The effects of fly ash composition on the chemistry of pore solution in hydrated cement pastes

This paper reports the findings of an investigation to determine the influence of fly ash composition on the evolution of the pore solution chemistry in Portland cement/fly ash systems. Twelve fly ashes, selected to represent the wide range of composition of North American ashes, were used in the study. In addition to pore solution expression and analysis, inner hydration products were analyzed using energy-dispersive X-ray analysis. The study shows that the alkalinity of pore solution increases as the calcium and alkali content of the fly ash increase, and decreases as the silica content of the ash increases. However, there is no consistent trend between the composition of the inner calcium-silicate hydrate and fly ash composition.     

Methods of obtaining pore solution from cement pastes and mortars for chloride analysis

Two techniques for the recovery of pore solution from cement mortars are examined: pore solution expression and miscible displacement using a high pressure permeameter. In the former, the pore solution is expressed from the mortar by crushing; in the latter, it is eluted from the mortar over 30 min by miscible displacement with water. Experimental results are presented for a range of cement pastes and mortars into which known amounts of chloride ion have been incorporated by using sodium chloride solution as the mix water. The results show that both eluted and expressed solutions exhibit a decrease in chloride ion concentration as the cement matrix ages, with the elution method showing a greater sensitivity to mix composition. Both methods show a decrease in chloride concentration as the water: cement ratio of the mix is increased. Overall, the high pressure elution method is capable of recovering a significantly higher proportion of the incorporated chloride. The application of these techniques to pore solution analysis is discussed.     

Accelerated carbonation testing of alkali-activated binders significantly underestimates service life: The role of pore solution chemistry

The carbonation resistance of alkali-activated binders is often tested via accelerated test protocols designed for Portland cements, without questioning whether the tests replicate the mechanisms observed in service. Thus, validation of accelerated methods is required to enable realistic prediction of material performance. Changes in pore solution equilibria cause the formation of sodium bicarbonates during accelerated carbonation, compared with hydrous sodium carbonates in natural carbonation. This shifts the carbonation mechanism to favour more rapid reaction progress, to give a higher apparent degree of acceleration (compared to natural conditions) than in Portland cements. The pore solution pH under accelerated carbonation is significantly lower than at natural CO₂ concentrations, leading to a falsely short predicted service life (time to expected corrosion of embedded steel), as natural CO₂ concentrations appear not to reduce the pH below 10. Thus, accelerated carbonation testing is unduly aggressive towards alkali-activated binders, and test results must be cautiously interpreted.     

Effects of activated carbon surface chemistry and pore structure on the adsorption of organic contaminants from aqueous solution

The objective of this research was to develop activated carbon selection criteria that assure the effective removal of trace organic contaminants from aqueous solution and to base the selection criteria on physical and chemical adsorbent characteristics. To systematically evaluate pore structure and surface chemistry effects, a matrix of activated carbon fibers (ACFs) with three activation levels and four surface chemistry levels was prepared and characterized. In addition, three granular activated carbons (GACs) were studied. Two common drinking water contaminants, relatively polar methyl tertiary-butyl ether (MTBE) and relatively nonpolar trichloroethene (TCE), served as adsorbate probes. TCE adsorbed primarily in micropores in the 7-10 Å width range while MTBE adsorbed primarily in micropores in the 8-11 Å width range. These results suggest that effective adsorbents should exhibit a large volume of micropores with widths that are about 1.3 to 1.8 times larger than the kinetic diameter of the target adsorbate. Hydrophobic adsorbents more effectively removed both TCE and MTBE from aqueous solution than hydrophilic adsorbents, a result that was explained by enhanced water adsorption on hydrophilic surfaces. To assure sufficient adsorbent hydrophobicity, the oxygen and nitrogen contents of an activated carbon should therefore sum to no more than about 2 to 3 mmol/g.     

Changes in structure and chemistry of cement mortars stressed by a sodium chloride solution

Cement mortars, one-sidedly ctressed by a sodium chloride solution of 20 % for 140 days, show a marked area at a distance from the surface of nearly 30 mm. Its position is reflected in concentration profiles of the water soluble and nitric acid soluble parts of chloride, sulphate, sodium, potassium, and aluminium, in the mineral content as well as in the pore size distribution. This could serve as the starting point for deteriorations caused by cycles of freezing and thawing in connection with deicing salts, because destroying mechanisms could easily attack here.Further studies must be carried out and the observation of stressed cement mortars and concretes has to be intensified to get a better insight into the principles and the mechanisms of such processes.     

The pore solution phase of carbonated cement pastes

Samples of hydrated cement pastes were exposed to atmospheres with various carbon dioxide concentrations at relative humidities controlled by different saturated salt solutions. When carbonated throughout their thickness, as indicated by the phenolphthalein test, they were resaturated with water and subjected to pore solution expression and analysis. The effects of the various carbonating environments on the pore solution composition and on aspects of the pore structure and mineralogy of the carbonated products are reported. Implications regarding the likely effects of different accelerated carbonation regimes on the corrosion behaviour of steel in concrete are discussed. In particular, it is shown that the use of saturated sodium nitrite solution to control the relative humidity of atmospheres with high concentrations of carbon dioxide may cause an evolution of gaseous oxides of nitrogen, which can result in the contamination of the pore solution with nitrite and nitrate salts.     

Immobilized penicillin G acylase on mesoporous silica: The influence of pore size, pore volume and mesophases

Penicillin G acylase (PGA) was immobilized on KIT-6 and SBA-15 with different pore sizes to study the influence of pore size, pore volume and mesophases on the immobilized enzyme (IME) activity. The results show that the pore size, pore volume, mesophase and surface area have an obvious influence on the IME activity, of which the pore size is the most important factor. The activity of PGA immobilized on KIT-6/130 reaches to 3522 IU/g by dry support, which is higher than that ever reported for carrier-bound penicillin G acylase [A.I. Kallenberg, F. van Rantwijk, R.A. Sheldon, Adv. Synth. Catal. 347 (2005) 905–926]. Because of the covalent immobilization, the operational stability of IME increases.     

The influence of substrate absorbency on coating surface chemistry

The composition of the top surface of a coating layer can influence its functional properties or subsequent processing steps. The effect of the substrate absorbency on the coating surface chemistry is reported. Different coating systems containing a kaolin clay pigment, fine or coarse precipitated calcium carbonates, and a common latex binder were examined. The influence of a soluble polymer added into the coating was characterized. The surface chemistry was measured with attenuated total internal reflectance (ATR) and X-ray photoelectron spectroscopy (XPS).

Absorbent substrates generate bulky coatings with high voids and low gloss. Rapid dewatering by the absorbent substrate pulls the small particles, like latex binder, away from the top layers causing a low latex concentration at the surface. On non-absorbent substrates, the addition of the soluble polymer generates coating layers with higher void volume, lower gloss, and lower latex concentrations at the coating surface. However, on absorbent substrates, polymer addition causes coatings with lower void volumes and higher gloss. In this case, the rapid dewatering and mobility of particles is reduced by the polymer, which helps to retain the small particles at the surface. As a result, latex concentration at the surface increases with polymer addition on absorbent substrates.     

Aspects of the pore solution chemistry of blended cements related to the control of alkali silica reaction

The effects of four pulverised fuel ashes (PFA) and three ground blastfurnace slags (GBFS) on the alkalinity of the pore solution phase of hardened cement pastes has been studied. It has been found that the total alkali content of a PFA is an important factor, but not the only one, determining its effectiveness in reducing the hydroxyl ion concentration of the pore solution. For GBFS, however, there was found to be no direct correlation between the total alkali content of the slag and the composition of the pore solution. Implications regarding the roles of PFA and GBFS in reducing expansion associated with alkali silica reaction (ASR) are discussed.     

氯离子对硝铵磷水溶液热安全性影响研究

利用自制临界爆炸装置对80%硝铵磷水溶液的热安全性进行测试实验。结果表明,含氯离子硝铵磷水溶液比纯硝铵磷水溶液的临界爆炸温度要低;一定浓度的氯离子有促进硝铵磷水溶液爆炸的作用,硝铵磷水溶液的临界爆炸温度随氯离子浓度的增大呈先降低后升高的趋势。研究结果对使用硝铵磷生产复合肥安全生产具有重要指导意义。     

聚丙烯腈纤维孔隙结构对预氧化的影响

采用湿法纺丝,通过不同的牵伸条件,制备具有相同的化学组分和不同孔隙率(体密度)的聚丙烯腈纤维,然后在相同的条件下预氧化。借助红外吸收光谱(FT-IR)、场发射扫描电子显微镜(FESEM)、差示扫描量热(DSC)等表征手段对原丝和预氧丝的环化度、皮芯结构及预氧丝横截面的氧径向分布进行分析对比。实验结果表明,随着孔隙率降低(体密度增加),纤维径向的氧含量梯度变大,皮芯结构趋于严重。     

氯离子对硫铵结晶系统的影响及对策

研究了硫铵结晶系统中氯离子的来源以及对硫铵结晶系统的影响,并制定了控制氯离子含量的对策。硫铵结晶系统由于氯离子进出严重不平衡,导致母液中的氯离子含量高,造成设备腐蚀,影响产品质量和系统安全,因而必须控制氯离子的含量。     

The role of hydrodynamic conditions and solution chemistry on protein fouling during ultrafiltration

This study investigates the effect of hydrodynamic conditions and solution chemistry on protein fouling during ultrafiltration. Drastic flux reduction was observed at high initial flux and/or low cross-flow velocity. A limiting flux existed during BSA filtration, beyond which membrane flux cannot be sustained. Further increase in pressure over the limiting value did not enhance the stable flux. The rate and extent of BSA fouling were also strongly dependent on the feedwater composition, such as BSA concentration, pH, and ionic strength. Foulant concentration had no effect on the stable flux, although the rate approaching to the stable flux increased proportionally with increasing foulant concentration. Fouling was most severe at the isoelectric point of BSA (pH 4.7), where the electrostatic repulsion between foulant molecules is negligible. Membrane fouling became less severe at pHs away from the isoelectric point. Increasing ionic strength at pH 3.0 promoted severe fouling likely due to electric double layer (EDL) compression. On the other hand, the flux behavior was insensitive to salt concentration at pH 4.7 due to the lack of electrostatic interaction. At a solution pH of 5.8, effect of ionic strength on long-term flux behavior was directly opposite to that on the transient behavior. While the long-term flux was lower at higher ionic strength due to EDL compression, the transient behavior was also affected by the BSA retention of the membrane.     

The influence of chloride ions on the kinetics of iron dissolution

The anodic dissolution of pure iron was studied in oxygen-free solutions at high concentrations of chloride and hydrogen ions at 25°C under potentiostatic steady-state conditions. In the range c_H⁺ ? 1 M the following kinetic data were obtained: Tafel slope b₊ ? +100 mV, electrochemical reaction order related to C_H⁺, n_+.H⁺ = +1·1, and electrochemical reaction order related to the chloride ion concentration, n_+,Cl^? = +0·6. These values cannot be correlated to the currently proposed mechanisms of iron dissolution, another mechanism is suggested for the described conditions. The correlations to known mechanisms are discussed.     

Reinforcing steel passivation in mortar and pore solution

Under field conditions, steel is embedded in concrete for a long period of time before chlorides penetrate. In studying the corrosion behaviour of steel in concrete, mortar or in simulated pore solution, it is essential to allow enough time for the steel to create a passive layer which is the subject of this study. This time is given to steel in chloride free concrete, naturally; while it should be provided to steel in synthetic pore solution, before adding chloride to the solution. For determining this time, samples were made with steel with different surface conditions: as-received with mill scales and sand-blasted. One set of steel bars (as-received and sand-blasted) were embedded in mortar and one set were immersed in synthetic pore solution. Corrosion of each steel bar was monitored every hour by LPR technique for total time of 300 h. Also, half-cell potential of steel bars was measured during that time. Results show that steel needs to be kept at least three days in synthetic pore solution and seven days in mortar to be passivated.     

Influence of pore water chemistry on the swelling behavior of compacted clays

The influences of the exchange complex and pH of the solution used for cation saturation on Atterberg limits, compaction, and swelling potential of a compacted clay were investigated. The study involved transforming the exchange complex from a heterogeneous to a homogeneous one so that a frame of reference can be set for the clay behavior under such an ideal condition. The employed method for altering the exchange complex successfully yielded homo-ionic clay. The introduction of different species of cations gave rise to different particles associations. When introduced to the tested clay, potassium cations bond its particles with a rather strong bond (K-linkage), causing a drastic decrease in the specific area of the clay (about one-fourth of its untreated specific area), a decrease in the CEC, as well as a drastic decrease in the swell potential. For example, the swell pressure decreased from 1.87 kg/cm² for the untreated samples to 0.4 kg/cm² for the K-treated samples (under the same conditions). Also, the swell potential vs. time relationships can be modeled accurately using a rectangular hyperbola.     

Effect of temperature on pore solution composition in plain cements

Cement pastes with a water-cement ratio of 0.6 were prepared using three ordinary portland cements with C₃A contents of 2.43, 7.59 and 14%. Three levels of chlorides 0.3, 0.6 and 1.2% by weight of cement, derived from sodium chloride, were added through mix water. The pastes were allowed to cure in sealed containers at 20 and 70°C for 180 days and then subjected to pore solution extraction. The expressed pore solutions were analyzed for chloride and hydroxyl ion concentrations. Results show that increase in temperature from 20 to 70°C increased unbound chlorides and decreased hydroxyl ion concentration of pore solutions for all the three cements. The simultaneous increase in unbound chlorides and decrease in hydroxyl ion concentration drastically increased Cl⁻/OH⁻ ratio of the pore solution, thereby indicating an increase in corrosion risk. This adverse effect of increase in the Cl⁻/OH⁻ ratio of the pore solution with increase in temperature is higher in the high 14% C₃A cement than in the low C₃A cements, and is also higher for the low 0.3% chloride treatment level than the higher chloride inductions. Increase in temperature is also expected to cause an increase in ionic diffusion to steel embedded in concrete as well as in the rate of corrosion reaction. All these factors tend to increase corrosion risk of steel reinforcement in concrete with an increase in temperature.     

The effect of precursor chemistry and preparation conditions on the formation of pore structure in metal-containing carbon fibers

Activated carbon fibers (ACFs) prepared from petroleum isotropic pitch and the same containing silver and cobalt nitrate, cobalt and palladium acetylacetonates, as well as mixtures of two salts with a total metal or metal mixture content of 1 wt% have been studied. The processing parameters are summarized for activated carbon fibers containing individual metals and metal mixtures. The results suggest that the generation of metal-containing particles and the formation of pore structure depend on many different factors including the composition of the metal and pitch precursors, the interaction of the metal and pitch precursors during the fiber production process, and the interaction between the two metal precursors when more than one metal salt is used. The addition of silver and cobalt in the form of nitrate salts enlarges the micropores and generates small mesopores with a narrow range of sizes. The addition of palladium as an acetylacetonate salt leads to the formation of both small micropores and larger mesopores. The cobalt additive as an acetylacetonate salt catalyzes the activation process, creating large mesopores and macropores. Mixing of two different metal precursors affects the particle composition and size. This, in turn, controls the pore structure of the final activated fibers. During activation, the two metal precursors can act independently (Ag/Co mixture). However, in other cases their effect can be additive (Co/Pd mixture), or even synergistic (Ag/Pd mixture).     

Effect of solution chemistry on membrane resistance and flux decline

Variations in the membrane resistance due to the adsorption of cakes of Glutamicum onto polysulphone membrane surface were evaluated by measuring the change in the permeation of pure water at constant pressure. Relations giving the membrane resistance as a function of contact time at varying bulk concentration, pH and ionic strength were obtained, by analogy with adsorption laws. Static (zero pressure) and dynamic (crossflow) experiments were then compared in order to determine the effect of convective flow and electrostatic interactions on cell adsorption, irreversible resistance and flux decline. Although convective forces tended to increase the amount of material accumulated near the membrane surface, it was electrostatic interactions that strongly affected cell adsorption and irreversible resistance, as evident in the irreversible adsorption and resistance results from the static and dynamic cases. Cell-cell interactions affect the porosity of the cake layer on the membrane, while cell-membrane interactions affect irreversible adsorption onto the membrane. Solution chemistry affects both types of interactions, as evident in the increased irreversible resistance of the cake layer and irreversibly adsorbed cells at the isoelectric point of cells (IEP). Additionally, the irreversible resistance of the fouled layer is dependent on its compactness, which is directly affected by solution chemistry. The flux decline rapidly decreased after the first 10 minutes of filtration. Flux decline is more pronounced at the IEP of the cell, also indicating that fouling and adsorption are strongly dependent on cell-cell and cell-membrane interactions.     

冷喂料胎面挤出断面气孔原因分析及解决措施

胎面挤出是轮胎制造过程中的重要工序之一,胎面挤出质量的好坏与轮胎质量息息相关。目前冷喂料挤出是国内比较先进的胎面生产方式,但挤出的半成品胎面断面气孔会影响到轮胎的耐磨性,容易出现崩花、掉块、沟裂等质量问题,因此解决冷喂料挤出胎面断面气孔是一个很重要的课题。一、原因分析对断面气孔产生的机理和影响因素从人、机、料、法、环等方面进行分析。人员方面:要求熟悉挤出工艺知识、掌握操作技能;机械方面:要求保证设备正常运转;原料方面:要求胎面胶料符合工艺性能要求;挤出工艺方面:一是螺杆吃料是否很密实,二是主机各段温度是否设…