矿物聚合材料:研究现状与发展前景

矿物聚合材料是以铝硅酸盐矿物或工业固体废物为主要原料 ,以高岭石作配料 ,硅酸钠作结构模板剂 ,氢氧化钠作激活剂而制成的一类新型无机非金属材料。其形成过程为 :铝硅酸盐固体组分的溶解络合、分散迁移、浓缩聚合和脱水硬化。由铝硅酸盐凝胶相形成的基体相 ,其化学组成与沸石相近 ,微结构极可能与蛋白石类似 ,物理形态上呈三维网络结构 ,将未溶解的固体颗粒胶结为坚硬块体 ,是材料获得良好力学性能和化学稳定性的结构基础。矿物聚合材料的性能主要受配料组成和聚合反应的动力学过程所控制 ,其抗压强度随固化时间的延长而呈抛物线式发展。系统研究配料组成和固化条件对铝硅酸盐聚合反应的影响 ,建立表征矿物聚合材料组成结构性能的物理模型 ,是对其进行结构性能设计的理论基础 ,也是利用铝硅酸盐聚合反应实现工业固体废物资源化的技术关键。     

New approaches to laser desorption/ionization of chemical compounds for geochemical studies

Two new versions of surface-assisted laser desorption/ionization method are considered. One version is based on a combination of this method with thermal desorption sample injection and may be applied for determination of chemical compounds that are transformed into a gas phase without decomposition by heating. Another version is based on laser-induced electron-transfer desorption/ionization and could be used for determination of compounds with low proton affinity. The possibilities of the new approaches are illustrated by the example of determination of aminoacids, medical compounds, chlorophyll, as well as gold in sulfide ores.     

Pyrolysis of immature Torbanite and of the resistant biopolymer (PRB A) isolated from extant alga Botryococcus braunii. Mechanism of formation and structure of torbanite

Immature Torbanite and the resistant biopolymer (PRB A) isolated from extant B. braunii were previously compared using bulk spectroscopic methods. In the present work, analysis of 400°C pyrolysis products and pyrolysis residues provided further information on their structure and possible relationships. It appears that such polymers are based upon unbranched, saturated, cross-linked hydrocarbon chains up to C₃₁. In addition to these bridging structures, a substantial part of the alkyl chains is singly bound, as esters of unbranched, saturated or cis unsaturated, even fatty acids. These esters are sterically protected, against chemical degradations, by the network of the bioand geopolymer.Quantitative and qualitative observations derived from 400°C pyrolysis confirm that the chemical structure of PRB A and immature Torbanite are closely related. The pyrolysis residues show a similar evolution and numerous common features are noted, with respect to the nature and the distribution of the major constituents of the pyrolysates (hydrocarbons and fatty acids). Accordingly, Botryococcus provides what seems to be the first example of a close structural relationship between a biopolymer produced in large amounts by an extant alga and the geopolymer of an immature kerogen. The essential role of PRB A in Torbanite formation is ascertained. Moreover, it is found that the resistant biopolymer does not undergo important structural changes during the first stages of diagenesis. Thus, owing to steric protection, the esters of immature Torbanite show a distribution quite close to the one of PRB A esters, with exclusively even constituents and a large contribution of unsaturated acids.Recent observations pointed to the possible genesis of some algal kerogens principally by selective preservation of resistant macromolecules. Such a type of formation is clearly predominant in Torbanite, where the bulk of the fossil organic matter corresponds to a selectively preserved and weakly altered, resistant biopolymer, while incorporation of lipids into the kerogen structure during diagenesis seems to play a minor role.     

Identifying the source of a strong fullerene envelope arising from laser desorption mass spectrometric analysis of meteoritic insoluble organic matter

Insoluble organic matter (IOM) has been obtained from two carbonaceous chondrite meteorites and subjected to analysis by laser desorption mass spectrometry (LDMS) using standard operating conditions that were optimized for fullerene detection (3-6 μJ pulses at 337 nm focused to a spot size of approximately 100 μm in diameter). The preparation process yields no free C₆₀ in the IOM, and other experiments suggest that this material does not contain appreciable amounts of fullerenes. Nevertheless, a pronounced high-mass envelope is observed in LDMS, extending from 720 amu to about 4000 amu, with peaks spaced apart every 24 amu (corresponding to the gain or loss of C₂ units). We attribute this high-mass envelope to the existence of various fullerene molecules. The present work demonstrates that these fullerene molecules are created by the laser desorption laser ionization process under typical laser conditions used for studying free fullerenes in organic solvent extracts of natural samples (toluene and 1,2,4-trichlorobenzene). The implications of this false positive detection of fullerene molecules on the reports of fullerenes in other meteoritic samples have been investigated by introducing IOM into typical fullerene extraction procedures and examining the LDMS results. We found that IOM is capable of producing false positive signals in these experiments. The effect of ambient laboratory contamination producing fullerene signals is also described. It is found that extensive centrifugation of the meteoritic extracts is able to reduce the observed fullerene envelope, which points to an association of this envelope with IOM particulates that have passed through the filtering steps. We suggest the exercise of extreme caution in interpreting fullerene data from LDMS experiments.     

食品中有机氯农药和多氯联苯气相色谱-质谱分析的离子化方式

对食品中有机氯农药和多氯联苯的气相色谱-质谱联用(GC-MS)分析方法中三种离子化方式,电子轰击电离(EI)、正化学电离(PCI)和负化学电离(NCI)进行了总结和比较。PCI-MS/MS方法和EI-MS/MS方法都有很高的选择性和较高的灵敏度;PCI方法在分析含硝基、羰基等基团的化合物时有明显优势,EI则在分析狄氏剂、异狄氏剂、硫丹及其代谢物时比PCI表现稍好,而NCI-MS的灵敏度最高,但抗干扰能力稍弱,且不适合分析滴滴涕类和多氯联苯类化合物。在食品安全分析中,三种质谱方法的准确性好,精密度高,检测限较低,都能够满足食品中农残检测的要求,在日常检测工作中可互为补充和替代。同时指出,GC在有机氯化合物分析中仍表现出明显的优越性;常规的GC-MS尤其在EI电离模式下,易受到基质干扰而使谱图变得复杂;新型离子化方式包括高选择性化学电离技术的应用,将是食品安全中GC-MS联用分析的发展方向之一。     

地质聚合物技术的发展近况

概要介绍了一种无机聚合物———地质聚合物。首先对地质聚合物材料的制备过程作了介绍。根据原料的不同,地质聚合物材料的制备可以有两种途径:一种是以偏高岭石为基础原料,一种是以粉煤灰为主要原料。通常以硅酸钠水溶液作为单体硅源,氢氧化钠溶液作为碱激发剂以提高原料的溶出性。对某些在常温和低于100 ℃下制备的独石材料作了介绍。对煅烧高岭石,叶蜡石,粉煤灰和钢渣的溶出特性作了阐述。应用SEM EDX,对以粉煤灰为原料的地质聚合物材料的化学组成作了分析。最后对地质聚合物材料的经济性以及在环境保护等领域的应用前景,特别是在减少二氧化碳排放与废弃物处理方面的意义作了介绍。     

An Application of Multivariate Simulation in the Cement Industry

The profitability of a cement plant depends largely on its capacity to produce homogeneous cement with chemical composition close to specified targets for the cement type produced. One crucial step is the mixing of limestone with other raw materials in proportions calculated to meet these targets. Major design and operation decisions depend on the efficiency of this homogenizing step. The adequate modeling of the mixing process requires simulation of representative cross-correlated time series of chemical compositions of the raw materials involved. The chemical composition signals are obtained by multivariate geostatistical simulation using an LU (Cholesky) decomposition of the covariance matrix. Modifications to the usual LU method are presented. First, the effect on the raw covariance matrix of the closure property of chemical analysis is imposed. Second, the problem of memory space limitations in the LU method is tackled by using overlapping sliding neighbourhoods. The simulation algorithm is applied to the Joppa cement plant owned by Lafarge North America. The simulated raw material input streams are fed into the quality mix control (QMC), a proprietary software that models and controls the mixing operation to produce an output stream with cement characteristics as close as possible to desired targets. Two signal series are studied, one autocorrelated with a moderate temporal range and one with no autocorrelation. The QMC produces C₃S output signals having comparable short scale periodic variograms except that the variance of the uncorrelated signal is four times greater than those of the autocorrelated signal and the real Joppa data. The raw material feeder variograms have the same sill for both the white noise and the autocorrelated signals. However, the autocorrelated signal feeder variogram presents lower short term dispersion variance, a characteristic feature of Joppa operations. Our results show the importance of simulating the right temporal structure of the raw materials to realistically forecast the behavior of the output signals. We also discuss some practical implications of these findings for the design and operation of a cement plant.     

煤系固废基绿色充填材料制备及其性能研究

充填技术是绿色开采的重要组成部分,研发成本低廉、性能可靠、低碳环保的充填材料,是发展充填技术的关键。采用煤矸石(CG)和煤系偏高岭土(MK)为原材料制备煤系固废基绿色充填材料,探讨配合比和碱激发剂对充填材料强度以及流动度的影响,并结合X射线衍射(XRD)、傅里叶变换红外吸收光谱仪(FTIR)、热重分析(TG)和扫描电镜能谱分析(SEM-EDS)等表征手段,揭示充填强度发展机理。综合强度、流动性和环境指标,优化充填材料配比。研究结果表明:绿色充填材料体系中,煤系偏高岭土通过碱激发水化反应起到胶凝作用,体系强度随偏高岭土的增加呈线性增长,磨细的煤矸石充当惰性填料,协同Na₂SiO₃改善流动性。该充填材料主要水化产物为N―A―S―H和沸石,Si―O―Si发生聚解,随即四面体Al―O键部分取代Si―O键,由(SiO₄)4?变成(AlO₄)4?,进一步聚合形成Si―O―Al基团。当碱激发剂中Na₂SiO₃与NaOH比例为1∶1时,聚合程度最高。水化产物填充了煤矸石颗粒间孔隙,使基质致密,提高充填材料强度。综合指标评价推荐偏高岭土与煤矸石的配比为3∶7,此时不仅满足强度和流动性的要求,而且碳排放指数仅有0.257。本研究为开发成本低廉、性能可靠、低碳环保的充填材料提供新的思路,具有较好的实用性和经济性。      

The Development of Laser Ablation ICP-MS and Calibration Strategies: Examples from the Analysis of Trace Elements in Volcanic Glass Shards and Sulfide Minerals

This contribution presents a review of the recent developments in laser ablation inductively coupled plasma-mass spectrometry. We describe the important developments which have occurred in the laser systems used, leading to a spatial resolution of around 20 (im, and give an overview of the major instrument developments which have affected the geological applications of laser ablation ICP-MS. We describe the calibration of laser ablation for the analysis of trace elements in two different matrices: volcanic glass shards and sulfide minerals. We show how single glass shards can be analysed using the National Institute of Standards and Technology (NIST) glass certified reference materials for calibration and demonstrate the effect of using single spot analyses compared to rastering of the calibration sample. We show the importance of inter-shard variation and demonstrate that averaged single shard analyses produce data which compare well with bulk analyses. The calibration of the laser system for sulfide mineral analysis is discussed and two different strategies are proposed, one using spiked pressed powder pellets of sulfides and the other metal reference materials. We present conclusions and recommendations for the calibration of laser ablation ICP-MS instruments.     

Geopolymer formation and its unique properties

The characteristic property of naturally-occurring geopolymers is a high content of humic materials that are recognized by the nitrogen function. Through a simulated geopolymerization, biopolymers with non-nitrogen function, such as xanthan gum, were found to have the characteristics of humic acid by means of UV–Vis spectrometry. This fact ascertains that any kind of biopolymer may naturally transform to a geopolymer. A geopolymer is a type of crosslinked long-chain compound, built in three-dimensional structures whose property is immune to microbial degradation. A crosslinked biopolymer was shown to have the same characterization as a geopolymer that has a long life due to its crosslinking capacity and anti-microbial properties. In this study, the formation of petroleum-based geopolymers (e.g., kerogen) was introduced. This study may elucidate the structure of geomacromolecules and the mechanism of their formation, closely related with crosslink reaction between inorganic and organic molecules. This will further change the conventional definition of geopolymer that involves only the inorganic geopolymer.     

电感耦合等离子体发射光谱法测试地质样品中的基体效应及校正办法

电感耦合等离子体发射光谱（ICP-AES）法分析速度快、干扰较少并能同时测定多种元素，被广泛应用于地质调查样品的分析测试中，成为通用的无机化学元素分析测试工具.在测定复杂基体样品时，由于基体效应产生的各种干扰也会影响分析测试结果，包括光谱干扰、物理干扰、化学干扰、电离干扰等.以ICAP-6000型号仪器为例，结合仪器特点及实际工作经验，对复杂基体地质样品测定中出现干扰的原因、特点进行分析，探讨基体消除的方法以保障测试结果的准确性.     

低温氮吸附法判识构造煤的实验研究

煤体结构是煤与瓦斯突出防治和煤与瓦斯共采的重要地质因素之一。为了区分煤体结构在地应力作用下的破坏程度,采集了淮北矿业股份有限公司桃园煤矿8283采煤工作面煤样,基于自相似原理和实验室内对煤样的加压模拟实验,通过煤基质纳米级孔隙在低温氮吸附-解吸曲线上的响应对比分析,建立了低温氮吸附法判识煤体结构的方法,并对淮北矿业股份有限公司桃园煤矿10号煤层内1026和1035工作面煤体宏观结构及微观孔隙发育特征进行了对比研究。结果表明,煤体微观孔隙结构变化与构造煤发育程度密切相关;随着煤体破坏程度的提高,在吸附-解吸曲线上表现为吸附量明显增大,纳米级孔隙的比表面积和比孔容明显增加,平均孔径略有增加;构造煤解吸曲线上有明显的陡降点,而原生结构煤的解吸曲线不具有这个特征。     

In situ and nondestructive characterization of mechanical properties of heritage stone masonry

The necessity of conserving and preserving the heritage is nowadays a developing study line for several researchers. From a civil engineering perspective, one of the most important issues for the conservation of historical buildings is to ensure the structural stability. For this purpose, it is necessary to determine the mechanical properties of the ancient construction materials. However, these structures cannot be evaluated by destructive tests due to politics and restrictions for preserving the heritage built. As a consequence, new methods that do not put in risk the integrity of the materials and the structure are becoming useful tools for researchers who work on structural engineering of heritage buildings. This paper presents a nondestructive method (NDM) that has been used to characterize the mechanical properties of different constructive systems of the San Antonio de Padua Temple, which is a religious icon in Aguascalientes, Mexico. This method includes the measuring of seismic waves’ travel time in order to obtain shear and compressional velocity waves. Results show that with this method mechanical properties of masonry can be obtained such as Young’s modulus, Poisson ratio and bulk density, which are needed for the structural analysis using numerical simulation models.     

偏高岭土协同石灰钝化红黏土水敏性的机制

红黏土水敏性强,添加石灰等碱性材料处治后,能获得即刻的改良效果,但由于红黏土呈弱酸性,石灰改良后其长期性能会衰减。为提高石灰稳定红黏土（简称La+L）的长期性能,添加偏高岭土（4%）协同石灰（5%）稳定红黏土（简称La+L+MK）,改善其水敏性和酸?碱互损作用。制备8种初始含水率的压实试样（初始孔隙比相同）,养护到预定时间后开展无侧限抗压强度试验,同时,测定试样的钙离子浓度、电导率和pH值。结果表明：初始含水率为26%左右时,改良土的无侧限抗压强度最高,初始含水率偏高或偏低都不利于改良土的强度增长。究其原因,试样偏干时,缺少水分,石灰水化不充分,不能形成游离态钙离子,无法进行火山灰反应,颗粒之间无法形成胶结;试样偏湿时,火山灰反应形成的胶结强度不及过量水分引起的基质吸力丧失量。试样的钙离子浓度和电导率变化规律,证实了以上原因解释的猜想。当然,添加偏高岭土后,能够显著改善偏湿状态下的石灰土强度。即使浸水饱和后,相对石灰改良土,也能够保持较高的强度,充分证明偏高岭土能够有效降低石灰土水敏性,提高其耐久性。偏高岭土直接提供了大量硅、铝氧化物,且将土体pH值降到有利于硅、铝氧化物溶解的碱性范围,加速火山灰反应,缓减或抑制石灰?红黏土的互损作用。     

Modeling of the formation of complex molecules in protostellar objects

The results of molecular composition modeling are presented for the well studied low-mass star-forming region TMC-1 and the massive star-forming region DR21(OH), which is poorly studied from a chemical point of view. The column densities of dozens of molecules, ranging from simple diatomic to complex organic molecules, are reproduced to within an order of magnitude using a one-dimensional model for the physical and chemical structure of these regions. The chemical ages of the regions are approximately 105 years in both cases. The main desorption mechanisms that are usually included in chemical models (photodesorption, thermal desorption, and cosmic-ray-induced desorption) do not provide sufficient gasphase abundances of molecules that are synthesized in surface reactions; however, this shortcoming can be removed by introducing small amount of reactive desorption into the model. It is possible to reproduce the properties of the TMC-1 chemical composition in a standard model, without requiring additional assumptions about an anomalous C/O ratio or the recent accretion of matter enriched with atomic carbon, as has been proposed by some researchers.     

Lunar regolith can allow the synthesis of cement materials with near-zero water consumption

With the continuous development of science and technology and the human understanding of the moon, many scientists have planned the creation of a space station on the moon using lunar building materials. Environmental factors mainly include large temperature differentials, and the presence of a hard vacuum on the surface of the moon is a huge challenge for the performance of lunar building materials. Geopolymer materials have the following properties: approximately zero water consumption, resistance to high- and low-temperature cycling, vacuum stability and good mechanical properties. Additionally, they meet most of the requirements for use in the lunar environment. Here, we present a potential lunar cement material that was fabricated using volcanic ash and sodium hydroxide solution as activator, based on geopolymer technology. The compressive strengths of the volcanic ash geopolymer specimens processed for 24 h under vacuum conditions and 30 freeze-thaw cycles in liquid nitrogen are 45.53 and 44.95 MPa, respectively. Additionally, 98.61% of water could be recycled, in consistence with the water recycling-simulated lunar environment in the lab. Although volcanic ash is not equivalent to the lunar soil, we speculate that the alkali activation of lunar soil could be very close to that of volcanic ash because of their similar chemical and mineralogical composition. In summary, this study provides a feasible approach for the development of near-zero water consumption lunar cement materials based on geopolymer technology.     

An Experimental Study on the Conductivity Changes in Coal during Methane Adsorption-Desorption and their Influencing Factors

During the processes of methane adsorption and desorption, the internal structure of coal changes, accordingly leading to changes in electrical conductivity. In this paper, using low rank coal seams of the Yan’an Formation in the Dafosi field as the research subject, the relationship between coal resistivity, methane adsorption quantity, and equilibrium pressure is analyzed through proximate analysis, mercury injection tests, low temperature liquid nitrogen adsorption tests, and coal resistivity measurements during methane adsorption and desorption. The results show that during the process of pressure rise and methane adsorption, the conductivity of coal increases, resulting from heat release from methane adsorption, coal matrix swelling and adsorbed water molecules replaced by methane, but the resistivity reduction gradually decreases. The relationship between coal resistivity and methane adsorption quantity and equilibrium pressure can be described by a quadratic function. During the processes of depressurization and desorption, the resistivity of coal rebounds slightly, due to decalescence of methane desorption, coal matrix shrinkage and water-gas displacement, and the relationship coincides with a linear function. Methane adsorption leads to irreversible changes in coal internal structure and enhances the coal conductivity, and resistivity cannot be restored to the initial level even after methane desorption. The resistivity and reduction rate of durain are higher than those of vitrain, with relatively greater homogeneous pore throat structure and fewer charged particles in the double electric layer. In addition, moisture can enhance the conductivity of coal and makes it change more complexly during methane adsorption and desorption.     

高岭土的深加工与新材料

煅烧高岭土由于晶体结构的改变而引起理化性能的变化，所表现出的性能更加优异。利用高岭土的特殊层状结构，将一些强极性有机小分子插入到结构层间，生成有机插层材料，这种新的复合物将黏土矿物和有机化合物的各自特性有机结合，极大地开阔了高岭土的应用领域和“档次”。以高岭土为原料而开发成功的Sialon材料，由于所具备的优越的力学性能、高温性能及化学稳定性等，在冶金、航空、化工机械和药学等方面显现出了极好的应用前景。地聚物材料是以偏高岭土、碱激发剂为主要原料，具有与陶瓷性能相似的一种新材料。     

Comparison of UV and IR Laser Ablation ICP-MS on Silicate Reference Materials and Implementation of Normalisation Factors for Quantitative Measurements

Direct analysis of geological reference materials was performed by LA-ICP-MS using two Nd:YAG laser systems operating at 266 nm and 1064 nm. The aim of this work was to compare UV and IR laser ablation and to assess the potential of the technique for the quantitative bulk analysis of rocks, sediments and soils. The laser sampling process was investigated and the analytical performance of both systems was compared. The influence of the laser operating conditions and the nature of the matrix on ICP-MS response factors calculated for major, minor and trace elements was evaluated. Under consistent laser settings, the response factors appeared to be matrix dependent. For a given matrix, the response factors were also significantly different for the two lasers. Normalisation with a single matrix element was effective only for matrices with similar mineralogy. When operating at 266 nm instead of 1064 nm, matrix effects could be reduced but not overcome. However, variations of the response factors between the different matrices appeared to be similar within distinct groups of elements, reflecting geochemical associations. When using multiple internal standards, matrix effects but also effects of the laser wavelength, could be fully compensated.     

蔡家营铅锌银多金属矿床的绿泥石结构特征

本文运用电子探针、红外光谱、X射线衍射分析等技术方法对蔡家营铅锌银多金属矿床绿泥石进行了研究。