Non-destructive spectroscopic characterization of parchment documents

Membranaceous substrates - widely found in library heritage - are truly challenging, due to the variety of manufacturing traditions, the intrinsic variability of the animal's skin and the different degradation patterns affecting documents along ageing. Moreover, when dealing with unique and delicate objects as cultural heritage specimens, sampling is never recommended and often explicitly forbidden. Aim of the research presented in this work is to achieve correct protocols for unambiguous characterization of the document's materials chemical structure and of the possible surface treatments.Experimental results allow us to evidence that the chosen non-destructive techniques (Raman, ATR-FTIR and SEM/EDS) provide a good differentiation between parchment manufacturing procedures, western with lime and eastern with enzymatic treatment. Incrustations of salts on the surface as well as superficial treatment with tannin can be clearly detected. Origin of tannin - from the surface or in ink - can also be distinguished.Choice of the better technique is sample-dependent, since preparation methods, degradation, presence of incrustations, amount of tannin, dehairing method can differently affect the spectral features. For instance, Raman appears to be the most effective molecular technique on western parchment, whereas ATR-FTIR allows distinguishing the enzymatic dehairing procedure from the chemical one.     

Gamma radiation induced effects on slaughterhouse wastewater treatment

A preliminary study using gamma radiation on slaughterhouse wastewater samples was carried out. Chemical oxygen demand (COD), biochemical oxygen demand (BOD) and total suspended solids (TSS) results were obtained at a dose rate of 0.9 kGy h⁻¹. A decrease of COD, BOD and colour was observed after irradiation at high absorbed doses. The microbiological results, following irradiation in the same conditions, correlated with the BOD results. The results obtained highlight the potential of this technology for wastewater treatment.     

Gamma radiation effects on molecular characteristic of vegetable tannins

The influence of gamma radiation on tannins extracted from Pinus caribaea bark and on tannin acid has been investigated in this study with the aim of searching for evidences of structural and/or conformational changes. To fulfill this purpose, the samples of tannins, such as tannic acid and P. caribaea tannin bark, were irradiated at different doses (from 5 to 35 kGy) using a cobalt-60 gamma irradiator. The changes were analyzed by a Fourier transform infrared spectrometry and by high resolution liquid chromatography. The results pointed out some structural and conformational changes under the effects of gamma radiation for doses higher than 5 kGy for P. caribaea tannin bark. However, no changes were detected on the irradiated tannic acid. The observed behavior suggests the loss of carbonyl groups. This could be associated to a decarboxylation process with the corresponding release of CO₂ from the molecule. Evidences of some conformational changes were also noted.     

Gamma radiation effects on an amine antioxidant added in an ethylene-propylene copolymer

The aim of this work was to compare the gamma radiation induced effects on samples of an ethylene-propylene copolymer antioxidant free with samples loaded with an antioxidant characterised by the presence of an -NH functional group. The employed techniques were Electron Spin Resonance spectroscopy (ESR) and High Performance Liquid Chromatography (HPLC). Stable radicals R---NO° due to the interaction of free radicals produced in the irradiated polymer with the antioxidant have been observed by ESR at room temperature. The time evolution of the ESR signals following the irradiation was examined at different doses. The amount of antioxidant not involved in the oxidation reactions has been determined using HPLC.     

Gamma radiation effects on physico-chemical parameters of apple fruit during commercial post-harvest preservation

The physico-chemical parameters (including moisture, total soluble solids, antioxidant activity, phenolic content and firmness) of cv. Red Delicious apple subjected to γ radiation were evaluated for their ability to avoid the post-harvest blue mold caused by Penicillium expansum during cold storage. Freshly harvested apples were inoculated with P. expansum. Treated fruits were irradiated at doses of 0, 300, 600, 900 and 1200 Gy and stored at 1 °C. Apples were evaluated at three month intervals. The results showed that there was a clear link between phenolic content and antioxidant activity, so that dose range of 900 Gy and higher significantly decreased phenolic content and antioxidant activity. The moisture percent of stored apples was more responsive to irradiation (at doses of 900–1200 Gy) than storage time and pathogen. Lesion diameter of pathogen-treated non-irradiated apples was significantly increased after three months. This means that storage at low temperature is not enough to avoid blue mold growth. As dose and storage time increased firmness decreased; also pathogen accelerated softening of stored apples. This study showed conclusively that low irradiation doses (300 and 600 Gy) combined with cold storage is a way to minimize apple quality losses during nine month storage period.     

Gamma radiation induced effects on silica and on silica-polymer interfacial interactions in filled polysiloxane rubber

We report in our studies to assess the impact of gamma radiation on silica and on the silica-polymer interface in filled polysiloxane rubber. Electron spin resonance (ESR) and solid-state nuclear magnetic resonance (NMR) studies have been performed on samples exposed to gamma radiation. In an effort to probe directly the effect of gamma radiation on the silica surface, we employed ¹H and ²⁹Si NMR. Our ESR studies show trapped paramagnetic species (positive holes and/or trapped electrons) within the host silica matrix for all samples exposed to gamma radiation. A sample of pure cab-o-sil irradiated to a dose of 50 kGy also shows an ESR signal. Our studies on real-time aged samples (derived from field trials) also show ESR signatures indicative of silica based trapped paramagnetic species. The growth of trapped paramagnetic species as a function of gamma dose was investigated. This shows that the build up of trapped species occurs rapidly at low gamma dose before reaching saturation at about 20-30 kGy. Radiation induced band gap excitation is the likely process leading to the creation of these paramagnetic species which may be trapped in regions of local charge deficit within the silica matrix. Species that are not trapped may take part in silica surface reactions leading to changes in filler-polymer interfacial interactions. NMR studies combined with ammonia modified swell studies have shown increased polymer segmental chain mobility (softening) at low gamma dose indicative of a possible reduction in filler-polymer interfacial interactions. For those samples exposed to high gamma dose, our ammonia modified swell studies suggest increased polymer-filler interactions presumably through silica-polymer crosslinking effects. Our ¹H and ²⁹Si NMR studies on irradiated silica suggest that the silica surface is sensitive to gamma radiation. Our observations are important as they highlight the need to better control the quality (size, purity, etc.) of the silica constituent in filled polymer components used in gamma radiation environments.     

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 ionizing radiation on physical properties of native and chemically modified starches

Cationic and anionic starches (chemically modified) and native starch (non-modified) were exposed to electron-beam irradiation at doses of 25, 75 and 150 kGy. The increasing solubility in water, due to chain scission and creation of polar groups as already mentioned in the literature, has been confirmed using several physical methodologies. Impedance Spectroscopy (IS) on water solutions was carried out in order to calculate the relaxation parameters of the Cole–Cole model and α and β parameters of the Jones–Dole equation, which show the influence of radiation dose on increasing polarity, decreasing of molecular mass and increasing of electrostatic attraction between chains. Infra-red spectroscopy (FTIR) and Differential Scanning Calorimetry (DSC) confirm the formation of polar groups that retain water. The aim of this work was to confirm that the control of chain scission and functionalization of starches with irradiation could then be used in a future work to create nanoparticles by complex coacervation in an aqueous base.     

Gamma radiation influence on technological characteristics of wheat flour

This study aimed at determining the influence of gamma radiation on technological characteristics of wheat (Triticum sativum) flour and physical properties of pan breads made with this flour. The bread formulation included wheat flour, water, milk, salt, sugar, yeast and butter. The α-amylase activity of wheat flour irradiated with 1, 3 and 9 kGy in a Gammacell 220 (AECL), one day, five days and one month after irradiation was evaluated. Deformation force, height and weight of breads prepared with the irradiated flour were also determined. The enzymatic activity increased—reduction of falling number time—as radiation dose increased, their values being 397 s (0 kGy), 388 s (1 kGy), 343 s (3 kGy) and 293 s (9 kGy) respectively, remaining almost constant over the period of one month. Pan breads prepared with irradiated wheat flour showed increased weight. Texture analysis showed that bread made of irradiated flour presented an increase in maximum deformation force. The results indicate that wheat flour ionizing radiation processing may confer increased enzymatic activity on bread making and depending on the irradiation dose, an increase in weight, height and deformation force parameters of pan breads made of it.     

Long term environmental effects on physical properties of vinylester composite pipes

Glass fiber reinforced vinylester pipes (GFRP) have been exposed to outdoor conditions for 60 months. The effect of the outdoor exposure on the glass transition temperature (Tg) and the crosslinking index is discussed. The Tg and the degree of crosslinking has been determined using differential scanning calorimetry (DSC). DSC has become a preferred technique for rapid determination of transition temperatures and crosslinking for pure polymers, however, the use of this technique for composites is quite complex. This complexity arises from the fact that, in addition to the temperature overlap between the Tg and that of the crosslinking range, the amount of glass fibers in the GFRP is not constant. For this reason, a special measuring technique has been developed for the measurement of the amount of crosslinking of GFRP material. In this paper, it is illustrated that the DSC results clearly show the glass transition temperature and the exothermic crosslinking reaction of the vinylester composites. The results show that the glass transition temperature of the vinylester rapidly increases with respect to exposure time up to 12 months and then slightly decreases for longer exposure times. Similar trends were also observed for the change of the degree of crosslinking. The outdoor environment has also affected the weight of the exposed GFRP samples. It is observed that the weight of GFRP has gradually decreased with the exposure time. These physical changes of Tg, crosslinking and weight have impact on the tensile strength of the GFRP. For the initial outdoor exposure up to 24 months there is a 12% increase in strength from 250 MPa to 280 MPa. This increase is attributed to about 12% increase in crosslinking of the GFRP. However, for longer exposure the tensile strength has decreased back to 250 MPa due to slight decrease in crosslinking and small reduction of weight. It is observed that most of the weight loss has taken place at the surface of the GFRP samples.     

Surfactant effects on the physical properties of mesoporous silica and silicates

Mesostructured silicas and silicates have been synthesized using hydrogels with molar composition: M:26.0SiO₂:5.2(C₂H₅)₄NOH:7.5[CH₃(CH₂)₁₅N(CH₃)₃]₂O:790H₂O, where M=0, Zr(OC₃H₇)₄ or Ti(OC₄H₉)₄. In all preparations, colloidal silica (Ludox) was used as the source of silica. The hydrothermal transformation at 110°C of these gels produced solids with the hexagonal structure typical of MCM-41 type materials. The effects of chain length and surfactant terminal alkyl groups on the properties of mesoporous materials containing Ti or Zr, have been investigated by using different surfactants such as cetyl trimethyl ammonium bromide and chloride, cetyl dimethyl ethyl ammonium bromide, and myristyl trimethyl ammonium bromide. When the surfactant's carbonyl chain decreased to 14 from 16 carbon atoms, a reduction in unit cell dimension and average pore diameter was observed in the mesoporous silicas, titaniumsilicates and zirconiumsilicates under study. Replacement of methyl groups with ethyl groups on the surfactant hydrophobic head, had no measurable effects on crystals' properties. However, a surfactant with a bulky aromatic head group, such as cetyl pyridinium chloride, inhibited crystallization. In general, the use of bromide in place of chloride salts yielded more ordered MCM-41 type crystals. The high thermal stability (to 800°C), surface area (1000–1500 m²/g), pore volume (0.90–1.20 cm³/g) and uniform mesoporosity (with pore diameter in the 2.9 nm–3.6 nm range), of these metalsilicates could be of particular interest in the preparation of catalysts requiring siliceous metal supports.     

Nonlinear effects of laser radiation and physical model of laser agglomeration process

Nonlinear effects of pulsed and continuous laser radiation on mineral samples from technogenic placers in the Amur river region, containing submicron gold which cannot be extracted by modern gravity separation methods, were studied. The formation of self-organized gold structures on the surface of silicate matrix was detected, and general relations for the agglomeration and concentration of “nonrecoverable” gold species were found. The agglomeration process was simulated by a nonlinear heat conduction equation for onedimensional case including laser radiation parameters.     

The effects of ionizing radiation on the thermophysical properties of substituted Sr-ferrites

Different samples of Sr-ferrites have been synthesized by the usual ceramic and high temperature sintering technique. On these samples, several measurements have been undertaken namely, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), the temperature dependence of DC electric conductivity before and after -absorbed dose, and the temperature dependence of dielectric constant. Results obtained were explained, correlated, interpreted and discussed in detail on the basis of the interaction of temperature, dopant cations and -radiation with the Sr-ferrite lattice. The activation energy (E), energy gap for semiconduction and activation energy for -radiation-induced carrier liberation () were evaluated for the first time. Finally, a mechanism for semi-conductivity in terms of energy band picture in intrinsic ferrite semiconductors is suggested and discussed.     

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.     

Carboxylic acid functionalization of nylon 6 by radiation grafting and conversion to zinc salts: Effects on physical properties

 Functionalization of polymers by grafting monomeric species on to the backbone of molecular chains with the use of γ-radiation has been used extensively. In this work methacrylic acid was grafted onto a commercial grade of polycaproamide (Nylon 6) by preirradiating the polymer granules to 15 kGy at a rate of 1.0 kGy per hour and subsequently immersing these in a 10% aqueous solution of methacrylic acid in the presence of small quantities of FeSO₄ as homopolymerization inhibitor. The polymer was subsequently neutralized by mixing it with zinc acetylacetonate in a laboratory scale melt mixing device. The acid-grafting polymer modification resulted in an increase in glass transition temperature, while the addition of zinc acetylacetonate gave rise to two transitions: The lower transition corresponds to a miscible mixture of free polyamide and acid-grafted polymer, both plasticized with undecomposed zinc compound, while the upper transition corresponds to the zinc salt of the acid grafted polyamide. Through rheological measurements it was shown that both the acid-grafted polymer and the derived zinc salt have a branched structure, possibly containing also some crosslinked domains. Large improvements in solvent resistance were observed for both type of polymer modifications. Received: 13 December 1996 Accepted: 10 February 1997     

Gamma irradiation effects on poly(hydroxybutyrate)

Brazilian poly(hydroxybutyrate), PHB, as well as its copolymer, poly(hydroxybutyrate-co-valerate), P(HB-co-HV), containing 6.3 mol% of valerate, were irradiated with γ radiation (⁶⁰Co) at ambient temperature and in the presence of oxygen. The viscosity-average molar mass (M_v) was analyzed by the viscosity technique using an Ostwald-type capillary viscometer. The polymers showed a decrease in molar mass with the increase in dose, reflecting the scissions that occurred at random in the main chain. The value G (scissions/100 eV of energy transferred to the system) and the parameter α (scissions per original molecule) were also obtained by the viscosity technique. The melting temperature (T_m) was determined by differential scanning calorimetry (DSC) and showed a decrease with increasing irradiation dose. Analyses of DSC also revealed double endothermic peaks, associated with the polymorphic transitions, which became a single peak with increased dose. Thermogravimetry analysis (TGA) revealed small differences between the decomposition temperatures of the irradiated and non-irradiated samples. The degree of crystallinity of PHB samples, on the other hand, which were obtained by the DSC and X-ray diffraction techniques, increased with the irradiation dose. Changes in the lattice parameter of the irradiated samples and in the size of the crystallites were also observed by X-ray diffraction. The samples used in this work did not pass through any purification process and were analyzed in powder form, exactly as they arrived from the factory.     

Gamma radiation synthesis of rapid swelling superporous polyacrylamide hydrogels

In this report a simple route for gamma radiation induced synthesis of superporous hydrogel (SPH) is described. Conventional SPH synthesis requires foaming and cross-linking reactions to take place simultaneously. However, in radiation synthesis it is difficult to introduce foaming during the cross-linking reactions. In order to overcome this limitation, the foaming and radiation cross-linking reactions were decoupled and carried out in two stages. The polyacrylamide SPH synthesized by this approach has very fast swelling kinetics compared to the non-porous hydrogel.     

Design of modified plastic surfaces for antimicrobial applications: Impact of ionizing radiation on the physical and mechanical properties of polypropylene

Surface modification of polypropylene (PP) sheets was carried out by radiation induced graft polymerization of hydrophilic functional molecules such as N,N-dimethylacrylamide (DMA) and [2-methacryloyloxy)ethyl] trimethylammonium chloride, which is a quaternary ammonium salt (QAS).Polypropylene sheets were activated prior to the grafting reaction by using electron beam radiation. The changes in morphology, crystallinity and tensile parameters like deformation and stress at yield and deformation at break of PP after irradiation were investigated. The results showed that a minor crystalline reorganization takes place during the irradiation of PP at 100 kGy.The grafting has been observed to be strongly dependent on the monomer dilution in the reaction medium. After grafting of QAS (40%) and DMA (20%) it was possible to develop highly hydrophilic surfaces (water contact angle comprised between 30 and 41°). The surfaces of virgin, irradiated and grafted PP were studied using polarized optical microscopy (POM) and scanning electron microscopy (SEM). Spherical particles (i.e. polystyrene or silica beads) adhering to the modified samples were studied according to the surface parameters. Adhesion tests confirmed the strong influence of substrate type (mainly hydrophilicity and roughness) and to a lesser extent underlined the role of electrostatic interactions for the design of plastic surfaces for antimicrobial applications.