Long-term effectiveness and mechanism of LiOH in inhibiting alkali-silica reaction

A practical alkali reactive aggregate-Beijing aggregate was used to test the long-term effectiveness of LiOH in inhibiting alkali-aggregate reaction (AAR) expansion. In this paper, the most rigorous conditions were so designed that the mortar bars had been cured at 80 °C for 3 years after being autoclaved for 24 h at 150 °C. At this condition, LiOH was able to inhibit long-term alkali-silica reaction (ASR) expansion effectively. Not only was the relationship between molar ratio of n(Li)/n(Na) and the alkali contents in systems established, but also the governing mechanism of such effects was studied by SEM.     

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.     

The current state of the accelerated concrete prism test

Expansions due to alkali-silica reaction (ASR) in the accelerated concrete prism test (ACPT-60 °C) show a significant reduction at 13 weeks compared to 52 week testing in the standard concrete prism test (CPT-38 °C). Previous work indicated that increased leaching, higher mass loss and a reduction in the pH were observed when temperature was increased from 38 to 60 °C. After further investigation the authors have revealed that non-reactive fine aggregate from certain sources combined with the same reactive coarse aggregate exhibited further reduction in expansion in the ACPT. Expansion data for a wide range of reactive coarse aggregates in 38 and 60 °C testing regimes is shown. Data investigating the Spratt reactive coarse aggregate combined with seven different non-reactive sands will be shown to demonstrate the dramatic effect of the non-reactive sand. Selected pore solution analyses will be given to further elucidate this issue.     

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.     

An STM study of phosphoric acid inhibition of the oxidation of HOPG and carbon catalyzed by alkali salts

The role of phosphoric acid as an inhibitor in the oxidation of HOPG and as a neutralizer of alkali salt catalysts is examined using scanning tunneling microscopy, supported by thermogravimetric analysis of carbon powder samples. HOPG samples were oxidized in air primarily at 700 °C, with a few samples oxidized at 800 °C. Reaction time was 20 min. Powder samples were oxidized for 5 min at temperatures ranging from 500 °C to 900 °C and rates of oxidation were determined. STM images of impurity deposits and oxidized samples are presented and analyzed. Two alkali salts are examined, sodium hydroxide and potassium acetate, and both catalyze oxidation at 700 °C. Phosphoric acid proves to be an inhibitor at 700 °C but begins to lose its inhibiting effect at 800 °C. It also demonstrates neutralization of potassium acetate at 700 °C but results for NaOH/phosphoric acid mixtures are less conclusive.     

硅粉抑制碱集料反应的试验研究

通过对青海地区的集料调研分析,发现青海大部分地区的集料存在高的碱活性.采用西宁城北地区典型的砂石集料以及大通地区的集料进行了试验研究,对比分析了不同掺量的硅粉对碱集料反应的抑制效果.结果表明:对于城北石、大通石两种碱活性较低的集料,选择掺量10％、15％、20％硅粉时,其14d膨胀率均小于0.1％,均能有效抑制碱集料反应的膨胀.而对于城北砂碱活性较高的集料,选择掺量20％硅粉时,其14d膨胀率小于0.1％,可以有效抑制碱集料反应的膨胀.     

Influence of steel fibers on the development of alkali-aggregate reaction

This work presents the results of an experimental research concerning the use of fibers in mortar specimens subjected to alkali-aggregate reaction (AAR). Two types of steel fibers (0.16 mm diameter and 6.0 mm length, and 0.20 mm diameter and 13.0 mm length) were used with fiber volume contents of 1% and 2%. Besides the expansion accelerated tests, compressive tests and flexural tests have also been carried out to display the main mechanical characteristics of the fiber-reinforced mortars after being subjected to AAR. Moreover, the microstructure of the specimens was analyzed by scanning electron microscopy and energy dispersive X-ray. The results shown that the addition of steel fibers reduced the expansion due to AAR for the experimental conditions studied in this paper. The most expressive benefit corresponded to the addition of 13.0 mm fibers in the mixture containing 2% fiber content. This fiber volume content also corresponded to the maximum increment in the mechanical properties compared to the reference mortar, mainly for the post-cracking strength and for the toughness in bending. It was observed that the fibers have a beneficial effect on the material, without compromising its main mechanical properties.     

Composition, morphology and nanostructure of C-S-H in white Portland cement pastes hydrated at 55 °C

The C-S-H present in water- and alkali-activated hardened pastes of white Portland cement hydrated at 55 °C has been characterized. The mean length of the aluminosilicate anions in the C-S-H was similar in both systems and increased with age. Inner product C-S-H generally had a fine scale, homogeneous morphology. Outer product C-S-H was generally fibrillar with water, and foil- or lath-like with alkali. There were some regions of C-S-H with coarse morphology. It was not possible to determine the chemical composition of C-S-H using the SEM; TEM-EDX was necessary. The C-S-H formed in the alkali-activated paste had a lower mean Ca/(Al + Si) ratio than that formed with water, which was offset by a larger quantity of calcium hydroxide. The potassium in the KOH-activated paste was present either within the C-S-H structure charge balancing the substitution of Al³⁺ for Si⁴⁺, or adsorbed on the C-S-H charge balancing sulfate ions.     

Study of the influence of processing parameters on the production of carboxymethylchitin

Carboxymethylchitin was prepared at different reaction temperatures and from alkali chitin with different concentrations of alkali. Properties of the product were studied. Alkali chitin were prepared using freshly prepared sodium hydroxide of 45, 50, 55, 60 and 65% (w/w) concentration and carboxymethylated using monochloroacetic acid at controlled (35-40 °C) and uncontrolled (30-80 °C) temperature conditions. Molecular weight, viscosity, degree of deacetylation, etc. of the resultant product, i.e. carboxymethylchitin were determined. It was found that the reaction temperature has a profound influence on the property of the product than alkali concentration. A hygroscopic and completely water-soluble product was formed. Optimum conditions for the production of carboxymethylchitin were found to be 60% NaOH concentration and at 35-40 °C reaction temperature. At these conditions, it was obtained with a molecular weight of 4.11×10⁶ Da, viscosity 1926 cP and degree of deacetylation 45.02%.     

Alkali-activated fly ash: Effect of thermal curing conditions on mechanical and microstructural development - Part II

The development of mechanical strength and the mineral and microstructural characteristics of the alkali activated fly ash (AAFA), reveal the importance of the role played by the curing conditions prevailing during setting and hardening process: curing in a covered mould (CCM) at 95 °C; dry curing (DC) at 150 °C, or steam curing (ST) at 95 °C. CCM yields the highest compressive strength (up to 102 MPa after 8 h of curing) and can be readily used in any AAFA system. DC is only recommended for NaOH-based systems (low SiO₂/Al₂O₃ ratio), since waterglass-based mixes tend to retard reaction kinetics. SC, in turn, has an intermediate effect on strength development, between CCM and DC.     

Thermal behavior and characteristics of fired geopolymers produced from local Cameroonian metakaolin

The thermal behavior along with certain characteristics of geopolymers produced from local Cameroonian metakaolin and heated up to 1000 °C were examined. Geopolymers fired up to 900 °C had the same physical aspect as initial ones and those fired at 1000 °C warped, were glazed and blistered. The TG showed elimination of water according to two stages. The dilatometric curves of preheated samples showed shrinkage between 90 and 250 °C followed by expansion and sintering. The samples heated up to 700 °C were amorphous and new crystalline phases appeared around 900 °C. The microstructure of geopolymers heated between 300 and 900 °C showed progressive disruption and the linear shrinkage increased. The water absorption of the samples fired up to 700 °C increased slightly and tremendously around 900 °C. A drastic decrease of compressive strength was observed with the samples fired between 300 and 900 °C. Hence, the characteristics of geopolymers lessened with elimination of the water which forms hydration spheres around the compensating cations (Na⁺) opposed to tetrahedral groups AlO₄⁻ along with transformation of amorphous phase.     

Solid particle impact erosion of alumina-based refractories at elevated temperatures

Solid particle erosion tests have been conducted on three different alumina-based refractories at elevated temperatures up to 1400 °C, using sharp SiC particles between 325 and 830 μm in diameter. The impact speed is 50 m/s and the impact angle is varied between 30° and 90°. The objective of this study is to ascertain the effects of temperature and impact angle on the erosion resistance of alumina refractories. The experimental results reveal that the alumina-based refractories, in general, exhibit increasing erosion resistance with increasing temperature and decreasing impact angle, with the minimum erosion rate at 1200 °C and 30° impact angle. Chrome corundum refractory brick is the most resistant to vertical erosion, due to its highest alumina content, and associated hardness and density, as well as strongly bonded aggregate and binder phase. The primary material removal mechanisms are fracture and chipping of binder phase and aggregate, as well as aggregate pull-out.     

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.     

Halide aerosols in circulating fluidised bed co-combustion. Role of coal bound kaolin

An experimental campaign was carried out with a circulating fluidised bed (CFB) pilot scale combustor to study the role of coal bound kaolin in the fate of solid recovered fuel (SRF) originated halide aerosols. A combustion experiment was carried out with SRF-Spruce Bark mixture as a reference. High kaolinite coal and paper pigment kaolin, one at a time, were mixed with the SRF-Bark in increasing proportions until dp < 1 μm fine particles were absent as measured from 780 °C combustion gases by means of a dilution probe and low pressure impactor (LPI). This fine particle mode was absent after mixing sufficiently either coal or kaolin with SRF-Bark and only traces of water soluble alkali metal salts were found in the CFB fly ash. These conditions were achieved when kaolin was mixed with the SRF-Bark for 52 times on a molar basis compared to the Na + K initially found in the aerosols. This proportioning was found to be the same for the additive kaolin and coal bound kaolinite. Na and K in the fly ash seem to be bound chemically to the kaolin as alkali aluminosilicates rather than in water soluble alkali sulphates. This is indicated by their solubility behaviour.     

Comparison of rapid and slow sintered pulverised fuel ash

This study has investigated the properties of sintered PFA using conventional (20 °C/min) and rapid heating rates. Rapid heating was achieved by directly placing pressed PFA samples into a furnace preset at the sintering temperature. Slow sintered PFA samples show an increase in shrinkage and fired density and a reduction in water absorption as the sintering temperature increases, with maximum density obtained at around 1250 °C. At higher temperatures samples show a bloating effect associated with the enlargement of closed porosity. This peak in density is not observed in rapidly sintered PFA. Rapid sintering at temperatures between 1150 °C and 1300 °C resulted in constant values of shrinkage (6.5%), fired density (1.4 g/cm³) and water absorption (15%). During rapid sintering the residual carbon in the PFA is present in the sample at the sintering temperature whereas conventional sintering removes the carbon at lower temperatures before sintering occurs. Rapid sintering also retains significant carbon in the core of the sintered sample. This carbon is believed to act as rigid inclusions that inhibit PFA sintering, limiting shrinkage and densification. Rapid sintering is associated with black coring which is also characteristic in lightweight aggregate manufactured from PFA sintered on a sinter strand. The rapid heating rate experienced by PFA pellets on a sinter strand and the associated inhibition of sintering by carbon is essential for producing sintered PFA products with properties appropriate for use as lightweight aggregate.     

Changes of tomato powder qualities during storage

Changes of tomato powder qualities at different storage temperatures (0, 25, and 37 °C) for 5 months were evaluated in this study. Color parameters (L*, a*, b*), glass transition temperature (Tg) and pH decreased significantly, while 5-Hydroxymethylfurfural (HMF), browning degree (BD) and titratable acid (TA) increased significantly (P < 0.05) at 25 and 37 °C after 5 months. The increased HMF and BD followed a combined kinetics model well. There were insignificant changes for these indicators at 0 °C during storage (P > 0.05). Sucrose, fructose and total sugar (TS) exhibited significant reduction (P < 0.05) only at 37 °C. Free amino acids (FAAs), l-ascorbic acid and solubility of tomato powder underwent significant reduction and total color change ^ΔE significantly increased after 5 months regardless of storage temperatures (P < 0.05), while lycopene and total soluble solid (TSS) showed no significant changes (P > 0.05). SEM micrographs indicated that tomato powder tended to aggregate with increasing the storage temperature or time, which conformed to decreased Tg. There were good correlations between HMF and total free amino acids (TFAA), TS, l-ascorbic acid, BD, L*, a*, b* when stored at 25 and 37 °C.     

Effect of drying treatments on texture and color of vegetables (pumpkin and green pepper)

The present work evaluates the effect of different drying treatments on the color and textural attributes of green bell peppers and pumpkin, which were dried using two different methods: air drying and freeze-drying. The treatments in air drying were carried out at 30 °C and 70 °C.From the results it is possible to conclude that the increase in drying temperature reduced drastically the hardness of green peppers and the freeze drying had an intermediate effect between vegetables dried at 30 °C and 70 °C. Moreover, the springiness was higher in dried green peppers but an opposite effect was observed on chewiness. With respect to pumpkin, any dependence between the fiber orientation and the hardness of the fresh vegetable was not found. In addition, increasing temperature from 30 °C to 70 °C particularly reduced the hardness and the chewiness of dried product and maintained cohesiveness and springiness approximately constant.Regarding the color, it was possible to conclude that air drying at 30 °C produced small changes in color of green pepper whereas air drying at 70 °C and freeze drying originated more intense color changes. The increase of temperature on air drying augmented the color saturation of dried pumpkin while decreased the hue angle by a linear relationship. In addition, the chroma of dried pumpkin decreased significantly with the freeze drying, while the hue angle was maintained constant as compared with the fresh vegetable.     

Stabilization of water-in-octane nano-emulsion. Part I: Stabilized by mixed surfactant systems

In this paper, four nonionic binary mixed surfactant systems (Tween 80/Span 80, Tween 80/Span 85, OP 10/Span 80 and OP 10/Span 85) were used to emulsify water/octane mixture. The influence of emulsion composition and preparation method on the stability of water-in-octane emulsion was investigated systematically. The mixture of Tween 80/Span 80 had the best synergistic effect. Those mixed surfactant systems with HLB = 9 stabilized water-in-octane emulsion the best. Under optimal condition, water-in-octane nano-emulsion (the effective diameter of water droplets = 200 nm) could be made. These water-in-octane nano-emulsions could be stored for more than 26 days at 25 °C without phase separation.     

Elucidating enzyme-based cleaning of protein soils (gelatine and egg yolk) using a scanning fluid dynamic gauge

The enzyme-based cleaning of two model protein soils was investigated using a scanning fluid dynamic gauge (sFDG). The sFDG device allows data to be collected from more than one sample or location during a single experiment and therefore makes a range of comparative studies feasible. The sFDG was modified to allow the forces imposed on the surface to be controlled during a test. Gelatine films on stainless steel swelled in the presence of alkali at 20 °C but were not removed. Enzymes from a commercial dishwasher product interrupted swelling when the mean water volume fraction of the film reached ∼0.9 and promoted removal. The enzyme effectiveness decreased over time. Egg yolk deposits (spray dried on mica) were studied in a protease/buffer solution at 40 °C. The deposits swelled on contact with alkali, and removal started after ∼40 min. Some flow over the deposit was required to achieve complete cleaning, but the time taken to clean exhibited a weak dependence on the shear stress imposed by the flow for shear stresses above 10 Pa. The cleaning behaviour was strongly influenced by the nature of the deposit. Baking the deposit at 150 °C reduced the rate and extent of swelling as well as the rate of removal, and could result in the formation of a residual film that exhibited yield stress characteristics.     

Effect of carbonization rate on the properties of a PAN/phenolic-based carbon/carbon composite

The effect of carbonization rate in a wide range (1, 100 and 1000 °C/min) on the properties of a PAN/phenolic-based carbon/carbon (C/C) composite was studied. The results indicated that the composite processed at a higher carbonization rate had a higher porosity level, more large pores and a more graphitic structure than that processed at a lower carbonization rate. After second graphitization the bending properties of composites carbonized at 1 °C/min and 1000 °C/min were comparable. The composite carbonized at 1000 °C/min had the highest fracture energy. The composite carbonized at 100 °C/min showed the worst mechanical performance among three. The large increase in carbonization rate can be beneficial to the industry from an economic point of view.