基于LIBS技术的水泥粉末在线成分分析

在工业现场生产水泥的过程中，各种成分的含量直接影响着水泥的质量，因此如何快速准确地监测水泥中各个成分的含量意义重大。采用的实验方式为，将不经过任何预处理的水泥粉末直接放入位于二维移动平台上的物料盒中，通过激光诱导击穿光谱(LIBS)直接对水泥粉末表面的不同位置进行激发检测，对得到的光谱数据首先进行归一化和主成分分析等预处理操作，然后针对水泥中Ca, Si, Al, Fe, Mg五种元素，分别建立偏最小二乘(PLS)和支持向量回归(SVR)两种定量分析模型进行方法比较。此外，对比了粉末状水泥与压片式水泥两种测量方式的结果。实验结果表明，采用粉末状水泥直接测量的方式下，针对水泥样品元素浓度与所得到的光谱中特征线强度的关系，SVR方法比PLS方法更具优势，粉末状水泥直接测量的精度接近压片式测量的精度，说明LIBS技术对水泥粉末状样品直接在线测量具有可行性。     

Recent advances of ultrasonic testing of cement based materials at early ages

To summarize some of the most important findings in the field of ultrasonic (US) testing of early age hydration and formation of structure of different cement based materials (CBMs), a review of literature with focus on US P-wave transmission and S-wave reflection methods is presented in this paper. The review shows a great ability of both US techniques to observe setting phenomena and to determine different milestones during the early age formation of CBM’s microstructure. Clear physical basis, high accuracy, and non-destructive nature of the method indicate that US methods could become standardized in the near future.     

陕北晋西砂黄土的胶结物与胶结作用研究

在野外调查的基础上,采用SEM、XRD、土壤物理和土壤化学等方法,对陕北晋西12个县市的48个马兰黄土样品进 行了全分散法粒度组成测定、聚集体分析以及黄土胶结物组成的测试分析。结果表明,砂黄土中的粘土矿物和超细碳酸盐、 游离氧化物和有机质等胶结物质主要是以聚集体包膜的形式存在于碎屑颗粒表面,并构成砂黄土骨架间的结构联结,具有弱 胶结特性。砂黄土中粘土矿物和有机质为非水稳性胶结物质,仅在干燥状态具有较弱的胶结作用;黄土中的CaCO3呈粗颗粒 骨架和细分散超细碳酸钙两种形式存在,并分别起着骨架作用和胶结作用,超细碳酸钙为不可逆的胶结材料,在聚集体形成、 保存以及聚集体与碎屑颗粒之间的联结方面发挥着重要作用;非晶质游离氧化物(SiO2、Fe2O3、Al2O3)含量虽低,但由于他们 是以薄膜形式分布在颗粒表面,在黄土胶结作用中也是不可忽视的,并与上述各种胶结物共同起作用。通过统计分析认为, 凝聚系数可以较好地反映黄土的胶结程度,成为联系黄土胶结特性与黄土物理力学性质之间的桥梁。黄土胶结物组成及其 胶结机理的研究不仅有助于深化砂黄土工程特性的认识,而且对揭示黄土高原表生地球化学环境具有重要意义。     

The use of the capillary rheometer for the rheological evaluation of extrudable cement-based materials

In this paper, the rheological properties of an extrudable cement-based paste are investigated by means of an original ram extrusion apparatus (capillary rheometer). The experimental results indicate that a careful measurement of the die pressure is necessary to obtain a realistic viscosity vs shear rate curve, as required in extrusion technology. In particular, it is shown that the optimal test configuration is when the pressure measurement is made directly inside the rheometer die. By applying this rheological methodology in steady-state conditions, it has been observed that the extrudable cement-based material here evaluated obeys to a simple power–law equation, in the range of shear rates investigated, which are suitable for an industrial extrusion process. This paper was presented at the third Annual European Rheology Conference (AERC) held in Hersonissos, Crete, Greece, April 24–27, 2006.     

基于数字图像的土、岩和混凝土内部结构定量分析和力学数值计算的研究进展

土、岩及混凝土是一种内部结构极其复杂的材料,内部细观组成和结构决定了它们在外力作用下内部应力和应变等物理场的分布状态,在很大程度上控制了它们的宏观力学响应和破坏机理和过程。自1995年以来,数字图像处理技术作为一种材料细观空间结构及几何形态的精确量测和数字表述手段快速地被应用于沥青混凝土、水泥混凝土、土和岩体材料细观结构定量分析中来。本文在研究相关文献的基础上,分析和研究了数字图像技术在土、岩及混凝土内部结构定量分析和力学数值计算中的发展过程和研究成果,内容包括:单个骨料颗粒形态特征定量分析;土、岩和混凝土内部结构定量分析;岩体结构定量分析中的应用;基于数字图像处理的土、岩和混凝土细观结构力学计算。在此基础上,本文进一步对数字图像技术在岩土领域中的应用进展及未来的发展趋势进行了探讨,认为数字图像作为一种空间分布测量手段和数字表述方法使得它具有巨大的潜力,特别是在岩土领域的纵深发展过程中,它可能实现考虑细微观结构性的岩土力学和工程分析和预测的、新的方法和理论。     

水泥与生石灰处理吹填土对比试验研究

吹填土是由水力吹填形成的,颗粒很细,固结性能差,吹填以后要经过很长时间才能自然沉积固结,待表面形成硬壳后方可进行加固处理,因此,缩短沉积固结时间,使吹填土尽快地从泥浆状态转变为具有一定承载力的地基,是亟待解决的问题。在室内进行模拟加固方法的沉降柱试验,对吹填土加添固化剂以加速其沉积固结。固化剂主要选用水泥和生石灰,对两种添加方式的机理及固结效果进行详尽的分析和研究,初步找出加固效果产生差异的原因,从而揭示其固化机理,为吹填土地基的加固提供一种更加经济可行的方法。     

外掺剂加固吹填泥浆的机理分析

以吹填土的粒度成分、化学成分、物理化学性质测试为基础,从物理化学角度出发,对混合体系中的物理化学反应进行分类阐述,结合加固后土体结构强度的测算和微观结构特征分析,对外掺剂加固吹填泥浆的机理加以探讨。     

湿度对水泥生料近红外光谱检测的影响及补偿方法

近红外光谱检测已被应用于水泥生料成分的快速检测,但现场环境中的湿度等因素会对光谱产生干扰,从而降低检测精度。为了提高检测精度,在实验分析湿度对水泥生料近红外光谱检测影响的基础上研究了补偿方法。在水泥厂选取了24份水泥生料样本,其中18份作为校正集,6份作为验证集;水泥生料中的有效成分为SiO2,Al2O3,Fe2O3和CaCO3,各成分含量的标准值由X射线荧光光谱分析测出。首先,将校正集的18份样本每份重复装样测5次光谱,用得到的90个光谱建立模型Ⅰ;再每份样品制作5个湿度梯度样本,其获得过程为,先将样本放置在电加热平台上,用玻璃棒将样本摊平,180℃下加热30 min,再将样本放置在散热片上进行降温,待样品恢复室温后取出进行第一次光谱扫描,得到1个光谱,将测量后的样本放入搅拌器,使用装有去离子水的喷雾器对其喷雾两次,然后搅拌30 s混合均匀,测量混合后的样本得到下一个光谱,重复该过程,得到具有湿度梯度的5个光谱。所有样本均采用烘干法进行湿度测量,样本湿度变化区间在0.6%~2%以内。对每个湿度梯度的样本测量1次,用得到的这90个光谱建立模型Ⅱ。然后,将验证集的6份样本每份制作5个湿度梯度,获取方式与校正集相同,对每个湿度梯度的样本测量1次,得到30个光谱。所有光谱均采用多元散射校正预处理,拟合波段选择4000~5000 cm^-1,建模方法采用偏最小二乘法。比较同一份样本的5个湿度梯度,可以看到在5200 cm^-1处光谱差异最大,在其他位置也有肉眼可见的明显差异,因此,湿度变化对全波段光谱有明显的影响。最后,将这30个光谱输入模型Ⅰ与模型Ⅱ进行验证,并对比模型Ⅰ与模型Ⅱ的预测均方根误差RMSEP。模型Ⅱ中SiO2,Al2O3,Fe2O3和CaCO3的预测均方根误差RMSEP比模型Ⅰ分别减小了25%,31.3%,33.3%和25%。实验结果表明,水泥生料样本湿度对近红外光谱模型的预测结果具有一定的影响,采用具有湿度梯度的样本进行建模可有效降低湿度对预测结果的影响。     

Quantitative analysis of cement powder by laser induced breakdown spectroscopy

Determination of elemental composition of cement powder plays an important role in the cement and construction industries. In the present paper, Laser induced breakdown spectroscopy (LIBS) is used for measuring the concentration of cement ingredient. Cement powder samples are pressed into pellets. Laser pulses are focused on the surface of pellets. A microplasma is formed in the front of samples. The plasma emission contains information about the elemental composition of the samples. By assumption of local thermodynamic equilibrium (LTE) and using several standard cement samples, a calibration curve is prepared for each element. The major and minor elements of cement such as Ca, Si, K, Mg, Al, Na, Ti, Mn and Sr are qualitatively and quantitatively determined. For verification of LTE conditions, plasma parameters such as plasma electron temperature and electron density are computed. According to the obtained results, the LIBS technique could be a suitable method for determination of elemental composition in the cement production industries.     

A low-cost method for determination of calcium carbonate in cement by membraneless vaporization with capacitively coupled contactless conductivity detection

This work presents a flow analysis method for direct quantitation of calcium carbonate in cement without pretreatment of the sample. The method is based on online vaporization of CO₂ gas following acidification of the sample inside a small chamber that has a flow of acceptor solution passing around it. Solubilization of the CO₂ gas into the acceptor stream changes the conductivity of the acceptor solution causing an increase of signal at the capacitively coupled contactless conductivity detection (C⁴D) placed at the outlet of the vaporization chamber. This chamber is an adaption from previous work reported on ‘membraneless vaporization’ (MBL-VP).The method can be used in the quality control of production of mixed cement. These cement materials usually have calcium carbonate contents at high concentration range (e.g., 33-99% (w/w) CaCO₃). Analysis of samples by this method is direct and convenient as it requires no sample pretreatment. The method is low-cost with satisfactory accuracy and acceptable precision.