Evaluation of polymers for conservation treatments of outdoor exposed stone monuments. Part I: Photo-oxidative weathering

The commercial acrylic polymers, Paraloid B72 and Paraloid B67, and a silicon-based product, Dri-Film 104, commonly used as water repellents/consolidants in the restoration of stone artefacts, have been tested to evaluate their performances when submitted to ageing, simulating the outdoor conditions of treated stone. After full characterization, the three polymers were applied as thin films on slides, as thick film on petri dishes and on marble by brush or by imbibition and the resulting samples were submitted to photo-oxidative weathering (λ = 340 nm). The weathering evolution was checked by ultrasonic and colorimetric measurements and by FT-IR, NMR and SEC determinations. Removability tests were also performed. All the polymers underwent irreversible modifications with reduction of their conservative properties, colour change and, above all, impossibility of their complete removal.     

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.     

Polypropylene film chemical and physical modifications by dielectric barrier discharge plasma treatment at atmospheric pressure

Dielectric barrier discharge (DBD) technologies have been used to treat a polypropylene film. Various parameters such as treatment speed or electrical power were changed in order to determine the treatment power impact at the polypropylene surface. Indeed, all the treatments were performed using ambient air as gas to oxidize the polypropylene surface. This oxidation level and the surface modifications during the ageing were studied by a wetting method and by X-ray photoelectron spectroscopy (XPS). Moreover polypropylene film surface topography was analyzed by atomic force microscopy (AFM) in order to observe the surface roughness modifications. These topographic modifications were correlated to the surface oxidation by measuring with a lateral force microscope (LFM) the surface heterogeneity. The low ageing effects and the surface reorganization are discussed.     

Optical Chemical Hydrazine Sensor from Hybrid Organic-Inorganic Materials

Original hybrid organic-inorganic materials have been synthesised, characterised and used as optical chemical hydrazine sensors. Because of its optical and chemical properties, 4-(dimethyl)aminobenzaldehyde (DMAB) was chosen as indicator. DMAB has been immobilised by physical entrapment in a microporous silica network or by a chemical bonding on a colloidal silica network. The response time of the sensor was essentially governed by the diffusion of hydrazine in the host matrix whereas its life time was dependent on the retention of DMAB. These two features were controlled by the nature and the quantity of the network agent and the catalyst, by the ageing time of the sol, and the drying and thermal treatment of the films.     

The ageing of model pigment/linseed oil systems studied by means of vibrational spectroscopies and chemometrics

We used Fourier Transform - Near Infrared (FT-NIR) and micro-Raman spectroscopies to follow the changes occurring in a thin layer of linseed oil in the presence of lead white (basic lead carbonate) and zinc white (zinc oxide), which were due to the natural ageing process.The curing of linseed oil is a very complicated process, owing to different mechanisms that occur simultaneously, ones which may be further modified by the presence of pigments and by environmental conditions (e.g. light, humidity, temperature). Both lead white and zinc white pigments affect this process, leading to the formation of films with different properties. Previous studies have already characterised the ageing of binders alone, including linseed oil. We investigated, by means of a combined analysis of the results of two different vibrational spectroscopy methods, the role of these two white pigments on the ageing of a linseed oil film. Model samples were prepared, and we followed their evolution over a 24-month period. Two ten-year-old oil mock-ups, which were prepared by using lead and zinc white pigments (comparable to contemporary oil painting), were analysed within the framework of the present results.Lastly, we exploited the potentiality of Principal Component Analysis (PCA) on the combined FT-NIR and Raman spectra in order to define a possible ageing trend for two oil-white mixtures. Furthermore, we tested the statistical models by comparison with spectra related to the two ten-year-old mock-ups.     

Effect of surface modification on the properties of plasma-polymerized hexamethyldisiloxane thin films

Plasma-polymerized hexamethyldisiloxane (pp-HMDSO) thin films have been deposited in a radiofrequency (RF) remote plasma-enhanced chemical vapor deposition (PECVD) system, on different types of substrates: silicon wafers, glass, quartz crystals, and chemiresistor structure. The as-grown thin films have been post treated in two types of reactive plasmas produced in SF₆ and O₂ gases. The effect of this surface modification on different properties of the as-grown pp-HMDSO thin film (chemical structure, elemental composition, surface morphology, film density and thickness, optical bandgap, and electrical resistivity) has been investigated. It is found that SF₆ plasma and O₂ plasma surface modifications of the as-grown pp-HMDSO thin film induce property changes different from each other. SF₆ plasma converted the as-grown pp-HMDSO film to a more porous material and caused a narrowing of its optical band gap of about 33%, while O₂ plasma induced a lowering of film electrical resistivity of about two orders of magnitude.     

Photo-oxidation of acrylic-urethane thermoset networks. Relating materials properties to changes of chemical structure

Acrylic-urethane thermoset photo-ageing was investigated by various techniques including IR spectroscopy, dynamic-mechanical thermal analysis (DMTA), and micro-hardness testing. These results were used to identify the sites at which the chain oxidation reaction is initiated and the main pathways through which the degradation reaction proceeds. The chemical modifications induced by photo-ageing were qualitatively and quantitatively correlated with the modifications observed in the architecture and mechanical properties of the thermoset network. The results of this work also allow for the development of a quantitative kinetic model based on the identified mechanisms and a multi-scale approach from the molecular to the macroscopic level, which highlights the effect of the changes of the chemical structure on the modification of the macromolecule arrangement and thus on the mechanical properties. Finally, the impact of stabilisers on material ageing was studied.     

Ageing of polylactide and polylactide nanocomposite filaments

An experimental study was carried out in order to check the influence of various parameters on the ageing of PLA filaments performed in a climatic room. Initially, two grades of PLA with different d-isomer contents were analysed. Even after several weeks of ageing, properties of PLA filaments with less than 0.5% d-isomer content did not vary extensively. On the other hand, the mechanical and thermal properties of PLA filaments with 4% d-isomer content underwent strong modifications. Subsequently, a selected organomodified bentonite (Bentone^®104 - noted as B104) was blended with PLA and then melt-spun to study the influence of a nanofiller on the ageing of PLA filaments. Faster degradation of PLA nanocomposite filaments was then observed.     

Radiation induced polymerization of vinyl monomers and their application for preparation of wood-polymer composites

Polymerizing effects of high energy radiation has been found suitable for preparation of wood-polymer composites. In the present work after evaluating polymer products that have been obtained by irradiation method, wood-polymer composites have been prepared by in situ polymerization of vinyl acetate, acrylic acid and acrylic acid/styrene mixture using two samples of Iranian hardwoods, Beech and Hornbeam. These woods and their composites have been tested for their physical and mechanical properties. The results have shown that chemical bonding between polymer and the cell wall component lead to better strength properties in the composites.     

Structure and optical properties of CVD molybdenum oxide films for electrochromic application

Vibrational and optical properties of MoO₃ thin films have been studied by Raman and infrared spectroscopy. The films were deposited onto Si substrates at a temperature of 150 °C by chemical vapor deposition of Mo(CO)₆ at atmospheric pressure and different amounts of oxygen in the reactor. The Raman and IR spectral analyses show that the as-deposited films are in general amorphous. Post-deposition annealing at 300 and 400 °C leads to crystallization and the MoO₃ film structure is a mixture of orthorhombic and monoclinic MoO₃ modifications. Transformation of the monoclinic crystallographic modification to a thoroughly orthorhombic layered structure is observed for films heated at temperatures above 400 °C. Electronic Publication     

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.     

NMR study of PMR-15 prepolymerization steps

Variations in PMR-15 composites properties could be due to differences in their chemical compositions occurring during the curing cycle. Variations in the composition of the PMR-15 resin were studied for four different curing cycles, to determine the influences of parameters such as the heating rate or the presence of a temperature stage. The resin mixture was sampled at the same four different temperature points in each cycle and analyzed mainly by ¹H- and ¹³C-NMR. Quantitative analysis of the different chemical species were realized by deconvolution of NMR spectra. At a given temperature, the resin contains the same molecules but in proportions which depend on the curing conditions and which reflect differences in the chemical reactivity of the monomeric species. We have precisely defined the temperature ranges at which each of the key reactions (amidization, imidization, exoendo isomerization) occurs. An imine condensation product of NE and MDA has been identified and shown to be present in the resin mixture even at low temperature. As a result of this study, two possible causes of resin alteration during ageing can be put forward: the presence of nonimidized BTDE moieties and the endo-exo isomerization reaction which will result in deformation and, possibly, microcracking, if reticulation of the end-capped nadimides is not total. © 1994 John Wiley & Sons, Inc.     

Measurement of the surface tension of liquid marbles

The capillary rise and Wilhelmy plate methods have been used to study the "surface tension" of water marbles encapsulated with polytetrafluoroethylene (PTFE) powders of 1-, 35-, and 100-μm particle size. With the capillary rise technique, a glass capillary tube was inserted into a water marble to measure the capillary rise of the water. The Laplace pressure exerted by the water marble was directly measured by comparing the heights of the capillary rise from the marble and from a flat water surface in a beaker. An equation based on Marmur's model was proposed to calculate the water marble surface tension. This method does not require the water contact angle with the supporting solid surface to be considered; it is therefore a simple but efficient method for determining liquid marble surface tension. The Wilhelmy method was used to measure the surface tension of a flat water surface covered by PTFE powder. This method offers a new angle for investigating liquid marble shell properties. A discussion on the nature and the realistic magnitude of liquid marble surface tension is offered.     

Accelerated artificial ageing of new dimer fatty acid-based polyamides

Replacing petroleum-based raw materials with renewable resources is now a major challenge in terms of economical and environmental viewpoints. Vegetable oils are expected to be an interesting alternative to produce a new generation of bio-based polymers. Due to the possible outdoor exposure in diverse applications, knowledge of the resistance to weather of these new materials is an important issue, not only for aesthetic aspects as in rapid yellowing, but also for changes in their properties. New innovative dimer acid-based bio-polyamides (DAPA) were exposed to an artificial ageing environment produced by a UV/condensation weathering device for different times. To follow and to evaluate this material ageing, several techniques were employed to correlate the chemical modifications, with the morphology and the mechanical properties. The formation of peroxide was found to be very rapid and accompanied by high gel fraction formation and chain breaking. Infrared spectroscopy showed a build-up of carbonyl absorption in the range 1700-1780 cm⁻¹, due to primary and secondary photo-oxidation products. In correlation with these morphological evolutions and in agreement with the high decrease of fusion enthalpy by differential scanning calorimetry, X-Ray diffraction showed an amorphous solid state after ageing. Strain-stress measurements revealed a change in DAPA behaviour, varying from a ductile to an elastomeric material, before and after ageing, respectively.     

Artificial ageing of double base rocket propellant

The ageing of double base rocket propellants (DB rocket propellants), which is a consequence of chemical reactions and physical processes that take place over time, has significant effect on their relevant properties (e.g. chemical composition, mechanical properties, ballistic properties, etc.). The changes of relevant properties limit the safe and reliable service life of DB rocket propellants. This is the reason why numerous research efforts are devoted to finding out reliable methods to measure the changes caused by ageing, to assess the quality at a given moment of time, and to predict remaining life-time of DB rocket propellants. In this work we studied dynamic mechanical properties of DB rocket propellant artificially aged at elevated temperatures, in order to detect and quantify changes in dynamic mechanical properties caused by the ageing. Dynamic mechanical properties were studied using dynamic mechanical analyser (DMA). The results obtained have shown that the ageing causes significant changes of DMA curve’s shape and positions. These changes are quantified by following some characteristic points on DMA curves (e.g. glass transition temperatures; storage modulus, loss modulus and tanδ at characteristic temperatures, etc.). It has been found out that the most sensitive parameters to the ageing process are: storage modulus at viscoelastic and softening region, peak width and height on loss modulus curve, glass transition and softening temperature, and tanδ at viscoelastic region.     

Synthesis of Atomically Thin Boron Films on Copper Foils

Two‐dimensional boron materials have recently attracted extensive theoretical interest because of their exceptional structural complexity and remarkable physical and chemical properties. However, such 2D boron monolayers have still not been synthesized. In this report, the synthesis of atomically thin 2D γ‐boron films on copper foils is achieved by chemical vapor deposition using a mixture of pure boron and boron oxide powders as the boron source and hydrogen gas as the carrier gas. Strikingly, the optical band gap of the boron film was measured to be around 2.25 eV, which is close to the value (2.07 eV) determined by first‐principles calculations, suggesting that the γ‐B₂₈ monolayer is a fascinating direct band gap semiconductor. Furthermore, a strong photoluminescence emission band was observed at approximately 626 nm, which is again due to the direct band gap. This study could pave the way for applications of two‐dimensional boron materials in electronic and photonic devices.     

Improved controlled relative humidity dynamic mechanical analysis of artists’ acrylic emulsion paints

After improvements were made to a modified Polymer Labs MkIII DMTA instrument to facilitate repeatable controlled humidity (RH) experiments using isothermal and thermal scanning conditions, the viscoelastic properties of titanium white pigmented artists’ acrylic emulsion films were measured in tensile mode. The effects of temperature, relative humidity and accelerated ageing regimes on two brands of titanium white paints were explored. These paints are highly responsive to changes in temperature and relative humidity, formulation differences affect properties slightly, and while light ageing had a negligible effect, thermal ageing resulted in decreased storage modulus and increased film density.     

Electrooptical properties of gel-glass dispersed liquid crystals

Liquid crystal microdroplets can be trapped into silica gel-glasses by sol-gel processes. Several silica matrices containing different non-reacting organic radicals have been employed for preparing gel-glass dispersed liquid crystals (GDLC). The optical properties of thin GDLC layers may be modified by coating the material with transparent electrodes and applying external AC-voltage signals. Switching between opaque and transparent states is achieved. The sample transmission depends on the scattering properties of the material; no polarizers are required. The transmission of the transparent state is improved by matching the refractive indices of the gel-glass matrix and the liquid crystal. This can be achieved by adding high refractive index dopants to the starting mixture, or by substituting the non-reacting organic group of the silica matrix. Both approaches have been tested. Phenyl and methyl monomers have been used as well as titanium-based dopants. The resulting GDLC materials have been optimized by controlling the starting mixture composition, the reaction conditions, and the film preparation. The optics, dynamics, and stability of GDLC films are analyzed.     

Dewatering of crude oil emulsions 1. Rheological behaviour of the crude oil—water interface

Rheological properties of Buchan crude oil—water interfaces have been determined using a biconical bob rheometer. The effects of temperature and the presence of surface-active demulsifiers on film characteristics have been evaluated. Free oscillation and creep modes have been used, depending on the relative viscoelastic behaviour of the films. Film ageing is particularly significant, whilst temperature and the nature and concentration of any demulsification chemicals also contribute significantly. Further detailed understanding of interfacial film rheology is considered to be desirable for a complete appreciation of the stability of water-in-crude oil emulsions.     

Photodegradation of tetramethylpolycarbonate (TMPC): Correlation of properties with chemical modifications

The consequences of tetramethylpolycarbonate (TMPC) photoageing (λ > 300 nm) on the surface modifications of the material have been analysed. Roughness and stiffness measurements were performed using AFM (Atomic Force Microscopy). Gel fraction measurements, DMTA (Dynamic Mechanical Thermal Analysis) measurements and infrared analyses were also performed. The results indicate that the three-dimensional network forms as a result of crosslinking reactions. The modifications of the properties measured using each technique were followed as functions of the irradiation time, and the influence of oxygen was characterised. The surface modifications are explained in light of the modifications of the chemical structure. Quantitative correlations were obtained between the main relevant criteria characterizing the surface degradation from the chemical structure to the mechanical properties.