Near-crater discoloration of white lead in wall paintings during laser induced breakdown spectroscopy analysis

During Laser-Induced Breakdown Spectroscopy (LIBS) analysis of white lead pigment (basic lead carbonate, 2PbCO₃·Pb(OH)₂), used in wall paintings of historical interest, a yellow–brown discoloration has been observed around the crater. This phenomenon faded after a few days exposure under ambient atmosphere. It was established that the mechanism of this discoloration consists in lead oxides (PbO) formation. It was verified by further experiments under argon atmosphere that recombination of lead with oxygen in the plasma plume produces the oxides, which settle around the crater and induce this discoloration. The impact of discoloration on the artwork's aesthetic aspect and the role of atmosphere on discoloration attenuation are discussed. The mechanism is studied on three other pigments (malachite, Prussian blue and ultramarine blue) and threshold for discoloration occurrence is estimated.     

Stabilization of γ-sterilized biomedical polyolefins by synergistic mixtures of oligomeric stabilizers

The stabilization of polyolefins against γ-sterilization has been studied with single or binary additive system. The present attempt is to utilize synergistic mixtures of stabilizers which are approved for food contact applications. Ethylene-propylene (EP) copolymer has been melt-mixed with hindered amine stabilizers (HAS), phenolic antioxidants and organo-phosphites (hydroperoxide decomposer). Samples were sterilized with different doses of γ-radiation. Stabilization was characterized in terms of changes in the functional groups (oxidation products), tensile properties, yellowing and surface morphology by FTIR spectroscopy, Instron, colorimetry (reflectance) and scanning electron microscopy (SEM), respectively. Results were discussed by comparing the stabilizing efficiency of mixtures with and without phenol system. Among phenol containing systems, where we mostly observe discoloration due to the oxidation of hindered phenol and the combination of secondary HAS, tertiary HAS, organo-phosphite and hindered phenol exhibited improved stabilization efficiency than single or binary additive systems. The mixture of secondary HAS and tertiary HAS, has shown antagonistic effect of stabilization whereas their combination with organo-phosphite has exhibited synergistic effect of stabilization even at higher doses of γ-sterilization. The effects have been explained through the interaction between the stabilizers.     

Enhanced visible-light-driven photodegradation of Acid Orange 7 azo dye in aqueous solution using Fe-N co-doped TiO2

FeN -co-doped TiO₂ photocatalysts are prepared by sol–gel method using titanium tetraisopropoxide, urea and iron(II) acetylacetonate as precursors of titania, nitrogen and iron, respectively. The prepared samples are analysed from chemical-physical point of view by X-ray diffraction (XRD), Raman spectroscopy, UV–Vis diffuse reflectance spectroscopy (UV–Vis DRS), specific surface area measurements and scanning electron microscopy (FESEM). UV–Vis DRS spectra evidence that the co-doping of TiO₂ with N and Fe leads to the narrowing of the band gap value (2.7 eV) with respect to Fe-doped TiO₂ (2.8 eV) and N-doped TiO₂ (2.9–3 eV). XRD patterns show that photocatalysts are mainly in anatase phase and Fe and N ions are successfully incorporated into the TiO₂ lattice. The average crystallite size of Fe-N co-doped TiO₂ is slightly lower than the other samples and equal to about 7 nm and the specific surface area of the co-doped sample results to be 117 m² g⁻¹. Photocatalytic performances of all prepared samples are evaluated by analysing the degradation of Acid Orange 7 azo dye under visible light irradiation. Photocatalytic efficiency obtained using FeN co-doped TiO₂ strongly increases compared to undoped TiO₂, N-doped TiO₂ and Fe-doped TiO₂ photocatalysts. In detail, using the co-doped photocatalyst, dye discoloration and mineralization result equal to about 90 and 83% after 60 min of LEDs visible light irradiation, underlining the best performances of the FeN co-doped TiO₂ photocatalyst both in terms of treatment time and electric energy consumption.     

Synergistic effect of maleimido phenyl urea derivatives mixed with some commercial stabilizers on the efficiency of thermal stabilization of PVC

Four novel antimicrobial maleimido phenyl urea stabilizers 1–4 were synthesized from N-[4-(chlorocarbonyl) phenyl] maleimide with phenyl urea and its derivatives (p-methyl, o-chloro and p-carboxy). The effect of mixing maleimido phenyl urea stabilizer 2 with each of the reference stabilizers, dibasic lead carbonate (DBLC), cadmium-barium-zinc stearate (Cd-Ba-Zn stearate) or n-octyltin mercaptide (n-OTM), on the stabilization efficiency in thermal degradation of rigid PVC at 180 °C in air, has been investigated. Mixing was effected in the range of 0–100 wt% of stabilizer 2 relative to each of the reference stabilizers. The stabilizing efficiency was evaluated by measuring the length of the thermal stability period (Ts), the period during which no detectable amount of hydrogen chloride gas could be observed, and also from the rate of dehydrochlorination as measured by continuous potentiometric determination, and by the extent of discoloration of the degraded polymer samples. The results show a true synergistic effect from the combination of stabilizer 2 with any of the reference stabilizers. Mixing of the stabilizers improves the Ts values, decreases the rate of dehydrochlorination and lowers the extent of discoloration of the polymer. The maximum synergism was attained when stabilizer 2 is mixed with either of the three reference stabilizers in equivalent weight ratio (50%/50%). The observed synergism may be attributed to the different mechanisms by which the investigated and the reference stabilizers work.     

表面活性剂增敏动力学光度法测定痕量铜

建立了以表面活性剂为增敏剂,过氧化氢还原中性红褪色催化光度法测定痕量铜的新方法。找到了反应的最佳条件,并测定了一些动力学参数。据此建立了测定痕量铜的催化动力学分析法,线性范围为０－３．２μｇ／２５ｍＬ,检出限为８．２＊１０＾－１１ｇ／ｍＬ。方法具有线性范围宽,干扰离子少的优点,对于人发和指甲中铜的测定,结果满意。     

Discoloration of celluloses treated with amino compounds

Degradation and discoloration of celluloses treated with different amino compounds, including primary amines and hexamethylenetetramine (HMTA), were studied using spectroscopic techniques. The colour generation was measured using standard colorimetry and the degradation and discoloration were characterized using diffuse reflectance FTIR spectroscopy and diffuse reflectance UV-visible spectroscopy. The colour of all the treated celluloses was due to the same chromophores, thus revealing that the discoloration mechanism was essentially the same. The most important reaction was the condensation between carbonyl and amino groups to form coloured imines, and secondary processes were detected at high temperatures and long heating times. The discoloration of celluloses modified with primary amines followed first-order kinetics. However, the discoloration of HMTA-treated cellulose showed an induction period which was related to the thermal decomposition of HMTA.     

The effect of metal catalyst on the discoloration of poly(ethylene terephthalate) in thermo-oxidative degradation

Titanium-based catalyst and ethylene glycol antimony were used as catalysts to prepare poly(ethylene terephthalate) (PET), and the effect of the catalysts on the discoloration of PET in thermo-oxidative degradation was studied by UV-visible spectroscopy, Fourier transform infrared spectroscopy (FTIR) and fluorescence spectroscopy. Hydroxylation was found during thermo-oxidative degradation of both the titanium- and antinomy-containing PETs. However, more hydroxylated products were further changed into quinonoid species in the presence of titanium catalyst, which directly results in obviously enhanced coloration of the PET. It indicates that the PET synthesized with titanium-based catalysts is more susceptible to formation of quinonoid groups and discoloration than the PET prepared with ethylene glycol antimony.     

Thermal oxidation and molding feasibility of cycloolefin copolymers (COCs) with high glass transition temperature

Cycloolefin copolymers (COCs) with high glass transition temperature (T_g = 203 °C) have been synthesized and pelletized by extrusion molding. However, their colors change from transparent to yellow during extrusion molding because of thermal oxidation and generation of alkene groups. We have successfully blended several antioxidants (Irganox 1010, Irgafos 168, Irganox HP2225 and Irganox HP2921) into lab-made COCs to avoid the discoloration. The experimental results show that Irganox HP2921 is the best antioxidant among the antioxidants used and can effectively not only suppress thermal oxidation but also eliminate the color stain.     

Monitoring the degradation of stabilization systems in polypropylene during accelerated aging tests by liquid chromatography combined with atmospheric pressure chemical ionization mass spectrometry

Degradation pathways of three commonly used antioxidants were successfully studied by using accelerated aging tests for polymers. Additionally, thermal stability and resistance to discoloration of seven stabilizers were investigated by aging pure stabilizers dissolved in the polymer-mimicking solvent squalane. Methods based on high-performance liquid chromatography hyphenated with highly sensitive tandem mass spectrometric detection (HPLC-MS) were developed for structural elucidation of degradation products. Subsequent quantification was done using UV-detection. While Irganox 1330, Irganox 3114 and Cyanox 1790 showed a similar degradation mechanism with highly colored decomposition products, no corresponding oxidized species could be found for other stabilizers and less discoloration was observed. For Irganox 1010, hydrolysis was the preferred degradation mechanism, leading to products with an increased solubility in water. Therefore this stabilizer is less suitable for materials intended for water applications. In the aged materials previously unknown degradation mechanisms were observed for Irganox 1010 and Irgafos 168 which also contribute to the inhibition of autoxidation of the polymer.     

Gelatine sizing and discoloration: A comparative study of optical spectra obtained from ancient and artificially aged modern papers

The role of gelatine sizing in ancient paper discoloration is still subject to debate. In this report we have addressed this issue by comparing the optical reflectance of sized and non-sized artificially aged modern papers with reflectance data obtained from a set of ancient specimens. We have used different ageing procedures and prepared the gelatine following methods set down in ancient recipes. Gelatine-sized aged papers showed an optical response comparable with that of ancient paper specimens, while very small reflectance modifications were observed in pure cellulose unsized samples under the same ageing conditions. In addition, measurements carried out on pure gelatine films confirmed that gelatine plays a major role in paper discoloration. Some differences in discoloration effects induced by artificial and natural ageing on sized paper are discussed and a possible explanation is proposed.