中国古建筑中几种石灰类材料的物理力学特性研究

为探讨适宜于岩土文物保护加固的石灰类材料,对中国古建筑中几种石灰类材料及欧洲水硬石灰的化学组成和物理力学特性进行对比研究。研究表明烧料礓石、烧阿嘎土、欧洲水硬石灰NHL5及改性捶灰的化学组成主要是气硬性胶凝材料石灰CaO(或Ca(OH)2)和水硬性胶凝材料β-硅酸钙(β-CS)及铝硅酸钙(CAS),并且这些材料的结石体具有大的孔隙率及非常小的收缩变形性等特点,适宜于岩土文物的保护加固。除此之外,石灰、糯米灰浆、蛎灰、传统捶灰的主要化学组成为石灰CaO(或Ca(OH)2),实验研究结果显示,浆液的凝固速度慢,弹性波速小且上升速率慢,结石体虽然孔隙率大,但强度在短期内较低,易产生收缩变形,不适宜用于短时间内有强度要求的岩土文物保护加固,所以有必要对蛎灰和传统捶灰做进一步的改性研究,以便更广泛地应用于岩土文物的保护加固中。     

湖南何家皂北宋墓出土纺织品附着灰蓝色物质的科学分析

出土于湖南衡阳何家皂北宋墓的纺织品上观察发现有灰蓝色固体物质附着,为查明其性质,采用扫描电镜-能谱法、激光拉曼光谱法和X射线衍射法结合能量色散X射线荧光光谱法和光学形貌观察等手段进行科学分析。结果表明,该物质为磷酸亚铁矿物——蓝铁矿[Vivianite:Fe_(3)(PO_(4))_(2)·8H_(2)O],其多形成于富铁、富磷、有机物含量较高且贫硫的缺氧还原沉积环境中,微生物活动亦对其生成有影响。该矿物的发现对墓葬环境特征与保存状态的研究有指示意义,在考古遗存中或可作为判断特殊埋藏条件的标志自生矿物之一。     

明秀寺大殿彩塑病害调查与保护建议

明秀寺大殿明代彩塑在保存过程中发育了丰富的病害。调查显示,该大殿彩塑颜料层脱落、表面沉积和缺损等严重,点状脱落、地仗层脱落、裂隙、龟裂和空鼓等较为广泛,而酥粉、起甲、雨渍和划痕相对较少。对塑像表面的彩绘颜料分析显示,黑色是炭黑(C),红色是铅丹(Pb3O4),黄色是雌黄(As2S3),蓝色是青金石((Na,Ca)_(7-8)(Al,Si)_(12)(O,S)_(24)SO_4)和石青(Cu_2(OH)_2CO_3),绿色是氯铜矿(Cu_2Cl(OH)_3),均为我国古代彩绘文物常用的矿物颜料。在此基础上,分析了环境温湿度、粉尘及人为因素与塑像病害产生的关系,建议应加强明秀寺古建筑的日常管理和维护,适当控制大殿环境,实时修复,整体以预防性保护为主,减缓文物病害的发生与蔓延。     

广东“南澳Ⅰ号”明代沉船出水铜器腐蚀产物分析

由于海水环境中含有大量氯化物,海洋出水铜器在出水前已发生腐蚀,生成铜的氧化物及氯化物等。本文以广东"南澳Ⅰ号"明代沉船出水的22件铜器残片为研究对象,运用X-射线荧光仪(XRF)、X-射线衍射仪(XRD)和扫描电镜与能谱仪(SEM-EDS)等分析其腐蚀产物和矿物组成,结果表明腐蚀产物主要为铜的碱式氯化物,如Cu2(OH)3Cl和Cu(OH)Cl等,与国外已有研究成果类似,但Cu(OH)Cl在国外海洋出水铜器腐蚀产物中并不常见。     

山西忻州九原岗北朝墓葬壁画颜料及颜色变化分析

出土彩绘文物在环境突发剧烈变化的情况下常有变色或褪色现象,影响文物的安全及其艺术展示。为了解山西忻州九原岗北朝墓葬壁画发掘出土后色彩的变化规律,跟踪监测了该墓葬壁画红色、黄色、蓝色和黑色绘画区域的色度及相应的表面水含量,同时对颜料进行拉曼光谱分析。研究结果表明:该墓葬壁画所用颜料红色为HgS,黄色为FeO·OH,蓝色为(Na,Ca)_(7-8)(Al,Si)_(12)(O,S)_(24)[SO_4,Cl_2(OH)_2],黑色为C;壁画出土后轻微的褪色现象主要与环境湿度有密切关系。新出土壁画表面湿度较高,颜色鲜艳。随着画面干燥,壁画表面含水量的降低导致颜色饱和度降低,壁画色彩变浅。盐结晶的析出以及颜料颗粒脱落导致画面色彩饱和度降低,也可能导致壁画色彩变浅。     

典型硫酸盐环境中砖质文物的脱盐与加固材料

中国保存有众多砖质文物建筑,目前这些文物多处于户外环境中,面临严重盐害导致的掏蚀损毁问题。因而,研究兼具脱盐功能的加固材料成为砖质文物等保护的一种创新思路,加固材料的研制和工艺技术的开发是其重点和难点,具有重大的社会需求和急迫性。为此,本工作从可溶性盐的破坏机制出发,研究出一种双组分无机加固材料,加固方法是Ba(OH)_2甲醇溶液与H_2C_2O_4、H_3PO_4乙醇溶液交替滴加,并模拟可溶性盐(NaCl、KCl、Na_2SO_4)分布的典型环境,进行加固、除盐,借助X射线衍射仪(XRD)、X射线荧光光谱仪(XRF)和无线阻尼抗钻仪等现代科学仪器,追踪盐的流出与转化过程。结果表明,本材料不仅能够加固模拟样品,同时能对最具破坏性的盐Na_2SO_4实现不可逆转化,生成重晶石的主要成分BaSO_4,加固与脱盐一次完成,是一种具有实际应用潜力的新材料。     

明《天工开物》之“风吹成粉”工法初步研究

1637年(明崇祯十年)出版的《天工开物》记录了我国古代建筑石灰的消解采用"置于风中,久自吹化成粉"的工艺,"用以砌墙石,则筛去石块,水调黏合"。为复配"风吹成粉"工法并研究采用这种工法得到的石灰性能,实验采用传统立窑对源自浙-皖交界处原材料"青石"烧制而成的生石灰使用"风吹法"消解,并参照现代标准BS-EN-459-2015等相关检测方法进行性能研究。结果发现"风吹法"消解的石灰含有水硬性组分如硅酸二钙等,并具有凝结时间短、强度适中等特点。研究表明,"风吹"20~30天左右得到的石灰性能相当于欧洲标准的天然水硬石灰NHL1或NHL2。研究还表明,"风吹成粉"的石灰可以用作砌筑、修复、注浆等粘合剂,其快凝等特性非常有利于湿冷环境下的施工。若对文献、明及以前的建筑进一步考证并采取系统全面的深化研究,有望考证出我国380年前的明朝对天然水硬石灰消解及应用技术的掌握程度,并开发出融合中华传统智慧的文物建筑保护材料。     

山东长清灵岩寺宋代罗汉像彩绘分析研究

山东省济南市长清区灵岩寺彩绘罗汉像是我国宋代泥塑罗汉的代表作,具有极高的历史、艺术和科学价值。但罗汉像保存现状较差,彩塑存在颜料脱落、残损、酥碱等病害,亟待保护修复。为此,本工作选取彩绘脱落严重的两尊宋代彩塑罗汉像,利用光学显微镜(OM)、拉曼光谱(Raman)、扫描电子显微镜与能谱仪(SEM-EDS)等分析其彩绘颜料样品。结果表明,彩绘罗汉像从塑制之初至今,经过数次彩绘,可确定的多达六次。黑色颜料为炭黑(C);红色颜料为朱砂(HgS),铅丹(Pb_3O_4),以及朱砂、铁红(Fe_2O_3)和方解石(CaCO_3)混合物;绿色颜料为巴黎绿(Cu(C_2H_3O_2)·3Cu(AsO_2)_2)和舍勒绿(Cu(AsO_2)_2),还发现有斜氯铜矿(CuCl(OH)_3)及其与铅白(2PbCO_3·Pb(OH)_2)的混合物;橙色颜料为铅铬黄(PbCrO_4)和铅丹混合物;蓝色颜料为蓝铜矿(2CuCO_3·Cu(OH)_2),人工合成群青(Na_3CaAl_3Si_3O_(12)S);白色颜料为铅白和方解石;黄色颜料为铁黄(FeO(OH));金色为金箔(Au);沥粉的主要成分是方解石。白色底层为铅白和以硅、铝、钙为主的细白土。彩塑罗汉像重绘过程中,保持了将细白土作为底层和衣领镶边沥粉贴金的传统。彩绘颜料所用铅铬黄、巴黎绿、舍勒绿表明,彩塑罗汉像最近一次彩绘在清末之际,与文献记载相符,且这些人工颜料应是西方舶来之物。本分析研究结果为灵岩寺罗汉像艺术史研究提供了丰富信息,同时为保护修复工作开展提供了可靠依据。     

福建晋江宋代磁灶窑出土铅釉陶的腐蚀研究

铅釉陶瓷是我国古陶瓷的重要品类,因其耐腐蚀性较差,器表易产生"银釉""虹彩"等腐蚀现象。采用体视显微镜、扫描电子显微镜及能谱仪和拉曼光谱仪分析了福建晋江宋代磁灶窑出土的7件釉陶样品,目的是阐明铅釉在埋藏环境中的长期腐蚀现象、腐蚀产物和过程。结果表明,釉层主要成分为PbO和SiO_2,以Cu和Fe作为着色元素,陶胎为非钙质黏土,推测釉胎交界处的白色薄层为K-Pb长石晶体层。釉面中"虹彩"现象呈现出多层结构,主要是因为水的侵蚀,使得玻璃相中的部分择优组分(碱金属、碱土金属、铅氧化物等)转入环境介质中,即H~+与釉中Pb~(2+)、Cu~(2+)、K~+、R~(n+)等发生离子交换反应,形成缺碱的富硅层[硅凝胶Si(OH)_4·n(H_2O)],呈现出"虹彩"现象。釉面腐蚀物中有磷酸铅盐、碳酸铅和碳酸钙,是溶出离子与埋藏环境反应在釉层表面沉积生成。     

秦陵出土青铜水禽锈体组织结构的初步分析

本研究旨在研究秦始皇帝陵园出土彩绘青铜水禽锈体的结构形貌及其形成原因。采用扫描电镜能谱(SEMEDS)、X射线荧光光谱(XRF)、金相显微分析和离子色谱分析(IC)等多种分析手段,对青铜水禽锈体的组织结构及其埋藏土壤进行了分析检测。结果表明:高湿、火烧、人为破坏的特殊埋藏环境是该批青铜水禽严重矿化的主要原因,而有些矿化严重的部分为稳定的粉状锈蚀物,并非传统意义上的“有害锈”;从组织的微观腐蚀特征来看,铸态枝晶结构的样品α相优先腐蚀;而铸后受热组织则呈晶间腐蚀的特点,腐蚀由晶粒间界向晶粒发展;锈体层状结构的产生与Cu₂O溶解产生空隙,并在合适的环境条件下生成了孔雀石有关。     

Chemical and Microscopic Study of Masonry Mortar in Ancient Pagodas in East China

Ancient mortars played a crucial role in the construction of historical architectures due to their physical and chemical compatibility with traditional building materials such as stones and bricks. Therefore, the analysis and optimization of the ancient mortar formula are significant in the restoration and preservation of historical sites. In this work, 20 mortar samples selected from five ancient stone pagodas in Zhejiang Province, China, were analyzed. The results showed that mud, lime-soil mortar, lime-sand mortar, and lime-gypsum mortar were used as binders in these pagodas. The Ca(OH)₂/aggregate ratio ranging from 0.3 to 2.7 was usually used to prepare lime mortar. Protein and polysaccharide were also found in some samples.     

Low‐temperature dunite hydration: evaluating CH4 and H2 production from H2O and CO2

Abiotic methane (CH₄) and hydrogen (H₂) produced after hydration of mafic/ultramafic rocks represent energy sources for microbes that may thrive in the deep subsurface regions of Earth and possibly on other planets. While H₂ is a direct product of serpentinization, CH₄ can form via Fischer–Tropsch Type (FTT) reactions (carbon reduction) that, due to potential H₂ migration, can be spatially and temporally detached from serpentinization. We tested an alternative process hypothesized by some scholars, in which CO₂ can be reduced through dunite hydration without initially added H₂, implying that CH₄ can form in the same serpentinized fluid–rock system. The experiment used natural dunite sand (Forsterite 92), CO₂ with δ¹³C ~ ?25‰ (VPDB), and a 1 mm dissolved SiO₂ solution mixed in 30 glass bottles (118 mL) stored for up to 8 months at low temperature (50°C) to simulate land‐based serpentinization systems. In addition, 30 control bottles without olivine were used as blanks. Trivial amounts of CH₄ (orders of 0.2–0.9 ppmv) were detected in both samples and blanks, likely representing analytical noise; essentially, no significant amount of CH₄ formed under the experimental conditions used in this work. Low amounts of H₂ (~2.55 ± 1.39 ppmv) were generated, with production yields that were one order of magnitude lower than in previously published experiments. Moderate concentrations of SiO₂ appeared to hinder low‐temperature H₂ production. Our experiment confirms that the low‐temperature reduction of CO₂ into CH₄ through direct olivine hydration, without initial H₂, is sluggish and not straightforward, which is consistent with previous studies. The presence of substantial amounts of H₂, as well as suitable metal catalysts, appears to be essential in the low‐temperature production of abiotic CH₄, as observed in published FTT experiments.     

Effects of pore fluid flow and chemistry on compaction creep of calcite by pressure solution at 150°C

Uni‐axial compaction creep experiments were performed on crushed limestone and analytical grade calcite powders at 150°C, a pore fluid pressure of 20 MPa, and effective axial stresses of 30 and 40 MPa. Previous experiments have shown that compaction under these conditions is dominated by intergranular pressure solution (IPS). The aim of the present tests was to determine the inter‐relationship between pore fluid chemistry, compaction rate and the rate‐controlling process of IPS. Intermittent flow‐through runs conducted using CaCO₃ solution showed no effect on creep rate at low strains (<4–5%) but a major acceleration at high strains (5–10%). Measurements of the Ca concentration present in fluid samples revealed the build‐up of a high super‐saturation of CaCO₃ during compaction under zero flow conditions, especially at high strains. Active flow‐through led to a drop in Ca concentration, which corresponded with creep acceleration. Addition of NaCl to the pore fluid, at a concentration of 0.5 m , increased the creep rate of the analytical grade calcite samples roughly in proportion to the enhancement of calcite solubility. Addition of Mg²⁺ and to the pore fluid, in concentrations of 0.05 and 0.001 m, respectively, caused major retardation of compaction creep. Integrating our mechanical, flow‐through and chemical data points strongly to diffusion‐controlled IPS being the dominant deformation mechanism in the calcite‐water system under closed‐system (zero flow) conditions at low strains (<4–5%), giving way to precipitation control at higher strains. Our fluid composition data suggest that this transition is because of accumulation of impurities in the pore fluid. As Mg²⁺ and phosphate ions are common in natural pore fluids, it is likely that retarded precipitation will be the rate‐limiting step of IPS in carbonates in nature. To quantify diagenetic compaction and porosity‐permeability reduction rates by IPS in carbonates needs to account for this.     

Quantitative analysis of COH fluids synthesized at HP–HT conditions: an optimized methodology to measure volatiles in experimental capsules

The quantitative assessment of COH fluids is crucial in modeling geological processes. The composition of fluids, and in particular their H₂O/CO₂ ratio, can influence the melting temperatures, the location of hydration or carbonation reactions, and the solute transport capability in several rock systems. In the scientific literature, COH fluids speciation has been generally assumed on the basis of thermodynamic calculations using equations of state of simple H₂O–nonpolar gas systems (e.g., H₂O–CO₂–CH₄). Only few authors dealt with the experimental determination of high‐pressure COH fluid species at different conditions, using diverse experimental and analytical approaches (e.g., piston cylinder + capsule piercing + gas chromatography/mass spectrometry; cold seal + silica glass capsules + Raman). In this contribution, we present a new methodology for the synthesis and the analysis of COH fluids in experimental capsules, which allows the quantitative determination of volatiles in the fluid by means of a capsule‐piercing device connected to a quadrupole mass spectrometer. COH fluids are synthesized starting from oxalic acid dihydrate at P = amb and T = 250°C in single capsules heated in a furnace, and at P = 1 GPa and T = 800°C using a piston‐cylinder apparatus and the double‐capsule technique to control the redox conditions employing the rhenium–rhenium oxide oxygen buffer. A quantitative analysis of H₂O, CO₂, CH₄, CO, H₂, O₂, and N₂ along with associated statistical errors is obtained by linear regression of the m/z data of the sample and of standard gas mixtures of known composition. The estimated uncertainties are typically <1% for H₂O and CO₂, and <5% for CO. Our results suggest that the COH fluid speciation is preserved during and after quench, as the experimental data closely mimic the thermodynamic model both in terms of bulk composition and fluid speciation.     

RESEARCH ON THE PIGMENTS FROM PAINTED CERAMICS EXCAVATED FROM THE YANGQIAOPAN TOMBS OF THE LATE HAN DYNASTY (48 BC – AD 25)

The analysis of pigments on painted ceramics excavated from the Yangqiaopan Tombs of the late Western Han Dynasty was undertaken using optical microscopy (OM), micro‐Raman spectroscopy (μ‐RS), scanning electron microscopy with energy‐dispersive X‐ray spectrometry (SEM–EDS), X‐ray diffraction (XRD) and Fourier‐transform infrared spectroscopy spectra (FTIR). The pigments were identified as red lead (Pb₃O₄), carbon (C), malachite [Cu₂CO₃(OH)₂], Chinese purple (BaCuSi₂O₆) and illite {[K,H₃O]Al₂Si₃AlO₁₀(OH)₂}. Fibrous materials were observed in some pigment samples. When observed by SEM, one showed a large amount of fibre in solidified gum, which indicated that gum of ramie could have been used as the binding medium to make the pigment particles adhere together. These results provide significant insights into the characteristics of these pigments in the Qin and Han Dynasties.     

Density and isothermal compressibility of supercritical H2O–NaCl fluid: molecular dynamics study from 673 to 2000 K, 0.2 to 2 GPa,and 0 to 22 wt% NaCl concentrations

We report on molecular dynamics (MD) simulations for predicting the density and isothermal compressibility of an H₂O–NaCl fluid as a function of temperature (673–2000 K), pressure (0.2–2.0 GPa), and salt concentration (0.0–21.9 wt%). The atomistic behavior was analyzed via the hydration number of ions and number of ion pairs. Hydration numbers of Na⁺ and Cl^? increased with increasing pressure and decreasing temperature. Conversely, the fraction of Na–Cl ion pairs increased with decreasing pressure and increasing temperature. This hydration and association behavior is consistent with the low dielectric constant of H₂O under these conditions. The presence of polynuclear clusters of Na–Cl was confirmed at high temperatures, low pressures, and high salt concentrations. We propose a purely empirical equation of state (EoS) for H₂O–NaCl fluids under high temperatures and pressures that should be useful for estimating the fluid distribution in Earth's crust and upper mantle in relation to effects on earthquakes and volcanic eruptions.     

Infra-red Photoacoustic and Secondary Ion Mass Spectrometry Measurements of Obsidian Hydration Rims

A procedure has been developed for measuring obsidian hydration rim thicknesses on archaeological artefacts using infra-red photoacoustic spectroscopy (IR-PAS). Calibration of the IR-PAS values with depth was completed using secondary ion mass spectrometry (SIMS) and optical microscopy to relate the quantity of diffused water to the measured thickness of the hydration layer. By monitoring the absorbance intensity at 1630 cm⁻¹wavenumbers, hydration rims between approximately 1 μm and 12 μm may be accurately measured and used for chronometric age estimates. SIMS depth profiling has the ability to measure layers less than 1 μm thick, extending the age calibration to samples of less than 100 years in age.     

三种含Cu、As绿色颜料的拉曼光谱研究

分析和确认古代颜料的成分是文物研究中的一项重要工作。为对四个来自不同地区的含Cu、As元素的绿色颜料进行鉴别,应用拉曼光谱仪并辅助以扫描电镜能谱分析仪(SEMEDX)和X射线衍射仪(XRD)进行研究。结果表明其分别为墨绿砷铜矿、氯砷钠铜石以及巴黎绿。对其来源分别进行了讨论,因巴黎绿在国内青铜修复和古建彩画当中的大量应用,过去对于含有Cu、As的绿色颜料通常鉴定为巴黎绿。墨绿砷铜矿和氯砷钠铜石为在文物彩绘中新发现的两种矿物颜料,为绿色颜料的鉴定提供了新的思路。     

The Glaze Technology of Hispano‐Moresque Ceramic Tiles: A Comparison Between Portuguese and Spanish Collections

For the first time, Hispano‐Moresque glazed tiles from Portuguese and Spanish collections were studied together and compared. This work is included in a wider study tackling the technology of Hispano‐Moresque tile production from several collections in the Iberian Peninsula. While showing many similarities, differences were identified between collections, regarding both chemical and morphological characteristics. The collection from the Mosteiro de Santa Clara‐a‐Velha (Coimbra) stands out from the other collections, with higher SnO₂ content (up to 14 wt%), the highest Fe₂O₃ contents in amber glazes and a Ca‐rich interface layer (mostly comprised of wollastonite, CaSiO₃). Samples from Palácio Nacional de Sintra (near Lisbon) and Seville‐attributed samples (from the Instituto Valencia de Don Juan) are chemically similar, except that most Sintra's samples display a K‐rich glaze/ceramic interface, whereas the ones from Seville exhibit both K‐rich and Ca‐rich inclusions. The samples attributed to Toledo show glazes with many inclusions, contrasting with the homogeneous glazes in most Hispano‐Moresque tiles. From these results, we identify differences that can be used as markers in future studies on Hispano‐Moresque tiles.     

Spatial coupling between spilitization and carbonation of basaltic sills in SW Scottish Highlands: evidence of a mineralogical control of metamorphic fluid flow

In a geochemical and petrological analysis of overprinting episodes of fluid–rock interaction in a well‐studied metabasaltic sill in the SW Scottish Highlands, we show that syn‐deformational access of metamorphic fluids and consequent fluid–rock interaction is at least in part controlled by preexisting mineralogical variations. Lithological and structural channelling of metamorphic fluids along the axis of the Ardrishaig Anticline, SW Scottish Highlands, caused carbonation of metabasaltic sills hosted by metasedimentary rocks of the Argyll Group in the Dalradian Supergroup. Analysis of chemical and mineralogical variability across a metabasaltic sill at Port Cill Maluaig shows that carbonation at greenschist to epidote–amphibolites facies conditions caused by infiltration of H₂O‐CO₂ fluids was controlled by mineralogical variations, which were present before carbonation occurred. This variability probably reflects chemical and mineralogical changes imparted on the sill during premetamorphic spilitization. Calculation of precarbonation mineral modes reveals heterogeneous spatial distributions of epidote, amphibole, chlorite and epidote. This reflects both premetamorphic spilitization and prograde greenschist facies metamorphism prior to fluid flow. Spilitization caused albitization of primary plagioclase and spatially heterogeneous growth of epidote ± calcic amphibole ± chlorite ± quartz ± calcite. Greenschist facies metamorphism caused breakdown of primary pyroxene and continued, but spatially more homogeneous, growth of amphibole + chlorite ± quartz. These processes formed diffuse epidote‐rich patches or semi‐continuous layers. These might represent precursors of epidote segregations, which are better developed elsewhere in the SW Scottish Highlands. Chemical and field analyses of epidote reveal the evidence of local volume fluctuations associated with these concentrations of epidote. Transient permeability enhancement associated with these changes may have permitted higher fluid fluxes and therefore more extensive carbonation. This deflected metamorphic fluid such that its flow direction became more layer parallel, limiting propagation of the reaction front into the sill interior.