氟碳涂料在铁质文物封护中的应用研究

氟碳涂层有良好的耐候性、抗腐蚀性,作为文物封护材料在我国已经得到了一些应用,然而按照工业方法直接实施封护,不能很好满足文物封护保护低光泽度、可再处理等特殊要求。为此,对氟碳涂料在铁质文物保护中的实施工艺进行了研究。研究了一系列氟碳涂层的封护性能,测试了涂层的机械性能、防腐性能、耐候性能和热性能,使用红外光谱对暴晒前后的涂层进行了分析,结果表明:在氟碳涂料中添加纳米二氧化硅和采用复合涂层可以有效的保护室外铁质文物,二氧化硅的加入提高了涂层的热稳定性。     

大雁塔盐害及劣化模拟试验研究

易溶盐富集是陕西西安大雁塔砖体表面风化、结构破坏、强度衰减的主要原因。为分析盐害对大雁塔砖体结构、强度的影响机理,采用以饱和硫酸钠溶液为介质,对大雁塔砖体进行易溶盐结晶循环模拟劣化试验。在Na₂SO₄反复结晶、溶解过程中,测定试样的质量、波速及单轴抗压强度等指标,分析其变化规律。结果表明,在盐害作用下,试验砖体表现出与塔体表面类似的风化破坏现象;Na₂SO₄晶体在试样孔隙内不断发育,晶体挤压效应导致孔隙率增大,内部结构破损;质量、波速、单轴抗压强度随循环的次数呈先增加后减小的变化规律。砖体对盐害耐受力约为砖体质量的0.5%。     

大理岩石刻文物黑色结壳清洗研究

大理岩是古代石刻和建筑的主要石材之一。随着近现代工业发展,很多大理岩石刻文物表面出现了大量黑色结壳——不仅严重影响了文物外观审美,而且会不断吸附各种污染物,吸收更多的辐射热量,造成文物的进一步劣化,因此亟需清洗。在前期对北京地区石刻文物本体及黑色结壳科技分析的基础上,选用碳酸铵法、乙二胺四乙酸法、物理法进行清洗试验用于对比,并于北京不同区域的6处典型石刻上进行现场试验,根据实际情况做出优化改良。采用便携式X射线荧光光谱仪、分光测色仪、显微镜和离子色谱仪对清洗前后状态及可溶盐含量进行评估,结果表明碳酸铵法对大理岩石刻文物表面黑色结壳具有较好的清洗效果,清洗方案比较高效合理,有助于相关石质文物病害的清洗和保护。     

The geochemical evolution of very dilute CO2‐rich water in Chungcheong Province,Korea: processes and pathways

A geochemical study was carried out on the CO₂‐rich water occurring in granite areas of Chungcheong Province, Korea. In this area, very dilute and acidic CO₂‐rich waters [62–242 mg l^?1 in total dissolved solid (TDS), 4.0–5.3 in pH; group I) occur together with normal CO₂‐rich waters (317–988 mg l^?1 in TDS, 5.5–6.0 in pH; group II). The concentration levels and ages of group I water are similar to those of recently recharged and low‐mineralized groundwater (group III). Calculation of reaction pathways suggests that group I waters are produced by direct influx of CO₂ gas into group III type waters. When the groundwater is injected with CO₂, it develops the capacity to accept dissolved solids and it can evolve into water with very high solute concentrations. Whether the water is open or closed to the CO₂ gases becomes less important in controlling the reaction pathway of the CO₂‐rich groundwater when the initial pco ₂ is high. Our data show that most of the solutes are dissolved in the CO₂‐rich groundwater at pH > 5 where the weathering rates of silicates are very slow or independent of pH. Thus, groundwater age is likely more important in developing high solute concentrations in the CO₂‐rich groundwaters than accelerated weathering kinetics because of acidic pH caused by high pco ₂.     

陇山地区宋金砖室墓述议

宋金时期陇山地区流行仿木结构砖室墓,墓室砖雕内容有孝子故事、家居活动与动植物等,在墓葬形制、砖雕装饰与丧葬习俗方面与其他地区既有相似性,又有地域特点。部分砖雕的异域风格表现了宋金时期陇山地区居民在墓葬文化上的兼容并包。陇山地区的宋金砖墓为研究本地区宋金时期丧葬文化特点与周边地区的关系、地域文化特征提供了重要的考古资料。     

Chemical analysis of white porcelains from the Ding Kiln site, Hebei Province, China

The Ding kilns were some of the most famous early kilns of medieval China, producing huge quantities of white and cream-white porcelains of outstanding technical and aesthetic quality. Since 1949 they have been excavated three times, in 1965, in 1987, and in 2009 respectively. In this latest study 69 white porcelain sherds from assured contexts and from the 2009 excavations were analyzed using laser ablation techniques (ICP-AES). The samples date from Five Dynasties, Northern Song and Jin Dynasties respectively (early 10^th to early 13^th C CE). The results show that Ding wares of different times show different characteristics that can be demonstrated through chemical composition. During the early phase of production the Ding ware bodies consisted largely of high firing kaolinitic clays with predominantly calcareous materials as fluxes. After the early Northern Song Dynasty, some calcareous material was replaced by a more potassic material. The compositions of the glazes show a parallel evolution to the bodies. However, because the glazes are very low in titania it seems unlikely that the main clay ingredients of the bodies could have been used in the glaze recipes. For much of the kiln site’s history the glazes appear to have been made mainly from the same siliceous flux-rich materials that had been blended with the main body-clays used to make the Ding ware porcelains, plus some extra calcareous material. The P₂O₅ contents of the glazes suggest that wood ash may have been one source of CaO in the glaze recipes.     

临水窑与介休窑白底彩绘工艺的对比研究

白底黑花装饰风格的瓷器,始终是陶瓷、科技界和陶瓷爱好者关注的热点。临水窑(磁州窑)与介休窑白底黑花风格的瓷器之间有着密切的联系,但是对于两窑产品的科技分析甚少,至于两者的对比研究更是无从谈起。因此,本工作利用岩相分析、SEM-EDS等方法分析了临水窑(磁州窑)、介休窑样品的瓷胎、化妆土及瓷釉的化学成分和显微结构。比较分析显示,两窑样品的瓷胎均为低硅高铝配方,且介休窑瓷胎中的Al2O3含量更高;两窑瓷胎粗糙,Fe2O3、TiO2含量较高,致使其呈浅黄色。瓷胎表面均施有化妆土,所不同的是,介休窑的瓷胎表面施有两层化妆土,其靠近釉的一层化妆土(h2),Fe2O3、TiO2含量极低,靠近胎的一层化妆土(h1),Fe2O3、TiO2含量较高;临水窑样品的瓷胎表面仅施一层化妆土,其Fe2O3、TiO2含量较低,但高于介休窑近釉层化妆土中的相应含量。介休窑瓷釉为典型的高钙釉,而临水窑则为典型的碱钙釉和钙碱釉。不难认识到,介休窑似在临水窑白底黑花及化妆土工艺的基础上,因地制宜,勇于创新,形成了成本低廉、技术先进的两层化妆土工艺,在当地原料较为粗糙的条件下,生产出质量较好的白底釉下彩绘瓷器。     

Decreasing CO2 partial pressure triggered Mg–Fe–Ca carbonate formation in ancient Martian crust preserved in the ALH84001 Meteorite

We retrace hydrogeochemical processes leading to the formation of Mg–Fe–Ca carbonate concretions (first distinct carbonate population, FDCP) in Martian meteorite ALH84001 by generic hydrogeochemical equilibrium and mass transfer modeling. Our simple conceptual models assume isochemical equilibration of orthopyroxenite minerals with pure water at varying water‐to‐rock ratios, temperatures and CO₂ partial pressures. Modeled scenarios include CO₂ partial pressures ranging from 10.1325 to 0.0001 MPa at water‐to‐rock ratios between 4380 and 43.8 mol mol^?1 and different temperatures (278, 303 and 348 K) and enable the precipitation of Mg–Fe–Ca solid solution carbonate. Modeled range and trend of carbonate compositional variation from magnesio‐siderite (core) to magnesite (rim), and the precipitation of amorphous SiO₂ and magnetite coupled to magnesite‐rich carbonate are similar to measured compositional variation. The results of this study suggest that the early Martian subsurface had been exposed to a dynamic gas pressure regime with decreasing CO₂ partial pressure at low temperatures (approximately 1.0133 to 0.0001 MPa at 278 K or 6 to 0.0001 MPa at 303 K). Moderate water‐to‐rock ratios of ca. 438 mol mol^?1 and isochemical weathering of orthopyroxenite are additional key prerequisites for the formation of secondary phase assemblages similar to ALH84001’s ‘FDCP’. Outbursts of water and CO_2(g) from confined ground water in fractured orthopyroxenite rocks below an unstable CO₂ hydrate‐containing cryosphere provide adequate environments on the early Martian surface.     

洛阳洛龙区关林庙宋代砖雕墓发掘简报

2009年10～11月,洛阳市文物工作队在洛龙区关林庙东南发掘了一座宋代墓葬,为一座仿木结构单室砖墓,由墓道、甬道和墓室三部分组成,已被盗扰。墓室呈八边形,墓壁有砖雕装饰,小型砖雕内容为孝子故事,共10件23幅,除一幅外,均有榜题;大型砖雕内容为散乐、备宴、杂剧等。这些砖雕质地坚硬,制作规整,表面无刀刻痕迹,人物线条圆润流畅,可能是将砖坯放入刻好的模子内成形。根据墓葬形制和砖雕内容,推断此墓的时代应为北宋晚期。     

PIGMENT IDENTIFICATION IN GREEK POTTERY BY RAMAN MICROSPECTROSCOPY*

Raman microspectroscopy (RMS) is now established as a key technique for the identification of pigments of archaeological pottery that permits the in situ study of art objects by a non‐destructive procedure. The information obtained represents a great aid to restoration and conservation techniques. In this work, the chemical nature of the red, black and white pigments of five samples of Greek pottery from the end of the fifth century and the first half of the fourth century bc , exhumed from the Iberian necropolis of Cabezo Lucero (Guardamar del Segura, Alicante, Spain), has been identified. The black and the red pigments are found to be magnetite (Fe₃O₄) and hematite (α‐Fe₂O₃), respectively. The white pigment is found, for the first time, to be composed of alumina (α‐Al₂O₃ and γ‐Al₂O₃) probably yielded by the thermal decomposition of Greek bauxite.     

北石窟寺表面防风化材料筛选

甘肃石窟分布广泛,洞窟大多开凿在砂岩上。在长期自然环境作用下,砂岩石窟表面风化严重,有部分区域甚至风化成砂土,砂岩石窟浅表层风化防治将成为重要的研究方向。本工作针对北石窟寺砂岩典型风化病害,选用0.5%羟甲基纤维素、5%砂岩加固材料、1.5%有机硅改性丙烯酸、1.5%丙烯酸、20%纳米SiO₂、10%正硅酸乙酯、3%PS共7种保护材料,基于室内试验测试这些材料的防风化性能,以加固前后宏观和微观特征进行定性描述,以色度、体积变化率、波速、表面硬度、抗压强度、透气性和吸水性作为加固定量评价指标,优选出砂岩加固材料、有机硅改性丙烯酸、纳米SiO₂、PS和正硅酸乙酯作为北石窟砂岩表面防风化加固建议材料。研究结果为北石窟寺砂岩质石窟表面防风化技术研发与应用积累了基础研究数据。     

山东香山汉墓出土陶质彩绘文物材质及制作工艺的初步研究

山东青州香山汉墓陪葬坑出土了数量巨大,种类齐全陶质彩绘文物,尤其是陶马和陶俑上的彩绘保存完好,色彩鲜艳,绘画工艺精湛,非常罕见。为了研究汉代彩绘及其制陶工艺等信息,本研究使用拉曼光谱(RS)、带能谱的扫描电镜(SEM-EDX)、偏光显微镜(PLM)、体式显微镜(OM)、X射线荧光光谱(XRF)、X射线衍射(XRD)、热膨胀仪等分析方法,对出土的陶质彩绘文物进行了分析研究。结果表明这批陶质彩绘文物制作工艺是就地取土,与水混合塑型,在900~1000℃烧制陶胎。其彩绘所使用的颜料均为矿物颜料,其中白色为方解石(CaCO3)、红色为赭石(Fe2O3)和朱砂(HgS)、黑色为炭黑(C)、紫色为人造汉紫(BaCuSi2O6),采用胶料调和颜料调涂刷绘制而成。这批文物的制作工艺属于典型的秦汉时期彩绘陶器的制作方法。研究成果可为相关文物的保护提供科学数据。     

重庆大足大佛湾彩绘绿色和蓝绿色颜料的分析研究

为了确定重庆大足大佛湾彩绘含铜、砷元素的绿色及蓝绿色颜料显色成分,应用便携式X射线荧光光谱仪(XRF)、便携式显微镜等无损调查方法,结合X射线衍射分析仪(XRD)、扫描电镜-能谱仪(SEM-EDX)、X射线光电子能谱分析仪(XPS)、显微拉曼光谱仪(RM)等分析方法,对取自大佛湾塑像的绿色及蓝绿色颜料进行调查和分析。结果表明绿色颜料显色成分为为巴黎绿,蓝绿色颜料显色成分为氯砷钠铜石[NaCaCu₅(AsO₄)₄Cl·5H₂O]。根据研究结论推断,氯砷钠铜石可能为巴黎绿的变色产物。该结果为探讨近代人工合成颜料变色机理提供了新的线索和方法。     

浙江松阳出土南宋剔犀漆器的制作工艺及材质的研究

为了研究中国古代漆器的髹漆工艺并为漆器的保护修复提供相应的科学依据,本研究通过显微镜、显微红外光谱、扫描电镜、X射线荧光光谱、显微激光拉曼光谱等方法对浙江松阳出土南宋剔犀漆器残样的制作工艺和材质进行了研究分析。分析结果说明该漆器采用杉木作为漆胎,并在其上涂刷了以高岭土(AL2_O_3·2SiO_2·2H_2O)与动物毛发为主要成分的胎地填料(底灰)。然后分别在器物内外表面上髹饰上调制而成黑色和红色的天然生漆。将外表面红色漆膜雕刻成如意云纹,并在云纹边缘描绘黑漆线作为修饰,最后再在其上髹饰一层红色面漆。漆器红漆和黑漆层由同种天然生漆髹漆而成,但是两者采用的颜料分别为HgS和含Fe的黑色颜料。     

A Holiday Journal of 1774

Abstract

Early illustrations of Ledsham church do not show carvings around the Anglo-Saxon doorway into the tower, and examination of the physical condition of the stonework suggests that it is unlikely that the carvings could have survived from the Anglo-Saxon period. The peculiar features of the doorway and its carvings are best explained by the work being a nineteenth-century replacement by the Victorian architect, Henry Curzon.     

有机-无机复合疏水型二氧化硅涂层制备及性能

为研究制作保护石质文物的加固材料,采用溶胶-凝胶法,以两种有机硅材料(正硅酸乙酯(TEOS)和甲基三乙氧基硅烷(MTES))为共同前驱体,少量正辛胺为催化剂,聚二甲基硅氧烷(PDMS)(方法 1)或硅烷偶联剂KH-570(方法 2)为有机改性剂,制备了有机-无机复合疏水型Si O2涂层。通过红外光谱(FT-IR)、扫描电镜(SEM)和水接触角(WCA)来表征在砖块表面形成的SiO_2膜层化学组成、表面形貌以及疏水性能,然后再通过测试砖块加固前后外观、吸水性能和孔隙率的变化来验证实际加固效果。结果表明,两种方法均可以制备骨架带-CH3基团的SiO_2溶胶。采用方法 1(添加前驱体质量10%的PDMS)或者方法 2(MTES/TEOS质量比为2),加固后的砖块对水接触角均超过140°,毛细吸水率降低到未处理时的1%~2%,并且砖块的色差和光泽度改变较小。通过耐候性能测试表明,方法 2的保护效果相对较好,说明用此种方法合成的疏水性二氧化硅涂层可以作为砖块加固材料。     

Chemical Weathering of Detrital Sediments in the Taklamakan Desert,Northwestern China

Based on the analysis of major‐element compositions of detrital sediments from the Taklamakan Desert of northwestern China, this paper aims to study chemical weathering in a hyper‐arid desert environment. The major‐element compositions are basically similar to the Upper Continental Crust but show a clear enrichment of CaO and depletion of Na₂O and K₂O, indicating the enrichment of carbonates and the decomposition of sodium and potassium silicates. The indexes of chemical alteration are relatively low and correlate negatively with the content of Na₂O, implying that the degree of chemical weathering is weak and mainly controlled by the weathering of sodium feldspars. An A‐CN‐K model demonstrates that the detrital sediments from the Taklamakan Desert have a high homogeneity in the trend of chemical weathering. They are weathered less than sands and soil in many other Chinese deserts, and also less than similar detrital sediments in many other countries. This evidence suggests a low degree of mineralogical maturity in the Taklamakan Desert. The aeolian sediments of different ages have similar indexes of chemical weathering, suggesting that the degree of chemical weathering was consistent in the Taklamakan Desert throughout the period of aeolian deposition. The low degree of chemical weathering is caused principally by extreme aridity, rapid rejuvenation of detrital sediments associated with strong aeolian processes, and an intensive input of fluvial deposits, as well as a lack of vegetation. Due to the high concentration of erodible minerals, the desert is quite vulnerable to soil erosion and land degradation.     

结合热力学对古建筑墙体砖(雕)风化侵蚀机理探究

为了揭示古砖的风化侵蚀机理,采用X射线衍射法(XRD)、X射线荧光光谱法(XRF)、扫描电子显微镜观察(SEM)进行微观结构分析,结合压汞仪测试孔的性质,并使用热力学软件(HSC)对砖内的化学反应进行验证。研究结果表明:对于靠近地面一定高度内的古建筑墙体砖,地下水及离子通过砖内的毛细管网络不断向上部和表面进行迁移,在砖内可溶性盐类的结晶以及水结冰时产生的压力是造成墙体砖风化破坏的主要因素;对于NO X、SO 2浓度较高、酸雨较多的地区,酸性物质进入砖体并与钾长石,钠长石等发生反应形成新的盐类,盐的结晶、溶解、流失也是导致古砖破坏的一个不可忽略的因素,尤其是对于地下水无法渗透到的墙体砖,这些可能成为主要的物理化学损毁因素。本研究为古砖以后的保护提供了一种新的研究思路以及科学的理论基础。     

馆藏明代加彩木雕坐像保护前期研究

为更好地了解馆藏明代加彩木雕坐像的价值和病害情况,以期实施科学的保护和修复,利用超景深三维显微光学系统、拉曼光谱、红外光谱、X射线衍射、扫描电镜、X射线荧光能谱等分析方法对馆藏两件明代加彩木雕坐像的材质组成、制作工艺及病害情况等进行了综合分析。分析表明,两件木雕文物材质为樟科樟木属,加彩层为彩绘层,施彩工艺为先于木胎上打白灰层,而后铺一层纺织纤维,再于纤维布上涂颜料层,颜料层表面涂刷一层防护膜。其中,白灰层为石膏,纺织纤维为棉织物,所用颜料多为矿物颜料,蓝色显示物质为群青,黑色为炭黑,金色疑为铜金粉,而红色显色物质为植物染料-茜草。表面防护膜层为醇酸树脂。腐朽木材碎片和加彩层表面均有大量真菌孢子和菌丝,可以认为菌虫的侵染是引起木雕腐朽的主要因素之一。研究结果为更好地认识两件木雕文物,以及对其实施科学、有效的保护奠定了基础。     

Geochemical fingerprinting of hydraulic fracturing fluids from Qusaiba Hot Shale and formation water from Paleozoic petroleum systems,Saudi Arabia

Provenance studies of produced water are essential to trace flow dynamics and reservoir compartmentalization in petroleum systems and to quantify fluid recovery rates from unconventional fracturing. Produced water from a hydraulically fractured well in the Qusaiba Hot Shale in the Northern Exploration Area, Saudi Arabia, was daily monitored and analyzed for water chemistry, and environmental (δ²H, δ¹³C, δ¹⁸O_H2O, δ¹⁸O_SO4, δ³⁴S_SO4, δ³⁷Cl, ⁸⁷Sr/⁸⁶Sr) and cosmogenic isotopes (³H, ¹⁴C, ³⁶Cl), to differentiate from reference fluids of supply water, fracturing fluids, and formation water from adjacent Paleozoic units. Initially, recovered water is composed of fracturing fluids and subsequently replaced by a homogeneous cut of pristine formation water. Formation water is composed of dominant meteoric water (approximately 84 vol%) and minor fossil evaporated seawater. The young ¹⁴C‐apparent age between 6000 and 6700 years BP and depleted δ¹⁸O/δ²H values for the meteoric component confirm the infiltration of surface water into the Qusaiba Hot Shale interval or adjacent units during the Early Holocene Pluvial Period under cooler and wetter climatic conditions than present, which suggest the presence of a very recent, dynamic hydraulic flow system. ³⁶Cl/Cl ratios between 102 × 10^?15 and 31 × 10^?15 are ambiguous and can be attributed to atmospheric recharge close to the coast, mixing of ³⁶Cl‐enriched Quaternary meteoric recharge with ³⁶Cl‐depleted fossil seawater, and/or hypogene production by U‐Th‐enriched host rock. Produced waters from Qusaiba Hot Shale are within the compositional range of Na‐Cl‐type formation water from Paleozoic reservoir units in northern Saudi Arabia with salinities from 30 000 to 130 000 mg l^?1. As a novel technological approach for exploration wells in Northern Saudi Arabia, multi‐isotopic methods were successfully implemented to quantify flowback volumes from hydraulic fracturing, and to fingerprint pristine formation water or pore water in Paleozoic systems on their provenance, residence time, migration pathways, and secondary alteration processes.