Application of a pyrolysis-GC/MS system incorporating with micro-UV irradiation to rapid evaluation of the weatherability of acrylic coating paints for house exterior walls

A pyrolysis-GC/MS system incorporating with micro-UV irradiator (Xe-Hg lamp) was applied to the evaluation of the weatherability of the acrylic coating paints for house exterior walls. The deterioration of the materials during UV irradiation under thermal, and oxidative atmosphere was evaluated within a relatively short period of time with evolved gas analysis-mass spectrometry (EGA-MS) using a sub-milligram polymer sample. The EGA-MS thermograms indicated that both micro-UV irradiator with Xe-Hg lamp and weather meter with metal halide lamp caused similar photo, thermal, and oxidative degradation to the coating paint samples. Strong correlations between the results obtained by the UV/Py-GC/MS and that obtained by conventional weathering test using metal halide lamp was observed. It was suggested that UV/Py-GC/MS method could be used for compensating the conventional method by reducing the test period.     

In situ monitoring the thermal degradation of PCPDTBT low band gap polymers with varying alkyl side‐chain patterns

The degradation pattern of a series of low band gap PCPDTBT polymers under thermal stress is investigated by in situ UV–vis and FT‐IR techniques combined with thermal degradation analysis. Thermogravimetric analysis is used to predetermine the decomposition intervals, revealing that thermolysis occurs in two stages. TG‐TD‐GC/MS shows that loss of the alkyl side chains predominantly happens within the first temperature regime and degradation of the polymer backbone occurs thereafter. UV–vis spectroscopy is used to monitor the evolution of the optical properties upon heating, reflecting the thermal stability of the conjugated backbone, whereas FT‐IR spectroscopy is applied to evaluate the chemical changes under thermal stress, with an emphasis on the polymer periphery. The influence of the side chains and possible defects, dependent on the synthesis protocol applied, on the thermal stability of the final polymers is discussed and is related to the application of said materials in organic photovoltaics. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4912–4922     

Photodegradation of azodyes: comparison of different catalytic systems and control of the effective mineralisation

Three different azodyes were used as target molecules to test the efficiency of the photodegradation process catalysed by titanium dioxide under UV irradiation. A comparison of different catalytic systems was performed using the catalyst both free in solution (system I) and immobilised in a polymeric membrane (system II). Iron oxalate and a conducting polymer (polyaniline, PA) were added to the I and II systems respectively to check an eventual synergetic effect. The research evolved through three different steps involving each one the use of a different analytical method. Shortly, the UV spectrophotometry were preliminarily used to monitor the bleaching process and allowed to choose the best catalytic system, HPLC and GC/MS were used to monitor the appearance and disappearance of the photodegradation intermediates and, lastly, the effective mineralisation was tested by an indirect ICP (Inductively Coupled Plasma) determination of the produced carbon dioxide.     

Deterioration of surface structure of lacquer films due to ultraviolet irradiation

The mechanism of deterioration due to ultraviolet irradiation of black (with iron ion) and kurome (translucent) lacquer films that had been dried at 15–20 °C in 60–70% relative humidity environment was revealed. The lacquer film changes were evaluated by observations of the surface by microscopy, IR, and XPS. A particulate material and toroidal shapes appeared in the black lacquer film during UV irradiation within 48 h, but they did not appear in the kurome lacquer film under UV irradiation before 240 h. The IR peak at ～3445 cm^?1 increased owing to the hydroxyl group, and the C 1s peak decreased and O 1s increased in the XPS spectra as the UV irradiation time increased, implying that a chemical reaction occurred on the surface of the lacquer film. On the top surface of the coating film, many toroidal shapes were observed in the black lacquer film, which showed that the black lacquer film deteriorated more quickly than the kurome lacquer film. In addition, the structural changes in the black lacquer film are also discussed in detail, on the basis of the results of the Py‐GC/MS measurement. Copyright © 2006 John Wiley & Sons, Ltd.     

In situ modification of pyrolysis products of macromolecules in an analytical pyrolyser

An application of pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) is presented for the fast on-line testing of solid catalysts activity in upgrading pyrolysis oils and/or gases of natural and synthetic polymers. Evaluation of the chemical conversion by a catalyst is simply and quickly performed in a Py-GC/MS instrument without any modification either of the micropyrolyser or the GC inlet. The pyrolysis products evolved from the sample pass through catalyst microbeds of some mm length and the GC/MS analysis of the converted products is performed on-line. Modification of polyolefin, styrene copolymer, polyester, polyamide, brominated epoxy resin and wood pyrolysate was carried out applying sodium type zeolite and medium acidic mesoporous aluminosilicate in the microbeds. The primary pyrolysis products are converted over the microbeds due to the catalytic activity of the bed material. Intramolecular hydrogen transfer reactions promoted by Na zeolite results in the isomerisation of alkenes and alkadienes evolved by pyrolysis from polyethylene and polypropylene. These basic catalysts were found to be effective for the elimination of brominated phenols from the pyrolysate of brominated epoxy resin. Cracking of alkane and alkene oligomer products of polyolefins to light isoalkenes occur over acidic mesoporous aluminosilicate. Certain compounds with polar groups evolved from polyester, polyamide, cellulose or lignin are removed by this catalyst. Alkenylaromatic compounds are simultaneously hydrogenated and polyaromatised in pyrolysis oils of styrene copolymers over both acidic and basic aluminosilicate catalysts tested.     

Pyrolysis of flame retardants and fire protected polymers

The simultaneously working combination of thermal analysis and mass spectrometry (TA/MS) is a very useful method for studying the degradation process of polymeric materials during thermal treatment [1–7]. Beside the thermal effects, as recorded from thermogravimetry (TG) or differential thermal analysis (DTA) the evolved degradation products can be determined and identified by the on - line coupled mass spectrometer. Additional their temperature depending abundance can be registrated. Combustion of polymers in horizontal (BIS) or vertical (VCI) furnaces and subsequent off line high resolution GC/MS analysis of pyrolysis products is suitable for the simulation of burning processes     

QDTA/T/EGD/GC在线联同技术 Ⅵ.煤的热氧化、燃烧反应过程及其机理的研究

应用QDTA/T/EGD/GC在线联同技术及其装置,测定了四种不同变质程度的煤质之DTA/EGD/GC燃烧特性曲线,从中可提供如下三方面的信息和数据:(1)依据DTA测得的燃烧特性曲线,可取得在氧化、燃烧全过程中各项热特性的表征温度。(2)依据跟踪DTA逸出气成份的浓度变化所测得的EGD曲线,可了解不同煤质在热解、着火和燃烧特性等方面的差异。(3)依据DTA/EGD曲线的演变,可截取各个反应温度下之逸出气,进行在线的GC分析。在上述实验结果的基础上,应用过氧化物学说探讨煤的低温氧化反应机理。     

UV ageing studies: evaluation of lightfastness declarations of commercial acrylic paints

The lightfastness declarations of several different commercial acrylic paints and different quality series were tested by artificial UV ageing. To evaluate their lightfastness declarations, three acrylic colours (cadmium red, ultramarine blue and chromium oxide green) from six companies (Lascaux, Liquitex, Lukas, Rembrandt, Schmincke, and Winsor & Newton) were analysed before and after UV exposure. Characterisation and identification of these materials were carried out with Py–GC/MS, FTIR–ATR analyses, and colour measurements. Particular attention was focused on the Py–GC/MS measurements and on comparison of the single-shot method for pyrolysis of polymers and the double-shot mode which enables a unique combination of pyrolysis methods for analysis of polymers and thermal desorption for documentation of the volatile compounds. Depending on the particular company and the specific value of the lightfastness declaration, different binding media (i.e. poly(EA/MMA), poly(nBA/MMA), and poly(2-EHA/MMA)), and fillers (i.e. kaolinite, calcium carbonate, barite, and talc) were characterised and identified by Py–GC/MS and FTIR–ATR analyses. After UV exposure, several alteration processes with consequent formation of volatile compounds or new products were observed by both techniques, especially for the blue paints. In particular, the double-shot mode of Py–GC/MS enabled the detection of oxidation products, which could not be detected with the single-shot mode. Comparison of the lightfastness declarations for each of the blue, green, and red paints and the noted alterations broadly agreed for most of the paints.     

Degradation efficiencies and mechanisms of the ZnO-mediated photocatalytic degradation of Basic Blue 11 under visible light irradiation

A ZnO-mediated photocatalysis process was used to successfully degrade Basic Blue 11 (BB-11) under visible light irradiation. The effects of influential factors like initial dye concentration, catalyst dosage, and initial pH were studied. To obtain a better understanding the mechanistic details of ZnO-assisted photodegradation of the BB-11 dye with low watt visible light irradiation, a large number of the intermediates resulting from the photodegradation were separated, identified, and characterized by high-performance liquid chromatography–photodiode array-mass spectrometry (HPLC–PDA-MS) techniques. The results indicated that the N-de-alkylation and oxidative degradation of BB-11 dye took place and that N-hydroxyalkylated intermediates were generated during the process. From the same identified intermediates we got under UV or visible light irradiation, it is proposed that the major oxidant under visible light irradiation was OH radical, not O₂⁻. HPLC–PDA-MS analysis verified the identity of intermediates, and a reaction mechanism based on them was proposed.     

A pyrolysis-GC–MS investigation of poly(vinyl phenyl ketone)

The thermal decomposition process and pyrolysis products of poly(vinyl phenyl ketone) (PVPK) were investigated by thermogravimetric analysis (TGA) and on-line pyrolysis-gas chromatography–mass spectrometry (Py-GC–MS). TGA showed a largest weight loss rate around 380 °C. Py-GC–MS was used for the qualitative analysis of the pyrolysis products at 350, 500, 600, 700 and 850 °C. The major volatile thermal decomposition product was found to be 1-phenyl-2-propenone, which dominated all other volatile species especially under the least severe pyrolysis conditions (<600 °C). At higher temperatures a much wider range of pyrolysis products was obtained. The results have been interpreted assuming that primary random chain scission reactions occur followed by typical unzipping mainly producing monomer units; detachment of the side-group occurs only under more severe pyrolysis conditions. Py-GC–MS showed to be effective in PVPK detection in ink and paint formulations.     

Thermal Characterization of Materials Using Evolved Gas Analysis

Thermal analysis combined with evolved gas analysis has been used for some time. Thermogravimetry (TG) coupled with Fourier transform infrared (FTIR) spectroscopy(TG/FTIR), Thermogravimetry (TG) coupled with mass spectrometry (TG/MS), and Thermogravimetry (TG) coupled with GC/MS offers structural identification of compounds evolving during thermal processes. These evolved gas analysis (EGA) techniques allow to evaluate the chemical pathway of the degradation reaction by determining the decomposition products. In this paper the TG/FTIR, TG/MS, and Pyrolysis/GC-MS systems will be described and their applications in the study of several materials will be discussed, including the analysis of the degradation mechanisms of organically modified clays, polymers, and coal blends. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal Degradation Studies of Some Aliphatic Polyamides Using Hyphenated Techniques (TG-MS,TG-FTIR)

The thermal degradation of the aliphatic polyamides 6 and 66 was investigated by means of the combined techniques TA-MS and TA-FTIR. The analyses were performed in three different devices. Sample mass ranged from 13 mg to 1 g and heating rates of 2.6 and 10 K min^–1 were used in both air and nitrogen atmospheres. The most important decomposition products were caprolactam for PA 6 and cyclopentanone for PA 66. Evolution of NH₃ and HCN was registered. The findings of the two hyphenated techniques led to the same results and complemented each other well. The evolved products were captured and analyzed off-line by GC/MS for further confirmation of results.This revised version was published online in November 2005 with corrections to the Cover Date.     

TiO2膜电极光电催化降解苯甲酸的机理研究

利用自制纳米TiO2薄膜作电极, 对苯甲酸光电催化降解过程进行了系统研究. 同时利用扫描电镜(SEM)、X射线衍射图谱(XRD)和光电流-电压响应谱分析光催化剂的微观性质和光电性能. 选取较高的pH 10.5, 以利于苯甲酸降解中间产物的检测(GC/MS). 通过对比光电催化与单一的TiO2光催化体系中苯甲酸的降解动力学、总有机碳(TOC)的去除率、降解产物的生成(GC/MS)及活性自由基物种的产生(ESR), 提出光电催化降解苯甲酸的具体反应路径和氧化机理. 羟基化的苯甲酸在羟基自由基与活性氧自由基的共同作用下, 经由含六个碳原子的二酸(顺式己二烯二酸), 被进一步氧化成小分子酸和CO2.     

Synchronous fluorescence spectroscopy and gas chromatography to determine the effect of UV irradiation on crude oil

The fate of the crude oil under irradiation was studied. After the UV irradiation, the fraction present in the highest percentage shifted from C8–C9 fraction to C13 one, in GC–MS analysis. An increase of the relative amount of the C13–C25 fraction was observed, while a decrease in the relative amount of the C7–C12 fractions was present. The synchronous fluorescence spectrum showed a maximum at 396 nm. Two hours irradiation of the sample induced an increase of the fluorescence emission in the region 420–550 nm. After 20, 40, 60, and 100 h irradiation we observed a decrease of the fluorescence emission.     

Development of a multi-sample micro UV irradiator for accelerated deterioration of polymers

The authors previously developed a pyrolysis-gas chromatograph/mass spectrometry (Py-GC/MS) system incorporating a micro ultraviolet (UV) irradiator which allowed more rapid deterioration of polymeric materials compared to outdoor exposure tests and various accelerated weathering test methods such as weather meters. The micro UV irradiator, however, could handle only a single sample at a time. To achieve multi-sample deterioration in a short time, herein a new UV irradiator was developed by which up to 18 samples on a rotatable sample cup holder can be simultaneously deteriorated at a desired temperature under UV irradiation. The basic performance of the irradiator is evaluated in terms of the rate and reproducibility of accelerated deterioration by using high impact polystyrene (HIPS) as the test sample. The HIPS samples before and after deterioration are subjected to evolved gas analysis-mass spectrometry (EGA-MS) focusing on the changes in the peak width observed in the thermograms. High precision in the peak width measurements among the samples irradiated at various positions on the rotatable sample cup holder is observed with RSD values less than 4.3%. The newly developed irradiator for multi-samples requires a six times longer period to accomplish a comparable deterioration level than the previously developed irradiator. This lengthening can be attributed to the difference in the light intensities of both irradiators at the sample position. However, the relationship between the peak width and the irradiation time has similar profiles for both irradiators. This similarity indicates a good correlation of data measured by both irradiators.     

Analytical characterization of binding medium used in ancient Chinese artworks by pyrolysis–gas chromatography/mass spectrometry

In the present work, we attempted to characterize the natural organic binding medium mostly used in ancient Chinese artworks by using the pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS) technique. Chinese lacquer, tung oil, deer glue, colophony and peach gum were broadly used as binding media in Chinese paintings or painted pottery, and have been selected as the study materials in this paper. Artificially aged samples have been analyzed by Py–GC/MS in order to establish a useful reference as convenient and rapid analyses of real samples. The method is based on the on-line derivatization in the presence of excess tetramethylammonium hydroxide (TMAH) (25% aqueous solution) as methylating agent. Analyses results revealed that this simultaneous pyrolysis with methylation derivation technique (SPM) is very useful to the characterization of Chinese lacquer, tung oil and colophony but no obvious improvement to deer glue and peach gum. The fingerprint ions of each studied binding medium were established.     

Synthesis and characterization of saturated and unsaturated polysulfide polymers and their thermal degradation processes investigated by flash pyrolysis–gas chromatography/mass spectrometry

The synthesis of polysulfide polymers with unsaturated and saturated units in the backbone and their characterization by Fourier transform infrared, NMR, gel permeation chromatography, thermogravimetric analysis, and differential scanning calorimetry are reported. This is the first report on an analysis of the thermal degradation of an unsaturated polysulfide polymer [poly(2‐butene sulfide)] carried out by pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS). A unique phenomenon of exothermic degradation has been detected by differential thermal analysis and has been attributed to the energetics of the unsaturated polysulfide linkage during degradation. The thermal degradation products studied by Py–GC/MS indicate that the formation of sulfur‐containing products is more favored than the formation of non‐sulfur‐containing products. Furthermore, a comparative study of the thermal degradation of unsaturated and saturated polysulfide polymers has been conducted with thermogravimetry and Py–GC/MS analyses. These analyses have shown that the mechanisms of degradation of these polymers are different, and the lower number of pyrolysis products indicates a selective cleavage of the polymer during degradation in the saturated polysulfide polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 638–649, 2005     

High chemical and solvent resistant,branched terpene methacrylate polymers—Preparation,thermal properties,and decomposition mechanism

Branched terpene methacrylate polymers under UV‐polymerization process of methacrylates prepared based on naturally occurring terpene alcohols such as geraniol, nerol, and citronellol have been obtained. Amine catalysed reaction of geraniol, nerol, or citronellol with methacryloyl chloride allowed obtaining terpene methacrylate monomers with high yield. Their structure was confirmed by spectroscopic methods (¹HNMR, ¹³CNMR, ATR‐FTIR). The structure of the resulting polymers was evaluated by applying the ¹³C/CP MAS and ATR‐FTIR. The chosen physicochemical properties such as chemical resistance, solvent resistance, and thermal properties in inert and oxidative atmospheres have been studied. In addition, the detailed pyrolysis and oxidative degradation mechanism by applying the TG/DSC/FTIR/QMS‐coupled method was evaluated. The results indicated the potential application of novel, branched terpene methacrylate polymers for manufacturing products which could be utilized under corrosive conditions, due to their high resistance in both acidic and basic environments and different polarity solvents, as well as satisfactory thermal resistance.     

TiO2膜电极光电催化降解苯甲酸的机理研究

利用自制纳米TiO2薄膜作电极, 对苯甲酸光电催化降解过程进行了系统研究. 同时利用扫描电镜(SEM)、X射线衍射图谱(XRD)和光电流-电压响应谱分析光催化剂的微观性质和光电性能. 选取较高的pH 10.5, 以利于苯甲酸降解中间产物的检测(GC/MS). 通过对比光电催化与单一的TiO2光催化体系中苯甲酸的降解动力学、总有机碳(TOC)的去除率、降解产物的生成(GC/MS)及活性自由基物种的产生(ESR), 提出光电催化降解苯甲酸的具体反应路径和氧化机理. 羟基化的苯甲酸在羟基自由基与活性氧自由基的共同作用下, 经由含六个碳原子的二酸(顺式己二烯二酸), 被进一步氧化成小分子酸和CO2.     

Multifunctional, photochromic, acidichromic, electrochromic molecular switch: Novel aromatic poly(azomehine)s containing triphenylamine Group

Novel multifunctional polyazomethines containing triphenylamine structure in the main chain have been prepared via polycondensation of 4,4′-diformyltriphenylamine with aromatic diamines, which were characterized by elemental analysis, ¹H NMR, TG, DSC, and XRD techniques. The polymers with the decomposition temperatures of about 450 °C were heat resistant and amorphous. The UV–visible and PL spectra of polyazomethines were dependent on the diamines structures. The polyazomethines emit blue–green light at about 470 nm in pristine state and emit reddish orange at about 590 nm due to being doped with electrooxidation, acid or UV irradiation, respectively. The doped polyazomethines can go back pristine state under NH₃ vapor. The results suggest that the polyazomethines can be used as molecular switches, sensors or emitting dyes. The morphologies were investigated by AFM to be different appearance due to the natural structures of macromolecules and the convolution of self-assemblies during vaporization of solvent.