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Alite

Alite is the predominant mineral phase in Portland cement clinker, comprising an impure form of tricalcium silicate with the chemical formula Ca₃SiO₅, typically making up 50–70% of the clinker's mass and serving as the key contributor to the early-age strength development of concrete due to its high reactivity during hydration.^[1]^[2] This phase forms through a high-temperature solid-state reaction between calcium oxide and silica in the cement kiln, often at temperatures exceeding 1,400°C, resulting in multiple polymorphs—such as monoclinic M1, M3, rhombohedral R, and triclinic T1 forms—that are stabilized by minor impurities like aluminum, iron, and magnesium oxides incorporated into the crystal lattice.^[3]^[4] Alite crystals exhibit a characteristic hexagonal cross-section in microscopic views and range from euhedral (well-formed) to anhedral (irregular) shapes, sometimes containing inclusions of other clinker phases like belite or ferrite.^[1] Upon contact with water, alite undergoes rapid hydration, the fastest among cement's major phases, producing an amorphous calcium silicate hydrate (C-S-H) gel that provides the binding matrix for concrete and crystalline calcium hydroxide (portlandite, CH) as a byproduct, while generating substantial heat that influences setting behavior.^[1]^[5] The hydration kinetics feature an initial rapid exothermic dissolution phase lasting about 15 minutes, followed by a dormant induction period of 2–4 hours that maintains workability, then an acceleration stage where C-S-H nucleation drives rapid strength gain, and finally a deceleration phase as the reaction slows due to product layer formation.^[1]^[6] With an activation energy of approximately 50 kJ/mol, alite's reactivity is highly temperature-sensitive, making it central to optimizing cement performance in various applications.^[7]

Overview and Composition

Definition and Importance

Alite is an impure form of tricalcium silicate, chemically denoted as C₃S (Ca₃SiO₅ or 3CaO·SiO₂), and serves as the predominant mineral phase in Portland cement clinker, typically comprising 50-70% of its mass.^[8] This phase forms during the high-temperature sintering of raw materials in cement production and is essential to the material's hydraulic properties.^[9] The name "alite" was introduced in 1897 by Swedish geologist Axel Wilhelm Törnebohm, who identified it as the major constituent of cement clinker through pioneering microscopic examinations that revealed its crystalline structure.^[10] Törnebohm's work marked a foundational advancement in cement mineralogy, distinguishing alite from other clinker phases and enabling detailed studies of their roles in hydration.^[10] Alite plays a pivotal role in Portland cement by driving early-age strength in concrete through its rapid hydration reaction with water, which forms calcium silicate hydrate gel and portlandite.^[11] In contrast, belite (C₂S) hydrates more slowly and contributes primarily to later-stage strength development, highlighting alite's dominance in initial setting and structural performance.^[12] This rapid reactivity makes alite indispensable for applications requiring quick load-bearing capacity.^[11] Due to its formation at elevated temperatures above 1250°C, alite persists as a metastable phase at room temperature only when the clinker is rapidly quenched during cooling, preventing decomposition into more stable silicates.^[13] This kinetic stabilization is critical for maintaining alite's reactivity in commercial cements.^[14]

Chemical Composition

Alite possesses the nominal chemical formula \ce{Ca3SiO5}, commonly abbreviated as \ce{C3S} in cement chemistry notation, where \ce{C} denotes \ce{CaO} and \ce{S} denotes \ce{SiO2}.^[15] This notation simplifies the representation of cement minerals by treating oxides as modules.^[15] In its pure form, \ce{C3S} consists of approximately 73.7% \ce{CaO} and 26.3% \ce{SiO2}, but alite as found in Portland cement clinker is an impure solid solution with a typical oxide composition of roughly 71.6% \ce{CaO} and 25.2% \ce{SiO2}. These values reflect the incorporation of minor substituent oxides that substitute for \ce{Ca^{2+}} and \ce{Si^{4+}} ions in the crystal lattice.^[16] Typical impurities constitute about 3-4% of the alite phase by mass, including 1-2% \ce{Al2O3}, 0.5-1% \ce{Fe2O3}, 0.5-2% \ce{MgO}, and trace amounts of other oxides such as \ce{Na2O}, \ce{K2O}, and \ce{P2O5}. These substitutions form a continuous solid solution, enhancing the stability of alite under industrial sintering conditions.^[16] The precise chemical composition of alite varies with the raw material sources and clinker burning conditions, such as temperature and atmosphere, which can alter the extent of substitution and thereby affect the phase's reactivity during cement hydration.^[17] Such variability underscores the importance of controlled manufacturing to optimize performance.^[17]

Crystal Structure and Polymorphs

Crystal Structure

Alite possesses an orthosilicate crystal structure featuring discrete SiO₄ tetrahedra isolated from one another and interconnected by Ca²⁺ cations arranged in a distorted lattice framework. This arrangement results in a three-dimensional network where the silicate tetrahedra act as the primary structural units, coordinated by calcium ions in irregular polyhedral sites, typically with coordination numbers ranging from 6 to 8. The distortion in the lattice arises from the packing inefficiencies and the need to accommodate the ionic radii and charges within the structure.^[18] The predominant form of alite at room temperature is monoclinic, belonging to the space group Cm, with unit cell parameters approximately a = 33.08 Å, b = 7.03 Å, c = 18.50 Å, and β = 94.2°. These parameters describe the superstructure, while a subcell approximation yields a ≈ 12.2 Å, b ≈ 7.0 Å, c ≈ 9.3 Å, and β ≈ 116.3°, reflecting the underlying repeating motif. The structure accommodates up to 72 calcium sites and 18 silicate tetrahedra per unit cell in the full monoclinic description, with bond lengths for Si-O varying slightly between 1.6 and 1.7 Å due to the isolated nature of the tetrahedra.^[18]^[19] Impurities commonly present in industrial alite, such as Mg²⁺ substituting for Ca²⁺ and Al³⁺ incorporating into the lattice, induce further lattice distortions and enable the formation of extensive solid solutions. For instance, magnesium incorporation up to 0.11 atoms per formula unit (as in Ca_{2.89}Mg_{0.11}SiO_5) alters Ca-O bond distances and tetrahedral angles, enhancing structural flexibility and preventing complete crystallization into pure phases. These substitutions expand the solid solution range, with Al³⁺ often balancing charge by entering interstitial sites or replacing Si⁴⁺, leading to measurable shifts in unit cell volume and peak broadening in diffraction patterns.^[18]^[20] Alite exhibits metastability at ambient conditions, being kinetically stabilized but thermodynamically unstable below approximately 620°C in its pure form; rapid quenching from synthesis temperatures above 1000°C is essential to retain the high-temperature structure and avoid reversion to the triclinic T1 phase. This kinetic trapping is facilitated by the impurity-induced distortions, which raise the energy barrier for polymorphic transitions.^[21]

Polymorphs

Alite, or impure tricalcium silicate (C₃S), exhibits extensive polymorphism, with seven known structural variants that differ in crystal symmetry and stability as a function of temperature and composition. These polymorphs include three triclinic forms (T₁, T₂, T₃), three monoclinic forms (M₁, M₂, M₃), and one rhombohedral form (R). In pure C₃S, the stability fields are as follows: T₁ is stable below approximately 620°C, T₂ between 620°C and 920°C, T₃ between 920°C and 980°C, M₁ between 980°C and 990°C, M₂ between 990°C and 1070°C, and the high-temperature R form above 1070°C.^[22]^[23] The polymorphs undergo displacive phase transitions upon heating or cooling, with increasing symmetry at higher temperatures. The R polymorph, characterized by its rhombohedral symmetry (space group R3m), represents the highest-temperature form and is metastable at room temperature; it can be preserved through rapid quenching, which kinetically inhibits transformation to lower-symmetry variants. In contrast, slow cooling allows equilibration to low-temperature triclinic or monoclinic forms, such as T₁ or M₁, depending on the thermal history.^[22]^[24] Impurities commonly present in industrial alite significantly influence polymorph stabilization by altering the energy landscape of phase transitions. For instance, Mg²⁺ ions preferentially stabilize the M₃ monoclinic polymorph (space group Cm) over the lower-temperature M₁ form, with concentrations above 1.35 wt% MgO favoring M₃ even at ambient conditions. Similarly, Al³⁺ and other foreign ions (e.g., Fe³⁺, SO₄²⁻) can extend the stability of high-temperature polymorphs like M₃ or M₁ to room temperature, suppressing the formation of triclinic variants.^[25]^[26] These polymorphic behaviors have critical implications for the phase relations in the CaO-SiO₂ system under cement clinker conditions. The pseudo-phase diagram for C₃S shows narrow stability fields for intermediate polymorphs, where cooling rates dictate the final mineralogy: rapid industrial quenching (e.g., >100°C/min) preserves metastable M₃ or R-like structures to enhance reactivity, while slower rates promote decomposition or inversion to less reactive T₁, impacting clinker quality and hydration performance.^[22]^[27]

Production and Synthesis

Industrial Production in Cement Clinker

Alite, the primary silicate phase in Portland cement clinker, is produced industrially through the high-temperature sintering of a raw mix primarily consisting of limestone (providing CaCO₃), clay (supplying SiO₂ and Al₂O₃), and iron ore (contributing Fe₂O₃) in a rotary kiln.^[28]^[29] The process occurs in the kiln's burning zone, where the raw meal is heated to temperatures between 1450°C and 1500°C, enabling the chemical reactions necessary for phase formation.^[28]^[30] The reaction sequence begins with the decarbonation of limestone, where CaCO₃ decomposes to CaO and CO₂ at temperatures up to around 900–1000°C in the preheating and calcining zones.^[28]^[29] Subsequently, the CaO combines with SiO₂ from the clay to form dicalcium silicate (C₂S, or belite) at 900–1250°C.^[28]^[31] In the final stage, belite reacts with free lime (CaO) to produce tricalcium silicate (C₃S, or alite) rapidly above 1400°C, typically completing within 10–20 minutes as the material passes through the sintering zone.^[28] Key process parameters significantly influence alite formation, including burnability—which measures the raw mix's reactivity and ease of sintering—and the development of a liquid phase (20–30% at peak temperature) that promotes clinker nodule formation by binding solid particles.^[28]^[30] Rapid cooling of the clinker, typically at rates of 50–100 °C/min in the initial hot zone of industrial grate coolers, is essential to stabilize the high-temperature polymorphs of alite and prevent reversion to lower-temperature forms.^[32] Alite typically constitutes 50–70 wt% of the clinker, with its proportion modulated by the chemistry of the raw materials (e.g., lime saturation factor) and the kiln atmosphere (e.g., oxygen levels affecting oxidation states).^[28]^[29]^[33]

Laboratory Synthesis

Laboratory synthesis of alite, or tricalcium silicate (C₃S), typically employs controlled solid-state reactions to produce pure samples for research. In this method, high-purity calcium carbonate (CaCO₃) and silica (SiO₂, often as quartz or amorphous fumed silica) are mixed in a 3:1 molar ratio (Ca:Si), homogenized (e.g., by wet milling), dried, and pressed into pellets or self-supporting shapes. The mixture is then heated in a furnace to 1400–1500°C (or up to 1650°C for higher purity) for several hours to promote the reaction 3CaCO₃ + SiO₂ → Ca₃SiO₅ + 3CO₂, followed by rapid quenching in air or water to stabilize the desired polymorph, such as the triclinic T₁ form.^[34]^[35] Wet chemical methods, such as sol-gel or precipitation, offer alternatives for synthesizing alite at lower temperatures by forming homogeneous precursors. In sol-gel synthesis, tetraethyl orthosilicate (TEOS) and calcium nitrate (Ca(NO₃)₂·4H₂O) are used as starting materials in a 1:3 Si:Ca ratio, with hydrolysis and condensation occurring in an acidic medium (e.g., nitric acid) to form a gel, which is dried and calcined at approximately 1200–1400°C for 2–12 hours to yield crystalline C₃S. Precipitation methods similarly involve aqueous solutions of calcium and silicate salts to form a coprecipitate, followed by drying and calcination under comparable conditions, enabling finer particle sizes and more uniform composition compared to solid-state routes.^[36]^[37] Achieving high purity (>95% C₃S) in laboratory synthesis remains challenging due to incomplete reactions, free lime (CaO) formation, and secondary phases like dicalcium silicate (C₂S). Free lime content is typically minimized to <0.4 wt% through iterative sintering cycles and precise stoichiometry, but impurities from raw materials or incomplete CO₂ decomposition can persist. To address this, fluxes such as boron oxide (B₂O₃) at 0.5 wt% are added to lower the synthesis temperature by 50–100°C, enhancing reaction kinetics and promoting alite formation while reducing energy demands and impurity levels.^[35]^[36]^[38] These pure alite samples are primarily synthesized for isolated studies of hydration kinetics and polymorph behavior, allowing researchers to examine fundamental reaction mechanisms without interference from other cement phases. For instance, kilogram-scale productions enable detailed kinetic modeling of early-age hydration, while controlled polymorph stabilization facilitates investigations into phase transitions under varying thermal conditions.^[34]^[35]

Properties and Stability

Physical Properties

Alite exhibits a density of 3.15 to 3.25 g/cm³, with variations primarily attributed to the level of impurities such as aluminum, iron, and magnesium oxides commonly found in cement clinkers.^[39] Pure tricalcium silicate has a slightly lower density of approximately 3.12 g/cm³, while impurities in alite increase this value.^[39] Alite undergoes incongruent decomposition at approximately 2070°C, though in the context of cement clinker production at 1400–1500°C, it forms via solid-state reactions without decomposition and is preserved in a metastable state by rapid cooling.^[40] For the monoclinic polymorph, the refractive indices are nα ≈ 1.72, nβ ≈ 1.73, and nγ ≈ 1.75, contributing to its optical anisotropy.^[2] In its pure form, alite appears colorless to pale green, forming prismatic or tabular crystals that display birefringence under polarized light, with second-order interference colors. Within cement clinker, alite crystals typically range in particle size from 15 to 50 μm, influencing their overall behavior in the material.^[41]

Chemical and Thermal Stability

Alite demonstrates high thermal stability during cement clinker production, remaining intact up to approximately 1450°C under typical rapid cooling conditions, though pure tricalcium silicate is metastable below about 1250°C and can slowly decompose into dicalcium silicate and free lime if annealed isothermally at lower temperatures for extended periods.^[14] At higher temperatures exceeding 2000°C, alite undergoes incongruent decomposition to dicalcium silicate and free lime, as indicated by the peritectic boundary in the CaO-SiO₂ phase diagram near 2070°C.^[40] Chemically, alite exhibits considerable inertness, with low solubility in water on the order of 0.1–0.3 g/L, though it readily reacts with water to initiate hydration.^[42] It shows relative resistance to dilute acids compared to phases like portlandite, but prolonged exposure to stronger acids such as citric or sulfuric acid leads to degradation through dissolution and transformation into lower Ca/Si ratio products, eventually yielding amorphous silica.^[43] The stability of alite is significantly influenced by the atmospheric conditions during clinker burning; oxidizing environments promote its formation and preservation by maintaining the necessary redox state for silicate crystallization, whereas reducing conditions—often arising from insufficient oxygen or excess fuel—induce decomposition into belite, free lime, and potentially other phases like tetracalcium aluminoferrite, compromising clinker quality.^[14] In hardened concrete, alite enhances long-term durability through the formation of dense calcium silicate hydrate gels, but its hydration byproduct, calcium hydroxide, renders the matrix vulnerable to sulfate attack, where sulfate ions react to form expansive ettringite and gypsum, resulting in cracking and reduced structural integrity over time.^[44]

Hydration and Reactivity

Hydration Mechanism

The hydration of alite, or tricalcium silicate (C₃S), is a complex, multi-stage process that begins immediately upon contact with water and proceeds through dissolution, nucleation, growth, and diffusion-controlled phases. In the initial dissolution stage, C₃S particles rapidly dissolve at the surface, releasing Ca²⁺ ions and OH⁻ into the aqueous solution, which increases the pH to around 12.5–13 and drives the exothermic reaction forward.^[45] This stage is characterized by a high initial rate, often quantified as approximately 10 μmol m⁻² s⁻¹, and is highly dependent on the particle surface area.^[46]^[47] Following dissolution, the supersaturated solution leads to the nucleation stage, where calcium silicate hydrate (C-S-H) and calcium hydroxide (CH, or portlandite) begin to precipitate. Nucleation of C-S-H occurs preferentially on the C₃S surface or in solution, while CH forms as rhombohedral crystals, often intergrown with C-S-H.^[48] The overall simplified reaction can be represented as:

$2 \ce{C3S} + 6 \ce{H} \rightarrow \ce{C3S2H3} (\ce{C-S-H}) + 3 \ce{CH}

where H denotes water molecules, C-S-H is the poorly crystalline gel, and CH is portlandite; this equation captures the stoichiometry but simplifies the variable composition of C-S-H.^[49] The process is strongly exothermic, liberating approximately 138 kJ/mol of heat during early dissolution, which can elevate local temperatures and accelerate subsequent steps.^[46] In the propagation stage, nucleation gives way to growth, where C-S-H forms a dense, foil-like gel that envelops the C₃S particles, and CH crystals continue to expand. This growth phase is initially rapid but transitions to diffusion control as the products thicken, limiting ion transport to the unreacted core.^[45] Rate factors include temperature, with enhanced dissolution and nucleation kinetics at elevated temperatures.^[50] Surface area remains critical, as higher specific surface areas (e.g., >1 m²/g) sustain faster growth by providing more reactive sites.^[47] As hydration proceeds into the deceleration phase, the C-S-H gel forms a product layer around the C₃S grains that passivates the surface and significantly slows further hydration by impeding water and ion diffusion; this metastable barrier contributes to the long-term diffusion-limited reaction.^[48]^[46] Modern models emphasize that this layer's formation, rather than complete product coverage, governs the transition to long-term, diffusion-limited hydration.^[45]

Reaction Products and Kinetics

The hydration of alite (tricalcium silicate, C₃S) primarily yields an amorphous calcium silicate hydrate (C-S-H) gel and crystalline portlandite (Ca(OH)₂). The C-S-H gel, which constitutes approximately 50-60% of the hydration product volume, forms a nanoscale, disordered structure responsible for the binding properties in cementitious materials. Portlandite accounts for 20-35% of the volume and precipitates as hexagonal plates, contributing to the pH increase in the pore solution.^[51] The kinetics of alite hydration are commonly described using the Avrami equation, which models the nucleation and growth processes. The degree of hydration \alpha follows the form

\alpha = 1 - \exp(-k t^n)

where k is the rate constant, t is time, and the Avrami exponent n typically ranges from 2 to 3, reflecting a combination of nucleation and anisotropic growth mechanisms.^[52] This model captures the sigmoidal progression of hydration, with initial slow dissolution accelerating into rapid precipitation. Hydration is exothermic, releasing approximately 500 J/g of heat, primarily during the main peak associated with C-S-H formation, as measured by isothermal calorimetry.^[53] Over longer periods, such as up to 28 days, the C-S-H undergoes densification, reducing its internal porosity and enhancing mechanical strength through increased packing density.^[54]

Applications and Historical Significance

Role in Portland Cement

Alite, or tricalcium silicate (C₃S), serves as the primary phase responsible for early-age strength development in Portland cement, contributing significantly to strength gains within the first few days and up to 28 days through its hydration.^[55] This rapid hydration leads to the formation of calcium silicate hydrate (C-S-H) gel and portlandite, enabling quick setting and initial structural integrity in concrete.^[55] In ordinary Portland cement (OPC), alite typically constitutes 50-70% of the clinker mass, optimizing for high early strength suitable for general construction applications.^[56] In contrast, sulfate-resistant Portland cements (Type V) typically have comparable or slightly lower alite content to minimize heat evolution and enhance durability in sulfate-rich environments, with tricalcium aluminate (C3A) limited to less than 5%, though this results in slower early strength gain compared to OPC.^[56] To enhance alite's reactivity, cement manufacturers employ finer grinding of clinker, increasing the specific surface area and accelerating hydration rates without altering the phase composition.^[57] Additionally, additives such as gypsum (calcium sulfate) are incorporated at 3-5% by weight to regulate the setting time by controlling the initial flash set from alite and other phases, ensuring workability during placement.^[8] The high lime (CaO) content required for alite formation—derived from limestone calcination—significantly contributes to the cement industry's CO₂ emissions, accounting for about 60% of the process-related greenhouse gases in Portland cement production.^[58] Efforts to mitigate this include developing alternative low-alite cements, such as belite-rich (higher C₂S) or calcium sulfoaluminate formulations, which reduce lime demand and cut emissions by up to 10-30% while maintaining comparable long-term strength. As of 2025, innovations such as electric cement recycling and advanced calcium sulfoaluminate (CSA) formulations have demonstrated potential CO₂ reductions of up to 50% in pilot scales.^[59]^[60] These innovations aim to balance alite's performance benefits with sustainability goals in modern concrete applications.^[61]

Precursor in Medieval Lime Mortars

Archaeological analyses of medieval lime-based mortars have revealed the presence of calcium silicate hydrate (C-S-H) and calcium hydroxide (CH) phases, indicative of hydraulic reactivity akin to that of alite hydration. For instance, mortars from the 12th-century Notre-Dame Cathedral in Tournai, Belgium, exhibit C-S-H gels with a Ca/Si ratio of approximately 1.3, alongside CH, as identified through electron microprobe analysis. These hydration products suggest that the lime was produced by burning impure limestone at elevated temperatures of 900–1200°C, sufficient to form minor belite-like (dicalcium silicate) phases from inherent silica impurities.^[62] The formation of these alite-like phases occurred during incomplete decarbonation processes in traditional wood-fired kilns, where variable temperatures and reducing atmospheres led to reactive lime incorporating silicate impurities from the limestone feedstock. This resulted in low-grade dicalcium silicate (C₂S) or similar hydraulic components, whose hydration mimicked modern alite behavior by producing C-S-H and CH upon mixing with water. Such conditions were common in pre-industrial kilns, where fuel like wood created localized hot zones promoting partial clinkerization without full Portland cement development.^[63] Archaeological studies employing Raman spectroscopy and X-ray diffraction (XRD) have identified relict C₃S phases in historical lime mortars, providing evidence of these early hydraulic binders. While traces date back to Roman-era pozzolanic limes, such phases became prominent in medieval European construction, as seen in analyses of binder remnants from various sites. Raman imaging, for example, detects C₃S marker bands around 879 cm⁻¹, confirming unhydrated silicate relics stabilized by impurities during kiln cooling. XRD further corroborates these findings by revealing crystalline calcium silicates resistant to full hydration.^[64]^[62] The significance of these alite-like phases lies in their role within early hot-mixing techniques, where quicklime was combined directly with aggregates and water to create durable mortars capable of setting in damp conditions. This approach, predating 19th-century Portland cement, enhanced mortar longevity in exposed structures like cathedrals by forming a robust C-S-H network, as evidenced in Roman and medieval applications.^[65]

Analysis and Detection

Detection Methods

The early detection of alite in cement clinker relied on microscopic examination, with Swedish geologist Alfred Elis Törnebohm pioneering the use of petrographic microscopy in 1897 to identify and name the primary silicate phases, including alite as the dominant triclinic or monoclinic form of tricalcium silicate (C₃S).^[66] Petrographic microscopy remains a fundamental qualitative and quantitative method for identifying alite in polished thin sections or powder mounts of clinker and cement samples. Alite crystals are distinguished by their optical properties under transmitted or reflected light, including moderate to high relief in refractive index liquids (typically n = 1.716–1.724) and birefringence values of approximately 0.005 (varying from 0.004 to 0.006) for the common monoclinic M1 polymorph, appearing as gray to white interference colors in crossed polars.^[67] For quantification, point counting techniques involve systematically traversing the sample field and tallying intersections with alite grains, often achieving phase abundances within 5% accuracy using 200–3000 counts per sample.^[68]^[69] X-ray diffraction (XRD) provides a robust technique for both qualitative identification and quantitative analysis of alite in bulk clinker or cement mixtures, leveraging its crystalline structure. Using Cu Kα radiation, monoclinic alite exhibits characteristic diffraction peaks at 2θ ≈ 32.5° and 51.9°, corresponding to key hkl planes that distinguish it from other phases like belite (β-C₂S). These peaks, often analyzed in the 20–60° 2θ range, allow detection down to a few percent alite content, though overlaps with belite require careful peak deconvolution.^[70] For precise phase quantification in complex mixtures, Rietveld refinement of XRD patterns refines structural models against the full diffraction profile, yielding alite contents with uncertainties typically under 2 wt%. This method incorporates known crystal structures of monoclinic C₃S (e.g., M1 or M3 polymorphs) and accounts for preferred orientation and microabsorption effects, making it a standard for industrial quality control and research on Portland cement clinkers.^[71]

Characterization Techniques

Scanning electron microscopy (SEM) combined with energy-dispersive X-ray spectroscopy (EDS) is widely employed to visualize the morphology of alite crystals and map elemental distributions, revealing impurities such as magnesium or aluminum substitutions within the tricalcium silicate phase.^[72] This technique provides high-resolution images of alite's prismatic or plate-like crystal habits in clinker samples, with EDS enabling quantitative analysis of local compositions to identify deviations from the ideal Ca₃SiO₅ stoichiometry.^[73] For hydrated systems, SEM-EDS helps distinguish unreacted alite grains from hydration products by contrasting their distinct elemental signatures, such as higher calcium-to-silicon ratios in alite.^[74] Nuclear magnetic resonance (NMR) spectroscopy, particularly ²⁹Si and ²⁷Al magic-angle spinning (MAS) NMR, offers insights into the atomic environment of silicon and aluminum in alite, probing the coordination of SiO₄ tetrahedra and any aluminate substitutions.^[75] In anhydrous alite, ²⁹Si NMR typically shows a resonance around -71 ppm indicative of isolated Q⁰ silicate units, while shifts upon hydration reflect polymerization into Q¹ and Q² species in calcium silicate hydrate (C-S-H).^[76] ²⁷Al NMR detects octahedral aluminum at approximately 10 ppm if present as substitutions, aiding in quantifying doping levels that influence reactivity.^[77] These spectra, often acquired at high fields like 9.4 T, enable precise structural characterization without requiring crystalline order.^[78] Infrared (IR) and Raman spectroscopy are essential for identifying vibrational modes associated with alite's silicate framework, with characteristic Si-O stretching bands appearing in the 900-1000 cm⁻¹ region.^[79] In IR spectra, alite exhibits prominent absorption bands at around 920 cm⁻¹ and 980 cm⁻¹ attributed to asymmetric stretching of isolated SiO₄ tetrahedra, which broaden and shift during hydration due to C-S-H formation.^[80] Raman spectroscopy complements this by highlighting symmetric stretching modes near 850-920 cm⁻¹, providing a non-destructive means to assess polymorphic variations in alite, such as between triclinic and rhombohedral forms.^[81] These techniques are particularly useful for in-situ analysis of cement blends, where band deconvolution reveals alite content relative to other phases.^[82] Thermogravimetric analysis (TGA) quantifies the hydration extent of alite by measuring mass loss from calcium hydroxide (CH) decomposition, typically occurring between 400-500°C.^[83] The CH content, derived from the endothermic peak and weight loss in derivative thermogravimetry (DTG), correlates directly with alite hydration since C₃S reacts to form CH and C-S-H.^[84] For accurate degree of hydration calculations, TGA data is normalized against the initial alite fraction, often cross-validated with bound water measurements up to 600°C.^[85] This method is robust for aged samples, as it integrates total volatile loss while minimizing interference from carbonates below 800°C.^[86]

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Aug 21, 2023 · Three triclinic phase modifications exist T1 < 620°C, T2 620°C –. 920 ... At a starting temperature of 1450°C, alite is formed with this ...
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[PDF] Tricalcium silicate Ca3SiO5 superstructure analysis - HAL
Feb 13, 2012 · In this paper, we present a structural model for the M1 polymorph of tricalcium silicate Ca3SiO5 from Powder X-Ray.
[20]
[PDF] Polymorphism of tricalcium silicate in Portland cement - HAL
May 12, 2008 · This inversion was related to the (a/b) ratio of the orthohexagonal unit cell parameters: a/b < √3 for M2 alite and a/b > √3 for M3 alite. As ...
[21]
An Ordered Alite Cement Clinker Phase (Ca 3 SiO 5 , aP162) from ...
Sep 18, 2021 · Alite, prepared from natural resources and used in the cement industry, often contains additional ions like Fe, Mg or Al which have a certain ...<|control11|><|separator|>
[22]
[PDF] Incorporation of minor constituents into Portland cement tricalcium ...
A sample presenting the highest predominance of the C3S M1 polymorph (HM) was chosen in order to evaluate the C3S M1 crystal structural model. Grinding ...
[23]
Synthesis of M1 and M3 alite polymorphs and accuracy of their ...
Its amount is usually over 60 wt%. It consists mainly of tricalcium silicate (C3S) and minor impurities of Al2O3, MgO, Fe2O3, and many other oxides within its ...Missing: unit cell
[24]
Everything you need to know about Advances in Cement Clinkering
During clinker cooling, the microstructural relationships developed at peak temperatures are broadly preserved. Thus alite, which is thermodynamically unstable ...
[25]
Clinker: reactions in the kiln - Understanding Cement
Reactions in the kiln include decomposition of raw materials, alite formation and other reactions in the burning zone, and cooling of the clinker.
[26]
Clinker Production - an overview | ScienceDirect Topics
Clinker production is defined as the process in which raw material, or raw meal, is heated in a rotary kiln at approximately 1450 °C to undergo chemical and ...
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[PDF] Cement (pdf) - U.S. Environmental Protection Agency
Once the clinker is formed in the rotary kiln, it is cooled rapidly to minimize the formation of a glass phase and ensure the maximum yield of alite (tricalcium ...
[28]
Morphological Analysis of White Cement Clinker Minerals - NIH
The formation of alite is very complex. Alite is only formed in the presence of excess CaO, that is, at CaO/SiO2 > 1 and is thermodynamically stable above 1250 ...
[29]
Industrial-scale prediction of cement clinker phases using machine ...
May 24, 2025 · In contrast, alite, belite, and ferrite are the actual phases in clinker, influenced by impurities and process variations, making their ...
[30]
[PDF] Synthesis and Hydration of Tricalcium Silicate - ICCC
Pure triclinic silicate (pure C3S), was prepared from a 1:3 stoichiometric mixture of high purity quartz powder and CaCO3 (both Merck). After homogenisation ...Missing: B2O3 quenching 95%
[31]
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[PDF] Alite-Belite-Ye'elimite cements: effect of dopants on the clinker ...
Nevertheless, there are some problems concerning the clinkering of ABY binders since the optimum temperatures for the synthesis of alite and ye'elimite. Page ...
[35]
Alite – Knowledge and References - Taylor & Francis
Alite is a form of tricalcium silicate, represented by the chemical formula 3CaO.SiO2 or C3S, and is one of the two most important constituents of Portland ...Missing: definition | Show results with:definition
[36]
Tricalcium Silicate and Its Stability Within the System CaO-SiO 2
The estimated accuracy of these temperatures is ±3° relative to one another, and ± 10° relative to the melting points of alumina and dicalcium silicate, for ...
[37]
What Is Clinker? A Simple 3-Minute Guide for Beginners - CEMENTL
Jul 6, 2025 · It is rounded crystals with a crystal size between 5-40 microns. Belite is less reactive than alite and helps to increase the later strength. It ...
[38]
Conductance of tricalcium silicate in water - ScienceDirect
... dissolution of tricalcium silicate in water (up to 0.3 g/L). Also the conductance of saturated and supersaturated solutions of tricalcium silicate at ...Missing: solubility | Show results with:solubility
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None
### Summary of Acid Resistance of Portland Cement and Tricalcium Silicate
[40]
Time to failure for concrete exposed to severe sulfate attack
Sulfate attack of concrete may lead to cracking, spalling, increased permeability, and strength loss. Therefore, to ensure long periods of satisfactory ...
[41]
https://www.cementl.com/what-is-clinker-a-simple-3-minute-guide-for-beginners/
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[PDF] Hydration of Cement and its Mechanisms - IOSR Journal
Abstract: The current state of knowledge of cement hydration mechanisms is reviewed, including the origin of the period of slow reaction in alite and cement ...
[43]
Multiscale understanding of tricalcium silicate hydration reactions
Jun 4, 2018 · Tricalcium silicate, the main constituent of Portland cement, hydrates to produce crystalline calcium hydroxide and calcium-silicate-hydrates ( ...
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[PDF] A Micromechanical Model for the Elastic Properties of Hydrated ...
As the main products of hydration, they occupy roughly 50-60% and 20-35% of the hydration product volume, respectively[5]. C-S-H and CH result from the ...
[48]
[PDF] Effects of D2O and Mixing on the Early Hydration Kinetics of ...
Avrami Fits to the Kinetic Data. The data from each run were fit to the four-parameter Avrami equation relating rate of reaction to hydration time (eq 3). A.<|separator|>
[49]
Influence of organosilicon admixtures on the hydration of Portland ...
Jul 17, 2021 · The heat of hardening is determined by the heat of hydration of the dominant component of cements: alite (with hydration heat of about 500 J g−1) ...
[50]
Effect of the densification of C–S–H on hydration kinetics of tricalcium silicate
### Summary of Long-Term C-S-H Densification Over 28 Days in Alite Hydration
[51]
Pore structure development during hydration of tricalcium silicate by ...
Tricalcium silicate (C3S), accounting for 50 to 70% of Portland cement clinker composition, largely determines the hydration mechanisms of cement [1]. Although ...
[52]
(PDF) The Influence of the Alite Polymorphism on the Strength of the ...
Aug 8, 2025 · The factors influenced the alite modification are related to the process of burning and cooling of clinker. Other factors can influence the ...Missing: quenching preservation
[53]
A Closer Look: Cement Types I Through V | NPCA
Mar 18, 2020 · Lower C3A contents in cement correspond to increased sulfate resistance. Therefore, Type II cement, which is intended for moderate sulfate ...Missing: alite | Show results with:alite
[54]
Variability of cement - Understanding Cement
The fineness to which the cement is ground will evidently affect the rate at which concrete strengths increase after mixing. Grinding the cement more finely ...The Main Physical Cause Of... · Chemical Causes Of Strength... · Effect Of Alkalis On...
[55]
Electric recycling of Portland cement at scale - Nature
May 22, 2024 · Cement production causes 7.5% of global anthropogenic CO2 emissions, arising from limestone decarbonation and fossil-fuel combustion.
[56]
Alternative Clinker Technologies for Reducing Carbon Emissions in ...
Dec 28, 2021 · It happens that only alite and belite are hydraulically active [26], with alite presenting higher reaction kinetics when compared to belite.
[57]
Potential of Reducing CO2 Emissions in Cement Production through ...
Sep 25, 2024 · The results indicated up to 45.5% energy and 35.1% CO2 reduction using alternative clinkers compared to ordinary Portland cement (OPC) clinker.
[58]
[PDF] Hydraulicity in Historic Lime Mortars: a Review - RILEM
Sep 24, 2010 · This article starts with a tentative definition of hydraulicity and then discusses the chemistry and mineralogy of some commercial hydraulic ...
[59]
https://pmc.ncbi.nlm.nih.gov/articles/PMC8746203/
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Jun 14, 2019 · Raman Microspectroscopic Imaging of Binder Remnants in Historical Mortars Reveals Processing Conditions. by. Thomas Schmid.
[61]
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CONCRETE PETROGRAPHY - PAST, PRESENT, AND FUTURE
... microscopes to study portland cement clinkers. In 1897, Tornebohm used microscopy to determine alite, belite, celite, felite, and an interstitial glassy ...
[63]
[PDF] Optical microscopy of cement clinker - petrog
... indices of refraction and in alite crystals there are two indices, corresponding to the 'fast' light ray and the 'slow' light ray. The difference between ...
[64]
Cement Clinker - petrog
... XRD/XRF techniques. Point counting is primarily used to determine the relative proportions of four constituents: alite, belite, aluminate, and ferrite.
[65]
Effect of nanoparticulate CaCO3 on the biological properties of ... - NIH
Jan 2, 2025 · The peaks in the XRD pattern indicate the presence of tricalcium silicate (C3S) (2θ = 29.3°, 32.1°, 32.5°, 34.3°), dicalcium silicate (C2S) (2θ ...
[66]
[PDF] Instructions in Using GSAS Rietveld Software for Quantitative X-ray ...
Jun 1, 2015 · This document is an instructional guide in the use of Rietveld software for quantitative phase analysis of portland cement and related materials ...
[67]
Optimization of SEM-EDS to determine the C–A–S–H composition in ...
Cement is composed of four main phases: alite (impure C3S1), belite (C2S), aluminate (C3A) and ferrite (C4AF). They react with water at different rates to ...
[68]
[PDF] Phase Analysis of Portland Cement by Combined Quantitative X ...
Apr 11, 2016 · Minerals with strong cleavage planes, such as alite, calcite, and gypsum all are susceptible to preferred orientation. Corrections for preferred ...
[69]
Scanning Electron Microscopy Imaging of Hydraulic Cement ...
Aug 10, 2025 · Use of the scanning electron microscope (SEM) with X-ray microanalysis allows study of clinker and cements; permitting measuring bulk phase ...
[70]
29 Si and 27 Al high-resolution NMR characterization of calcium ...
A set of hardened pastes of 28 days age were analyzed by 29 Si and 27 Al high-resolution nuclear magnetic resonance (NMR) at 9.4 T.
[71]
The Application of 29Si NMR Spectroscopy to the Analysis of ... - NIH
29Si NMR is used to investigate the structures of anhydrous calcium silicate phases and the early C-S-H gel product, and to determine hydration extent and ...
[72]
27 Al and 29 Si Solid-State NMR Characterization of Calcium ...
Therefore, from the 27Al NMR quantitative results and the chemical composition of each sample, the intensity of each resonance line in the 29Si spectra was set.
[73]
Characterization of the Calcium Silicate and Aluminate Phases in ...
27Al and 29Si magic-angle spinning (MAS) NMR spectroscopies have proven to be valuable tools for characterization and quantitative analysis of the anhydrous ...
[74]
Infrared and Raman vibrational modelling of β-C2S and C3S ...
This study uses DFT to model IR and Raman spectra of β-C2S and C3S, synthesizing compounds and using X-ray analysis. The study shows good agreement with ...Missing: historical | Show results with:historical
[75]
[PDF] Infrared Spectroscopy in the Analysis of Building and Construction ...
Apr 25, 2012 · The other calcium silicate phase spectra, 2 , exhibits strong bands in the area 1000-800 cm-1 with maximums at 990 and 840 cm-1 due the ...
[76]
FTIR study on the polymorphic structure of tricalcium silicate
Aug 8, 2025 · The IR bands assignable to alite (tricalcium silicate), belite (dicalcium silicate) [25, 26] and monoclinic ... Ca3SiO5 [3] are displayed in ...
[77]
[PDF] raman spectroscopy:application - Digital CSIC
The 1200-800 cm-1 region encompasses Si- O silicate symmetrical stretching bands. The frequency of these bands increases with polymerization, thus, silicate ...
[78]
Determination of the degree of hydration of Portland cement using ...
The aim of this paper is to use three approaches to determine the degree of hydration: portlandite quantification, scanning electron microscopy and bound water ...
[79]
Determination of the degree of hydration of Portland cement using ...
Aug 6, 2025 · Cement paste hydration is a complex physical-chemical process. The aim of this paper is to use three approaches to determine the degree of ...
[80]
[PDF] Characterization of hydration processes of cement pastes by means ...
Thermal analysis was selected as the main method, as its performance is not limited by the age of the materials. More precisely, thermogravimetry can quantify ...
[81]
[PDF] Determination of the degree of hydration of Portland cement using ...
Determination of the degree of hydration by thermogravimetric analysis (TGA) ... decomposition of calcite. 281 temperature. In this case, the loss of weight ...