Improvement of the durability of glass fiber reinforced cement using blended cement matrix

Blended cements prepared with two fly ashes were used as matrices in glass fiber reinforced cement (GRC) composites in an attempt to improve their durability. The hydrated matrices from the two blended cements investigated here had similar strength and composition. Both fly ashes reduced the Ca(OH)₂ content to the same extent but in both cases the pH level was only slightly reduced compared to the portland cement matrix. In spite of these similarities, the GRC prepared with one fly ash showed considerable improvement in durability while the other one had only a small positive effect. SEM observations indicated that the improved durability in one case was associated with modification in the microstructure of the hydration products deposited in between the glass filaments, resulting in a much more open structure compared to that of portland cement matrix or the other blended cement. It is therefore suggested that the potential of the blended cement matrix to improve the durability of GRC is associated with its ability to modify the microstructure of the paste at the glass interface. This characteristic is not necessarily related to the overall composition of the blended cement matrix and to the reactivity of fly ash with Ca(OH)₂.     

Influence of cement and superplasticizers type and dosage on the fluidity of cement mortars—Part I

Concrete quality is controlled by the flow behavior of cement paste, which is related to the dispersion of cement particles. Superplasticizers (SPs) provide the possibility of a better dispersion of cement particles, thereby producing paste of higher fluidity. With the development of high strength, high performance concrete, SPs are becoming indispensable. SPs are adsorbed on the cement particles. This adsorption is uneven and depends upon the clinker composition of cement and the type of SP used. This work is focused on the study of the influence of lignosulfonic acid (LS)- and melamine sulfonic acid (SMF)-based SPs on the fluidity of mortars made with ordinary Portland (OPC), low alkali (LAC) and white cement (WC) at different water to cement ratio. It is shown that LS are more effective than SMF in providing better fluidity. Further WC has given the highest fluidity among the cements used. It is attributed to the lower C₃A+C₄AF and alkali content, and higher SO₃ content.     

Determining the water–cement ratio, cement content, water content and degree of hydration of hardened cement paste: Method development and validation on paste samples

We propose a new method to estimate the initial cement content, water content and free water/cement ratio (w/c) of hardened cement-based materials made with Portland cements that have unknown mixture proportions and degree of hydration. This method first quantifies the composition of the hardened cement paste, i.e. the volumetric fractions of capillary pores, hydration products and unreacted cement, using high-resolution field emission scanning electron microscopy (FE-SEM) in the backscattered electron (BSE) mode and image analysis. From the obtained data and the volumetric increase of solids during cement hydration, we compute the initial free water content and cement content, hence the free w/c ratio. The same method can also be used to calculate the degree of hydration. The proposed method has the advantage that it is quantitative and does not require comparison with calibration graphs or reference samples made with the same materials and cured to the same degree of hydration as the tested sample. This paper reports the development, assumptions and limitations of the proposed method, and preliminary results from Portland cement pastes with a range of w/c ratios (0.25–0.50) and curing ages (3–90 days). We also discuss the extension of the technique to mortars and concretes, and samples made with blended cements.     

The permeability of Portland limestone cement concrete

The effect of limestone addition on the air permeability, water permeability, sorptivity, and porosity of limestone cement concrete has been investigated. Six Portland limestone cements (PLCs) with different limestone content (10-35% w/w) were produced by intergrinding clinker, gypsum, and limestone. A water-to-cement ratio (w/c) of 0.70-0.62—depending on the cement strength class—was used to prepare concrete of the compressive strength class C20/25 of EN 206-1. A modified commercial triaxial cell for 100-mm-diameter samples was used for the determination of the gas (N₂) and the water permeability of concretes. In addition, the sorptivity and porosity of the samples were measured, while thin sections of the concrete specimens were examined by means of optical microscopy. It is concluded that the PLC concrete indicates competitive properties with the ordinary Portland cement (OPC) concrete. Furthermore, the limestone addition has a positive effect on the water permeability and the sorptivity of concrete.     

Slag cement utilization: Rheological properties and related characterization

Mortars prepared from slag-cement blends have been shown to exceed or equal the strengths of portland cement mortars at 7 to 28 days. Such cements have further potential advantages in their performance with regard to durability, and in their early stage properties which govern workability. The early stage rheological properties including mortar flow, yield stress, and viscosity were investigated, combined with zeta potential measurements, and used to explain the excellent workability. The working time of slag cement may be extended to later ages compared with portland cements through use of superplasticizers.     

Preparation and evaluation of an antibacterial dental cement containing quaternary ammonium salts

A novel PQAS‐containing antibacterial glass‐ionomer cement has been developed. The functional QAS and their constructed PQAS were synthesized, characterized, and formulated into the light‐cured cements. Compressive strength (CS) and bacterial (S. mutans and lactobacillus) viability were used to evaluate the mechanical strength and antibacterial activity of the cements. Flexural (FS) and diametral tensile strengths (DTS) were tested as well. Fuji II LC cement was used as control. The specimens were conditioned in distilled water at 37°C for 24 h prior to testing. All the PQAS‐containing cements showed a significant antibacterial activity, accompanying with an initial CS reduction. The effects of chain length, loading, and grafting ratio of the QAS were significant. Increasing chain length, loading, grafting ratio significantly enhanced antibacterial activity but reduced the initial CS of the formed cements. The antibacterial effect of the substitute chain lengths from free QAS seem more significant in water than those from their polymers (PQAS) after integrating to the cement. The experimental cement showed less CS reduction and higher antibacterial activity than Fuji II LC. The long‐term aging study indicates that the cement might have a long‐lasting antibacterial function with no PQAS leaching. Within the limitations of this study, it appears that the experimental cement is a clinically attractive dental restorative that can be potentially used for long‐lasting restorations due to its high mechanical strength and long‐lasting antibacterial function. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Active low-energy belite cement

The term ‘low-energy cement’ is used for cements that can be in some applications used instead of OPC, and which are produced with less energy. A more extensive utilization of these cements would lead to the lowering of expenses on production of binders as well as a reduction of undesirable emissions. The belite-rich cement belongs to this group. Pure belite clinkers with interstitial matter consisting of C₃A and C₄AF have not been produced, as they have insufficient strength. This work describes the results of hydraulic activation of belite-rich clinkers with sulfate anions. The principle of activation is used for the preparation of belite-rich clinkers with an increased Ca:Si ratio in the structure of dicalcium silicate and partial substitution of SiO₄⁴⁻  by SO₄²⁻. Cements, prepared from these belite-rich clinkers, containing up to 20% of alite, which are burned at 1350 °C, have the same technological properties, including early strengths, as OPC.     

Study on modification of the high-strength slag cement material

The influence of the slag powder's fineness, the amounts of activator, type and contents of modification addition on the dry-shrinkage and strength of the high-strength slag cement material was investigated. The experimental data showed that adding 9% Na₂SiO₃ activator and 10% Portland cement (PC) made the ratios of drying-shrinkage of high-strength slag cement material similar to the ratios of Portland cement and the compressive strengths as higher. The main hydration products are calcium alumina-silicate gels and a little CH; the gel ratio of CaO/SiO₂ is close to 1 and includes a little Na₂O and MgO for high-strength slag cement material, as shown by means of scanning electron microscope (SEM) and energy-dispersive X-ray analyzer (EDXA).     

The effect of excessive steam curing on Portland composite cement concrete

Steam curing at atmospheric pressure is an important technique for obtaining high early strength values in precast concrete production. Cement type, as well as curing period and temperature, is an important parameter in the steam-curing process. PC42.5 is the type of cement that is most commonly used in Turkish precast concrete plants. Its behavior is well known. Nowadays, the production of composite cements is becoming more popular every other day due to its advantages. The object of this study was to determine the properties of this relatively new binder comparatively with conventional PC42.5 under steam curing. For this purpose, 15-cm concrete cubes were prepared with a water/cement ratio (W/C) of 0.44 and were subjected to steam curing for five different curing periods of 4, 8, 16, 24 and 36 h under curing temperatures of 65 and 85 °C. Cement dosage was kept constant (400 kg/m³) for all specimens. The variation of compressive strength values and maturity for each condition has been presented comparatively within this study. Test results indicated that Portland composite cement (PKC/A42.5) can be used in place of PC42.5 for steam curing at atmospheric pressure in precast concrete production. However, in case of early high strength demand for early demolding purposes, curing temperature should be increased to 85 °C for PKC/A42.5 cement concretes.     

Characteristics of pastes from a Portland cement containing different amounts of natural pozzolan

This work is concerned with assessing the influence of natural pozzolan on the physical, mechanical and durability properties of blended Portland cement pastes. The results indicate that final setting times of natural pozzolan blended Portland cement pastes range from 4 to about 5 h. Naphthalene-type superplasticizer tends to retard the hydration process of plain and natural pozzolan blended Portland cement pastes. These blends show slightly higher setting times than those without superplasticizer. The use of superplasticizer is found to have a significant influence on the workability. At a lower level of Portland cement replacement by natural pozzolan, the addition of 1% superplasticizer by weight of blended Portland cement leads to a significant decrease in the water to Portland cement plus natural pozzolan ratio for a given workability. However, for the blended Portland cement with a high proportion of natural pozzolan, the increase in water content causes the porosity to increase with an accompanying decrease in compressive strengths. The variations in composition and cure time are found to provide significant changes in compressive strength. Depending on these parameters, the variation in compressive strength can be estimated by using the equation, σ=σ₀/[1+exp(a+bp+cp²)]ⁿ, where σ is the compressive strength of natural pozzolan blended Portland cement paste at a given cure time and natural pozzolan replacement level (MPa); σ₀ is the compressive strength of plain Portland cement pastes with or without superplasticizer at a given cure time (MPa); p is the natural pozzolan replacement level (%); a, b, c, n are the empirical constants to be determined. The blend with a composition of 80% Portland cement and 20% natural pozzolan and 1% superplasticizer provides superior strength and durability characteristics in comparison to the counterparts without superplasticizer and to the blends with a high proportion of natural pozzolan. At high contents of natural pozzolan, the resistance to freezing and thawing is found to be impaired. Moreover, these blended cements do not provide high durability performance against sulfate attack.     

Superplasticized portland cement: production and compressive strength of mortars and concrete

This paper deals with the effect of intergrinding different percentages of a naphthalene-based superplasticizer with Portland cement clinker and gypsum on the fineness of the product, and on the water requirement and the compressive strength of the mortars made with the superplasticized cement. The properties of the fresh and hardened concrete made with the superplasticized cements were also investigated. The results showed that the intergrinding of a given amount of a naphthalene-based superplasticizer with Portland clinker and gypsum reduced the grinding time required for obtaining the same Blaine fineness as that of the control Portland cement without the superplasticizer. The water requirement of the mortars made with the superplasticized cements was similar to that of the mortars made with the control Portland cements when the same amount of the superplasticizer was added at the mortar mixer; for a given grinding time and a Blaine fineness of 4500 cm²/g, the mortars made with the superplasticized cement had higher compressive strength than those made with the control Portland cement. For a given grinding time or Blaine fineness of cement ≥5000 cm²/g, the slump loss, air content stability, bleeding, autogenous temperature rise, setting times, and compressive strength of the concrete made with the superplasticized cements were generally comparable to those of the concrete made with the control Portland cements when the superplasticizer was added at the concrete mixer.     

The influence of potassium-sodium ratio in cement on concrete expansion due to alkali-aggregate reaction

In concrete containing potentially reactive aggregates, deleterious alkali-aggregate-reaction (AAR) can be prevented by the use of suitable mineral admixtures or by limiting cement content and alkalis (Na₂O-equivalent) of the cement. However, the Na₂O-equivalent of cement may not always accurately define the potential of cement to cause AAR. In this study, the potential reactivity of concrete produced with cements having similar Na₂O-equivalents but different K/Na-ratios has been measured and the composition of gel has been analyzed. Additionally, pastes and mortars have been produced to study the development of pore solution composition.The expansion of the concrete mixtures shows significant differences depending on the cement used. The different K/Na-ratio present in the cements is reflected in the pore solution of pastes and mortars and in the gel present in aggregates of the concrete mixtures. As the hydroxide concentration in the pore solutions of pastes and mortars produced with the different cements is nearly identical, the difference in K/Na-ratio has to be the reason for the observed differences in concrete expansion.     

Alternative blended cement with ceramic residues: Corrosion resistance investigation on reinforced mortar

Blended cements are largely used for concrete: they are usually considered cements with a low environmental impact, as they require less clinker than ordinary Portland cement (OPC). Different constituents can be used as supplementary clinker component usually leading to cement with high resistance to outdoor environment. Polishing residue (PR), coming from porcelain stoneware tiles production, can be successfully used as new constituent for blended cement, however its action for enhancing the durability of cement matrix must be assessed. With this purpose, electrochemical tests (half cell potential, impressed voltage and linear polarization techniques) have been carried out on steel reinforced mortar samples, prepared using a 25% PR based cement and 100% OPC as binder and exposed to a 3.5% NaCl solution. The corrosion resistance results and microstructure analysis highlight better durability performances for PR based cement than those exhibited by OPC, mainly for curing time > 28 days.     

Fundamental mechanisms for polycarboxylate intercalation into C3A hydrate phases and the role of sulfate present in cement

The fundamental reactions leading to the intercalation of polycarboxylate (PC) superplasticizers into calcium aluminum hydrates were studied by hydration of pure C₃A in the presence of PC at 75 °C. It was found that the amount of dissolved sulfate present in cement pore solution determines whether organo-mineral phases are formed or not. In the absence of sulfate, PCs easily intercalate during C₃A hydration in alkaline solution. Under these conditions, only excessive steric size of the PC will prevent intercalation. At low sulfate concentrations (SO₄²⁻/C₃A molar ratios of 0.1-0.35), PC intercalates with intersalated alkali sulfate, are formed. At high sulfate concentrations (SO₄²⁻/C₃A molar ratios of 0.7-2), PC can no longer intercalate. Instead, sulfate, because of its higher negative charge density, fills the interlayer space and monosulfoaluminates with different water contents are formed.Anion exchange experiments confirm that from the initially formed C₄AH₁₃, PC will exchange the interlayer OH⁻ anion whereas with monosulfoaluminates, no replacement of sulfate by PC was found. Consequently, in alkaline solution, PC intercalates will not exchange their PC against OH⁻ anions whereas sulfate will gradually replace the PC.Generally, intercalation of PC is an unwanted process because it consumes superplasticizer which is effective only when it adsorbs onto the cationic surfaces of AF_m and AF_t phases. Our experiments demonstrate that intercalation can be avoided by using PCs with long side chains or highly sulfated cements (SO₄²⁻/C₃A molar ratio ≥ 0.75) containing alkali or calcium sulfates which dissolve fast. In undersulfated cements, however, PC intercalates can be formed, either directly during the stacking process of the [Ca₂Al(OH)₆]⁺ main layer, with PC acting as the template which determines the interlayer distance, or by anion exchange between initially formed aluminate hydrates (e.g. C₄AH₁₃ or C₂AH₈) and the PC anion.     

Early stage hydration of slag-cement

The early hydration characteristics of slag cements (blends of separately ground granulated blast furnace slags with portland cement) have been examined. Isothermal calorimetry, chemical shrinkage and compressive strength measurements were made. The kinetics of hydration have been treated; apparent activation energies determined for a slag cement were ～49 KJ/mole compared with ～44 KJ/mole for the portland cement used in the blends.     

Binding of chloride and alkalis in Portland cement systems

A thermodynamic model for describing the binding of chloride and alkalis in hydrated Portland cement pastes has been developed. The model is based on the phase rule, which for cement pastes in aggressive marine environment predicts multivariant conditions, even at constant temperature and pressure. The effect of the chloride and alkalis has been quantified by experiments on cement pastes prepared from white Portland cements containing 4% and 12% C₃A, and a grey Portland cement containing 7% C₃A. One weight percent calcite was added to all cements. The pastes prepared at w/s ratio of 0.70 were stored in solutions of different Cl (CaCl₂) and Na (NaOH) concentrations. When equilibrium was reached, the mineralogy of the pastes was investigated by EDS analysis on the SEM. A well-defined distribution of chloride was found between the pore solution, the C-S-H phase, and an AFm solid solution phase consisting of Friedel's salt and monocarbonate. Partition coefficients varied as a function of iron and alkali contents. The lower content of alkalis in WPC results in higher chloride contents in the C-S-H phase. High alkali contents result in higher chloride concentrations in the pore solution.     

Rheology of foamed cement

Foams are being used in a number of petroleum industry applications that exploit their high viscosity and low density. Foamed cement slurries can have superior displacement properties relative to non-foamed cement slurries. This article presents results of an experimental study of foamed cement rheology. Viscosity curves of foamed cements were obtained using a flow-through rotational viscometer. Foamed cements with different foam qualities were generated under different pressures using a foam generator/viscometer apparatus. The foam qualities during the tests ranged from 0% to 30%, and the shear rate varied between 5 s^− 1 and 600 s^− 1. Experimental results indicate that: i) unlike conventional aqueous foams, low-quality cement foams have a lower viscosity than the base fluid; ii) as the cement foam quality (gas volumetric fraction) increases from 10% to 30%, the viscosity also increases; and iii) the viscosity of low-quality cement foam slightly increases after depressurization or expansion.     

Design and characterization of low-heat and low-alkalinity cements

Investigations were carried out to formulate and characterize low-alkalinity and low-heat cements which would be compatible with an underground waste repository environment. Several systems comprising Portland cement, a pozzolan (silica fume or fly ash) and blastfurnace slag were compared. All blends were characterized by high amounts of additions, the Portland cement (PC) fraction ranging only from 20 to 60%.Cement hydration was studied using several techniques: X-ray Diffraction, TGA-DTA, calorimetry, pore solution extraction and microscopy. The most important result obtained with some ternary blends was the drop in the pore solution pH by more than one unit as compared with control samples elaborated with commercial cements. The alkali content (≈ 1 to 4 mmol/L) of the interstitial solution was also strongly reduced. The blends exhibited a low-heat output as required. Leaching tests carried out in pure water indicated a very slow decalcification of the samples. Several techniques such as optical microscopy, SEM/BSE, X-ray microanalysis or X-ray diffraction were compared to estimate the degraded thickness.     

Use of gypsum/brucite mixed precipitate instead of gypsum in Portland cement

The possibility of replacing the natural gypsum used in cement production by a chemical precipitate consisting of gypsum (CaSO₄ ·2H₂O) and brucite (Mg(OH)₂), was investigated. This precipitate is a by‐product of a new hydrometallurgical process, which was developed in order to treat economically low‐grade nickel oxide ores. More specifically, it is obtained by hydrolytic precipitation of magnesium at temperatures not exceeding 80 °C, from sulfate solutions which result from heap leaching of nickel oxide ores with dilute sulfuric acid at ambient temperature, using calcium hydroxide as a neutralizing agent. The mixture generally consists of 20–30% non‐fibrous magnesium hydroxide, 60–75% gypsum and any excess of calcium hydroxide, depending on the precipitation conditions. In the present work, a mixture was produced by hydrolytic precipitation at 25 °C, using 1.1 times the stoichiometric quantity of Ca(OH)₂ required to precipitate all of the magnesium. The possibility of using the above precipitate as a substitute for gypsum in cement was examined by testing four different cement mixtures, one reference sample, containing 4.5% gypsum and 0.5% anhydrite ((PC)_Ref) and another three with 4.1%, 5.2% and 6.3% of gypsum/brucite mixed precipitate ((PC)_B/G), in the place of gypsum. All samples were tested by determining the grindability, setting time, expansion and compressive strength. The results of the physico‐mechanical tests showed that the replacement of natural gypsum by the above precipitate did not affect negatively the quality of the produced cements. Copyright © 2005 Society of Chemical Industry     

The role of alkali content of Portland cement on the expansion of concrete prisms containing reactive aggregates and supplementary cementing materials

This paper presents results covering the effects of alkali content of Portland cement (PC) on expansion of concrete containing reactive aggregates and supplementary cementing materials (SCM). The results showed that the alkali content of PC has a significant effect on expansion of concrete prisms with no SCM. When SCM is used, the expansion was found to be related to both the chemical composition of the SCM and, to a lesser extent, the alkali content of the PC. The concrete expansions were explained, at least partly, on the basis of the alkalinity of a pore solution extracted from hardened cement paste samples containing the same cementing blends. An empirical relation was developed correlating the chemical composition (Ca, Si and total Na₂O_e) of the cementing blend (PC + SCM) and the alkalinity of the pore solution. Results from accelerated mortar bar test (ASTM C 1260) and a modified version thereof are also presented.