Investigation into the stabilization/solidification performance of Portland cement through cement clinker phases

This research studied the influence of individual heavy metal on the hydration reactions of major cement clinker phases in order to investigate the performance of cement based stabilization/solidification (S/S) system. Tricalcium silicate (C3S) and tricalcium aluminate (C3A) had been mixed with individual heavy metal hydroxide including Zn(OH)2, Pb(OH)2 and Cu(OH)2, respectively. The influences of these heavy metal hydroxides on the hydration of C3S and C3A have been characterized by X-ray diffraction (XRD) and differential scanning calorimetry-thermogravimetry (DSC-TG). A mixture of Zn(OH)2, Pb(OH)2 and Cu(OH)2 was blended with Portland cement (PC) and evaluated through compressive strength and dynamic leach test. XRD and DSC-TG data show that all the heavy metal hydroxides (Zn(OH)2, Pb(OH)2 and Cu(OH)2) have detrimental effects on the hydration of C3A, but only Zn(OH)2 does to the C3S at early curing ages which can completely inhibit the hydration of C3S due to the formation of CaO(Zn(OH)2).2H2O. Cu6Al2O8CO(3).12H2O, Pb2Al4O4(CO3)(4).7H2O and Zn6Al2O8CO(3).12H2O are formed in all the samples containing C3A in the presence of metal hydroxides. After adding CaSO4 into C3A, the detrimental effect of heavy metals increases due to the coating effect of both calcium aluminate sulphates and heavy metal aluminate carbonates. The influence of heavy metal hydroxide on the hydration of C3S and C3A can be used to predict the S/S performance of Portland cement.     

Raman and infrared spectroscopic investigations on aqueous alkali metal phosphate solutions and density functional theory calculations of phosphate-water clusters

Phosphate (PO(4)(3-)) solutions in water and heavy water have been studied by Raman and infrared spectroscopy over a broad concentration range (0.0091-5.280 mol/L) including a hydrate melt at 23 degrees C. In the low wavenumber range, spectra in R-format have been constructed and the R normalization procedure has been briefly discussed. The vibrational modes of the tetrahedral PO(4)(3-)(aq) (T(d) symmetry) have been assigned and compared to the calculated values derived from the density functional theory (DFT) method for the unhydrated PO(4)(3-)(T(d)) and phosphate-water clusters: PO(4)(3-).H(2)O (C(2v)), PO(4)(3-).2H(2)O (D(2d)), PO(4)(3-).4H(2)O (D(2d)), PO(4)(3-).6H(2)O (T(d)), and PO(4)(3-).12H(2)O (T), a cluster with a complete first hydration sphere of water molecules. A cluster with a second hydration sphere of 12 water molecules and 6 in the first sphere, PO(4)(3-).18H(2)O (T), has also been calculated. Agreement between measured and calculated vibrational modes is best in the case of the PO(4)(3-).12H(2)O cluster and the PO(4)(3-).18H(2)O cluster but far less so in the case of the unhydrated PO(4)(3-) or phosphate-water cluster with a lower number of water molecules than 12. The asymmetric, broad band shape of v(1)(a(1)) PO(4)(3-) in aqueous solutions has been measured as a function of concentration and the asymmetric and broad band shape was explained. However, the same mode in heavy water has only half the full width at half-height compared to the mode in normal water. The PO(4)(3-) is strongly hydrated in aqueous solutions. This has been verified by Raman spectroscopy comparing v(2)(H(2)O), the deformation mode of water, and the stretching modes, the v(1)OH and v(3)OH of water, in K(3)PO(4) solutions as a function of concentration and comparison with the same modes in pure water. A mode at approximately 240 cm(-1) (isotropic R spectrum) has been detected and assigned to the restricted translational mode of the strong hydrogen bonds formed between phosphate and water, P-O...HOH. In very concentrated K(3)PO(4) solutions (C(0) > or = 3.70 mol/L) and in the hydrate melt, formation of contact ion pairs (CIPs) could be detected. The phosphate in the CIPs shows a symmetry lowering of the T(d) symmetry to C(3v). In the less concentrated solutions, PO(4)(3-)(aq) solvent separated ion pairs and doubly solvent separated ion pairs exist, while in very dilute solutions fully hydrated ions are present (C(0) < or = 0.005 mol/L). Quantitative Raman measurements have been carried out to follow the hydrolysis of PO(4)(3-)(aq) over a very broad concentration range. From the hydrolysis data, the pK(3) value for H(3)PO(4) has been determined to be 12.45 at 23 degrees C.     

Transmission infrared spectroscopy as a probe of Nafion film structure: analysis of spectral regions fundamental to understanding hydration effects

Transmission infrared spectroscopy was applied to investigate properties of the perfluorosulfonated polymer Nafion. Measurements were made on thin films formed by casting the polymer from solution onto ZnSe windows. Effects of water vapor permeation were studied. A complex band structure between 1350 and 1100 cm(-1) was analyzed qualitatively by fitting the region to Gaussian functions. Features associated with vibrational modes of -CF(2) and -SO(3)(-) groups were identified and observed to be sensitive to film hydration. The intensities of bands for the -SO(3)(-) modes increased with film hydration, while bands assignable to -CF(2) modes decreased. The results were applied to interpret infrared difference spectra of Nafion and shed light on the complicated features that appear. Vibrational bands for water were also examined. In partially hydrated films, the stretching mode of the free -OH group for interfacial water present in pores and channels of the polymer and bands for hydrated proton clusters were detected.     

Crystallization of polylactide and its stereocomplex investigated by two-dimensional fourier transform infrared correlation spectroscopy employing carbonyl overtones

The band origins and transitions of weak vibrational modes developed in the 3500 cm(-1) region of polylactide (PLA) spectra during crystallization are investigated. The band assignment to the OH stretching mode of terminal hydroxyls is unlikely because the trace amount of chain-ends is negligible considering the long chain of high molecular weight polymer. The band intensity can be enhanced for quantitative study by increasing the sample film thickness. The results show that the transition patterns of these bands mimic those of C=O stretching modes. Therefore, these are assigned to C=O overtones. Two bands associated with crystalline and amorphous characteristics are revealed during cold crystallization. The crystalline C=O bands of PDLA and its stereocomplex counterpart are located at 3510 cm(-1) and 3482 cm(-1), respectively, indicating a weaker C=O bond in the latter crystal structure. Two-dimensional Fourier transform infrared (2D-FT-IR) correlation spectroscopy is then applied to study the correlation between C=O overtones and the crystalline characteristic band located near 900 cm(-1). The transitions of the two vibrational modes observed in crystallization of the stereocomplex are in-phase with each other. This reflects an involvement of short-range hydrogen bonding in the stereocomplex crystal structure. In contrast, crystallization of PDLA shows that the C=O overtone varies prior to that of the C-H character, indicating that dipole-dipole force is a crystal-induced interaction.     

利用粘度法和二维红外相关光谱法研究胶原/羟丙甲基纤维素共混物的相互作用

采用粘度法和二维红外相关光谱法对胶原/羟丙甲基纤维素共混体系的相容性及相互作用进行了研究。粘度法测定结果表明,羟丙甲基纤维素含量<30%时共混体系相容,超过50%则不相容。二维红外相关光谱法的分析结果表明,当羟丙甲基纤维素含量<30%时,归属于羟丙甲基纤维素的C—O(H)伸缩振动峰1061cm-1与归属于胶原酰胺带的CO对称伸缩振动峰1660cm-1、N—H摇摆振动峰1553cm-1和N—H面内变形振动峰1238cm-1之间存在同步负交叉峰,表明胶原和羟丙甲基纤维素之间存在氢键作用;而当羟丙甲基纤维素含量>30%时,同步图中负交叉峰强度减小的同时同步峰1061cm-1的强度明显变大,表明此时羟丙甲基纤维素与胶原之间的氢键作用变弱,羟丙甲基纤维素更倾向于在自身分子之间形成氢键。     

PECVD非晶SiOx∶H薄膜的Si—O—Si键红外吸收特性研究

用傅里叶红外光谱(FT-IR)测试分析了等离子体化学气相沉积法沉积的非晶SiOx∶H(0≤x≤2.0)薄膜中的Si—O—Si伸缩振动模与氧含量x的关系。Si—O—Si伸缩振动模在1000和1150cm     

Characterization of titania thin films grown by dip-coating technique

A dip-coating technique was employed to prepare anatase phase of titania thin films. Fluorine doped tin oxide substrates were used to prepare titania thin films. The samples were annealed at 550 °C for 18 h. X-ray diffraction results revealed the amorphous and anatase phases of TiO₂ for as-synthesized and annealed samples, respectively. The crystallite size of anatase TiO₂ thin films was almost 25 nm for annealed samples. UV–visible confirmed the energy band gap 3.86 and 3.64 eV for as-prepared and calcinated titania thin films. The reduction in the energy band gap could be due to the change in crystallization and agglomeration of small grains after calcination. The morphology of the prepared films was investigated by field emission scanning electron microscopy which demonstrated the agglomeration of spherical particles of TiO₂ with average particle size of about 30 nm. The molecular properties (chemical bonding) of the samples were investigated by means of Fourier Transform Infrared (FTIR) spectroscopy. FTIR analysis exhibited the formation of titania, functional group OH, hydroxyl stretching vibrations of the C–OH groups, bending vibration mode of H–O–H, alkyl C–H stretch, stretching band of Ti–OH, CN asymmetric band stretching, and C=O saturated aldehyde.     

Catalytic effects of Ag2O additives on microstructure and recrystallization in borate glasses

A substitution of Ag2O for B2O3 in a 35BaO–25Fe2O3–(40−x)B2O3–xAg2O, x=0.0, 0.5, 1.0 and 3.0, glass series modifies the B2O3 network and changes infrared frequencies in the 1600–600 cm-1 region. Four bands at 1440, 1280, 1180 and 1120 cm-1 appear in glass containing no Ag2O additive. On adding the Ag2O, the 1120 cm-1 band (which belongs to the BO3→BO4 modified group in the B2O3 network) no longer appears, and the other three bands (belonging to the B–O stretching vibrations in the interconnected boroxol rings) shift 15–40 cm-1 to higher frequencies expected in the reduced structural defects of BO3→BO4 modified groups and non-bridging oxygens. This modified glass crystallizes (at 500–850°C) into acicular BaFe12O19 microcrystals of a higher coercivity of ∼5000 Oe, suitable for high energy-density magnets and other devices. This revised version was published online in November 2006 with corrections to the Cover Date.     

Use of infrared spectroscopy for the determination of electronegativity of rare earth elements

Infrared spectroscopy has been used to study a series of synthetic agardite minerals. Four OH stretching bands are observed at around 3568, 3482, 3362, and 3296 cm(-1). The first band is assigned to zeolitic, non-hydrogen-bonded water. The band at 3296 cm(-1) is assigned to strongly hydrogen-bonded water with an H bond distance of 2.72 A. The water in agardites is better described as structured water and not as zeolitic water. Two bands at around 999 and 975 cm(-1) are assigned to OH deformation modes. Two sets of AsO symmetric stretching vibrations were found and assigned to the vibrational modes of AsO(4) and HAsO(4) units. Linear relationships between positions of infrared bands associated with bonding to the OH units and the electronegativity of the rare earth elements were derived, with correlation coefficients >0.92. These linear functions were then used to calculate the electronegativity of Eu, for which a value of 1.1808 on the Pauling scale was found.     

Isotope (18)O/(16)O Ratio Measurements of Water Vapor by use of Photoacoustic Spectroscopy

We applied a photoacoustic spectroscopy technique to isotope ratio measurements of (16)O and (18)O in water-vapor samples, using a pulsed tunable dye laser pumped by a Nd:YAG laser. The fourth overtone bands (4nu(OH)) of water molecules near 720 nm were investigated. We identified the absorption lines of H(2)(16)O and H(2)(18)O in the photoacoustic spectra that we measured by using an (18)O-enriched water sample and the HITRAN database. We measured the difference in the (18)O/(16)O isotope ratios for normal distilled water and Antarctic ice, using the photoacoustic method. The value obtained for the difference between the two samples is delta(18)O = -32 ? 16 per thousand, where the indicated deviation was a 1varsigma value among 240-s measurements, whereas the value measured with a conventional isotope mass spectrometer was delta(18)O = -28 ? 2 per thousand. This method is demonstrated to have the potential of a transportable system for in situ and quick measurements of the H(2)(18)O/H(2)(16)O ratio in the environment.     

Hydrogen-deuterium exchange in bovine serum albumin protein monitored by Fourier transform infrared spectroscopy, part II: kinetic studies

The set of infrared spectra recorded at different levels of hydrogen-deuterium (H/D) exchange as a function of time were processed using spectral decomposition. The most precise information about H/D exchange of the NH groups of the protein backbone was retrieved by observing the intensity change of the nearest C=O stretching vibration. The H/D exchange at the protein backbone begins with NH groups bonded to C=O with a characteristic frequency of 1683 cm(-1). These amide groups were initially free and are the first to accept H-bonds from water during the hydration process. The NH groups, which are connected to C=O groups with a characteristic band at 1657 cm(-1), exchange at a slower rate. For both populations the pairs of comparable exchange rates were calculated with rate constants of 10(-3) min(-1), 0.014 min(-1), 0.0046 min(-1), and 0.09 min(-1). The appearance of two different exchange rates for each population is a consequence of the distinct exposure of particular molecular groups to the solvent. Two additional bands sensitive to exchange are attributed to NH bending modes in the side chains and are located at 1610 cm(-1) and 1585 cm(-1). These NH groups undergo H/D exchange at the beginning of the exchange with exchange rates of 0.019 min(-1) and 0.17 min(-1), respectively. The calculated exchange rate for hydrating water molecules is 0.037 min(-1). The distribution of water's exchange rate is extremely broad and covers almost the entire interval of the time-dependent experiment. From the efficiency of the exchange (96%) it is evident that some parts of the protein are completely forbidden to water molecules.     

Hydrogen-deuterium exchange in bovine serum albumin protein monitored by fourier transform infrared spectroscopy, part I: structural studies

The structure of the amide I band of bovine serum albumin (BSA) was determined using an H/D exchange experiment. The difference between the dry and hydrated exchange spectrum revealed the fine structure of the amide I band. The band at 1717 +/- 2 cm(-1) is due to the vibration of the COOH moieties from the protein side chains. Band components at 1682 +/- 2 cm(-1), 1655 +/- 2 cm(-1), and 1637 +/- 2 cm(-1) are assigned to the vibrations of the backbone C=O. These three bands belong to vibrations of three different populations of amide groups differing in the number of established H-bonds. The connectivity between the frequencies of various amide vibrations was determined by two-dimensional generalized correlation spectroscopy and spectral decomposition. About 7% of the whole exchangeable hydrogen atom population (NH, NH2, and OH groups from backbone and side chains) remains unexchanged, and these hydrogen atoms belong mainly to the NH groups, which are H-bonded to specific C=O groups. Moreover, this study concerns the approximately 10% of hydrogen atoms belonging to a particular HN...O=C population with a characteristic amide A frequency at 3290 cm(-1) and an amide I band at 1655 +/- 2 cm(-1), usually attributed to the alpha-helical structure that remains unexchanged. At higher temperature the exchange is more efficient. Upon heating, a further 4% of these NH groups are deuterated. The comparison of the exchange spectrum at higher temperature with the structural changes of the protein at the same temperature implies that the change in overall dynamics of the protein improve the level of exchange.     

采用二维红外技术研究交联对碱溶胶原结构的影响

以N-羟基琥珀酰亚胺己二酸酯(NHS-AA)为交联剂,交联改性碱溶胶原,采用二维红外相关光谱法研究了交联对胶原二级结构的影响。研究发现,交联未影响胶原红外特征吸收峰的位置,但1672、1554和1241cm-1归属于胶原酰胺I带的CO伸缩振动、酰胺Ⅱ带的C—N伸缩与N—H弯曲振动和Ⅲ带的N—H面内变形振动峰之间存在同步正交叉峰,表明随交联共价键的增加,胶原的链段构象发生了变化。在NHS-AA用量增加的过程中,胶原二级结构变化的顺序为:酰胺Ⅲ带>酰胺Ⅰ带>酰胺Ⅱ带>—CH3>—CH—。由此可见,二维红外相关分析法能提供由交联引起的胶原构象动态变化的微观信息,为进一步研究改性胶原结构与功能之间的关系提供实验依据。     

插层型蔗糖/蛭石纳米复合材料的制备

以蔗糖和蛭石为原料,在超声辅助条件下采用溶液插层法制备插层型蔗糖/蛭石纳米复合材料。X射线衍射（XRD）、红外光谱（FTIR）分析表明,蔗糖/蛭石复合物样品的d001值为1.852nm;样品的红外谱图中出现甲基和亚甲基特征峰2761cm-1和2969cm-1。将蔗糖/蛭石复合物在氮气氛下碳化后,样品的XRD（d001=1.247nm）和红外光谱结果（甲基和亚甲基特征峰2761cm-1和2969cm-1消失）表明,碳/蛭石复合材料层间夹有碳,进一步证实得到插层型蔗糖/蛭石复合材料。同时,确定了优化插层反应工艺条件,超声功率为400W,物料配比为蛭石：蔗糖=1：2.5,超声水化时间为0.5h,超声反应温度为70℃,反应时间为2.5h,静置时间2h。     

Fluorescence Associated with Impurities in Nanostructured Al_2O_3

The fluorescent spectra of nanostructured Al2O3 after heat-treating at different temperatureshave been systematically investigated. The results show that for η-Al2O3 and γ-Al2O3, two broadfluorescent bands P1 and P2 appear in the wavenumber range of 20000 cm-1 to 11500 cm-1,and P1 and P2 bands are located in the wavenumber range of 20000 cm-1 to 14500 cm-1 and14500 cm-1 to 11500 cm-1, respectively The P1 band can be attributed to the impurity Cr3+luminescence. This is consistent with other author's result for the Cr doped Al2O3. The P2band is a new fluorescent phenomenon, which has not been reported previously. In this paper,the condition of the appearance of P2 and its mechanism is discussed in detail.     

Hexavalent chromium in tricalcium silicate: Part I Quantitative X-ray diffraction analysis of crystalline hydration products

The hydration products of CrVI-doped tricalcium silicate (C3S) have been investigated. C3S is the main constituent of Portland cement responsible for the strength and stability of hardened Portland cement paste. Chromium trioxide (CrO3), added as a dopant to C3S, simulates hexavalent chromium waste that may be stabilized in ordinary Portland cement. X-ray diffraction was used to monitor the development of the hydration reaction products from the early stages to the late reaction stages. Leaching studies were carried out to evaluate the stability of the CrVI-containing phases in the hydrated C3S matrix.In monolithic waste forms containing hexavalent chromium, CaCrO4·2H2O was found to form within a few minutes of the hydration reaction. With increasing concentration of Ca2+ in the pore solution, Ca2CrO5·3H2O became the stable species. The chromium in this phase was found to be very mobile in a standard acetic acid leaching test.     

溶胶—凝胶制备TiO2／SiO2复合薄膜的FT—IR表征

ＦＴ－ＩＲ吸收谱用来研究具有多孔结构的ＴｉＯ２／ＳｉＯ２复合薄膜；薄膜在１２００ｃｍ＾－１有一较强的肩峰，其强度与峰位随热处理温度度而生变化。在９５５ｃｍ＾－１的吸收峰是由于Ｓｉ－Ｏ－Ｔｉ和Ｓｉ－ＯＨ的结果，并随着热处理 度的提高其吸收峰完全是Ｓｉ－Ｏ－Ｔｉ振动所引起的，其峰位随着ＴｉＯ２的增加，向低频区域移动。     

Significance of water/solid ratio and temperature on the physico-mechanical characteristics of hydrating 4CaO.Al2O3.Fe2O3

Tetracalcium alumino-ferrite in paste form, at water/solid (W/S) ratios of 0.3, 0.4, 0.5 and 1.0, and in pressed form at effective water/solid ratios of 0.13 and 0.08 has been hydrated for up to 45 days at temperatures of 23 and 80° C. Some prehydrated samples have also been subjected to autoclave treatment at 216° C. Of all the samples studied, that hydrated at a W/S=0.13 at 80° C indicated the highest ratio of cubic phase to hexagonal phase; that hydrated at a W/S=0.08 at 23° C showed the lowest.Thermograms gave evidence of the formation of hexagonal phases, although X-ray diffraction patterns did not. The specific surface area values depended on the degree of hydration and the nature of the product, autoclaved samples giving the lowest values. During the four days of hydration the specimen hydrated at 80° C expanded more than that hydrated at 23° C, but after that time the rates of expansion were reversed: that of the sample hydrated at 80° C was much lower than that of the sample hydrated at 23° C. Microstructural examination of the material formed at higher temperatures and lower water/solid ratios indicated a closely welded, continuous network of cubic phase. Such a structure yields a product of higher strength than that of a loose structure formed at higher water/solid ratios. A reasonably linear relation was found between porosity and logarithm of microhardness.     

Structural change of water with solutes and temperature up to 100 degrees C in aqueous solutions as revealed by attenuated total reflectance infrared spectroscopy

The attenuated total reflectance infrared (ATR-IR) spectra of several aqueous solutions have been measured by using a newly developed heatable rod-type ATR cell. The OH stretching bands showed systematic change with increasing solute concentrations and these changes can be explained by four different OH components based on curve-fitting results. NaCl solutions show longer H-bond distance character, while carbonate solutions present shorter ones. The Na2CO3 1 M solution conserves this shorter H-bond nature up to 100 degrees C. On the other hand, the loose nature of NaCl solutions becomes less pronounced at higher temperatures because of the dissociation of pure water clusters. These in situ observations of water structures are generally in agreement with the expected nature of fluids within the earth.     

Growth and characterization of Na3BaCl5·2H2O

Na₃BaCl₅·2H₂O crystals were prepared by the slow evaporation of an aqueous solution of a mixture of sodium chloride and barium chloride in stoichiometric ratio. Crystals were found to possess platelet habit. Crystals were analysed by infrared spectrophotometry, thermogravimetry and X-ray diffraction. The appearance of bands due to stretching and bending modes of water molecules in the IR spectra showed that the grown crystals were hydrated. X-ray oscillation and Weissenberg photographs were used to measure the dimensions of the unit cell.