Measurement of alkali-silica reaction progression by ultrasonic waves attenuation

Development of non-destructive methods, developed specifically for assessing the damage induced by alkali-silica reaction (ASR) in concrete structures, is needed in order to carry out a systematic evaluation of the concrete condition. The aim of this study is to monitor the evolution of the ASR-damage in laboratory with concrete samples with ultrasonic pulse velocity and attenuation of ultrasonic waves methods. For this study, results of both methods were compared with expansion and mass variation.One reactive concrete mixture was made with reactive aggregate, and one other mixture, incorporating non-reactive aggregate, was made as a control. Specimens were kept at 38 °C in a 1 mol l^− 1 NaOH solution to accelerate the reaction. Attenuation of transmitted ultrasonic waves appeared to be more appropriate for the evaluation of ASR-damage compared with pulse velocity. The attenuation of accelerated reactive concrete cylinders increased by 90% after 1 year while it increased by 40% for the non-reactive concrete used as a control. Major part of the attenuation increase in the non-reactive concrete is due to liquid absorption.This work suggests that in-situ non-destructive techniques based on ultrasonic wave attenuation, like ultrasonic attenuation tomography, should be developed in order to evaluate the development of ASR in concrete structures. Petrographic examination confirmed that damage to concrete is associated with ASR.     

Effects of seawater on AAR expansion of concrete

Recently, AAR was identified in submerged piles of some bridges in tidal waters. Microstructural examination detected chloroaluminate salts in some cracks. To clarify whether seawater had influenced the deterioration an experimental program was planned to examine the effects of sodium chloride on AAR under various curing conditions.Concrete prisms containing either of highly-reactive, slowly-reactive or nonreactive aggregate, and either low or high alkali contents, were stored in saltwater (representing seawater) or at 100% RH, at temperatures of 38, 60 and 80 °C, for expansion measurement over 600 days, after which the temperature for those stored in saltwater was lowered to 23 °C, to check its effect on further expansion, which could be attributed to precipitation of ettringite and/or Ca-chloroaluminate.The results indicate that the type of aggregate and concrete alkali content had the greatest effect on AAR expansion. Exposure to saltwater did not have any significant effect on the AAR expansion.     

Influence of grain size on high temperature oxidation behavior of Cr2AlC ceramics

The influence of grain size on the oxidation behavior of Cr₂AlC at 1100 °C and 1200 °C for different times was investigated using fine grained (2 μm) and coarse grained (60 μm) samples. The two materials show a good oxidation resistance owing to the formation of a dense and continuous Al₂O₃ layer. The oxidation rate of the fine grained Cr₂AlC is relatively faster than that of the coarse grained Cr₂AlC. The microstructure and phase composition of scale was characterized. After oxidation at 1100 °C and 1200 °C for long times up to 100 h, only a dense and continuous α-Al₂O₃ oxide layer formed on both the fine grained and coarse grained Cr₂AlC. However, after oxidation at 1100 °C for a relatively short 2 h period, a Cr₇C₃ compound was detected beneath the α-Al₂O₃ oxide layer on the coarse grained Cr₂AlC, yet no Cr₇C₃ was found in the fine grained Cr₂AlC. The oxidation mechanism of the fine and the coarse grained Cr₂AlC was discussed.     

Alkali mass balance during the accelerated concrete prism test for alkali-aggregate reactivity

The alkali mass balance was calculated in concrete specimens submitted to the storage conditions of the Canadian standard CSA A23.2-14A concrete prism test for expansion due to alkali-aggregate reaction (AAR). The alkali concentration of both the concrete pore solution expressed under high pressure and the water below specimens in storage pails (bottom water) was measured. Measurements were conducted over a 1-year period, which corresponds to the length of the above test. Two reactive aggregates were tested [Potsdam sandstone (PO) and Spratt limestone (SP)]. Each aggregate was incorporated in two concrete mixtures (mass concrete and structural concrete), for a total of four batches. Significant alkali leaching occurred at 38 °C while performing tests in high moisture storage conditions even though prisms were covered with plastic sleeves. After 52 weeks, the alkali loss ranged from 12% to 25% of the original Na₂O_e content of the concrete, depending on the mixture proportioning and the aggregate type. After estimation of the proportion of alkalis fixed in cement hydrates, it appears that about 23% to 39% of the original alkalis released by the cement are quickly sorbed on aggregate surfaces or have rapidly migrated inside aggregate particles, which may have been incorporated with time in the AAR product. After 52 weeks at 38 °C, the pore solution alkalinity expressed from mass concrete made with PO was 250 mmol/l, whereas the alkalinity was 270 mmol/l in mass concrete incorporating SP. Since prisms of both mixtures were still expanding at 1 year, these alkalinity values are above the thresholds required for sustaining AAR in these concrete mixtures.     

Experimental investigation of the mechanisms by which LiNO3 is effective against ASR

Various series of experiments were carried out on cements pastes, concretes made with a variety of reactive aggregates, composite specimens made of cement paste and reactive aggregate particles, and a variety of reactive natural aggregates and mineral phases immersed in various Li-bearing solutions. The main objective was to determine which mechanisms(s) better explain(s) the effectiveness of LiNO₃ against ASR and variations in this effectiveness as well with the type of reactive aggregate to counteract. The principal conclusions are the following: (1), the pH in the concrete pore solution does not significantly decrease in the presence of LiNO₃; (2), the concentration of silica in the pore solution is always low and not affected by the presence of LiNO₃, which does not support the mechanism relating to higher solubility of silica in the presence of lithium; (3), the only reaction product observed in the LiNO₃-bearing concretes looks like classical ASR gel and its abundance is proportional to concrete expansion, thus is likely expansive while likely containing lithium; this does not support the mechanisms relating to formation of a non or less expansive Si-Li crystalline product or amorphous gel; (4), early-formed reaction products coating the reactive silica grains or aggregate particles, which could act as a physical barrier against further chemical attack of silica, were not observed in the LiNO₃-bearing concretes, but only for a number of reactive materials after immersion in 1 N LiOH at 350 °C in the autoclave (also at 80 °C for obsidian); (5), higher chemical stability of silica due to another reason than pH reduction or early formation of a protective coating over the reactive phases, is the mechanism among those considered in this study that better explains the effectiveness of LiNO₃ against ASR.     

Carbonation of CH and C-S-H in composite cement pastes containing high amounts of BFS

3:1 BFS:OPC, 9:1 BFS:OPC and 9:1 alkali activated BFS:OPC pastes cured at 20 °C and 60 °C for 90 days were submitted to accelerated carbonation under 5% CO₂, 60% relative humidity and 25 ± 5 °C for 21 days. TGA/DTG was used to quantify the amounts of carbonates formed from calcium hydroxide (CH) and calcium silicate hydrate (C-S-H), based on the CH and carbonate contents before and after carbonation. Apparent dry density, apparent porosity and gas permeability were measured before and after accelerated carbonation testing, and the phenolphthalein method used to determine the accelerated carbonation rate. The results showed that samples cured at elevated temperature, i.e. 60 °C, were initially less porous and, therefore, had decreased levels of both total carbonation and C-S-H carbonation. In addition, the carbonation of C-S-H was significantly higher in pastes that contained less CH before carbonation. In the activated 9:1 BFS:OPC, the carbonation of C-S-H was extensive, despite a lower carbonation rate than the analogous non-activated system. In the particular case of activated 9:1 BFS:OPC, a shift in the DTG decarbonation pattern was observed and XRD showed that aragonite was present as one of the calcium carbonate polymorphs.     

Influence of stress restraint on the expansive behaviour of concrete affected by alkali-silica reaction

The primary objective of this study was to ascertain whether the Threshold Alkali Level (TAL) of the concrete aggregates may be taken as a suitable reactivity parameter for the selection of aggregates susceptible of alkali-silica reaction (ASR), even when ASR expansion in concrete develops under restrained conditions. Concrete mixes made with different alkali contents and two natural siliceous aggregates with very different TALs were tested for their expansivity at 38 °C and 100% RH under unrestrained and restrained conditions. Four compressive stress levels over the range from 0.17 to 3.50 N/mm² were applied by using a new appositely designed experimental equipment. The lowest stress (0.17 N/mm²) was selected in order to estimate the expansive pressure developed by the ASR gel under “free” expansion conditions. It was found that, even under restrained conditions, the threshold alkali level proves to be a suitable reactivity parameter for designing concrete mixes that are not susceptible of deleterious ASR expansion. An empirical relationship between expansive pressure, concrete alkali content and aggregate TAL was developed in view of its possible use for ASR diagnosis and/or safety evaluation of concrete structures.     

Electrical resistivity of porcelain bodies with natural zeolite addition

In this study, the effect of natural zeolite addition on the electrical properties of porcelain bodies was investigated. Clinoptilolite, which is a type of natural zeolite, was added partially or fully in replacement of quartz in selected electro-porcelain compositions. Samples were fired in an electric furnace with a heating rate of 10 °C/min at 1200 and 1250 °C with a period of 60 min. The electrical resistance measurements of samples were performed at 50, 200, 400 and 600 °C. It was shown that the resistivity of samples increased at 50 °C temperature after zeolite addition, while it was decreasing after zeolite addition at higher temperatures. At the same time, it was recognized that the resistivity of samples depends on sintering temperature. The activation energy of electrical resistivity of samples was found to be in the range of 0.79–0.87 eV.     

Formation of nanosize ZnO particles by thermal decomposition of zinc acetylacetonate monohydrate

Formation of ZnO particles by thermal decomposition of zinc acetylacetonate monohydrate in air atmosphere has been investigated using XRD, DTA, FT-IR, and FE-SEM as experimental techniques. ZnO as a single phase was produced by direct heating at ≥200 °C. DTA in air showed an endothermic peak at 195 °C assigned to the ZnO formation and exothermic peaks at 260, 315 and 365 °C, with a shoulder at 395 °C. Exothermic peaks can be assigned to combustion of an acetylacetonate ligand released at 195 °C. ZnO particles prepared at 200 °C have shown no presence of organic species, as found by FT-IR spectroscopy. Particles prepared for 0.5 h at 200 °C were in the nanosize range from ∼20 to ∼40 nm with a maximum at 30 nm approximately. The crystallite size of 30 nm was estimated in the direction of the a₁ and a₂ crystal axes, and in one direction of the c-axis it was 38 nm, as found with XRD. With prolonged heating of ZnO particles at 200 °C the particle/crystallite size changed little. However, with heating temperature increased up to 500 or 600 °C the ZnO particle size increased, as shown by FE-SEM observation. Nanosize ZnO particles were also prepared in two steps: (a) by heating of zinc acetylacetonate monohydrate up to 150 °C and distillation of water and organic phase, and (b) with further heating of so obtained precursor at 300 °C.     

Low temperature and microwave dielectric properties of TiO2/ZBS glass composites

TiO₂ based ceramic/glass composites were prepared by a non-reactive liquid phase sintering (NLPS) using zinc borosilicate (ZBS) glass having the deformation temperature of 588 °C. The compounds of Zn₂SiO₄ and Zn₄B₆O₁₃ were formed after the sintering process, indicating that the ZBS glass was a non-reactive one in this system. For TiO₂/50 vol% ZBS glass composite, the two-stage sintering behavior was conducted as the sintering temperature increased. The former might be correlated to the NLPS process and the latter appeared to be related to the crystallization. The dielectric constant (?_r) was mainly affected by the porosity and obeyed the logarithmic mixing rule. The quality factor (Q × f₀) showed an increase and then a steep decrease after the maximum at 850 °C. TiO₂/50 vol% ZBS glass composite sintered at 900 °C demonstrated 36 in the dielectric constant (?_r) and 7500 GHz in the quality factor (Q × f₀) for an application to LTCC filters.     

Binder removal via a two-stage debinding process for ceramic injection molding parts

Debinding binders in two stages is critical to maintaining the shape of injected parts; the resulting decomposition affects the strength and rigidity of a structure. This study determines the optimal debinding process on the basis of a higher binder removal rate and the production of defect-free parts. The feedstock used was a combination of alumina–zirconia powder with a binder that consists of high-density polyethylene (HDPE), paraffin wax (PW), and stearic acid (SA). During the first stage, the injected parts were immersed in an n-heptane solution at 50 °C, 60 °C, 65 °C, and 70 °C to remove PW and SA. Binder weight loss was evaluated as a function of time. In the second stage, HDPE was removed by using thermal debinding. The results show that the optimum solvent debinding process runs for 16 h at 60 °C. The weight loss of the binder reaches 41.1% and results in the formation of defect-free parts. The binders are degraded at approximately 550 °C during thermal debinding. This degradation resulted in decomposition of nearly 96.9% of the binders. Low heating rates (1 °C/min to 2 °C/min) prevent defects from forming in the injected parts.     

Na2O, K2O, SiO2 and Al2O3 release from potassic and calcic-sodic feldspars into alkaline solutions

The potential release of elements from potassic and calcic-sodic feldspars into the concrete pore solution was evaluated by ICP-MS using 1 N NaOH and KOH solutions at 80 °C in accordance with the conditions set in the chemical test method. Materials were characterized by petrography, XRD and by XRF analysis. The influence of textural and microstructural characteristics on the leaching process was also analyzed by immersing polished plates of each mineral in 1 N NaOH at 80 °C for 7 days. Optical microscope and SEM observations indicate that microstructural characteristics, such as cleavage zones, twins, grain-grain contact and the finer and less abundant phases in perthites, play a key role in the leaching process under alkaline conditions. Na₂O, K₂O, SiO₂ and Al₂O₃ are supplied by hydrolysis, although the participation of other processes cannot be ruled out.     

Soot-free synthesis of C60

A new synthetic medium for the production of C₆₀ has been found that does not produce soot. C₆₀ was produced in the liquid phase of an aerosol of precursor soot at 700 °C. The precursor soot aerosol, a high temperature stable form of hydrocarbon, was produced by pyrolysis of acetylene at atmospheric pressure in a flow tube reactor. At 700 °C, the effluent particles were found to contain PAHs, small hydrocarbons and fullerenes but no observable black material. However, when the reactor temperature was changed to 800 °C, soot was also produced in the effluent particles along with PAHs and other small hydrocarbons, and the fullerene product disappeared. These results show a clear competition between the production of fullerenes and other forms of carbon. The filter-collected effluent was shown to be completely soluble in conventional solvents suggesting the possibility of an efficient cyclic synthetic process. Fullerenes were only found in the particle phase implying the first observed liquid phase synthesis of C₆₀.     

Soot-free synthesis of C60

A new synthetic medium for the production of C₆₀ has been found that does not produce soot. C₆₀ was produced in the liquid phase of an aerosol of precursor soot at 700 °C. The precursor soot aerosol, a high temperature stable form of hydrocarbon, was produced by pyrolysis of acetylene at atmospheric pressure in a flow tube reactor. At 700 °C, the effluent particles were found to contain PAHs, small hydrocarbons and fullerenes but no observable black material. However, when the reactor temperature was changed to 800 °C, soot was also produced in the effluent particles along with PAHs and other small hydrocarbons, and the fullerene product disappeared. These results show a clear competition between the production of fullerenes and other forms of carbon. The filter-collected effluent was shown to be completely soluble in conventional solvents suggesting the possibility of an efficient cyclic synthetic process. Fullerenes were only found in the particle phase implying the first observed liquid phase synthesis of C₆₀.     

再生轻骨料混凝土抗压强度指标换算关系研究

为了研究再生轻骨料混凝土立方体抗压强度和轴心抗压强度,以及两者之间的换算关系,以再生轻粗骨料取代率为变化参数,制作了15个标准立方体试块和15个标准棱柱体试块,进行抗压强度试验.实测了试块的抗压强度,探讨了不同再生轻粗骨料取代率对于再生轻骨料混凝土抗压强度的影响规律,采用数据统计回归的方法,得到了再生轻骨料混凝土轴心抗压强度和立方体抗压强度之间的换算关系.研究结果表明:再生轻骨料混凝土的抗压强度均低于普通混凝土的抗压强度;随着再生轻粗骨料取代率的增加,再生轻骨料混凝土的抗压强度逐渐降低;再生轻骨料混凝土轴心和立方体抗压强度之间的换算关系和普通混凝土并不相同;基于实测数据,建立了再生轻骨料混凝土抗压强度指标之间的换算关系式.     

Mechanical activation of fly ash: Effect on reaction, structure and properties of resulting geopolymer

Geopolymerisation of mechanically activated fly ash was studied at ambient (27 °C) and elevated (60 °C) temperatures by isothermal conduction calorimeter. Under both the conditions, mechanical activation enhanced the rate and decreased time of reaction. It was interesting to observe that in the samples milled for 45 min (median size ∼5 μm), a broad peak corresponding to geopolymerisation initiated at 27 °C after 32 h. The rate maxima at 60 °C, a measure of fly ash reactivity, showed a non-linear dependence on particle size and increased rapidly when the median size was reduced to less than 5-7 μm. Improvement in strength properties is correlated with median particle size, and reactivity of fly ash. The characterisation of the geopolymer samples by SEM-EDS, XRD and FTIR revealed that mechanical activation leads to microstructure and structural variations which can be invoked to explain the variation in the properties.     

Injection and stabilization of mesophase pitch in the fabrication of carbon-carbon composites: Part II. Stabilization process

In the fabrication of carbon-carbon composites by mesophase injection through a fiber preform, it is essential to stabilize the flow-induced microstructure in the flow channels and to prevent relaxation and exudation of the mesophase. Oxidation stabilization studies were conducted on preforms injected with the naphthalene-based AR mesophase pitch. Oxidation mass gain (OMG) curves at 170, 222, and 270 °C were generated for 60°-wedges cut from full size composite disks. The rates of OMG at 170 °C of first- and second-cycle injection wedges and full-size disks were comparable to those using as-spun filaments 30 μm in diameter, and particles sieved to 200 to 340 μm. The results suggest that oxygen is accessible deep into a mesophase matrix and the transport is facilitated by connected array of shrinkage cracks. Oxidation at 170 °C has strong advantage over higher oxidation temperatures by having a higher carbon yield and lower OMG threshold and thus oxidation time required for stabilization. The 60°-wedges could be stabilized at 170 °C after a 25 h oxidation with a 7.2% OMG and attaining a carbon yield above 85%.     

Effect of elevated temperatures on geopolymer paste, mortar and concrete

Geopolymers are generally believed to provide good fire resistance due to their ceramic-like properties. Previous experimental studies on geopolymer under elevated temperatures have mainly focused on metakaolin-based geopolymers. This paper presents the results of a study on the effect of elevated temperature on geopolymer paste, mortar and concrete made using fly ash as a precursor. The geopolymer was synthesized with sodium silicate and potassium hydroxide solutions. Various experimental parameters have been examined such as specimen sizing, aggregate sizing, aggregate type and superplasticizer type. The study identifies specimen size and aggregate size as the two main factors that govern geopolymer behavior at elevated temperatures (800 °C). Aggregate sizes larger than 10 mm resulted in good strength performances in both ambient and elevated temperatures. Strength loss in geopolymer concrete at elevated temperatures is attributed to the thermal mismatch between the geopolymer matrix and the aggregates.     

Activated carbon supported bimetallic CoMo carbides synthesized by carbothermal hydrogen reduction

A carbothermal hydrogen reduction method was employed for the preparation of activated carbon supported bimetallic carbide. The resultant samples were characterized by BET surface area measurement, X-ray diffraction, and temperature-programmed reduction-mass spectroscopy. The results showed that nanostructured β-Mo₂C can be formed on the activated carbon by carbothermal hydrogen reduction above 700 °C. The particle sizes of β-Mo₂C increase with increasing reaction temperatures and Mo loading. The bimetallic CoMo carbide can be synthesized by the carbothermal hydrogen reduction even around 600 °C. The bimetallic CoMo carbide is from carbothermal hydrogen reduction of CoMoO₄ precursor and is easily formed when the Co/Mo molar ratio is 1.0. Separation of the bimetallic CoMo carbide phase into Mo carbide and Co metal occurs when the temperature of the reduction is above 700 °C. The addition of a second metal such as Co and Ni, decreases the formation temperature of carbide because the second metal promotes formation of CHx species from reactive carbon atoms or groups on carbon material and hydrogen, which further carburizes oxide precursors.