Effect of fly ash fineness on compressive strength and pore size of blended cement paste

This paper presents an experimental investigation on the effect of fly ash fineness on compressive strength, porosity, and pore size distribution of hardened cement pastes. Class F fly ash with two fineness, an original fly ash and a classified fly ash, with median particle size of 19.1 and 6.4 μm respectively were used to partially replace portland cement at 0%, 20%, and 40% by weight. The water to binder ratio (w/b) of 0.35 was used for all the blended cement paste mixes.Test results indicated that the blended cement paste with classified fly ash produced paste with higher compressive strength than that with original fly ash. The porosity and pore size of blended cement paste was significantly affected by the replacement of fly ash and its fineness. The replacement of portland cement by original fly ash increased the porosity but decreased the average pore size of the paste. The measured gel porosity (5.7–10 nm) increased with an increase in the fly ash content. The incorporation of classified fly ash decreased the porosity and average pore size of the paste as compared to that with ordinary fly ash. The total porosity and capillary pores decreased while the gel pore increased as a result of the addition of finer fly ash at all replacement levels.     

Influence of dispersing agents on the rheology and early heat of hydration of blended cements with high loading of calcined marl

The dispersing effectiveness of five commercial plasticizers; lignosulfonate (LS), naphthalene sulphonate–formaldehyde polycondensate (NSF) and three polycarboxylate ethers (PCEs) were quantitatively investigated in blended cements where ordinary Portland cement (OPC) was partly replaced by calcined marl (CM) up to 60%. CM drastically viscosified and decreased the flow of the cement due to high absorption of water. The performance of plasticizers mimics that in the OPC system except when PCEs were added. PCEs possessing long side chains were less effective as dispersants due to the consumption of these polymers via the ability of their PEO side chains to intercalate between the remaining layers in the calcined clay. Higher dosages were thus needed for effective dispersion. The decrease in PCE–OPC interaction led to little retardation in cement hydration except at high polymer dosages, whereas the performance of NSF and LS in CM blended cement is driven by clinker content.     

β-Belite cements (β-dicalcium silicate) obtained from calcined lime sludge and silica fume

The utilization of lime sludge (LS), a pulp and paper industry residue, and silica fume (SF), a ferrosilicon industry by-product, as raw materials for the preparation of β-dicalcium silicate (β-C₂S or β-belite) is investigated. β-phase belite is synthesized in a molar ratio of calcined LS/SF at 2.0 by hydrothermal method followed by calcination at 1000 °C for 2 h, which is lower temperature than conventional production temperature of about 1200 °C, and importantly without any chemical stabilizers. The produced belite cements containing 89.3% of β-belite, the rest being α-belite (5.93%), tobermorite (C–S–H, 1.71%), cristobolite (SiO₂, 1.83%) and free lime (CaO, 1.24%). The micro analytical characteristic of the raw materials and formed belite are examined by means of TG-DTA-DTG, XRF, XRD, SEM with EDAX, FT-IR, BET techniques and isothermal conduction calorimetry. The hydration of pastes and compressive strength of mortars of the formed β-belite blended with ordinary Portland cement are studied with a partial replacement of cement by 10%, 20% and 30%. The reaction of β-belite in combination with Portland cement is comparable up to 10% replacement of cement to the pozzolanic reactions of other materials used in similar ways. However, it is observed that the premature stiffening of belite incorporated cement pastes takes place with low heat of hydration because of higher reactivity of belite cement incorporation.     

Assessing the effect of biomass ashes with different finenesses on the compressive strength of blended cement paste

This study assesses the effect of biomass ashes with different finenesses on the compressive strength of blended cement paste. rice husk ash (RHA), palm oil fuel ash (POFA) and river sand (RS) were ground to obtain two finenesses: one was the same size as the cement, and the other was smaller than the cement. Type I Portland cement was replaced by RHA, POFA and RS at 0%, 10%, 20%, 30% and 40% by weight of binder. A water to binder ratio (W/B) of 0.35 was used for all blended cement paste mixes. The percentages of amorphous materials and the compressive strength of the pastes due to the hydration reaction, filler effect and pozzolanic reaction were investigated. The results showed that ground rice husk ash and ground palm oil fuel ash were composed of amorphous silica material. The compressive strength of the pastes due to the hydration reaction decreased with decreasing cement content. The compressive strength of the pastes due to the filler effect increased with increasing cement replacement. The compressive strengths of the pastes due to the pozzolanic reaction were nonlinear and were fit with nonlinear isotherms that increased with increasing fineness of RHA and POFA, cement replacement rate and age of the paste. In addition, the model that was proposed to predict the percentage compressive strength of the blended cement pastes on the basis of the age of the paste and the percentage replacement with biomass ash was in good agreement with the experimental results. The optimum replacement level of rice husk ash and palm oil fuel ash in pastes was 30% by weight of binder; this replacement percentage resulted in good compressive strengths.     

An experimental study of combined acid and sulfate attack of concrete

There is disagreement about the role of sulfuric acid in the thaumasite form of sulfate attack (TSA) of concrete. Some researchers suggest that thaumasite is formed only at pH above 10.5, whereas others report that the primary cause of deterioration in the affected M5 bridge foundations was sulfuric acid attack followed by neutral TSA. The aim of this work is to reconcile these conflicting views by undertaking parallel studies of concrete exposed to aggressive acid and sulfate solutions and concrete/clay interface work using weathered Lower Lias clay.

Concrete specimens have been exposed to BRE Digest 363 sulfate class solutions and acidic and acidic-sulfate solutions at 4.5 ± 0.5 °C. Selected samples are being characterised at intervals up to 5 years. At this stage, results are reported for 5-month samples. Various binders including Portland cement, Portland–limestone cement, blastfurnace slag cement, pulverized-fuel ash cement and sulfate-resisting Portland cement at water/binder ratios (w/b) from 0.35 to 0.5 have been studied.

Initial visual observations and X-ray diffraction analyses have identified thaumasite in some of the systems after 5 months immersion in solution.

An overview of the ongoing parallel concrete/clay interaction work is also presented to contextualise the concrete work.     

Use of a high-calcium fly ash in blended type cement production

Eighty percent of fly ash produced by Greek Public Power Corporation (PPC) is of a high-calcium variety. It has a low insoluble residue and a high content in CaO as well as in SO₃. It also shows self-cementing properties. About 20% of it is used by cement companies in blended type cement production.

In this paper mechanical strengths and some other characteristics concerning blended cement and concrete made with it are presented. Special difficulties anticipated in using such a marginal fly ash in cement are also mentioned.     

Some Engineering Properties of Limestone Concrete

In order to reduce energy consumption and CO₂ emission and increase production, cement manufacturers are blending or intergrinding mineral additives such as slag, natural pozzolans, sand, and limestone. The reduced cost of limestone is mainly due to energy savings by substitution of a portion of the calcined clinker with a small amount of limestone and to the presence of limestone deposits near cement kilns, and hence, reduced transportation costs. This paper reports on a preliminary study underway on the performance of limestone cement mortar and concrete. The effect of different levels of limestone cement replacement (0% to 35%) on physical and mechanical properties of cement mortar is reported, as well as the effect of fineness of both clinker and limestone. From the test results, it was found that it is possible to manufacture cement with limestone addition with comparable or superior performance to that of ordinary Portland cement, provided that proper limestone quality is selected with optimum content and the optimum levels of fineness of both limestone and clinker are used. However, further research is needed to determine long-term performance, especially in marine and hot environments.     

Influence of aging conditions upon the properties of calcined clay and its performance as supplementary cementitious material

The investigation aimed at determining a possible impact of various aging conditions on calcined clays and their performance as supplementary cementitious material (SCM). Two calcined clays were exposed to six different aging conditions. Chemo-mineralogical and physical parameters were measured to reveal possible changes. Aging of calcined clays at high relative humidity or in 3% CO₂ atmosphere resulted in a higher specific surface area and an increased water demand. This was in part due to the formation of calcite and gypsum. The latter promoted the development of heat of hydration. The aging of calcined clays itself had negligible influence on fresh mortar properties and no clear effect on strength of mortar made with these SCM. Nonetheless, most flexural and compressive strength values of mixes containing 20% aged calcined clay were higher than the reference mixes made with cement only.     

Synthesis of (Bi0.5Na0.5)TiO3 nanocrystalline powders by stearic acid gel method

Bismuth sodium titanate (Na_0.5Bi_0.5)TiO₃ (NBT), is considered to be an excellent candidate for a key material of lead-free piezoelectric ceramics. In this study, we propose a stearic acid gel method for the preparation of nanocrystalline single phase NBT powder at relatively low treatment-temperature. Infrared (IR) spectroscopy, differential thermal analysis (DTA), thermogravimetric analysis (TG) and X-ray diffraction (XRD) were used to characterize the process of crystallization. The particle size and morphology of the calcined powders were examined by TEM. It shows that pure single phase NBT powders could be obtained at 700 °C for 1 h, and the particle size is about 20 nm. With an increase in the calcination temperature, crystallite size increased. The powders were further pressed into disk and sintered at 1120 °C for 2 h in air, and its density and microstructure were compared with traditionally prepared samples.     

Calcined clays as binder for thermal insulating and structural aerogel incorporated mortar

Partial replacement of ordinary Portland cement with calcined clay as binder in the aerogel incorporated mortars (AIM) was shown to decrease their thermal conductivities while maintaining the mechanical strength. It was found that at an aerogel loading of between 40 vol% and 80 vol%, replacement of cement with calcined clay lowered the thermal conductivity by up to 20% when <70 vol% aerogel was present (0.410 W/(mK) to 0.370 W/(mK)), and by up to 40% with >70 vol% aerogel (0.164 W/(mK) to 0.145 W/(mK)), driven mainly by the innate thermal conductivity of the binders. At replacement level of up to ∼30% by weight of binder (%bwob), the properties of the mortar was independent of clay types. When the replacement increased to above 40%bwob, calcined smectite enriched clays were favoured for lowering the thermal conductivities of the mortars as compared to those containing kaolinite.     

Strength and chemical resistance of mortars containing brick manufacturing clays subjected to different treatments

This paper presents the results of an investigation of the properties of mortar in which a calcined clay was employed as a pozzolan. Mortars were prepared using either heat treated clay or ground waste clay bricks (from the same clay subjected to 1000 °C calcining) as a pozzolanic partial replacement for cement at replacement levels of 10%, 20% and 30%. The compressive strengths of the mortars were monitored up to 90 days and the resistance to sodium sulphate solution and synthetic seawater was monitored up to 300 days. The specimens were also monitored for weight changes. Partially replacing cement by ground brick or heat-treated brick clay gives early strengths that are lower than that of the control. At 90 days, however, the strengths are the same as or are greater than that of the control. Heat-treated clay is effective in reducing expansion during exposure of the mortar to sulphate solution and synthetic seawater. The rapidly cooled clay gives better performance, in terms of strength development and resistance to harmful solutions, than the slow cooled clay.     

Residential CO2 heat pump system for combined space heating and hot water heating

A theoretical and experimental study has been carried out for a residential brine-to-water CO₂ heat pump system for combined space heating and hot water heating. A 6.5 kW prototype heat pump unit was constructed and extensively tested in order to document the performance and to study component and system behaviour over a wide range of operating conditions. The CO₂ heat pump was equipped with a unique counter-flow tripartite gas cooler for preheating of domestic hot water (DHW), low-temperature space heating and reheating of DHW.

The CO₂ heat pump was tested in three different modes: space heating only, DHW heating only and simultaneous space heating and DHW heating. The heat pump unit gave off heat to a floor heating system at supply/return temperatures of 33/28, 35/30 or 40/35 °C, and the set-point temperature for the DHW was 60, 70 or 80 °C. Most tests were carried out at an evaporation temperature of −5 °C, and the average city water temperature was 6.5 °C. The experimental results proved that a brine-to-water CO₂ heat pump system may achieve the same or higher seasonal performance factor (SPF) than the most energy efficient state-of-the-art brine-to-water heat pump systems as long as: (1) the heating demand for hot water production constitutes at least 25% of the total annual heating demand of the residence, (2) the return temperature in the space heating system is about 30 °C or lower, (3) the city water temperature is about 10 °C or lower and (4) the exergy losses in the DHW tank are small.     

Utilization of ball clay adsorbents for the removal of crystal violet dye from aqueous solution

In this work, an attempt has been made to find the adsorption characteristics of crystal violet (CV) dye on calcined and uncalcined ball clay using batch adsorption technique. The ball clay adsorbents are characterized using thermo gravimetric analysis (TGA), particle size analysis, X-ray diffraction (XRD), nitrogen adsorption–desorption isotherm, and Fourier transform infrared (FT-IR) spectroscopy. The influence of pH and temperature on the adsorption of CV dye is examined. The experimental results of adsorption isotherms are fitted with Langmuir, Freundlich, and Redlich–Perterson models. Adsorption mechanisms of the CV dye on both the ball clays are investigated using thermodynamic parameters and analytical techniques. The results indicate that the Langmuir and Redlich–Peterson models are found to be the more appropriate model to explain the adsorption of CV dye on ball clays than that of Freundlich model. The maximum adsorption capacity of the calcined and uncalcined ball clay is found to be 1.6 × 10⁻⁴ and 1.9 × 10⁻⁴ mol g⁻¹, respectively. The lower adsorption capacity of the calcined ball clay is due to the reduction in the surface hydroxyl group and surface area. Adsorption capacity and percentage removal of the CV dye on calcined and uncalcined ball clay increase with an increase in the temperature and pH, respectively. The obtained negative ΔG ⁰ values indicate that the adsorption of CV dye on ball clay is feasible and spontaneous in nature at temperatures studied. The energy supplied for calcining the ball clay did not bring any improvement in the adsorption capacity. Rather, a reduction in the adsorption capacity of the CV dye on calcined ball clay suggests that the uncalcined ball clay would be more economic and efficient adsorbent for the removal of CV dye than the calcined ball clay. In conclusion, uncalcined ball clay could be used as a low cost alternate for the expensive activated carbon.     

Two-dimensional mathematical model of a reciprocating room-temperature Active Magnetic Regenerator

A time-dependent, two-dimensional mathematical model of a reciprocating Active Magnetic Regenerator (AMR) operating at room-temperature has been developed. The model geometry comprises a regenerator made of parallel plates separated by channels of a heat transfer fluid and a hot as well as a cold heat exchanger. The model simulates the different steps of the AMR refrigeration cycle and evaluates the performance in terms of refrigeration capacity and temperature span between the two heat exchangers. The model was used to perform an analysis of an AMR with a regenerator made of gadolinium and water as the heat transfer fluid. The results show that the AMR is able to obtain a no-load temperature span of 10.9 K in a 1 T magnetic field with a corresponding work input of 93.0 kJ m⁻³ of gadolinium per cycle. The model shows significant temperature differences between the regenerator and the heat transfer fluid during the AMR cycle. This indicates that it is necessary to use two-dimensional models when a parallel-plate regenerator geometry is used.     

Combined effect of chemical nature and fineness of mineral powders on Portland cement hydration

This paper focuses on the influence of the chemical nature and the fineness of the fillers on the hydration process and on the compressive strength development. Four different types of fillers are considered in combination with Portland cement: quartzite filler, alumina filler, limestone filler, and silica fume. The study deals with blended mortars having a 0.45 water to powder (cement and filler) ratio with a 10% substitution of cement by filler. Quartzite fillers do not seem to accelerate the hydration process in a significant way. No positive effect is noticed on the strength development either. The presence of a fine inert alumina powder increases the rate of early hydration of Portland cement. The greater the fineness, the faster the rate of hydration heat development. This reactivity leads to an increase in the compressive strength at early age for mortar containing the finest alumina powders. In case of coarse alumina powder, no acceleration effect is obtained. Finely ground limestone (calcite) fillers promote heterogeneous nucleation of hydrates which significantly accelerates hydration. At early age, this also results in an increased mortar compressive strength in comparison with the control mortar. From the obtained results, it is clear that both chemical natures as well as fineness are important with regard to the accelerating effect of the hydration process. With increasing fineness, the accelerating effect increases. For powders with comparable fineness, it is clear that limestone powder has a more significant accelerating effect than silica fume and alumina filler. Quartzite filler seems to have no significant effect.     

Use of perlite as a pozzolanic addition in producing blended cements

There are ∼6700 million tons of perlite reserves in the world and two thirds of this amount takes place in Turkey. Although perlite possesses pozzolanic properties, it has not been so far used in producing blended cements. This study focuses on the use of natural perlites in blended cement production. For this purpose, after examining the suitability of the perlites as pozzolans and their ease of grindability, 16 types of blended cements having 320 m²/kg or 370 m²/kg Blaine fineness were produced by using 20% or 30% perlite additions. Production of the blended cements were accomplished either by intergrinding or separate grinding. The performance of the cements was evaluated by conducting the following tests: particle size distribution by laser diffraction, normal consistency, setting time, soundness and compressive strength. The results showed that perlites possess sufficient pozzolanic characteristics to be used in production of blended cement.     

Boiling heat transfer of R-22, R-134a, and CO2 in horizontal smooth minichannels

This study examined convective boiling heat transfer in horizontal minichannels using R-22, R-134a, and CO₂. The local heat transfer coefficients were obtained for heat fluxes ranging from 10 to 40 kW m⁻², mass fluxes ranging from 200 to 600 kg m⁻² s⁻¹, a saturation temperature of 10 °C, and quality up to 1.0. The test section was made of stainless steel tubes with inner diameters of 1.5 mm and 3.0 mm, and a length of 2000 mm. The section was heated uniformly by applying an electric current to the tubes directly. Nucleate boiling heat transfer was the main contribution, particularly at the low quality region. An increasing and decreasing heat transfer coefficient occurred at the lower vapor quality with increasing heat flux and mass flux. The mean heat transfer coefficient ratio of R-22:R-134a:CO₂ was approximately 1.0:0.8:2.0. Laminar flow was observed in the minichannels. A new boiling heat transfer coefficient correlation based on the superposition model for refrigerants in minichannels was developed with a mean deviation of 11.21%.     

First principles calculations of thermal equations of state and thermodynamical properties of MgH2 at finite temperatures

We present the first principles calculations of the thermodynamical properties of magnesium hydride (MgH₂) over a temperature range of 0–1000 K. The phonon dispersions are determined within the density functional framework and are used to calculate the free energy of MgH₂ within the quasiharmonic approximation (QHA) at each cell volume and temperature T. Using the free energies the thermal equation of state (EOS) is derived at several temperatures. From the thermal EOS structural parameters such as the equilibrium cell volume (V₀) and elastic properties, namely, bulk modulus (K₀) and its pressure derivative are computed. The free energies are also used to calculate various thermodynamical properties within QHA. These include internal energy E, entropy S, specific heat capacity at constant pressure C_P, thermal pressure P_thermal(V, T) and volume thermal expansion ΔV/V (%). The good agreement of calculated values of S and C_P with experimental data exhibits that QHA can be used as a tool for calculating the thermodynamical properties of MgH₂ over a wide temperature range. P_thermal(V,T) increases strongly with T at all the volumes but it is a slowly varying function of volume for T = 298–500 K. According to Karki [B.B. Karki, Am. Miner. 85 (2000) 1447] such volume based variations can be neglected and so it is possible to estimate the thermal EOS only with the knowledge of the measured P_thermal(V, T) versus temperature at ambient pressure and isothermal compression data at ambient temperature. Temperature dependence of ΔV/V(%) shows that V₀ increased with increase in temperature. However, the percentage decrease in K₀ superseded this percentage increase in V₀ even at temperatures moderately higher than 298 K. Therefore, we suggest application of temperature (T > 298 K) as an approach to enhance the hydrogen storage capacity of MgH₂ because of its better compressibility at these temperatures.     

Improvement of early-age properties for glass-cement mortar by adding nanosilica

Poor early-age performance (e.g. lower early strength, longer setting time) is an important technical challenge for the application of blended cementitious materials containing low reactivity or high volumes of supplementary cementing materials. In this study, the mechanism of using nanosilica (NS) to improve the early-age properties for cement mortars blended with glass powder (GP) and glass aggregates has been investigated. The results indicate that the addition of NS into glass-based cement mortar largely improved the early stiffening which was dependent on high specify surface area of the NS rather than cement hydration. Combining the use of NS and GP was conducive to compensate the delayed setting times and the strength losses caused by the incorporation of GP. These beneficial behaviors were associated with the physical, acceleration, pozzolanic and pore refinement effects of NS. In terms of heat of hydration, the inclusion of NS intensified and accelerated the appearance of the third exothermic peak (AFt to AFm) due to the absorption of sulfate ions by the increased C-S-H formation. Also, the total hydration heat liberated was found to correlate linearly with the corresponding early-age compressive strength. Microstructural analysis suggest that NS significantly helped to densify the microstructure of the GP blended cement matrix and improved the interface between the GP particle and the binder matrix. This was verified by the contribution of NS on refining the coarse pore size caused by the use of GP as a replacement of cement.     

Thermal conductivity of BaWO4 single crystal

Barium tungstate (BaWO₄) single crystal has been grown using Czochralski technique. It belongs to the scheelite structure, forming the space group I4₁/a at room temperature and the primitive cell contains two formular units. The thermal expansion, specific heat and thermal diffusivity were measured, and then the thermal conductivity was calculated. These results show that BaWO₄ possesses large anisotropic thermal expansion and its thermal expansion coefficients are _a = 1.10 × 10⁻⁵/K, _b = 1.08 × 10⁻⁵/K, and _c = 3.51 × 10⁻⁵/K in the temperature range from 303 to 1423 K. However, its thermal conductivity shows small anisotropic in the temperature range from 297 to 563 K and even displays isotropic at about 428 K. The calculated thermal conductivities are 2.59 and 2.73 W m⁻¹ K⁻¹ at room temperature, along [1 0 0] and [0 0 1] directions, respectively.