PVAc和PVB改性硅溶胶加固保护陶质文物的研究

为加固保护陶质物,用以硅溶胶为主体,PVAc(白乳胶）和PVB（聚乙烯醇缩丁醛）对其共混改性制成的无机－有机复合材料作为陶质物的增强保护材料,用最佳材料配方（硅溶胶30％－50％、PVAc20％－40％、PVB0．5％－1％）,在常温,常压下通过浸泡工艺对古陶片进行浸渗处理,结果表明：处理后陶片的吸水率由原来的14．74％下降到5．06%,耐酸度由原来的95．53％提高到98．73％,耐碱度由原来的97．61％提高到99．34％,抗压强度提高47．09％,抗折强度提高107．9％,同时不影响陶片的外观,该材料制备简单,使用方便（浸、涂、喷均可）,价格低廉,水作溶剂,无毒无害,把它作为陶质物的增强保护材料是目前最佳的选择,具有一定的社会效益和经济效益。     

文物保护用有机高分子材料及要求

物保护是采用自然科学的手段,在尊重物人因素的前提下,恢复物的完整性,并尽量延长物寿命的科学技术,对物进行的修复和保护,必然要采用许多的技术手段和物质材料。有机高分子材料是物保护中使用的一类重要的材料,在物保护中被用做物的加固材料、粘接材料、表面封护材料等。在物保护中使用的高分子材料包括：1．天然有机高分子材料(多糖、蛋白质、蜡等);2．水溶性合成树脂;3．溶剂型合成树脂;4．反应型高分子材料;5．高分子树脂乳液等。对保护材料的性能要求,包括制备、运输、储存、应用效果及安全方面,尤其强调材料的耐久性。另外对用于不同用途的高分子材料,有不同的要求,如表面涂层材料要求不改变物的外观,加固材料要求有好的渗透能力等。     

论文物保护科学研究的内容与方法

物保护科学是一门理科交叉的技术科学,其基本内容包括物保存环境研究、物材料性质研究和物修复技术研究。中重点论述了物保护科学的研究方法,即在进行物保护时首先对物保存环境和物材料性质进行研究,了解物发生“病变”的原因与过程,才可能做到“对症下药”,产生正确、合理、有效的保护方法。对环境研究在物保护中的重要性以及物保存环境的主要内容进行了讨论。同时也对环境、材料、修复技术三的关系以及物保护所应遵循的基本原则讲行了简单的讨论．     

文物保护技术新世纪展望

新世纪中有机氟材料将在物保护领域广泛应用,纳米材抖将从物保护新材料中脱颖而出,抑制微生物腐蚀将成为物保护工作重中之重,互联网将在物保护工作中发挥巨大效率。     

氮氧化物对文物的危害和变化规律

氮氧化物作为当前主要的空气污染物对物的危害也越来越受到物保护工作的关注。本介绍氮氧化物,由氮氧化物带来的二次污染－光化学烟雾中的氧化剂（O3和PAN）以及氮氧化物在气相或物体表面形成的气态HNO3和酸雨中的液态HNO3对各类物的危害作用。API公司生产的200型NOx分析仪对上海博物馆在龙吴路的库房和实验大楼周围环境中NOx与时间,空间、气象等因素的关系进行了连续测定。结果表明：每天清晨6：00－9：00,傍晚15：00－17：30是NOx的高峰时段;晴天NOx浓度明显高于阴雨天气;此外,NOx浓度与空间位置也密切相关。本结果为分析氮氧化物污染来源,选择物进出或保护处理的适宜时段以及选择合适的检测位置提供参考。     

故宫东华门城楼天花颜料胶结材料的科学研究

为研究故宫东华门城楼井口天花所用颜料胶结材料,通过热裂解-气相色谱/质谱联用仪(Py-GC/MS)、红外衰减全反射(ATR)面扫描对东华门绢本、纸本天花绿色颜料层分别进行分析检测。PyGC/MS分析表明绢本天花绿色颜料层所用胶结材料应为动物胶,且天花上有油脂类污染物;红外ATR面扫描分析确定纸本天花绿色颜料层所用胶结材料为蛋白质类材料,且可能为动物胶。研究结果有助于故宫东华门城楼井口天花制作工艺的研究及保护方案的制订。     

《文物保护与考古科学》征稿启事

《物保护与考古科学》杂志由上海博物馆主办和出版,季刊。刊号为CN31--1652／K。国际标准连续出版物号为ISSN1005-1538。为了促进我国物保护与考古科学技术发展,欢迎广大从事和关心物、图书和考古事业的科技人员、物保护和修复人员、传统工艺技师或研究、考古工作、大专院校师生和科技管理干部等踊跃投稿。     

中国明代木质古建西安鼓楼彩绘的分析研究

鉴于有关中国木质古建彩绘材料及技术的研究报道较少,本工作通过光学显微镜、扫描电镜能谱(SEMEDX)、X射线衍射及气相色谱质谱(GC/MS)分析方法,对建于公元1380年的中国西安明代鼓楼木建表面彩绘样品进行了科学检测研究,分析了其中的无机材料组成及彩绘所用粘合剂,并收集了所涉及到的相关历史资料。分析结果表明,木建表面彩绘的材料组成和制作技术与历史调查获得的信息完全吻合。地仗层主要由粘土、石灰、干性油(桐油)及纤维织物组成,且地仗层保持最初的原材料。颜料分析结果显示,尽管修复时所使用的粘合剂与最初建造时的粘合剂完全相同,但目前彩绘的颜料即有原来使用的材料,也有十八世纪修复时所使用的材料。     

文物保护中的“水害”问题

水是地球上分布最广泛的物质,几乎占去了地球表面的四分之三,地面上的任何物体始终遭受空气和水分的物理及化学作用。本阐述了各种状态下的水以及水在相态转变时对不同物材料的损害作用,以引起物保护工作对这一问题的重视。对于馆藏物,应控制环境湿度;对于室外物应依据环境和材料特征,查明水的来源,寻求防治对策。并且结合实例讨论了物保护中根据具体情况防止不同形态的水对物材料老化作用的一些措施,以供借鉴使用。     

纸质文物的热裂解气相色谱-质谱应用研究

对纸质文物的科学认知是保护这类珍贵文化遗产的关键。本研究将热裂解气相色谱-质谱(Py-GC/MS)技术应用到中国传统的四类典型手工纸(竹纸、麻纸、桑皮纸和构皮纸)的分析中,结果表明竹纸中苯酚类物质含量较高,桑皮纸和构皮纸中含有大分子三萜类特征物(如β-香树脂醇、α-香树脂醇和豆甾-3,5-二烯等物质),而麻纸中则无此类特征物——利用这些特征化合物可以区分竹纸、麻纸和桑皮/构皮纸。将这一成果应用到一副清代蜡笺纸对联的分析中：确定了该书法用纸为皮纸(桑皮纸或构皮纸);检测出长链脂肪酸和醇类物质,表明蜡笺纸的制作使用了蜂蜡;检测出吡咯及其衍生物,表明该书法蜡笺纸装裱时所用的胶结材料为动物胶;另外检测到了生物碱类物质,表明该蜡笺纸使用了植物染料。综合以上研究表明,Py-GC/MS方法不仅能够确定中国传统纸质文物的纤维来源,同时可以确定纸质文物上蜡、胶结物及染料等信息;结合传统的赫兹伯格(Herzberg)染色法,进一步确定了皮纸的具体种类。蜡笺纸文物材料信息的检测识别可为文物保护与修复工作提供科学依据,此研究方法为纸质文物的科学认知提供新思路。     

DETERMINATION OF PIGMENTS AND BINDERS IN POMPEIAN WALL PAINTINGS USING SYNCHROTRON RADIATION – HIGH‐RESOLUTION X‐RAY POWDER DIFFRACTION AND CONVENTIONAL SPECTROSCOPY – CHROMATOGRAPHY

The employment of synchrotron techniques complemented by conventional laboratory systems has allowed us to deepen and improve our knowledge of Roman wall painting procedures. The palette identified in wall paintings from Pompeii and Herculaneum from the second century bc includes goethite, hematite, cinnabar, glauconite, Egyptian blue, and other components such as calcite and aragonite. Proof of the use of organic binders is provided by FTIR and PY–GC/MS. Therefore, the possibility of the use of ‘a secco’ techniques cannot be ruled out. Pigments in wall paintings are usually found in small percentages and conventional X‐ray diffractometers do not detect them. Synchrotron radiation – high‐resolution X‐ray powder diffraction has allowed identification with only a few micrograms of sample.     

Evidence of early tobacco in Northeastern North America?

While tobacco use was a widespread and important social practice among Native Americans during the Historic Period, the prehistoric origins of the practice are poorly understood. Smoking pipes significantly predate botanical evidence of tobacco in Eastern North America. A promising technique for addressing this problem is gas chromatography/mass spectroscopy (GC/MS) analysis to identify nicotine or related compounds in smoking pipe residues. GC/MS analysis of a smoking pipe dating to approximately 300 B.C. from the Boucher Site, a Middlesex-complex site from Vermont, has produced evidence of nicotine decay products. This is interpreted as evidence for an Early Woodland Period origin for tobacco use in Eastern North America. The cultural and chronological implications of this finding are discussed.     

Analysis of resinous material present on an alabaster lid excavated from Nabataean Moa in the Arava valley

An alabaster lid with a resinous accretion burnt or stuck next to the handle and on the base was uncovered in the Nabataean rest stop in Moyat Aawad (Moa) in the Arava valley in Israel. The analysis of this resin sample utilising GC‐MS revealed several types of compounds. The chemical analysis revealed compounds typically present in pine tar and plant lipid material (probably oil). The use of pine resin, tar and pitch derived from plant resins is documented in antiquity, not only as a sealant or caulking material but also as medicines, antiseptics and ritual balms.     

Integrated Analytical Techniques for the Study of Colouring Materials from Two Megalithic Barrows

We have determined the composition of rock art pigments from two megalithic barrows located in the north of Portugal. The use of XRD, SEM–EDS and FT–IR spectroscopy confirmed the presence of hematite and kaolinite in the red pigments from the Eireira barrow, and kaolinite in the white pigment from the Leira das Mamas barrow. The organic composition of the pigments was studied by GC–MS, suggesting that the red sinuous lines and dots from the Eireira barrow were prepared with cooked or heated algae and/or aquatic plants, with egg as binder, while the white pigment from the Leira das Mamas barrow revealed a mixture of vegetable oils for kaolinite moulding, which could be stabilized by temporary exposure to high temperatures. The multi‐analytical approach used on this study of megalithic pigments allowed the recovery of important data about north‐western prehistoric communities, namely the way in which they exploited existing resources and their ability to transform them.     

The painting of the Etruscan “Tomba della Quadriga Infernale” (4th century BC), in Sarteano (Siena, Italy): technical features

This work presents the results of an investigation of the painting technique used in the Etruscan tomb “Tomba della Quadriga Infernale”. This tomb was discovered in Sarteano (Siena, Italy) in October 2003 and dated back to the second half of the 4th century BC. Red, dark red, pink, yellow, white, black, and grey colours were used in the tomb in order to create paintings, which now represent a very precious record of the Etruscan art of wall painting in a hypogeal environment. The technical features of the painting were revealed by stratigraphy using optical and electronic microscopy. The components and preparatory layers of the painted areas were characterized using Fourier transform infrared spectroscopy (FTIR), energy dispersive X-ray microanalysis (SEM-EDS), X-ray diffraction (XRD), and gas chromatography/mass spectrometry (GC/MS). XRD, SEM-EDS, and optical microscopic techniques were also used for mineralogical analysis of the rock substrate. The SEM-EDS and FTIR analyses showed that red and yellow ochre, calcite, and vegetable charcoal were used to paint the walls of the tomb: the pigments, either alone or mixed together, were utilized to produce pure colours (red, yellow, white, and black) and intermediate tonalities (pink, dark red, and grey). SEM-EDS, FTIR, and XRD highlighted that the painting was made on a preparatory layer of calcite, applied onto a levelling material made up of calcite, clay minerals, quartz, and iron oxides. GC/MS analyses revealed that egg was used as an organic binder to disperse the pigments.     

Current research on smoking pipe residues

This paper presents research into the identification of tobacco residues in ancient smoking pipes. Two techniques have been used so far: gas chromatography/mass spectroscopy (GC/MS), and Raman microscopy. GC/MS has been used successful in the past by the author to identify ancient tobacco residues, and the results of this round of analysis support prior research. Raman microscopy, which has the advantage of working on dry samples without solvents, was not successful. It appears that combustion products overwhelm any useful signal that would identify the substance smoked. We are pursuing the use of Raman in non-combusted samples.     

Identification of organic materials in icons of the Cretan School of iconography

The Cretan School of iconography is the last great flowering of the traditional Byzantine painting manner, which is however influenced by different schools and western art. Despite their historical significance, icons of the Cretan School have been rarely studied through modern chemical techniques and therefore very few information is available on the materials used by the Cretan painters. In the present investigation, the organic materials contained in several icons of the Cretan School of Iconography from the collection of the Benaki Museum, Athens, Greece, are analyzed and identified by High Performance Liquid Chromatography coupled to a Diode Array Detector (HPLC–DAD) and Gas Chromatography with Mass Spectrometry (GC–MS).The HPLC–DAD results provide support to a recently published report which showed that kermes used in “Cretan” icons of 15th century and early 16th century was replaced by cochineal which was used in icons dated after early 16th century. This trend is known for western art and it is now proved for Cretan icons, showing thus the influence of the Cretan painters by other European painting schools. Other dyes detected in the historical samples, extracted from Cretan icons are madder (possibly Rubia tinctorum L., according to HPLC profiles) and indigoid dyes. Oils, such as linseed and walnut oil, are identified in samples extracted from the seven icons tested by GC–MS. Egg yolk is identified in the extract of only one icon and animal glue, originated most likely from the gesso ground, is found in six samples. Other organic materials detected by GC–MS were wax, as well as synthetic resins, applied during conservation treatments.     

SCIENTIFIC INVESTIGATIONS OF ANTIQUE LACQUERS FROM A 17TH‐CENTURY JAPANESE ORNAMENTAL CABINET

A recent restoration of a 17th‐century Japanese lacquer cabinet revealed various later treatments over the original black coating to maintain and preserve the high gloss of the oriental cabinet over the course of time and to meet changing tastes. The comprehensive investigation on a series of coating samples was executed by means of two hyphenated techniques: gas chromatography – mass spectrometry (GC–MS) and pyrolysis combined with GC–MS (Py‐GC–MS). The results showed that the original lacquer is based on urushi and linseed oil, while the past interventions are composed of sandarac, shellac and dammar. Additional microscopic studies proved the multi‐layer structure of the lacquer and the use of different pigments.     

QUANTIFICATION AND DISTRIBUTION OF LIPID IN ARCHAEOLOGICAL CERAMICS: IMPLICATIONS FOR SAMPLING POTSHERDS FOR ORGANIC RESIDUE ANALYSIS AND THE CLASSIFICATION OF VESSEL USE

Organic residue analysis has been performed on 62 reconstructed vessels from a single archaeological site (Rounds, Northamptonshire, U.K.). In order to establish regions of lipid accumulation within a vessel, sherds were sampled from different parts of a vessel, for example base, body and rim, and submitted to lipid extraction procedures. The techniques of high-temperature gas chromatography (GC) and GC/mass spectrometry (GC/MS) were then used to analyse the sherd lipid extracts. The quantitative results obtained show differential accumulation and preservation of lipid in various parts of the same vessel. This latter observation has serious implications for the sampling of potsherds for organic residue analysis. Furthermore, the amount of absorbed lipid varies quite considerably between vessel types. On this basis, a new method is proposed for classifying vessel use by comparing the concentration of lipid present in different parts of individual vessels.     

Analysis of adhering organic residues of two “coupes-à-socles” from the Neolithic funerary site “La Hougue Bie” in Jersey: evidences of birch bark tar utilisation

The “coupes-à-socle” (footed cups) are ceramics which can be found in domestic Neolithic contexts in Brittany (Castellic, Auzay-Sandun), but more generally in non-domestic areas. Their ceremonial function has often been evoked, in particular as a perfume burner. The analysis by GC and GC/MS of two samples from the “Hougue Bie” (Jersey) passage graves showed the presence of vegetable fatty acids, degraded n-alkanes and terpenoïds, biomarkers of birch bark tar. The presence of such substances could be explained either by the use of the “coupes-à-socle” for burning birch bark tar as an odoriferous product or their use as an everyday vessel for heating and increasing tar plasticity. However, the limited occurrence of this type of ceramic in habitat sites supports the former utilisation. This first report of the presence of birch bark tar in “coupes-à-socle” thus suggests use of this tar as an odoriferous product, in addition to its numerous, previously recognised, more technical uses.