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.     

Rheological properties of cementitious materials containing mineral admixtures

The rheological properties of cementitious materials containing fine particles, such as mineral admixtures (MA), were investigated using a Rotovisco RT 20 rheometer (Haake) with a cylindrical spindle. The mineral admixtures were finely ground blast furnace slag, fly ash and silica fume. The cementitious materials were designed as one, two and three components systems by replacement of ordinary portland cement (OPC) with these mineral admixtures. The rheological properties of one-component system (OPC) were improved with increasing the dosage of PNS-based superplasticizer. For two-components systems, yield stress and plastic viscosity decreased with replacing OPC with blast furnace slag (BFS) and fly ash (FA). In the case of OPC-silica fume (SF) system, yield stress and plastic viscosity steeply increased with increasing SF. For three components systems, both OPC-BFS-SF and OPC-FA-SF systems, the rheological properties improved, compared with the sample with SF. In the two and three components systems, the rheological properties of samples containing BFS improved much more than with FA replacement alone.     

Binary and ternary blends of polylactide, polycaprolactone and thermoplastic starch

In this study binary and ternary blends of polylactide (PLA), polycaprolactone (PCL) and thermoplastic starch (TPS) are prepared using a one-step extrusion process and the morphology, rheology and physical properties are examined. The morphology and quantitative image analysis of the 50/50 PLA/TPS blend transverse phase size demonstrate a bimodal distribution and the addition of PCL to form a ternary blend results in a substantial number of fine dispersed particles present in the system. Focused ion beam irradiation, followed by atomic force microscopy (AFM) shows that dispersed PCL forms particles with a size of 370 nm in PLA. The TPS phase in the ternary blends shows some low level coalescence after a subsequent shaping operation. Dynamic mechanical analysis indicates that the temperature of the tan δ peak for the PLA is independent of TPS blend composition and that the addition of PCL in the ternary blend has little influence on the blend transitions. Both the α and β transitions for the thermoplastic starch are highly sensitive to glycerol content. When TPS of high glycerol content is blended with PLA, an increase in the ductility of the samples is achieved and this effect increases with increasing volume fraction of TPS. The ternary blend results in an even greater ductility with an elongation at break of 55% as compared to 5% for the pure PLA. A substantial increase in the notched Izod impact energy is also observed with some blends demonstrating three times the impact energy of pure PLA. The mechanical properties for the ternary blend clearly indicate a synergistic effect that exceeds the results obtained for any of the binary pairs. Overall, the ternary blend approach with PLA/TPS/PCL is an interesting technique to expand the property range of PLA materials.     

Early activation and properties of slag cement

Early age activation of granulated blast-furnace slag (BFS) and blends of slag and portland cement (OPC) has been studied. Activators include sodium-hydroxide, sodium sulfate, alum (potassium aluminum sulfate), superplasticizer, and calcium aluminate cement. Heat of hydration, x-ray phase characterization, compressive strength, viscometry, pore size distribution and related characterization studies have been made. Activated BFS-cement mortars having equivalent strengths at 1 day to OPC have been prepared, which also have 28- and 90-day strengths exceeding those of the OPC. Mechanisms of activation are discussed.     

Changes in the miscibility of binary and ternary blends having the same chemical components and compositions

The phase behavior of ternary blends of dimethylpolycarbonate (DMPC), tetramethyl polycarbonate (TMPC), styrene-acrylonitrile (SAN) copolymer has been explored. The experimental phase behavior of ternary blends was compared with that of binary blends having the same chemical components and compositions except that the DMPC and TMPC were present in the form of copolycarbonates (DMPC-TMPC). Miscible region of DMPC/TMPC/SAN ternary blends is narrower than that of DMPC-TMPC/SAN binary blends. In addition, phase separation temperature of binary blend was higher than that of corresponding ternary blend. However, the entropic and energetic terms of ternary blends were more favorable for miscibility than those of binary blends. To understand the phase behavior of blends, phase stability conditions of binary and ternary blends were analyzed. Some ternary blends that have negative interaction energy were not miscible because these blends do not satisfy stability conditions. It was revealed that the addition of component, accompanied by the asymmetry in the binary interactions, results in destabilization of blend.     

Fingerprinting of South African ordinary Portland cements, cement blends and mortars for identification purposes — Discrimination with starplots and PCA

This investigation is an attempt to analyse some of the current commercial cements and cement blends in South Africa and mortars produced from them (1:3 mixtures of cementitious material with different sands) for a suite of minor and trace elements that will provide a unique fingerprint of the final product. It was found in both the case of the OPC and the blended cements that a suite of such elements can be successfully employed to uniquely characterise the materials. The contribution of such a fingerprint is that it can provide valuable information in the case of a forensic analysis for discrimination purposes.     

Strength optimization of “tailor-made cement” with limestone filler and blast furnace slag

The use of cements made with portland clinker and two or three additions has grown because they present several advantages over binary cements. Production of composite cements has produced a necessary shift in the manufacture process used in the cement industry. Now, it is known that the separate grinding and mixing technology is more convenient in order to produce these cements, called market-oriented or tailor-made cements. However, their optimum formulations require the help of methods of experimental design to obtain an appropriate performance for a given property with the least experimental effort.In this study, the interaction between limestone filler (LF) and blast-furnace slag (BFS) is analyzed in mortars in which portland cement (PC) was replaced by up to 22% LF and BFS. For this proposition, a two-level factorial design was used permitting to draw the isoresponse curves. Results show that compressive and flexural strength evaluated at 2, 7, 14, 28, 90 and 360 days are affected in different ways by the presence of mineral additions.     

Physico-chemical interaction between mineral admixtures and OPC–calcium sulfoaluminate (CSA) cements and its influence on early-age expansion

The present study aims at examining the physico-chemical factors influencing the expansion characteristics of OPC–CSA blend in the presence of mineral admixtures. Three different admixtures: Class ‘F’ fly ash (‘F’FA), Class ‘C’ fly ash (‘C’FA) and silica fume (SF) were used as 15%, 15% and 5% replacement of total cementitious binder. Longitudinal expansion of cement pastes prepared at w/cm – 0.44 showed that the Class ‘F’FA increased the expansion whereas the Class ‘C’FA and SF reduced the expansion. The pore solution of the OPC–CSA cement pastes was extracted at different ages to monitor the concentration of various ionic species. The saturation level of ettringite was determined using a geochemical modeling program (GEMS). Furthermore, an upper bound of crystallization stress was estimated. The expansion behavior in the presence of Class ‘F’FA and SF was found to be influenced by the changes in the stiffness, whereas the expansion of the Class ‘C’FA-based mixture was governed by faster hydration of ye'elimite.     

Probing the microstructure and water phases in composite cement blends

¹H nuclear magnetic resonance relaxometry has been used in combination with the more conventional techniques of mercury intrusion porosimetry, freeze-drying and thermogravimetric analysis to investigate the evolution of the microstructure and the distribution of water phases in two composite cement blends hydrating over a one year period. These two blends are composed of high substitution of Ordinary Portland Cement (OPC) with Blast Furnace Slag (BFS) at level of 75 wt.% (3:1 blend) and 90 wt.% (9:1 blend).After one year, the 3:1 blend microstructure is characterised by poorly interconnected gel pores filled with about 35 vol.% of water while less than 4 vol.% of water is trapped in remaining capillary pores. The 9:1 blend microstructure is characterised by a network of larger gel and capillary pores filled with about 21 and 22 vol.% of water respectively. Further hydration is ruled out for this blend.     

Role of alkaline nitrites in the corrosion performance of steel in composite cements

The influence of alkaline nitrites on the inhibition of corrosion of steel in binary and ternary cement environments was tested. pH measurements carried out for binary and ternary cement extracts showed that the alkalinity of the cement was not affected by making use of binary and ternary cements. Gravimetric measurements showed that the decrease in the corrosion rate of steel in different systems follows the order: Ternary > (OPC + PSC) > (OPC + PPC) > (PPC + PSC). Potential–time studies indicated that the ability to maintain the passivity of steel in different systems also follows the order as above. Potentiodynamic polarisation studies for steel in binary and ternary cement environments showed the favourable influence of the presence of higher amounts of chlorides. Nitrites of sodium, potassium and calcium act as anodic inhibitors and they compete with chloride ions for the ferrous ions at the steel to form a film of ferric oxide. An efficiency as high as 91% is obtained for the ternary system containing 1% chloride and 0.5% nitrite. The degree of surface coverage showed a maximum value for the ternary system (>0.9) even in the presence of a higher amount of chloride thereby indicating the better performance of the system.     

Studies on binary and ternary blends of polypropylene with SEBS,PS, and HDPE. II. Tensile and impact properties

Studies are reported on tensile and impact properties of several binary and ternary blends of polypropylene (PP), styrene-b-ethylene-co-butylene-b-styrene triblock copolymer (SEBS), high-density polyethylene (HDPE), and polystyrene (PS). The blend compositions of the binary blends PP/X were 10 wt % X and 90 wt % PP, while those of the ternary blends PP/X/Y were 10 wt % of X and 90 wt % of PP/Y, or 10 wt % Y and 90 wt % PP/X (PP/Y and PP/X were of identical composition 90:10); X, Y being SEBS, HDPE, or PS. The results are interpreted for the effect of each individual component by comparing the binary blends with the reference system PP, and the ternary blends with the respective binary blends as the reference systems. The ternary blend PP/SEBS/HDPE showed properties distinctly superior to those of PP/SEBS/PS or the binary blends PP/SEBS and PP/HDPE. Differences in the tensile yield behavior of the different samples and their correlation with impact strength suggested shear yielding as the possible mechanism of enhancement of impact strength. Scanning electron microscopic study of the impact fractured surfaces also supports the shear yielding mechanism of impact toughening of these blends.     

Autogenous healing of marine exposed concrete: Characterization and quantification through visual crack closure

Concrete can autogenously heal cracks potentially increasing construction durability. Studies quantifying this process are limited to fresh-water making the controlling parameters in sea-water unclear. Here we visually quantify the autogenous healing capacity of ordinary Portland cement (OPC) and blast-furnace slag (BFS) cement mortar specimens submerged in fresh- and sea-water. After 56 days, BFS cement specimens in sea-water healed 100% of cracks up to 104 μm, for OPC specimens it was 592 μm. In fresh-water, BFS cement specimens healed 100% of cracks up to 408 μm, while OPC specimens healed 100% of cracks up to 168 μm. Displaying greater healing efficiency OPC specimens in sea-water became weak, developing unacceptable losses in compressive strength. Differences in performance were attributed to the amount of calcium hydroxide in these mortars and specific ions present in sea-water. Visual crack-healing, therefore, should be assessed in conjunction with a material functional property.     

Studies on binary and ternary blends of polypropylene with ABS and LDPE. II. Impact and tensile properties

Studies on impact and tensile properties of binary blend of PP and ABS and ternary blend of PP, ABS, and LDPE are presented. Variation of impact strength and the fracture surface morphology with blend composition is examined and interpreted. Tensile behavior in the yield region is studied and the trends of variation of work of yield and impact strength are compared to ascertain the predominent mechanism of impact toughening in these binary and ternary blends. An analysis of yield–stress data in terms of theoretical models is presented to reveal the differences in these binary and ternary blends, attributable to the role of LDPE component in the ternary blend.     

Effect of Temperatures up to 90°C on the Early Hydration of Portland–Blastfurnace Slag Cements

Isothermal conduction calorimetry has been used to monitor the early hydration of Portland–blastfurnace slag (BFS)-blended cements. Portland:BFS composite cements with ordinary Portland cement replacements from 0 to 90 wt% were studied at curing temperatures from 12° to 90°C. Peak II, principally associated with alite (Ca₃SiO₅) hydration, was accelerated with increasing temperature for all blends. Peak S, associated with BFS hydration, was particularly noticeable at 40° and 60°C. At higher curing temperatures, peak S merged with peak II, indicating thermal activation of BFS. Novel plots of total heat output against percentage replacement show that BFS contributes to the heat of hydration, even at temperatures below its thermal activation.     

Effect of chitosan on morphology and conformation of electrospun silk fibroin nanofibers

The electrospinning of silk fibroin(SF)/chitosan(CS) blends with different composition ratios was performed with formic acid as a spinning solvent. The SF/CS blends containing up to the CS content of 30% could be electrospun into the continuous fibrous structure, although pure CS was not able to be electrospun into the fibrous structure. As-spun SF/CS blend nanofibers showed smaller diameter and narrower diameter distribution than pure SF nanofibers, and the diameter gradually decreased from 450 to 130 nm with the addition of CS in blends. However, at the blend compositions with above 40 wt% chitosan, the continuous SF nanofibers containing CS beads were produced. We also investigated the influence of the methanol treatment on the secondary structure of as-spun SF or SF/CS blend nanofibers by means of ATR-IR and solid-state CP-MAS ¹³C-NMR. Comparing with the pure SF nanofibers, the conformational change of the as-spun SF/CS blend nanofibers into β-sheet was faster because the CS with rigid backbone synergistically might promote the conformational transition of SF by an intermolecular interaction.     

Strength, permeability, and carbonation of high-performance concrete

This investigation is aimed at developing high-performance concrete and form part of an investigation into the optimization of a blended cementitious system for the development of high-performance concrete. Binary and ternary blended cementitious systems based on ordinary Portland cement (OPC), pulverised fuel ash (PFA) and silica fume (SF) were investigated. PFA up to 40% was used, and to these blends, 0%, 5%, 10% and 15% SF were incorporated as partial cement replacements. Results of compressive strength, tensile strength, oxygen permeability and carbonation of concrete are reported. A water-binder (w/b) ratio of 0.27 was used for the main group of mixes and w/b ratios of 0.40 and 0.50 were used for some selected mixes. Based on the experimentally obtained results, prediction models were developed which enabled the establishment of isoresponse contours showing the interaction between the various parameters investigated. It was found that the incorporation of 8-12% SF as cement replacement yielded the optimum strength and permeability values.     

Studies on binary and ternary blends of polypropylene with ABS and LDPE. I. Melt rheological behavior

Studies are presented on melt rheological properties of binary blend of polypropylene (PP) and acrylonitrile–butadiene–styrene terpolymer (ABS), and ternary blend of PP, ABS, and low-den-sity polyethylene (LDPE). Data obtained in capillary rheometer are presented to describe the effect of blending ratio, shear stress, and shear rate on flow properties, melt viscosity, and melt elasticity. At a blend composition corresponding to 10 wt % ABS content, both binary and ternary blends show maximum in melt viscosity accompanied by minimum in melt elasticity. Pseudoplasticity of the melt decreases with increasing ABS content. In ternary blends, LDPE facilitates the flow at low LDPE contents and obstructs the flow at high LDPE contents. Scanning electron microscopic studies are also presented to illustrate the state of dispersion and its variation with blend composition.     

The effect of interface characteristics on the static and dynamic mechanical properties of three‐component polymer alloys

The effect of interfacial characteristics on the structure‐property relationships of ternary polymer alloys and blends comprising polypropylene (PP), ethylene‐vinyl alcohol copolymer (EVOH) and glass beads (GB) or fibers (GF) was investigated. The systems studied were based on a binary PP/EVOH immiscible blend, representing a blend of a semi‐crystalline apolar polymer with a semi‐crystalline highly polar copolymer. The ternary systems studied consisted of filler particles encapsulated by EVOH, with some of the minor EVOH component separately dispersed within the PP matrix. Modification of the interfacial properties was done using silane coupling agents for the EVOH/glass interface and compatibilization using a maleic anhydride grafted PP (MA‐g‐PP) for the PP/EVOH interface. Both glass fillers increased the dynamic modulus and decreased the damping of the neat polymers and of their binary blends, especially in the rubbery region. GF has a more profound effect on both the modulus and the damping. Glass surface treatments and compatibilization have only a marginal effect on the dynamic mechanical behavior of the ternary blends. Yet, compatibilization shifted the polymers' T_gS to higher temperatures. Both glass fillers increased the elastic modulus of the binary blends, where GF performed better than GB as a reinforcing agent. GF slightly increased the strength of the binary blends while, GB reduced it. Both fillers reduced the ductility of the binary blends. The blends' mechanical properties were related to the morphology and their components' crystallinity. The compatibilizer increases both stiffness and strength and reduces deformability.     

Melt rheology and morphology of PP/SEBS/PC ternary blend

Melt rheological properties of the ternary blend of isotactic polypropylene (PP), styreneethylene–butylene–styrene terpolymer (SEBS), and polycarbonate (PC), PP/SEBS/PC, are studied in a wide range of composition, such that PP is the matrix and SEBS and PC are the minor components, with the proportion of one varying from 0 to 30% at various fixed compositions of the other. The respective binary blends, PP/SEBS and PP/PC, studied as the reference systems for interpretation of results on the ternary blends yielded interesting new information about the morphology development and its correlation with melt rheological properties of these binary blends. The studies include the measurement of melt rheological properties on a capillary rheometer in the shear rate range 10¹–10⁴ s^?1 at a fixed temperature of 240°C. The data presented as conventional flow curves are analyzed for the effect of blend composition and shear rate on pseudoplasticity, melt viscosity, and melt elasticity, and role of each individual component is identified. Morphology of dispersed phases of these blends is studied through scanning electron microscopy of the cryogenically fractured and suitably etched surfaces. Variations of morphology with blend composition and shear rate showed interesting correlation with melt rheological properties, which are discussed in detail. An important finding of the morphological studies is that in the PP/SEBS/PC ternary blend the SEBS phase forms two types of morphologies depending on the blend composition and shear rate: (i) simple droplets and (ii) boundary layer at the surface of the PC droplets. © 1993 John Wiley & Sons, Inc.     

Mechanical Properties and Thermooxidative Aging of a Ternary Blend,Pvc/Enr/Nbr,Compared with the Binary Blends of Pvc

In the quest to improve the thermooxidative aging of the poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) blend, nitrile rubber (NBR) was incorporated into the blend to yield a ternary blend of PVC/ENR/NBR. A Brabender Plasticorder with a mixing attachment was used to perform the melt mixing at 150°C and 50 rpm followed by compression molding. The mechanical properties, dynamic mechanical properties, and thermooxidative aging behavior of the ternary blend were compared with those of the binary blends (i.e., PVC/ENR and PVC/NBR). It was found that the ternary blend exhibits mechanical properties which are superior to those of PVC/ENR. A single glass transition temperature (T _g) obtained from dynamic mechanical analysis coupled with synergism in the modulus and some other mechanical properties indicate that PVC, ENR, and NBR form a single phase (miscible system) in the ternary blend. Di-2-ethyl hexylphthalate (DOP) plasti-cizer improves the aging resistance of the blends generally, whereas the presence of CaCO₃ as a filler only imparts minor influences on the properties and aging resistance of the blends.