement effect of the three aminosilane compounds tested persisted throughout the ageing, and in one case the mechanical properties even improved after ageing. Two of the aminosilanes tested were studied for their impact at the macromolecular level, on the molar masses of cellulose, using size-exclusion chromatography with multiangle light scattering detection. Their effectiveness in protecting paper from acid hydrolysis occurring during ageing was found significant.     

Thermal decomposition behaviour of cobalt(II)-picolyl-terminated poly(dimethylsiloxane)

Thermal, chemical and rheological properties of ultraviolet aged asphalt binder were characterized by differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) and dynamic shear rheometer (DSR), respectively. Asphalt binder samples were made with different film thickness (50, 100, 200 and 500 μm) and suffered different ageing time (0, 48, 96 and 144 h), at a certain UV radiant intensity of 20 w m^–2 in a self-made accelerated ageing oven. The results indicate that the UV light ageing would lead to the improvement of thermal behavior and the growth of the glass transition temperature of asphalt binder. This type of ageing can be also reflected from the FTIR spectra in terms of the characteristic peaks of the carbonyl groups and sulphoxides. The UV light ageing can change some rheological parameters of asphalt binder, such as complex modulus and phase angle. The ageing degrees of asphalt binder by this type of ageing test are mainly related to the ageing time and film thickness of the sample.     

Probing athletics tracks degradation using a microscratch technique

Continuous outdoor exposure of athletics tracks can lead to an important degradation of their mechanical and aesthetical properties. In this work, flat laboratory samples prepared from rubber blends of different colours were subjected to natural and artificial ageing, to investigate their effect on the surface properties. Compositional variations demonstrated a generalized oxidization of the outer (top) material layer, together with surfacing of inorganic additives; a small increase of the degradation temperature of the natural rubber component was reported, similar to the one previously observed on bulk track samples. The smooth surface of the present samples allowed their testing using a microscratching technique, able to mechanically probe the material within a few hundred microns below the top surface. The formation of a significantly harder outer crust layer was reported, potentially impacting the track performance since it is exactly the locus of interaction between the athlete and the sport surface. In particular, the increase in scratch hardness is accompanied by a significant reduction in the apparent friction coefficient. These surface modifications, previously unreported in the literature, are independent phenomena with respect to generalized bulk ageing. Microscratch data supported by microscopy evidenced a significantly varying sensitivity to ageing for the different colours (red, blue, green, neutral). Moreover, this sensitivity appeared strongly dependent on the applied ageing protocol (natural vs. artificial). In view of these results, care must be taken when accelerated artificial weathering is used to simulate long-term natural ageing of these materials.     

The influence of core-shell structured modifiers on the toughness of poly (vinyl chloride)

The core-shell structured grafted copolymer particles of polybutadiene grafted polymethyl methacrylate (PB-g-PMMA, MB) were prepared by emulsion polymerization. The MB particles were used to modify poly (vinyl chloride) (PVC) by melt blending. The mechanical properties of the PVC blends were investigated. The micro-morphology of the PVC blends was observed by scanning electron microscopy (SEM). The results indicated that the samples with the best impact strength could be obtained when the core-shell weight ratio of PB to PMMA is lower than 93:7, the mechanical properties correlated well with SEM morphologies, the addition of modifier with the ratio core to shell of 93:7 could reduce the domain size of the dispersed phase. Furthermore, the compatibility and properties of the blends were greatly enhanced and improved. The modifier particles could be well dispersed in the PVC matrix.     

Synthesis and mechanical characterisation of cellulose based textiles grafted with acrylic monomers

Grafting polymerisation of methyl methacrylate and ethyl acrylate onto linen and cotton was carried out in order to reinforce these materials, when they underwent degradation. Take into account this aim, an artificially ageing was performed onto cellulose based textiles by metaperiodate oxidation, in order to obtain degraded model samples. Carbonyl groups were introduced in the cellulose and used as photosensitive agents, allowing the formation of radical sites during the polymerisation reaction, that started by irradiating the substrate by ultraviolet light.In this paper the effectiveness of grafting polymerisation as a method for textile conservation is discussed, starting from the results obtained from several characterisations, as the grafting yields and the grafting efficacy evaluation, the DSC analysis, the FTIR spectroscopy and the SEM observations. Moreover the consolidating and the protective effects were investigated by evaluating the mechanical properties and the wetting behaviour of the grafted samples, and comparing them with the original and aged substrates. The mechanical strength of cellulose based textiles has been improved, as well as the wetting behaviour has been enhanced.