Thermal,XRD and spectrophotometric study on artificially degraded woods

Thermogravimetry, differential thermal analysis, differential scanning calorimetry in oxygen flux were used to characterize two wood types: fir and chestnut woods. They were characterized by the peak temperatures of DTA, DTG and DSC curves and by the different mass losses evaluated on the basis of the measured thermal data. The samples were woods in powder obtained during sawing. Complementary characterization of the woods was performed by estimating the crystallinity of cellulose by means of X-ray powder diffraction. In order to simulate the degradation of wet woods, fir and chestnut woods were put into deionised water and into artificial sea water for several weeks; some samples of woods contained Cu and Fe nails to ascertain the effect of these metals on the degradation process. The thermal and X-ray diffraction measurements were then performed on the wet woods, following the same previous procedure. X-ray fluorescence was used to investigate the penetration of metals into wood samples.     

A multi-analytical study of degradation of lignin in archaeological waterlogged wood

Historical or archaeological wooden objects are generally better conserved in wet environments than in other contexts. Nevertheless, anaerobic erosion bacteria can slowly degrade waterlogged wood, causing a loss of cellulose and hemicellulose and leading to the formation of water-filled cavities. During this process, lignin can also be altered. The result is a porous and fragile structure, poor in polysaccharides and mainly composed of residual lignin, which can easily collapse during drying and needs specific consolidation treatments. For this reason, the chemical characterization of archaeological lignin is of primary importance in the diagnosis and conservation of waterlogged wood artifacts. Current knowledge of the lignin degradation processes in historical and archaeological wood is extremely inadequate. In this study lignin extracted from archaeological waterlogged wood was examined using both Py-GC/MS, NMR spectroscopy and GPC analysis. The samples were collected from the Site of the Ancient Ships of San Rossore (Pisa, Italy), where since 1998 31 shipwrecks, dating from 2nd century BC to 5th century AD, have been discovered. The results, integrated by GPC analysis, highlight the depolymerization of lignin with cleavage of ether bonds, leading to an higher amount of free phenol units in the lignin from archaeological waterlogged wood, compared to sound lignin from reference wood of the same species.     

High-resolution multiparametric MRI of contemporary and waterlogged archaeological wood

High-resolution NMR images on three different present-day wood samples and an archaeological wood specimen were presented and discussed. Although the spatial resolution is still low to perform dendrology for the exact identification of the wooden species, the T₂-spin-density weighted images exhibit contrasts that are in excellent agreement with optical histological images. On the other hand, T₂* and T₁-weighted images provide physiological information that is not obtainable by the usual light microscopic investigations. Moreover, the diffusion-weighted images show the anisotropic behaviour of the water diffusion coefficient quantified along and perpendicularly to vascular bundles (vessels and tracheids), which can be related to the morphology and size of wooden microstructure. This work suggests that high-resolution multiparametric MRI may be a useful tool to increase the information obtainable from the waterlogged archaeological wood remains in a completely non-invasive and non-destructive approach. Therefore, it would be desirable to further develop the hardware and functional characteristics of MRI scanners to improve their potential application in the field of wooden cultural heritage.     

Effect of accelerated thermal ageing on the thermal behaviour of the recently made parchments

To reveal the fire injuring of parchment, the changes in the thermal behaviour of some goat parchments, obtained from skins originating from different animals, as a result of thermal aging were determined by thermal analysis methods (DSC; simultaneous TG/DTG, DSC; micro hot table (MHT)). Thermal aging of parchments was revealed to bring about the decrease in shrinkage temperature, absolute value of enthalpy of denaturation in water and some changes in non-isothermal parameters characteristic for dehydration process in static air atmosphere. The results obtained by DSC analysis performed in N₂ and O₂ flows as well as those obtained by simultaneous TG/DTG, DSC analyses have shown that both softening (melting) process parameters and parameters of thermo-oxidative processes have not been changed by thermal ageing. The results obtained by thermal analysis methods were correlated with those obtained by microscopic investigation of parchment samples immersed in water and scanning electron microscopy (SEM). The application of these microscopic techniques has revealed the morphology changes in the investigated parchments as a result of thermal degradation.     

Surface characterization of untreated and hydro‐thermally pre‐treated Turkey oak woods after UV‐C irradiation

The aim of this study was to determine the effect of UV‐C irradiation on the Turkey oak wood surface (Quercus cerris L.). In order to compare the effect of irradiation, both untreated wood samples and those treated with steam and heat were analyzed. The steam treatments were carried out in an autoclave at 130 °C; samples were then heated in an oven for 2 h at 180 °C. The physical and chemical changes brought about in the untreated and treated wood samples by the UV‐C light were monitored by colorimetry (color changes), X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) (chemical composition) and scanning electron microscopy (SEM) (microstructure and morphology). A detailed analysis of the results indicates that the UV‐C treatment caused irreversible changes in both the chemical composition and morphology of the wood samples via photooxidation and photodegradation processes. Depending on the type of pre‐treatment used, these processes affected the wood samples differently. Copyright © 2014 John Wiley & Sons, Ltd.     

Analysis of lignin from archaeological waterlogged wood by direct exposure mass spectrometry (DE-MS) and PCA evaluation of mass spectral data

The chemical characterisation of waterlogged archaeological wood is of fundamental importance to understand the degradation processes undergone by wooden objects and consequently to develop suitable consolidation and conservation procedures. Lignin extracted from archaeological waterlogged wood samples was characterized using direct exposure electron ionisation mass spectrometry (DE-MS). DE-MS achieves a mass spectral fingerprint of the sample in a few minutes, avoiding any chemical pre-treatment and requiring only few micrograms of material.Mass spectral data were put in relation to the chemical composition of lignin and evaluated by means of principal component analysis (PCA). The preliminary results, presented in this study, demonstrate the feasibility and the potential of DE-MS as a reproducible and rapid screening method for archaeological waterlogged wood samples.     

Thermal analysis of new,artificially aged and archival linen

The thermal degradation of new, and artificially aged fine Ulster linen and archival linen specimens from 19th century paintings were compared using thermogravimetric analysis and differential scanning calorimetry. Thermal degradation data from new and artificially aged linen were found to be similar in nature. Archival specimens showed a decreased major degradation temperature, an increase in char remaining at the end of the experiment and some evidence of a depressed glass transition temperature. These indicate natural ageing through chain scission. Evidence of a two-stage degradation process was observed in some archival specimens suggesting that an unknown additive was present. This revised version was published online in July 2006 with corrections to the Cover Date.     

Analytical pyrolysis vs. classical wet chemical analysis to assess the decay of archaeological waterlogged wood

The macromolecular complexity of wood limits the possibility of obtaining complete chemical information on its alteration in archaeological objects. This paper compares the results obtained in the characterisation of the components of archaeological wood by a classical wet chemical method and by an instrumental method based on pyrolysis in presence of hexamethyldisilazane coupled with gas chromatography/mass spectrometry, Py(HMDS)–GC/MS. We compare the results obtained with the two methods quantitatively. This enables us to evaluate the efficiency of Py(HMDS)–GC/MS in assessing the chemical composition and the state of conservation of degraded wood. The material analysed consisted of reference sound wood and waterlogged wood from the ?ó?te historical site, located on a small island on Lake Zarańskie in Poland. The samples are from the remains of settlements dating to a period between the 9th and the 12th centuries AD.     

Thermal Degradation Study of Polymerization of Monomeric Reactants (PMR) Polyimides

A novel PMR polyimides (TMBZ-15) based on substituted benzidines is examined and compared to state-of-the-art PMR-15. The mechanism for the thermal decomposition of two specific PMR polyimides is obtained using TG/FTIR/MS techniques. In order to verify the pathway of polyimide degradation, a pyrolysis/GC-MS technique was employed to evaluate the organic degradation products, particularly the larger components that are destroyed in traditional TG/MS. A proposed degradation mechanism involves two main stages of decomposition, each of which produce a variety of products. The first group includes aromatic hydrocarbons, aromatic amines and nitriles, which correspond to partial fragments of polymer chains. The second group consists largely of fluorene, naphthalene and phenanthrene, which are attributed to the isomerization, rearrangements and cyclizations of the aforementioned pyrolyzates at high temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

Solvent and enzyme induced recrystallization of mechanically degraded hemp cellulose

The structural degradation of cellulose fibre from hemp (Cannabis Sativa L.) by a ball-milling process and the recrystallization behavior of the product were studied. A linear increase in the Brunauer–Emmett–Teller specific surface area was observed; indicating the fibre bundles were being crushed and disrupted to single fibres, which was confirmed by SEM. An increase in the milling duration gradually destroyed the crystalline structure of the cellulose fibres, observed by a reduction of the 002 plane intensity in wide angle X-ray scattering measurements. The crystalline order index calculated from the area ratio of the 002 to the 021, 10 and 002 planes was decreased from 65 to 36 after milling for 330 min. Subsequently the lower thermal stability of ball-milled fibre was observed from a decrease in the temperature at the maximum mass loss rate using thermogravimetry. An increase in solvent polarity, solvent-fibre ratio, agitation speed and drying rate resulted in the rearrangement of ball-milled cellulose crystalline structure to a greater order. Moreover, an increase in the BET specific surface area and the amorphous fraction improved the scouring efficiency of the ball-milled cellulose using the pectate lyase enzyme (EC. 4.2.2.2).     

Nanotechnology for Vasa Wood De-Acidification

The conservation of the seventeenth-century Swedish warship Vasa is a challenge due the unique history of its recovery and the delicate interventions made for its preservation. In the past years the strong acidity of wood came out as a threat for its conservation. The large amount of sulfur, produced by metabolic action of bacteria in the seabed, partly converted to sulfuric acid, catalyzes the chemical degradation of the wood through the acid hydrolysis of cellulose. This contribution reviews recent studies on the degradation of Vasa wood. We show how wood acidity can be neutralized by the application of calcium or magnesium hydroxide nanoparticles, forming an alkaline reservoir inside the wood that protect it from further acid attack. This has been evidenced by the thermal analysis carried out on fresh wood, Vasa wood, artificially degraded wood, and paper samples studied as reference cellulose-made materials. Pyrolysis temperature of cellulose was studied, as an important parameter of degradation, also related to the acidity of wood. Decreases in the pyrolysis temperature of degraded cellulose were correlated to decreases of its polymerization degree. Thermal analysis has been also used to investigate the wood de-acidification efficacy after the treatment with alkaline nanoparticles. Hydro-thermally aging, carried out on de-acidified Vasa wood samples demonstrated that de-acidification with nanoparticles facilitates protection of wood toward further acid degradation.     

Thermal studies to determine the accelerated ageing of flares

Summary Thermal analysis is an interesting technique to determine kinetic parameters of separate components, and also of a complete system to receive adequate information on the ageing process of pyrotechnic compositions. The investigated tracer is a tracking tracer of a Swiss missile. It is attached to a missile and produces during burning a red flame. The missile system is already in use for 15 years. Periodic inspections of the system take place every three years. These inspections, however only give information on the actual state of the tracer and not on the future state. The aim of this investigation is to predict the ageing behaviour of the tracer system to give additional information about the future use of the missile system. After two ageing profiles the tracer systems were tested on the test range at Armasuisse in Thun. The results of the testing show that an ageing period of 4 weeks at 60°C gives no changes in performance (light output and burning time). On the other side also a quite heavy ageing period of 4 weeks at 150°C was applied on tracer systems, which gives a dramatically change in burning time. The light output was even higher after this ageing profile, although the intensity changes a lot.     

杉木热解及燃烧特性热天平模拟试验研究

对南方森林主要树种－杉木的变工况热解行为进行了热重分析（TG）和差热分析(DTG)研究。将试样分别加热到200 ℃、300 ℃、400 ℃和500 ℃做空气变氮气、氮气变空气热天平试验,模拟实际火场由于火势发展产生的局部缺氧状态及由缺氧状态转变为富氧的状态;在空气气氛下将试样分别加热到250 ℃、300 ℃、350 ℃、400 ℃和450 ℃,然后冷却到50 ℃再继续加热直到700 ℃,模拟火场中可燃物不完全燃烧后的回燃情况。通过试验结果分析,深入研究了环境气氛变化对试样热解的影响。给出了杉木热解的两阶段一级反应模型,通过模型计算得出在233.3 ℃～369.9 ℃、369.9 ℃～490.8 ℃热解二阶段的活化能分别为77.85 kJ·mol－1、138.18 kJ·mo－1,频率因子分别为1.95×106、 4.84×109。     

丙烯酸化环状磷腈/环氧丙烯酸酯光固化体系热降解动力学研究

以TGA为手段, 进行了丙烯酸化环状磷腈/环氧丙烯酸酯光固化体系热降解动力学的研究, 同时与加入粉末状环状磷腈混合体系进行了对照. 采用Kissinger, Flynn-Wall-Ozawa和Friedman三种方法计算了固化膜降解反应活化能, 证明了磷腈结构的引入, 使得体系在高温阶段的活化能有所提高, 表明降解变得困难, 热稳定性得到提高. 而反应型丙烯酸化环状磷腈相对粉末状环状磷腈混合体系具有更高的降解活化能.     

Preparation and Study of Epoxidized Natural Rubber

Epoxidized natural rubbers (ENRs) with different extents of epoxidation (B) were prepared under various reaction conditions. The effects of the amount of H₂O₂ and the reaction time on B are discussed. The glass transition temperature T_g, the thermal degradation temperature and the activation energy of thermal degradation of the ENRs increase with B. The results indicate that the thermal stability of the ENRs increases with B.This revised version was published online in November 2005 with corrections to the Cover Date.     

Reactivity of Waterlogged Archeological Elm Wood with Organosilicon Compounds Applied as Wood Consolidants: 2D 1H–13C Solution-State NMR Studies

Some organosilicon compounds, including alkoxysilanes and siloxanes, proved effective in stabilizing the dimensions of waterlogged archaeological wood during drying, which is essential in the conservation process of ancient artifacts. However, it was difficult to determine a strong correlation between the wood stabilizing effect and the properties of organosilicon compounds, such as molecular weight and size, weight percent gain, and the presence of other potentially reactive groups. Therefore, to better understand the mechanism behind the stabilization effectiveness, the reactivity of organosilicons with wood polymers was studied using a 2D ¹H–¹³C solution-state NMR technique. The results showed an extensive modification of lignin through its demethoxylation and decarbonylation and also the absence of the native cellulose anomeric peak in siloxane-treated wood. The most substantial reactivity between wood polymers and organosilicon was observed with the (3-mercaptopropyl)trimethoxysilane treatment, showing complete removal of lignin side chains, the lowest syringyl/guaiacyl ratio, depolymerization of cellulose and xylan, and reactivity with the C6 primary hydroxyls in cellulose. This may explain the outstanding stabilizing effectiveness of this silane and supports the conclusion that extensive chemical interactions are essential in this process. It also indicates the vital role of a mercapto group in wood stabilization by organosilicons. This 2D NMR technique sheds new light on the chemical mechanisms involved in organosilicon consolidation of wood and reveals what chemical characteristics are essential in developing future conservation treatments.     

Study on the Thermal Behaviour and Flammability of the Modified Polyacrylonitrile Fibers

The effects of some kinds of metal ions used as chemical modifications on the thermal properties of the modified polyacrylonitrile (PAN) fibers were studied by DTA, TG, GC and cone calorimetry. The apparent activation energies for the decomposition of the unmodified and modified PAN fibers were determined using Kissinger equation and Broido equation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Comparison of rheological properties of cross-linked and thermal-mechanically degraded HDPE

Rheological properties of a high-density polyethylene (HDPE) subjected to thermal-mechanical degradation were compared with those of the HDPE degraded by the addition of small quantities of peroxides as free radical initiator. The high molecular weight fraction of HDPE changes quantitatively during processing, which has a remarkable effect on the rheological properties of the material, when the MWD narrows and the HMW tail decreases. The molecular weight distribution, especially the highest molecular weight fraction, is concluded to be more important than the long chain for HDPE rheology. © 1995 John Wiley & Sons, Inc.     

热分析法研究聚全氟乙丙烯非等温裂解反应动力学

本文从非等温差示扫描量热(DSC)曲线研究聚(?)氟乙丙烯(FEP)在空气中热裂解过程分为两个阶段的机制及其微分动力学方程。利用峰形指数确定的两个阶段的裂解反应级数,用多项式回归了相应的裂解活化能,指前因子随裂解率变化的规律及其补偿效应。