The use of ZnO for the stabilisation of C3S polymorphs

The use of ZnO for the stabilisation of C3S polymorphs | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article The use of ZnO for the stabilisation of C3S polymorphs Luciana Queiroz, Waleska Barbosa, Ana Paula Kirchheim, Carlos Bergmann This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4745258/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 13 May, 2025 Read the published version in Materials and Structures → Version 1 posted 5 You are reading this latest preprint version Abstract The doping technique is widely used to stabilise C 3 S polymorphs, combined with synthesis temperature and cooling techniques. This work studied the doping technique using ZnO as a dopant at contents of 1.5, 2.0, 4.0, 8.0, and 10.0wt% and evaluated its effect on the polymorphism and reactivity of C 3 S. The characterisation of the phases in the anhydrous state was carried out by X-ray diffraction (XRD), and the effect of doping on chemical bonds and displacements in the crystalline structure was identified by Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy (RAMAN). Hydration was assessed using isothermal calorimetry and X-ray diffraction (XRD) techniques. The results show a delay in the hydration process in all the doped pastes, a reduction in the average crystallite size with increasing dopant content, and changes in the displacements and symmetry of the polymorphs. C3S polymorphism dopant reactivity Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 1. Introduction Portland cement is the most important material in construction and civil engineering. It is the primary building material worldwide and has played a fundamental role as a building material throughout the history of civilization and urbanization, being used in different applications such as concrete, precast concrete, mortars for cladding and laying blocks, adhesive mortars, among others [ 1 , 2 ] According to [ 2 ], clinker is mainly composed of the phases tricalcium silicate (C 3 S), which accounts for between 50 and 70% of its volume, dicalcium silicate (C 2 S) from 15 to 30%, tricalcium aluminate (C 3 A) in levels of 5 to 10%, and finally tetra calcium ferroaluminate (C 4 AF), which varies between 5 and 15%. Tricalcium silicate plays an important role in the mechanical strength properties of early age cement. Its nomenclature is found in the literature in two forms: the first comes from the process of synthesising a pure phase, free of any contamination, called tricalcium silicate (C 3 S), and the second for phases that have impurities either from contamination during the burning process (in co-processing) or the use of mineralisers or in the presence of dopant ions, which is called alite [ 3 , 4 ]. The pure tricalcium silicate (C 3 S) is obtained from a solid solution composed of CaO and SiO 2 at a molar ratio of 3:1 sintered at a temperature of 1450°C, and its crystal structure is composed of SiO 4 4− tetrahedra linked by Ca2 + ions, which are octahedrally coordinated by oxygen ions [ 5 , 6 , 7 ]. C 3 S is divided into three crystalline systems, which in turn have seven polymorphs classified as T1, T2, T3, M1, M2, M3 and (R) [ 3 , 6 , 8 ]. During the synthesis process, the solid solution of C 3 S crystallises initially in the rhombohedral system (R), then during the cooling process, it transforms into the monoclinic system (M) and/or the triclinic system (T) when no dopant ions are incorporated to stabilise the monoclinic system [ 3 , 7 ]. The polymorphic transition temperature is very close from one polymorph to the next, making most of them unstable at room temperature. The doping technique is one of the resources used to stabilise polymorphs at room temperature. It is characterised by the insertion of dopant ions into the crystal structure of C 3 S, causing minor imperfections or displacements that alter the crystal lattice, stabilising it. To apply this technique, the type of dopant ion, its content, and the synthesis temperature must be determined. Those factors affect the technique's efficiency [ 8, 9, 10, 11, 12, 13, 14]. Despite the recurrent use of the dopping technique in synthesising C 3 S, there is a lack of understanding of its efficiency. Since there is no consensus in the literature on which properties will be modified, the synthesis temperature, or the ideal doping content. In a study carried out by [ 3 ], different types of heavy metals were used as dopants at levels of 0.1, 0.5, 1.0, and 3.0 wt%, sintered at a temperature of 1450ºC, where polymorphs T1, T2, M1, M2, and R were stabilised. However, [ 15 ] doped C 3 S with Ba ions at a temperature of 1600ºC and stabilised polymorphs T1, T2 and T3. These are just a few examples found in the literature. Studies carried out from the 1960s to the present day refer to the use of dopants to stabilise C 3 S polymorphs and indicate that the technique alters different properties of C3S, such as the liquid phase's viscosity, grain growth, surface area, free lime content, average crystallite size, heat of hydration, and amount of C-S-H [ 5 , 15 , 16 , 17 , 18 , 19 , 20 ]. Zinc, either in oxide or salt form, is the most widely adopted dopant ion in synthesising C 3 S or solution during hydration [ 20 , 21 , 22 , 23 , 24 , 25 ]. Its effect in the doping process of C 3 S is associated with accelerating sintering by acting as a mineraliser [ 23 , 26 , 27 ]. It can reduce the synthesis temperature from 1450ºC to 1000ºC [ 25 , 28 , 29 , 30 , 31 ]. This temperature reduction is due to the combination of CaO with Zn [ 32 , 33 , 34 , 35 ], and there is also a polymorphic transition depending on the Zn content used in the doping. The main effect of using Zn as a dopant is in the hydration reaction of C 3 S. Studies have shown that contents above 1.0wt% are enough to promote delays in the hydration process due to the formation of new compounds such as zinc hydroxide or Ca[Zn(OH) 3 H 2 O] 2 , which causes a reduction in the mechanical properties such as compressive strength [ 3 , 16 , 20 , 22 , 24 , 25 , 26 , 27 , 30 , 36 , 37 ]. Although there have been negative impacts on the use of Zn as a dopant, the progress of studies on the effect of co-processing [ 38 , 39 , 40 , 41 ] waste as a substitute energy source for the production of Portland cement shows that there is little data on the concentration of the chemical elements that are inserted into the crystal structure and their effect on the properties of Portland cement. In studies carried out by [ 42 ], samples from 17 rotary kilns of Portland clinker production plants were collected, and it identified that around 74–99% of zinc is incorporated into the clinker; this impurity originates from the co-processing of scrap tires; however, the authors do not show which properties have been altered. On the other hand, [ 43 ] identified a total of 4520.02 ppm of zinc in oily residues used in co-processing, not showing the values incorporated into the crystalline structure and modifications in the phases of Portland cement. Thus, the main objective of this work was to study the doping technique through the incorporation of zinc in oxide form (ZnO) at high levels and to evaluate its effect on the polymorphism and reactivity of C 3 S. The composition of the phases (pure and doped) was characterised by X-ray diffraction (XRD), and the average crystallite size was calculated using the Debye-Scherrer equation [ 42 ]. The effect of doping on chemical bonds and displacements in the crystalline structure was identified by Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy (RAMAN); the hydration process and hydrated compounds were evaluated using isothermal calorimetry and X-ray diffraction (XRD) techniques. 2. Materials and methods The synthesis of pure C 3 S used CaCO 3 and SiO 2 (P.A.) in a molar ratio of 3:1, and the doping used ZnO (P.A.) at levels of 1.5, 2.0, 4.0, 8.0, and 10.0 wt% (Table 1 ). The dry materials were mixed manually for five minutes, and Milli Q water was added until they reached a paste-like consistency, and 2.5x5.0cm specimens were moulded and dried for 72 hours at a temperature of 100°C ± 5°C. After drying, the material was sintered at 1500°C for six hours and cooled abruptly by mechanical ventilation to room temperature. Table 1 shows the chemical composition and physical properties of the reagents. Table 1 – Chemical composition of the raw materials. Constituent CaCO 3 SiO 2 ZnO CaCO 3 99.84 - - SiO 2 - 99.88 - ZnO - - 99.00 Cl 0.001 0.1 0.001 F 0.0015 - - NO 3 - - 0.003 SO 4 0.01 - 0.01 NH 4 0.003 - - Pb 0.001 0.003 0.005 Fe 0.003 0.02 0.001 Ba 0.01 - - Mg 0.02 - - K 0.01 - - Na 0.1 - - Property Surface area (m²/g) 16.190 214.183 8.371 Dv 90 (µm) 5.69 120.61 3.47 Dv 50 (µm) 2.87 73.08 1,02 Dv 10 (µm) 1.22 33.89 0.26 ZnO Doped (wt%) P Z1 Z2 Z3 Z4 Z5 0 1.5 2.0 4.0 8.0 10.0 The X-ray diffraction technique, Phillips model X'Pert MDP, using Cu-Kα radiation (λ = 1.54184 Å) in analysis conditions in the 2θ range from 10 to 70°, step 0.05°/1s, slits: ½° and window: 20 mm, for analysis of phase transformation and composition. The Rietveld method and the ICSD database for quantitative analysis of the crystalline phases to calculate the average crystallite size calculation. The Debye-Scherrer equation (Eq. 1) applied to calculate the average crystallite size. \(\:\text{D}=\frac{\text{K}\text{*}{\lambda\:}}{\text{B}\text{*}\text{c}\text{o}\text{s}{{\theta\:}}_{\text{B}}}\) (Eq. 1) Where D is the average diameter of the particles, K is a constant that depends on the shape of the particles (sphere = 0.94), λ is the wavelength of the electromagnetic radiation, θ is the diffraction angle, and β (2θ) is the width at half the height of the diffraction peak. To analyse the changes in surface chemical bonds in the 4000 to 400cm − 1 region caused by the presence and concentration of the dopant, Fourier transform infrared spectroscopy (FTIR) was carried out using a Shimadzu IRAFFINITY 1 spectrometer with a resolution of 4cm − 1 , performing 16 scans per sample. Raman spectroscopy was used as a complementary analysis using a micro–Raman Spectrometer System, Model inVia (Renishaw), in the 100 to 800cm- 1 range with an excitation wavelength of 532 nm and a laser power of 0.5 mW. An isothermal calorimetry test was carried out using TAM Air equipment (TA Instruments) with eight channels capacity to assess the hydrated compounds' hydration kinetics. Samples weighing 2g were mixed and homogenised with distilled water at an a/s ratio 0.5. Heat flow (thermal energy, mW/g of solids) and accumulated heat (integral of thermal energy, J/g of solids) were recorded for up to 3 days at 22°C. 3. Results and discussion 3.1. Mineralogical composition From the X-ray diffraction (XRD) patterns shown in Fig. 1 , the effect of zinc on the phase composition and polymorphism of C 3 S can be seen. The phases identified were C 3 S (ICSD# 004331 and # 162744), CaO (ICSD# 75786) and ZnO (ICSD# 193696). As shown in Fig. 1 , as the dosage of ZnO increases, there is a change in the C 3 S peaks and an increase in the intensity of the peak (37º) characteristic of the ZnO phase. In the Z4 and Z5 samples, 7.1% and 14.2% of ZnO was formed, respectively, which was not incorporated into the C 3 S structure, a similar result found by [ 23 ]. The formation of ZnO in samples T4 and T5 is related to the excess content in the systems, forming a supersaturated solid solution. This behavior directly influenced the C 3 S content, where there was a reduction of 11.4% and 19.5% compared to the pure sample (P), indicating that the optimum doping content for the C 3 S synthesis configuration in this work is up to 4.0wt% since in the other samples (Z1, Z2, and Z3) there was no ZnO formation, and its content was inserted entirely into the C 3 S crystal structure. The f-CaO content is directly proportional to the increase in ZnO content and aligns with the literature [ 3 , 15 , 43 , 44 ]. As the ZnO content increases, there is a significant increase in the f-CaO content of up to 5.4% in the Z5 sample compared to the P sample. This behavior is directly related to the Ca 2+ ion substitution by Zn 2+ due to the weak binding energy between oxygen and calcium when compared to silicon and oxygen [ 18 , 24 , 45 ]. Furthermore, when considering a substitution reaction, the radii of Zn 2+ and Ca 2+ are 0.074 and 0.099nm, respectively. This favors the formation of a solid substitutional solution [ 16 , 46 ]. 3.2. Stabilised polymorph Figure 2 shows the polymorphic transition with changes in the peaks (31º and 32º; 51º and 52º) due to the effect of ZnO on the crystal structure of C 3 S. Only samples P, Z4, and Z5 stabilised a single polymorph, T3 and rhombohedral. The polymorphic transition from the triclinic to the monoclinic system occurs from the insertion of 1.5 wt% ZnO (sample Z1). However, when the content increases, the phase formed is composed of the T3 and M1 polymorphs, showing an instability in the synthesis process that may have been generated during cooling since the transition temperature of the polymorphs is close [ 6 ]. The firing temperature was constant for all the samples. Figure 3 shows the percentage of each polymorph, identifying the T3, M1, M3, and R polymorphs. For quantitative analysis, the structural models proposed for the T3 polymorph (ICSD# 004331, and # 162744); M1 polymorph (ICSD# 81100); M3 polymorph (ICSD# 64759); R polymorph (ICSD# 22501, and 24625).Because polymorphs are metastable at room temperature, the highest percentage of polymorph identified was considered for this analysis, classifying it as the predominant polymorph. The pure phase is composed of 98.7% of the T3 polymorph. For the doped phases, there is a polymorphic transition with increasing zinc oxide content of 54.8% of M1 and 43.8% of M3 for sample Z1, 23.5% of T3, and 75.2% of M1 for Z2, 25.3% of M3 and 72% of R for sample Z3 and samples Z4 and Z5 only the R polymorph was identified in 86.5% and 78.4%, respectively. There is no consensus on stabilising specific polymorphs based on the dopant content, which reflects what is identified in the literature. Some studies report that increasing Zn in the system does not change the polymorph formed [ 23 ]. In contrast, others have managed to stabilise several polymorphs with the same dopant content [ 30 ], and studies show the polymorphic transition or stabilisation of different polymorphs with different doping levels, as seen in Table 2 . The doping range used in this work aligns with some studies, such as [ 30 ] and [ 45 ]. Table 2 – Stabilized Polymorph. Ref. Stabilized Polymorph T1 T2 T3 M1 M2 M3 R [ 3 ] 3.0 [ 10 ] 3.2 4.8 and 6.4 6.4 6.4 [ 16 ] 0.084 0.415 and 0.817 2.416 [ 20 ] 1.0–3.0 0.5 [ 21 ] 0.2, 0.5, 0.8 and 1.5 [ 23 ] 1.0 and 3.0 [ 30 ]* 1.0–4.0 1.0–4.0 1.0–4.0 [ 32 ] 0.08 0.38 1.88 3.75 [ 33 ] 2.0, 4.0 and 6.0 [ 35 ] 0.03 0.4–0.9 1.2 1.4 1.5 and 1.6 [ 45 ]* 1.0, 3.0 and 5.0 1.0, 3.0 and 5.0 *Different polymorphs were identified for all contents, with differences only in the concentration of each polymorph. The stability of a single polymorph is a complex activity, given the entire synthesis process involved. In order to stabilize the polymorph, it is necessary to consider the type and content of the dopant used and the type of solid solution that will be formed. Solid solutions fall into two categories: interstitial or substitutional. In doping a solid solution to introduce an impurity into the interstitial spaces, understanding the size of the vacancy created at the synthesis temperature or determining if the interstice matches the impurity size becomes crucial. Conversely, when dealing with a substitutional solid solution, the physicochemical properties of the impurity need to align with those of the ion it substitutes. These properties include valence, electronegativity, crystalline system, unit cell volume, and more [ 33 , 47 ]. [ 3 ] explains that as the Zn content increased, the solid solution changed from substitutional to interstitial, keeping the synthesis temperature at 1400ºC. However, [ 46 ] clarify that the crystalline defects of C 3 S caused by the insertion of impurities with the same valence will result in the formation of substitutional defects, with the size of the ion being a decisive factor for the reaction, considering that an ion radius of less than 15% will result in the formation of a substitutional solid solution. The temperature range synthesising Zn-doped C 3 S varies between 1000ºC and 1600ºC [ 18 , 23 , 27 , 28 , 29 ]. The choice of temperature will guarantee the efficiency of the doping through the defects created and the incorporation of the ion into the crystalline structure. Although Zn has a mineralising effect [ 23 , 26 , 27 , 28 , 35 ] with a reduction in temperature, this effect may prevent the ion from entering the crystal structure, and the excess will be available in the form of ZnO [ 23 , 33 ]. Another change observed due to doping C 3 S with ZnO is the average crystallite size (Table 3 ). The insertion of ZnO into the crystalline structure of C 3 S leads to a slight reduction in the average crystallite size between samples Z1 and Z2 when compared to sample P, which can be explained by the complete insertion of the Zn 2+ ion into the crystalline structure due to the substitution of Ca 2+ for Zn 2+ in the formation of the substitutional solid solution [ 3 ]. Table 3 – Crystallite size. P Z1 Z2 Z3 Z4 Z5 Predominant polymorph T3 M1 M1 R R R Crystallite size (nm) 56.735 51.859 51.998 47.281 47.283 47.176 However, as the dopant content increases, the average crystallite size in samples Z3, Z4, and Z5 is reduced by approximately 9.5% compared to sample P, the same behavior found by [ 3 , 20 , 34 ]. This implies that the excess dopant caused minor defects in the network, transforming the interstitial solid solution into a substitutional one, as observed by [ 3 , 23 ]. 3.3. The effect of ZnO on the IR spectra of C 3 S The C 3 S formed comprises silicon tetrahedra, calcium, and zinc oxides, where the infrared absorption bands are in the 400 to 4000cm − 1 region. The [SiO] 4 4− tetrahedra have four fundamental vibration modes: ν 1 symmetrical stretching, ν 3 asymmetrical stretching, ν 2 in-plane bending, and ν 4 out-of-plane bending [ 16 , 48 ]. Figure 4 shows the behavior of the IR spectra of the C 3 S polymorphs doped with different levels of ZnO, and Table 4 shows the vibration bands. Table 4 – FTIR spectra assignments for different polymorphs of C 3 S. Phase Predominant polymorph Absorption IR band/cm − 1 ν 1 ν 2 ν 3 ν 4 P T3 859, 814 492, 461, 434, 418 1050, 1008 516 Z1 M1 855 490, 461, 427, 418 1050, 1017 516 Z2 M1 855 490, 453, 439, 418 1050, 1014 516 Z3 R 855 487, 459, 430, 418 1050, 1014 516 Z4 R 494, 459, 469, 423, 406 1050, 1014 511 Z5 R 492, 467, 452, 430, 418 1050, 1015 511 The pure phase of C 3 S (T3) shows symmetric stretching (ν 1 ) of the silicon tetrahedra [SiO] 4 4− at 859 and 814cm − 1 ; asymmetric stretching (ν 3 ) at 1050 and 1008cm − 1 ; in-plane bending (ν 2 ) at 492, 461, 434 and 318cm − 1 ; out-of-plane bending (ν 4 ) at 516cm − 1 ; The region of the vibrational modes are in agreement with the literature [ 16 , 48 ]. The monoclinic crystalline system (Z1 and Z2) showed the four vibrational modes (Table 4 ) with changes in the asymmetric stretching (ν 3 ) at 1050 and 1017cm − 1 of the Z1 sample about the Z2 sample due to the polymorphic composition since the Z2 sample shows a percentage of T3 (Fig. 4 ), this behavior is also observed in the in-plane bending vibrational mode (ν 2 ) at 490, 461, 427 and 418cm − 1 corroborating the results presented in the XRD (Fig. 2 ). [ 16 ] also described that it is possible to observe that increasing the ZnO content alters the symmetry of C 3 S due to the substitution of Ca 2+ ions. The R polymorph observed in samples Z3, Z4, and Z5 showed changes in vibrational modes. Sample Z3 showed all four vibrational modes, but it should be noted that its composition is 25.3% M3 and 72% R, with the symmetrical stretching (ν 1 ) of the [SiO] 4 4− silicon tetrahedra at 855cm − 1 corresponding to the M3 polymorph. Samples Z4 and Z5, on the other hand, did not show this due to the change in the orientation of the silicon tetrahedron, making the oxygen-silicon bond weaker as the dopant content increased and the Ca 2+ ions were released, thus altering the solubility of C 3 S [ 16 , 46 , 48 ]. By observing the polymorphic transition only in the in-plane bending (ν 2 ) and out-of-plane bending (ν 4 ) vibrational modes, it is possible to see the effect of the replacement of Ca 2+ ions by Zn 2+ and the saturation of the C 3 S solid solution (Fig. 4 ). As the ZnO content in C 3 S increases, the in-plane bending vibrations (ν 2 ) increase in number, with increases as the geometry of the crystalline system changes from T3 to M1 and M1 and then to R. Out-of-plane bending (ν 4 ) increases for the pure and doped samples up to 4.wt%. In the samples with 8.0 wt% and 10.0 wt% ZnO (Z4 and Z5) there is a decrease in the wave number due to the saturation of the solid solution and the accumulation of ZnO on the surface of the C 3 S crystal. 3.4. The effect of ZnO on the Raman spectra of C 3 S Raman spectrometry was carried out as a complementary analysis of the displacements generated in the ZnO-doped C 3 S polymorphs, which showed similar behavior to FTIR, as shown in Fig. 5 and Table 5 . The behavior of the Raman spectrum indicates greater intensity at 840, and 880cm − 1 which corresponds to the characteristic behavior of C 3 S [ 49 , 50 , 51 , 52 , 53 ]. The changes in behavior at 519, 542, 812, 840, 880 and 944cm − 1 indicate a change in the crystal structure [ 51 ] which is associated with the effect of the dopant contributing to the polymorphic transition of C 3 S. Table 5 – Main vibrations in the Raman spectra for differents polymorphs of C 3 S. Band Position (cm-¹) Assignment P Z1 Z2 Z3 Z4 Z5 440 Zn-O symmetrical bending 519 519 519 519 519 519 Symmetrical bending Ca-O 542 542 542 542 542 542 Asymmetric bending Si-O 610 Symmetrical stretching Si-O 641 812 840 840 840 840 840 840 880 880 880 880 880 880 944 Asymmetric stretching Si-O The pure phase (P) shows symmetrical bending at 519cm − 1 , and asymmetrical bending at 542cm − 1 this behavior is repeated for the other phases; however, symmetrical stretching at 610, 641, 812cm − 1 , and asymmetrical stretching at 944cm − 1 is only identified in the pure phase which corresponds to the T3 polymorph, a behavior similar to that found by [ 51 , 52 , 53 ]. The Z2 phase behaves similarly to the P phase (predominant M1 polymorph). However, the shoulder formed at 812cm − 1 and, the asymmetric stretching at 944cm − 1 disappears, and the intensity of the peak at 880cm − 1 is reduced. Phases Z2 and Z3 show similar spectra with predominant polymorphs at M1 and R with a peak reduction at 880cm − 1 . The Z4 phase (predominant R polymorph) shows behavior similar to the Z5 phase with a slight increase in intensity at 880cm − 1 with symmetrical stretching. However, the Z5 phase peaks with intensity at 400cm − 1 with symmetrical bending of the ZnO corresponding to the excess dopant in the crystal structure. 3.5. Calorimetry Figure 6 shows the heat flow and accumulated heat curves in the pure and doped C 3 S pastes during the first 72 hours of hydration. For all samples, the retardation effect occurs in comparison with the reference paste. In the analysis of heat curves for the pastes, it becomes evident that the heat released by the pure C 3 S paste surpasses that of all other phases, accompanied by a shorter induction period within the initial 72 hours. Upon comparing doped pastes, an observable trend emerges: with increasing dopant content, there is a corresponding decrease in heat release and an extension of the induction period. Furthermore, the accumulated heat remains lower than that of the pure paste, indicative of a subdued hydration rate across all doped pastes, consistent with findings in the literature [ 16 , 20 , 25 , 26 , 27 , 30 , 32 , 34 ]. The rationale behind this phenomenon has been discussed by [ 32 , 54 , 55 ], who propose that zinc exerts a retarding influence owing to the formation of heavy metal hydroxide Ca[Zn(OH) 3 H 2 O] 2 or the emergence of amorphous Zn(OH) 2 on grain surfaces. Throughout the hydration process, this hydroxide undergoes conversion, consuming calcium ions and mitigating the supersaturation of the C-S-H solution, thereby impeding the precipitation of crystals. However, the authors refrain from establishing a direct correlation between the levels of introduced Zn into the C 3 S. This impact is pronounced at 8.0wt% and 10.0wt%, where no discernible hydration process is observed. The compounds outlined in the literature were not identified in this study. Under the synthesis conditions of C 3 S and paste production, there exists a saturation point in dopant content, resulting in excess deposition of ZnO on grain surfaces. A portion of this excess reacts with calcium, silicon, and oxygen ions, forming a CaO 6 Si 2 Zn compound, while a percentage of CaO and C 3 S remains unreacted due to ZnO saturation, as illustrated in the XRD analysis depicted in Fig. 7 . Concerning the hydration process of the polymorphs, it can be seen that the order of reactivity obtained in this work is that the triclinic polymorphs are more reactive than the monoclinic polymorphs, which in turn are more reactive than the rhombohedral polymorphs. This result is similar to that found by [ 16 ], but it differs from what the literature shows: the monoclinic polymorphs are the most reactive [ 4 , 5 , 6 , 12 , 56 ]. However, this analysis can only be carried out by considering the effect of the dopant since its influence directly affects the hydration process and, depending on its content, inhibits the mechanism. Therefore, this technique cannot be used to classify the reactivity of polymorphs without considering the effect of the dopant. 4. Conclusion This study investigated the effect of high levels of ZnO doping on the polymorphism and reactivity of C 3 S using different techniques and analyzing its properties in the anhydrous and hydrated state. The results indicate that all the doping levels used in this work affected the behavior of C 3 S and its polymorphs about the pure phase. Stabilizing a single polymorph was only possible for the pure phase, and the phases doped with 8.0 and 10.0wt%. For the doped phases, two polymorphs of the three crystal systems (triclinic, monoclinic, and rhombohedral) were stabilized. Of the total seven polymorphs of C 3 S, this work stabilized four, these being T3, M1, M3, and R. Concerning the dopant content, for the synthesis conditions used, the maximum dopant content of ZnO indicated is 4.0wt%; for levels above this, there was saturation of the solution with surface deposition of ZnO on the C 3 S grains. The techniques of Fourier transform infrared spectroscopy and Raman spectroscopy proved to be efficient for identifying the effect of the dopant on the polymorphism of C 3 S and identifying the saturation of the solid solution by the excess dopant used. The behavior of the polymorphs regarding the doping technique in the hydration process indicated that all the doped phases showed a low hydration rate with a more extended induction period, and the pastes with dopant contents were 8.0 and 10. 0wt% no hydration process was identified. This behavior was due to the excess deposit of ZnO on the surface of the C 3 S grains, which, when it came into contact with water, inhibited the formation of C-S-H and reacted with the Ca and Si ions to form a CaO 6 Si 2 Zn compound. In terms of the reactivity of polymorphs in terms of the analysis of the hydration process, this study found that, unlike what has been found in the literature, the most reactive polymorphs are triclinic, followed by monoclinic and rhombohedral. However, to carry out this analysis, it is necessary to consider the effect of the dopant since its content will directly influence the speed of the hydration reaction and the inhibition of the process. Therefore, the isothermal calorimetry technique can only be used to classify the reactivity of polymorphs by considering the effect of the dopant. Declarations CRediT authorship contribution statement Queiroz, Luciana: Conceptualization, Investigation, Methodology, Writing – original draft. Barbosa, Waleska da Silva: Methodology & Review. Bergmann, Carlos: Supervision. Kirchheim, Ana Paula: Writing - Review & Editing, Supervision. Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgement The authors acknowledge the financial support of CAPES (Coordination for the Improvement of Higher Education Personnel). APK was sponsored by CNPq through the research fellowship 311893/2021-0. Thanks to Ms. Tailane Hauschild, Dr. Tania Basegio, and Dr. Marcia Machado from LACER - UFRGS for their help with the experiments. Thanks to Mr. Micael Rubens from LINCE – UFRGS for their support a calorimetry. References Supino S, Malandrino O, Testa M, Sica D (2016) Sustainability in the EU cement industry: the Italian and German experiences. 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Z für Kristallographie-Crystalline Mater 168:1–4. 197–212. https://doi.org/10.1524/zkri.1984.168.14.197 Urabe K, Nakano H, Morita H (2002) Structural modulations in monoclinic tricalcium silicate solid solutions doped with zinc oxide, M (I), M (II), and M (III). J Am Ceram Soc 85:423–429. https://doi.org/10.1111/j.1151-2916.2002.tb00106.x Urabe K, Shirakami T, Iwashima M (2000) Superstructure in a triclinic phase of tricalcium silicate. J Am Ceram Soc 83:1253–1258. https://doi.org/10.1111/j.1151-2916.2000.tb01363.x Segata M et al (2019) The effects of MgO, Na 2 O and SO 3 on industrial clinkering process: phase composition, polymorphism, microstructure and hydration, using a multidisciplinary approach. Mater Charact 155:109809. https://doi.org/10.1016/j.matchar.2019.109809 Ángeles G et al (2008) Crystal structure of low magnesium-content alite: Application to Rietveld quantitative phase analysis. 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J Am Ceram Soc 92:2337–2344. https://doi.org/10.1111/j.1551-2916.2009.03092.x Li X et al (2012) Statistical research on phase formation and modification of alite polymorphs in cement clinker with SO 3 and MgO. Constr Build Mater 37:548–555. https://doi.org/10.1016/j.conbuildmat.2012.07.099 Huang L et al (2018) Effects of aphthitalite on the formation of clinker minerals and hydration properties. Constr Build Mater 183:275–282. https://doi.org/10.1016/j.conbuildmat.2018.06.082 Zhang K et al (2019) Influence of ZnO-doping on the properties of high-ferrite cement clinker. Constr Build Mater 224:551–559. https://doi.org/10.1016/j.conbuildmat.2019.07.075 Kakali G, Parissakis G (1995) Investigation of the effect of Zn oxide on the formation of Portland cement clinker. Cem Concr Res 25:79–85. https://doi.org/10.1016/0008-8846(94)00115-F Fernandes WV et al (2020) Incorporation of minor constituents into Portland cement tricalcium silicate: bond valence assessment of the alite M1 polymorph crystal structure using synchrotron XRPD data. Cem Concr Res 136:106125. https://doi.org/10.1016/j.cemconres.2020.106125 Zhang Z et al (2023) Migration and solidification behavior of the semivolatile heavy metal elements Zn and Cd during high ferrite cement clinker (HFCC) calcination. Cem Concr Compos 139:105032. https://doi.org/10.1016/j.cemconcomp.2023.105032 Tao Y et al (2019) Understanding the zinc incorporation into silicate clinker during waste co-disposal of cement kiln: A density functional theory study. J Clean Prod 232:329–336. https://doi.org/10.1016/j.jclepro.2019.05.078 Li X, Scrivener KL (2022) Impact of ZnO on C 3 S hydration and CSH morphology at early ages. Cem Concr Res 154:106734. https://doi.org/10.1016/j.cemconres.2022.106734 Gineys N, Aouad G, Damidot D (2010) Managing trace elements in Portland cement–Part I: Interactions between cement paste and heavy metals added during mixing as soluble salts. Cem Concr Compos 32:563–570. https://doi.org/10.1016/j.cemconcomp.2010.06.002 Gineys N, Aouad G, Damidot D (2011) Managing trace elements in Portland cement–Part II: Comparison of two methods to incorporate Zn in a cement. Cem Concr Compos 33:629–636. https://doi.org/10.1016/j.cemconcomp.2011.03.008 Bordoloi D et al (1998) Influence of ZnO on clinkerization and properties of VSK cement. Cem Concr Res 28:329–333. https://doi.org/10.1016/S0008-8846(97)00266-4 Števula L, Petrovič J (1981) Hydration of polymorphic modification C 3 S. Cem Concr Res 11:183–190. https://doi.org/10.1016/0008-8846(81)90058-2 Souza M, Tramontin et al (2022) Single-burn clinkering of endodontic calcium silicate-based cements: Effects of ZnO in the C 3 S phase formation and hydration rate. Mater Lett 311:131556. https://doi.org/10.1016/j.matlet.2021.131556 Kolářová I (2014) Pavel Šiler, and František Šoukal. The influence of zinc on the hydration and compressive strength of Portland cement. Adv Mater Res 1000:43–46. https://doi.org/10.4028/www.scientific.net/AMR.1000.43 Stephan D et al (1999) High intakes of Cr, Ni, and Zn in clinker: Part I. Influence on burning process and formation of phases. Cem Concr Res 29:1949–1957. https://doi.org/10.1016/S0008-8846(99)00195-7 Zhu J et al (2021) Revealing the substitution preference of zinc in ordinary Portland cement clinker phases: A study from experiments and DFT calculations. J Hazard Mater 409:124504. https://doi.org/10.1016/j.jhazmat.2020.124504 Tao Y et al (2020) Atomic-level insights into the influence of zinc incorporation on clinker hydration reactivity. Open Ceram 1:100004. https://doi.org/10.1016/j.oceram.2020.100004 ODLER IVAN, M. I. R. SA, ABDUL-MAULA (1983) Polymorphism and hydration of tricalcium silicate doped with ZnO. J Am Ceram Soc 66:1–04. https://doi.org/10.1111/j.1151-2916.1983.tb09956.x Arliguie G, Ollivier JP, Grandet J (1982) Etude de l'effet retardateur du zinc sur l'hydratation de la pate de ciment Portland. Cem Concr Res 12:79–86. https://doi.org/10.1016/0008-8846(82)90101-6 Asavapisit S, Fowler G (1997) Cheeseman. Solution chemistry during cement hydration in the presence of metal hydroxide wastes. Cem Concr Res 27:1249–1260. https://doi.org/10.1016/S0008-8846(97)00109-9 Schindler AK, Steve R, Duke (2024) Braxton Galloway. Co-processing of end-of-life wind turbine blades in portland cement production. Waste Manag 182:207–214. https://doi.org/10.1016/j.wasman.2024.04.033 Yang Z et al (2018) Recycling of municipal solid waste incineration by-product for cement composites preparation. Constr Build Mater 162:794–801. https://doi.org/10.1016/j.conbuildmat.2017.12.081 Bogush AA et al (2020) Co-processing of raw and washed air pollution control residues from energy-from-waste facilities in the cement kiln. J Clean Prod 254:119924. https://doi.org/10.1016/j.jclepro.2019.119924 Baidya R, Ghosh SK (2016) Parlikar. Co-processing of industrial waste in cement kiln–a robust system for material and energy recovery. Procedia Environ Sci 31:309–317. https://doi.org/10.1016/j.proenv.2016.02.041 Scherrer P (1918) Nachr Ges wiss goettingen. Math Phys 2:98–100 Gawlicki M, Czamarska D (1992) Effect of ZnO on the hydration of Portland cement. J Therm Anal Calorim 38(9):2157–2161. https://doi.org/10.1007/BF01979629 Chung R-J et al (2003) Effect of hydroxyapatite nano-particle on properties of modified tricalcium silicate bone cements. J Med Biol Eng 23(4):199–204 Li J et al (2021) Effect of ZnO on the whiteness of white Portland cement clinker. Cem Concr Res 143:106372. https://doi.org/10.1016/j.cemconres.2021.106372 Wang S et al (2012) Effect of strontium dioxide on the crystal structure and properties of tricalcium silicate. Advances in cement research 24.6 : 359–364. https://doi.org/10.1680/adcr.11.00035 Suzuki K et al (1986) Effect of Na, K and Fe on the formation of α-and β-Ca 2 SiO 4 . Cem Concr Res 16:885–892. https://doi.org/10.1016/0008-8846(86)90012-8 Ren X, Zhang W, Ye J (2017) FTIR study on the polymorphic structure of tricalcium silicate. Cem Concr Res 99:129–136. https://doi.org/10.1016/0008-8846(86)90012-8 Timón V et al (2023) Infrared and Raman vibrational modelling of β-C 2 S and C 3 S compounds. Cem Concr Res 169:107162. https://doi.org/10.1016/j.cemconres.2023.107162 Krol M et al (2022) Full spectroscopic characterization of clinker minerals (anhydrous cement). J Mol Struct 1255:132454. https://doi.org/10.1016/j.molstruc.2022.132454 Ghosh SN (2001) IR spectroscopy. Handbook of Analytical Techniques in Concrete Science and Technology, Principles, Techniques, and Applications Potgieter-Vermaak SS, Potgieter JH, Van Grieken R (2006) The application of Raman spectrometry to investigate and characterize cement, Part I: A review. Cem Concr Res 36:656–662. https://doi.org/10.1016/j.cemconres.2005.09.008 Potgieter-Vermaak SS et al (2006) The application of Raman spectrometry to the investigation of cement: Part II: A micro-Raman study of OPC, slag and fly ash. Cem Concr Res 36:663–670. https://doi.org/10.1016/j.cemconres.2005.09.010 Weeks C, Hand RJ, Sharp JH (2008) Retardation of cement hydration caused by heavy metals present in ISF slag used as aggregate. Cem Concr Compos 30:970–978. https://doi.org/10.1016/j.cemconcomp.2008.07.005 Chen QY et al (2009) Immobilisation of heavy metal in cement-based solidification/stabilisation: A review. Waste Manag 29:390–403. https://doi.org/10.1016/j.wasman.2008.01.019 Saritas K, Ataca C (2015) Grossman. Predicting electronic structure in tricalcium silicate phases with impurities using first-principles. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4745258","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":335406609,"identity":"cd2f6988-608f-446e-beb3-a0fd145f6e39","order_by":0,"name":"Luciana Queiroz","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA+UlEQVRIiWNgGAWjYBACPiA+AOOAGHJgxgM8WtjQtRiDGQkEtKCAxAYQiVeLRPLDAz932Mnz3Ug+eLiioi59ftjhh0Bb7OR0G3BpSTM42Hsm2XDmjbSEg2fOsOVuvJ1mANSSbGx2AJeWHIYDvG3MCQY3cgwONrbx5G6cnQDSciBxGx4tB/+21QO15H8AapFIN5yd/oGglsO8bYdBtjAAtRgkyEvnELCF55nBYdm244YzzzwzONhwJsFwg3ROwYEEA9x+4WdPfvzxbVu1PN9xIKOhok5efnb65g8fKuzkcGlBAJgCAzDDgJByZC3yDcSoHgWjYBSMgpEEAAXYZlfFci7eAAAAAElFTkSuQmCC","orcid":"https://orcid.org/0000-0002-1285-5271","institution":"UFRGS: Universidade Federal do Rio Grande do Sul","correspondingAuthor":true,"prefix":"","firstName":"Luciana","middleName":"","lastName":"Queiroz","suffix":""},{"id":335406610,"identity":"a16b2e61-20fd-4de3-bc83-a7c2dac55af6","order_by":1,"name":"Waleska Barbosa","email":"","orcid":"","institution":"Positivo University: Universidade Positivo","correspondingAuthor":false,"prefix":"","firstName":"Waleska","middleName":"","lastName":"Barbosa","suffix":""},{"id":335406611,"identity":"8358d218-9a1c-462f-a5c7-63ee345b56fb","order_by":2,"name":"Ana Paula Kirchheim","email":"","orcid":"","institution":"UFRGS: Universidade Federal do Rio Grande do Sul","correspondingAuthor":false,"prefix":"","firstName":"Ana","middleName":"Paula","lastName":"Kirchheim","suffix":""},{"id":335406612,"identity":"b520d836-e250-4188-baf6-66d84c401cc9","order_by":3,"name":"Carlos Bergmann","email":"","orcid":"","institution":"UFRGS: Universidade Federal do Rio Grande do Sul","correspondingAuthor":false,"prefix":"","firstName":"Carlos","middleName":"","lastName":"Bergmann","suffix":""}],"badges":[],"createdAt":"2024-07-15 20:13:00","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4745258/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4745258/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1617/s11527-025-02675-0","type":"published","date":"2025-05-13T15:58:10+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":63546204,"identity":"4b5fdcad-b4b4-4442-9a61-f8097ce789a7","added_by":"auto","created_at":"2024-08-29 11:23:33","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":35563,"visible":true,"origin":"","legend":"\u003cp\u003ePadrão cristalográfico de cada fase.\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-4745258/v1/6a2074ff988ad086c3e0c6a0.png"},{"id":63545605,"identity":"ef8b0cdb-5a8d-4606-9c49-8dd0f1c50176","added_by":"auto","created_at":"2024-08-29 11:15:33","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":37535,"visible":true,"origin":"","legend":"\u003cp\u003eEffect of ZnO on C\u003csub\u003e3\u003c/sub\u003eS polymorphism.\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-4745258/v1/4cb22f116ec8c7d03b1b54a6.png"},{"id":63546202,"identity":"77b6a704-289d-4cee-b62a-b157847609f9","added_by":"auto","created_at":"2024-08-29 11:23:33","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":30666,"visible":true,"origin":"","legend":"\u003cp\u003ePolymorph formed in each phase.\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-4745258/v1/dbd498216629366b78570105.png"},{"id":63546885,"identity":"9f603363-d527-4c1e-a1a4-f837f4bcdc4d","added_by":"auto","created_at":"2024-08-29 11:31:33","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":68080,"visible":true,"origin":"","legend":"\u003cp\u003eFTIR spectrum of doped C\u003csub\u003e3\u003c/sub\u003eS.\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-4745258/v1/5f1e0d94ae1df5bc0cb0d71e.png"},{"id":63545600,"identity":"c271ccaa-2c6a-46fa-8e94-28331ad6dd9f","added_by":"auto","created_at":"2024-08-29 11:15:33","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":43519,"visible":true,"origin":"","legend":"\u003cp\u003eRaman Shift of doped C\u003csub\u003e3\u003c/sub\u003eS.\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-4745258/v1/aa4a0cf377ecf6b77cc6178d.png"},{"id":63545603,"identity":"0353fe04-9d4a-49d7-abce-6ee024a27c18","added_by":"auto","created_at":"2024-08-29 11:15:33","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":18391,"visible":true,"origin":"","legend":"\u003cp\u003eCurves in “a” are the hydration heat flow and “b” cumulative heat of samples.\u003c/p\u003e","description":"","filename":"floatimage6.png","url":"https://assets-eu.researchsquare.com/files/rs-4745258/v1/ff5f1bff4fc8b66c6871bc2a.png"},{"id":63545606,"identity":"d07ef12a-d30d-4aa1-b21a-1b686e3108ee","added_by":"auto","created_at":"2024-08-29 11:15:33","extension":"jpeg","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":363893,"visible":true,"origin":"","legend":"\u003cp\u003eXRD of hydrated C\u003csub\u003e3\u003c/sub\u003eS products doped with 8.0 and 10.0 wt%.\u003c/p\u003e","description":"","filename":"floatimage7.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-4745258/v1/03db2ca1673b6b8a24c883fc.jpeg"},{"id":83067884,"identity":"43d88a10-a7c3-4297-b78a-376054f99ace","added_by":"auto","created_at":"2025-05-19 16:07:32","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1433818,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4745258/v1/4ef70a37-9f69-4fef-8185-a26c46f475bd.pdf"}],"financialInterests":"","formattedTitle":"The use of ZnO for the stabilisation of C3S polymorphs","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003ePortland cement is the most important material in construction and civil engineering. It is the primary building material worldwide and has played a fundamental role as a building material throughout the history of civilization and urbanization, being used in different applications such as concrete, precast concrete, mortars for cladding and laying blocks, adhesive mortars, among others [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]\u003c/p\u003e \u003cp\u003eAccording to [\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e], clinker is mainly composed of the phases tricalcium silicate (C\u003csub\u003e3\u003c/sub\u003eS), which accounts for between 50 and 70% of its volume, dicalcium silicate (C\u003csub\u003e2\u003c/sub\u003eS) from 15 to 30%, tricalcium aluminate (C\u003csub\u003e3\u003c/sub\u003eA) in levels of 5 to 10%, and finally tetra calcium ferroaluminate (C\u003csub\u003e4\u003c/sub\u003eAF), which varies between 5 and 15%.\u003c/p\u003e \u003cp\u003eTricalcium silicate plays an important role in the mechanical strength properties of early age cement. Its nomenclature is found in the literature in two forms: the first comes from the process of synthesising a pure phase, free of any contamination, called tricalcium silicate (C\u003csub\u003e3\u003c/sub\u003eS), and the second for phases that have impurities either from contamination during the burning process (in co-processing) or the use of mineralisers or in the presence of dopant ions, which is called alite [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eThe pure tricalcium silicate (C\u003csub\u003e3\u003c/sub\u003eS) is obtained from a solid solution composed of CaO and SiO\u003csub\u003e2\u003c/sub\u003e at a molar ratio of 3:1 sintered at a temperature of 1450\u0026deg;C, and its crystal structure is composed of SiO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e4\u0026minus;\u003c/sup\u003e tetrahedra linked by Ca2\u0026thinsp;+\u0026thinsp;ions, which are octahedrally coordinated by oxygen ions [\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e, \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e, \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eC\u003csub\u003e3\u003c/sub\u003eS is divided into three crystalline systems, which in turn have seven polymorphs classified as T1, T2, T3, M1, M2, M3 and (R) [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e, \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e]. During the synthesis process, the solid solution of C\u003csub\u003e3\u003c/sub\u003eS crystallises initially in the rhombohedral system (R), then during the cooling process, it transforms into the monoclinic system (M) and/or the triclinic system (T) when no dopant ions are incorporated to stabilise the monoclinic system [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e]. The polymorphic transition temperature is very close from one polymorph to the next, making most of them unstable at room temperature.\u003c/p\u003e \u003cp\u003eThe doping technique is one of the resources used to stabilise polymorphs at room temperature. It is characterised by the insertion of dopant ions into the crystal structure of C\u003csub\u003e3\u003c/sub\u003eS, causing minor imperfections or displacements that alter the crystal lattice, stabilising it. To apply this technique, the type of dopant ion, its content, and the synthesis temperature must be determined. Those factors affect the technique's efficiency [ 8, 9, 10, 11, 12, 13, 14].\u003c/p\u003e \u003cp\u003eDespite the recurrent use of the dopping technique in synthesising C\u003csub\u003e3\u003c/sub\u003eS, there is a lack of understanding of its efficiency. Since there is no consensus in the literature on which properties will be modified, the synthesis temperature, or the ideal doping content. In a study carried out by [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e], different types of heavy metals were used as dopants at levels of 0.1, 0.5, 1.0, and 3.0 wt%, sintered at a temperature of 1450\u0026ordm;C, where polymorphs T1, T2, M1, M2, and R were stabilised. However, [\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e] doped C\u003csub\u003e3\u003c/sub\u003eS with Ba ions at a temperature of 1600\u0026ordm;C and stabilised polymorphs T1, T2 and T3. These are just a few examples found in the literature.\u003c/p\u003e \u003cp\u003eStudies carried out from the 1960s to the present day refer to the use of dopants to stabilise C\u003csub\u003e3\u003c/sub\u003eS polymorphs and indicate that the technique alters different properties of C3S, such as the liquid phase's viscosity, grain growth, surface area, free lime content, average crystallite size, heat of hydration, and amount of C-S-H [\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e, \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e, \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e, \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e, \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e, \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e, \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eZinc, either in oxide or salt form, is the most widely adopted dopant ion in synthesising C\u003csub\u003e3\u003c/sub\u003eS or solution during hydration [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e, \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e, \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e, \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e, \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. Its effect in the doping process of C\u003csub\u003e3\u003c/sub\u003eS is associated with accelerating sintering by acting as a mineraliser [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e, \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e, \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e]. It can reduce the synthesis temperature from 1450\u0026ordm;C to 1000\u0026ordm;C [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e, \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e, \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e, \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e, \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e]. This temperature reduction is due to the combination of CaO with Zn [\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e, \u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e, \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e, \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e], and there is also a polymorphic transition depending on the Zn content used in the doping.\u003c/p\u003e \u003cp\u003eThe main effect of using Zn as a dopant is in the hydration reaction of C\u003csub\u003e3\u003c/sub\u003eS. Studies have shown that contents above 1.0wt% are enough to promote delays in the hydration process due to the formation of new compounds such as zinc hydroxide or Ca[Zn(OH)\u003csub\u003e3\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003eO]\u003csub\u003e2\u003c/sub\u003e, which causes a reduction in the mechanical properties such as compressive strength [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e, \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e, \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e, \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e, \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e, \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e, \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e, \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e, \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eAlthough there have been negative impacts on the use of Zn as a dopant, the progress of studies on the effect of co-processing [\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e, \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e, \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e, \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e] waste as a substitute energy source for the production of Portland cement shows that there is little data on the concentration of the chemical elements that are inserted into the crystal structure and their effect on the properties of Portland cement.\u003c/p\u003e \u003cp\u003eIn studies carried out by [\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e], samples from 17 rotary kilns of Portland clinker production plants were collected, and it identified that around 74\u0026ndash;99% of zinc is incorporated into the clinker; this impurity originates from the co-processing of scrap tires; however, the authors do not show which properties have been altered. On the other hand, [\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e] identified a total of 4520.02 ppm of zinc in oily residues used in co-processing, not showing the values incorporated into the crystalline structure and modifications in the phases of Portland cement.\u003c/p\u003e \u003cp\u003eThus, the main objective of this work was to study the doping technique through the incorporation of zinc in oxide form (ZnO) at high levels and to evaluate its effect on the polymorphism and reactivity of C\u003csub\u003e3\u003c/sub\u003eS. The composition of the phases (pure and doped) was characterised by X-ray diffraction (XRD), and the average crystallite size was calculated using the Debye-Scherrer equation [\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e]. The effect of doping on chemical bonds and displacements in the crystalline structure was identified by Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy (RAMAN); the hydration process and hydrated compounds were evaluated using isothermal calorimetry and X-ray diffraction (XRD) techniques.\u003c/p\u003e"},{"header":"2. Materials and methods","content":"\u003cp\u003eThe synthesis of pure C\u003csub\u003e3\u003c/sub\u003eS used CaCO\u003csub\u003e3\u003c/sub\u003e and SiO\u003csub\u003e2\u003c/sub\u003e (P.A.) in a molar ratio of 3:1, and the doping used ZnO (P.A.) at levels of 1.5, 2.0, 4.0, 8.0, and 10.0 wt% (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). The dry materials were mixed manually for five minutes, and Milli Q water was added until they reached a paste-like consistency, and 2.5x5.0cm specimens were moulded and dried for 72 hours at a temperature of 100\u0026deg;C\u0026thinsp;\u0026plusmn;\u0026thinsp;5\u0026deg;C. After drying, the material was sintered at 1500\u0026deg;C for six hours and cooled abruptly by mechanical ventilation to room temperature. Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e shows the chemical composition and physical properties of the reagents.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003e\u0026ndash; Chemical composition of the raw materials.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003eConstituent\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eCaCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eSiO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eZnO\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003eCaCO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e99.84\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003eSiO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e99.88\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003eZnO\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e99.00\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003eCl\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.001\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.001\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003eF\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.0015\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003eNO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.003\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003eSO\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003eNH\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.003\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003ePb\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.001\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.003\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.005\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003eFe\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.003\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.02\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.001\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003eBa\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003eMg\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.02\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003eK\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003eNa\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"6\" nameend=\"c6\" namest=\"c1\"\u003e \u003cp\u003e\u003cb\u003eProperty\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003eSurface area (m\u0026sup2;/g)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e16.190\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e214.183\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e8.371\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003eDv 90 (\u0026micro;m)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e5.69\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e120.61\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3.47\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003eDv 50 (\u0026micro;m)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e2.87\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e73.08\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1,02\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"3\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003eDv 10 (\u0026micro;m)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.22\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e33.89\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.26\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"6\" nameend=\"c6\" namest=\"c1\"\u003e \u003cp\u003e\u003cb\u003eZnO Doped (wt%)\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eP\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cb\u003eZ1\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e\u003cb\u003eZ2\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e\u003cb\u003eZ3\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e\u003cb\u003eZ4\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e\u003cb\u003eZ5\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e4.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e8.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e10.0\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eThe X-ray diffraction technique, Phillips model X'Pert MDP, using Cu-Kα radiation (λ\u0026thinsp;=\u0026thinsp;1.54184 \u0026Aring;) in analysis conditions in the 2θ range from 10 to 70\u0026deg;, step 0.05\u0026deg;/1s, slits: \u0026frac12;\u0026deg; and window: 20 mm, for analysis of phase transformation and composition. The Rietveld method and the ICSD database for quantitative analysis of the crystalline phases to calculate the average crystallite size calculation. The Debye-Scherrer equation (Eq.\u0026nbsp;1) applied to calculate the average crystallite size.\u003cdiv class=\"BlockQuote\"\u003e\u003cp\u003e \u003cspan class=\"InlineEquation\"\u003e \u003cspan class=\"mathinline\"\u003e\\(\\:\\text{D}=\\frac{\\text{K}\\text{*}{\\lambda\\:}}{\\text{B}\\text{*}\\text{c}\\text{o}\\text{s}{{\\theta\\:}}_{\\text{B}}}\\)\u003c/span\u003e \u003c/span\u003e (Eq.\u0026nbsp;1)\u003c/p\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eWhere D is the average diameter of the particles, K is a constant that depends on the shape of the particles (sphere\u0026thinsp;=\u0026thinsp;0.94), λ is the wavelength of the electromagnetic radiation, θ is the diffraction angle, and β (2θ) is the width at half the height of the diffraction peak.\u003c/p\u003e \u003cp\u003eTo analyse the changes in surface chemical bonds in the 4000 to 400cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e region caused by the presence and concentration of the dopant, Fourier transform infrared spectroscopy (FTIR) was carried out using a Shimadzu IRAFFINITY 1 spectrometer with a resolution of 4cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, performing 16 scans per sample. Raman spectroscopy was used as a complementary analysis using a micro\u0026ndash;Raman Spectrometer System, Model inVia (Renishaw), in the 100 to 800cm-\u003csup\u003e1\u003c/sup\u003e range with an excitation wavelength of 532 nm and a laser power of 0.5 mW.\u003c/p\u003e \u003cp\u003eAn isothermal calorimetry test was carried out using TAM Air equipment (TA Instruments) with eight channels capacity to assess the hydrated compounds' hydration kinetics. Samples weighing 2g were mixed and homogenised with distilled water at an a/s ratio 0.5. Heat flow (thermal energy, mW/g of solids) and accumulated heat (integral of thermal energy, J/g of solids) were recorded for up to 3 days at 22\u0026deg;C.\u003c/p\u003e"},{"header":"3. Results and discussion","content":"\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e3.1. Mineralogical composition\u003c/h2\u003e \u003cp\u003eFrom the X-ray diffraction (XRD) patterns shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, the effect of zinc on the phase composition and polymorphism of C\u003csub\u003e3\u003c/sub\u003eS can be seen. The phases identified were C\u003csub\u003e3\u003c/sub\u003eS (ICSD# 004331 and # 162744), CaO (ICSD# 75786) and ZnO (ICSD# 193696).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAs shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, as the dosage of ZnO increases, there is a change in the C\u003csub\u003e3\u003c/sub\u003eS peaks and an increase in the intensity of the peak (37\u0026ordm;) characteristic of the ZnO phase. In the Z4 and Z5 samples, 7.1% and 14.2% of ZnO was formed, respectively, which was not incorporated into the C\u003csub\u003e3\u003c/sub\u003eS structure, a similar result found by [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eThe formation of ZnO in samples T4 and T5 is related to the excess content in the systems, forming a supersaturated solid solution. This behavior directly influenced the C\u003csub\u003e3\u003c/sub\u003eS content, where there was a reduction of 11.4% and 19.5% compared to the pure sample (P), indicating that the optimum doping content for the C\u003csub\u003e3\u003c/sub\u003eS synthesis configuration in this work is up to 4.0wt% since in the other samples (Z1, Z2, and Z3) there was no ZnO formation, and its content was inserted entirely into the C\u003csub\u003e3\u003c/sub\u003eS crystal structure.\u003c/p\u003e \u003cp\u003eThe f-CaO content is directly proportional to the increase in ZnO content and aligns with the literature [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e, \u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e, \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e]. As the ZnO content increases, there is a significant increase in the f-CaO content of up to 5.4% in the Z5 sample compared to the P sample. This behavior is directly related to the Ca\u003csup\u003e2+\u003c/sup\u003e ion substitution by Zn\u003csup\u003e2+\u003c/sup\u003e due to the weak binding energy between oxygen and calcium when compared to silicon and oxygen [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e, \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e, \u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e]. Furthermore, when considering a substitution reaction, the radii of Zn\u003csup\u003e2+\u003c/sup\u003e and Ca\u003csup\u003e2+\u003c/sup\u003e are 0.074 and 0.099nm, respectively. This favors the formation of a solid substitutional solution [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e, \u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e].\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e3.2. Stabilised polymorph\u003c/h2\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e shows the polymorphic transition with changes in the peaks (31\u0026ordm; and 32\u0026ordm;; 51\u0026ordm; and 52\u0026ordm;) due to the effect of ZnO on the crystal structure of C\u003csub\u003e3\u003c/sub\u003eS. Only samples P, Z4, and Z5 stabilised a single polymorph, T3 and rhombohedral.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe polymorphic transition from the triclinic to the monoclinic system occurs from the insertion of 1.5 wt% ZnO (sample Z1). However, when the content increases, the phase formed is composed of the T3 and M1 polymorphs, showing an instability in the synthesis process that may have been generated during cooling since the transition temperature of the polymorphs is close [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]. The firing temperature was constant for all the samples.\u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e shows the percentage of each polymorph, identifying the T3, M1, M3, and R polymorphs. For quantitative analysis, the structural models proposed for the T3 polymorph (ICSD# 004331, and # 162744); M1 polymorph (ICSD# 81100); M3 polymorph (ICSD# 64759); R polymorph (ICSD# 22501, and 24625).Because polymorphs are metastable at room temperature, the highest percentage of polymorph identified was considered for this analysis, classifying it as the predominant polymorph.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe pure phase is composed of 98.7% of the T3 polymorph. For the doped phases, there is a polymorphic transition with increasing zinc oxide content of 54.8% of M1 and 43.8% of M3 for sample Z1, 23.5% of T3, and 75.2% of M1 for Z2, 25.3% of M3 and 72% of R for sample Z3 and samples Z4 and Z5 only the R polymorph was identified in 86.5% and 78.4%, respectively.\u003c/p\u003e \u003cp\u003eThere is no consensus on stabilising specific polymorphs based on the dopant content, which reflects what is identified in the literature. Some studies report that increasing Zn in the system does not change the polymorph formed [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e]. In contrast, others have managed to stabilise several polymorphs with the same dopant content [\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e], and studies show the polymorphic transition or stabilisation of different polymorphs with different doping levels, as seen in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. The doping range used in this work aligns with some studies, such as [\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e] and [\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003e\u0026ndash; Stabilized Polymorph.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"8\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eRef.\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"7\" nameend=\"c8\" namest=\"c2\"\u003e \u003cp\u003eStabilized Polymorph\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eT1\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eT2\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eT3\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eM1\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eM2\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eM3\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c8\"\u003e \u003cp\u003eR\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e[\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e3.0\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e[\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e3.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e4.8 and 6.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e6.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e6.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e[\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.084\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.415 and 0.817\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e2.416\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e[\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.0\u0026ndash;3.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.5\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e[\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.2, 0.5, 0.8 and 1.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e[\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.0 and 3.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e[\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e]*\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1.0\u0026ndash;4.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1.0\u0026ndash;4.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e1.0\u0026ndash;4.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e[\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.08\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.38\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e1.88\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e3.75\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e[\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2.0, 4.0 and 6.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e[\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.03\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.4\u0026ndash;0.9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e1.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e1.5 and 1.6\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e[\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e]*\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.0, 3.0 and 5.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e1.0, 3.0 and 5.0\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e*Different polymorphs were identified for all contents, with differences only in the concentration of each polymorph.\u003c/p\u003e \u003cp\u003eThe stability of a single polymorph is a complex activity, given the entire synthesis process involved. In order to stabilize the polymorph, it is necessary to consider the type and content of the dopant used and the type of solid solution that will be formed.\u003c/p\u003e \u003cp\u003eSolid solutions fall into two categories: interstitial or substitutional. In doping a solid solution to introduce an impurity into the interstitial spaces, understanding the size of the vacancy created at the synthesis temperature or determining if the interstice matches the impurity size becomes crucial. Conversely, when dealing with a substitutional solid solution, the physicochemical properties of the impurity need to align with those of the ion it substitutes. These properties include valence, electronegativity, crystalline system, unit cell volume, and more [\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e, \u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e[\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e] explains that as the Zn content increased, the solid solution changed from substitutional to interstitial, keeping the synthesis temperature at 1400\u0026ordm;C. However, [\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e] clarify that the crystalline defects of C\u003csub\u003e3\u003c/sub\u003eS caused by the insertion of impurities with the same valence will result in the formation of substitutional defects, with the size of the ion being a decisive factor for the reaction, considering that an ion radius of less than 15% will result in the formation of a substitutional solid solution.\u003c/p\u003e \u003cp\u003eThe temperature range synthesising Zn-doped C\u003csub\u003e3\u003c/sub\u003eS varies between 1000\u0026ordm;C and 1600\u0026ordm;C [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e, \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e, \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e, \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e, \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e]. The choice of temperature will guarantee the efficiency of the doping through the defects created and the incorporation of the ion into the crystalline structure. Although Zn has a mineralising effect [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e, \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e, \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e, \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e, \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e] with a reduction in temperature, this effect may prevent the ion from entering the crystal structure, and the excess will be available in the form of ZnO [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e, \u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eAnother change observed due to doping C\u003csub\u003e3\u003c/sub\u003eS with ZnO is the average crystallite size (Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). The insertion of ZnO into the crystalline structure of C\u003csub\u003e3\u003c/sub\u003eS leads to a slight reduction in the average crystallite size between samples Z1 and Z2 when compared to sample P, which can be explained by the complete insertion of the Zn\u003csup\u003e2+\u003c/sup\u003e ion into the crystalline structure due to the substitution of Ca\u003csup\u003e2+\u003c/sup\u003e for Zn\u003csup\u003e2+\u003c/sup\u003e in the formation of the substitutional solid solution [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab3\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003e\u0026ndash; Crystallite size.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"7\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eP\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eZ1\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eZ2\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eZ3\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eZ4\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eZ5\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003ePredominant polymorph\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eT3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eM1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eM1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eR\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003eR\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eR\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eCrystallite size (nm)\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e56.735\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e51.859\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e51.998\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e47.281\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e47.283\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e47.176\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eHowever, as the dopant content increases, the average crystallite size in samples Z3, Z4, and Z5 is reduced by approximately 9.5% compared to sample P, the same behavior found by [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e]. This implies that the excess dopant caused minor defects in the network, transforming the interstitial solid solution into a substitutional one, as observed by [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e].\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e3.3. The effect of ZnO on the IR spectra of C\u003csub\u003e3\u003c/sub\u003eS\u003c/h2\u003e \u003cp\u003eThe C\u003csub\u003e3\u003c/sub\u003eS formed comprises silicon tetrahedra, calcium, and zinc oxides, where the infrared absorption bands are in the 400 to 4000cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e region. The [SiO]\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e4\u0026minus;\u003c/sup\u003e tetrahedra have four fundamental vibration modes: ν\u003csub\u003e1\u003c/sub\u003e symmetrical stretching, ν\u003csub\u003e3\u003c/sub\u003e asymmetrical stretching, ν\u003csub\u003e2\u003c/sub\u003e in-plane bending, and ν\u003csub\u003e4\u003c/sub\u003e out-of-plane bending [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e, \u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e]. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e shows the behavior of the IR spectra of the C\u003csub\u003e3\u003c/sub\u003eS polymorphs doped with different levels of ZnO, and Table\u0026nbsp;\u003cspan refid=\"Tab4\" class=\"InternalRef\"\u003e4\u003c/span\u003e shows the vibration bands.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab4\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 4\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003e\u0026ndash; FTIR spectra assignments for different polymorphs of C\u003csub\u003e3\u003c/sub\u003eS.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003ePhase\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003ePredominant polymorph\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"4\" nameend=\"c6\" namest=\"c3\"\u003e \u003cp\u003eAbsorption IR band/cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eν\u003csub\u003e1\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eν\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eν\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eν\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eP\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eT3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e859, 814\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e492, 461, 434, 418\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1050, 1008\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e516\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZ1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eM1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e855\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e490, 461, 427, 418\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1050, 1017\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e516\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZ2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eM1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e855\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e490, 453, 439, 418\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1050, 1014\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e516\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZ3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eR\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e855\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e487, 459, 430, 418\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1050, 1014\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e516\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZ4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eR\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e494, 459, 469, 423, 406\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1050, 1014\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e511\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZ5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eR\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e492, 467, 452, 430, 418\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1050, 1015\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e511\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eThe pure phase of C\u003csub\u003e3\u003c/sub\u003eS (T3) shows symmetric stretching (ν\u003csub\u003e1\u003c/sub\u003e) of the silicon tetrahedra [SiO]\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e4\u0026minus;\u003c/sup\u003e at 859 and 814cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e; asymmetric stretching (ν\u003csub\u003e3\u003c/sub\u003e) at 1050 and 1008cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e; in-plane bending (ν\u003csub\u003e2\u003c/sub\u003e) at 492, 461, 434 and 318cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e; out-of-plane bending (ν\u003csub\u003e4\u003c/sub\u003e) at 516cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e; The region of the vibrational modes are in agreement with the literature [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e, \u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e]. The monoclinic crystalline system (Z1 and Z2) showed the four vibrational modes (Table\u0026nbsp;\u003cspan refid=\"Tab4\" class=\"InternalRef\"\u003e4\u003c/span\u003e) with changes in the asymmetric stretching (ν\u003csub\u003e3\u003c/sub\u003e) at 1050 and 1017cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e of the Z1 sample about the Z2 sample due to the polymorphic composition since the Z2 sample shows a percentage of T3 (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e ), this behavior is also observed in the in-plane bending vibrational mode (ν\u003csub\u003e2\u003c/sub\u003e) at 490, 461, 427 and 418cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e corroborating the results presented in the XRD (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e). [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e] also described that it is possible to observe that increasing the ZnO content alters the symmetry of C\u003csub\u003e3\u003c/sub\u003eS due to the substitution of Ca\u003csup\u003e2+\u003c/sup\u003e ions.\u003c/p\u003e \u003cp\u003eThe R polymorph observed in samples Z3, Z4, and Z5 showed changes in vibrational modes. Sample Z3 showed all four vibrational modes, but it should be noted that its composition is 25.3% M3 and 72% R, with the symmetrical stretching (ν\u003csub\u003e1\u003c/sub\u003e) of the [SiO]\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e4\u0026minus;\u003c/sup\u003esilicon tetrahedra at 855cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e corresponding to the M3 polymorph. Samples Z4 and Z5, on the other hand, did not show this due to the change in the orientation of the silicon tetrahedron, making the oxygen-silicon bond weaker as the dopant content increased and the Ca\u003csup\u003e2+\u003c/sup\u003e ions were released, thus altering the solubility of C\u003csub\u003e3\u003c/sub\u003eS [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e, \u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e, \u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e]. By observing the polymorphic transition only in the in-plane bending (ν\u003csub\u003e2\u003c/sub\u003e) and out-of-plane bending (ν\u003csub\u003e4\u003c/sub\u003e) vibrational modes, it is possible to see the effect of the replacement of Ca\u003csup\u003e2+\u003c/sup\u003e ions by Zn\u003csup\u003e2+\u003c/sup\u003e and the saturation of the C\u003csub\u003e3\u003c/sub\u003eS solid solution (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e). As the ZnO content in C\u003csub\u003e3\u003c/sub\u003eS increases, the in-plane bending vibrations (ν\u003csub\u003e2\u003c/sub\u003e) increase in number, with increases as the geometry of the crystalline system changes from T3 to M1 and M1 and then to R. Out-of-plane bending (ν\u003csub\u003e4\u003c/sub\u003e) increases for the pure and doped samples up to 4.wt%. In the samples with 8.0 wt% and 10.0 wt% ZnO (Z4 and Z5) there is a decrease in the wave number due to the saturation of the solid solution and the accumulation of ZnO on the surface of the C\u003csub\u003e3\u003c/sub\u003eS crystal.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e3.4. The effect of ZnO on the Raman spectra of C\u003csub\u003e3\u003c/sub\u003eS\u003c/h2\u003e \u003cp\u003eRaman spectrometry was carried out as a complementary analysis of the displacements generated in the ZnO-doped C\u003csub\u003e3\u003c/sub\u003eS polymorphs, which showed similar behavior to FTIR, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e and Table\u0026nbsp;\u003cspan refid=\"Tab5\" class=\"InternalRef\"\u003e5\u003c/span\u003e. The behavior of the Raman spectrum indicates greater intensity at 840, and 880cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003ewhich corresponds to the characteristic behavior of C\u003csub\u003e3\u003c/sub\u003eS [\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e, \u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e, \u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e, \u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e, \u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e]. The changes in behavior at 519, 542, 812, 840, 880 and 944cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e indicate a change in the crystal structure [\u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e] which is associated with the effect of the dopant contributing to the polymorphic transition of C\u003csub\u003e3\u003c/sub\u003eS.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab5\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 5\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003e\u0026ndash; Main vibrations in the Raman spectra for differents polymorphs of C\u003csub\u003e3\u003c/sub\u003eS.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"7\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colspan=\"6\" nameend=\"c6\" namest=\"c1\"\u003e \u003cp\u003eBand Position (cm-\u0026sup1;)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eAssignment\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eP\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eZ1\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eZ2\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eZ3\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eZ4\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eZ5\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e440\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eZn-O symmetrical bending\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e519\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e519\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e519\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e519\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e519\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e519\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eSymmetrical bending Ca-O\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e542\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e542\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e542\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e542\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e542\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e542\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eAsymmetric bending Si-O\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e610\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\" morerows=\"4\" rowspan=\"5\"\u003e \u003cp\u003eSymmetrical stretching Si-O\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e641\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e812\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e840\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e840\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e840\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e840\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e840\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e840\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e880\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e880\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e880\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e880\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e880\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e880\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e944\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eAsymmetric stretching Si-O\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eThe pure phase (P) shows symmetrical bending at 519cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and asymmetrical bending at 542cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e this behavior is repeated for the other phases; however, symmetrical stretching at 610, 641, 812cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and asymmetrical stretching at 944cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e is only identified in the pure phase which corresponds to the T3 polymorph, a behavior similar to that found by [\u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e, \u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e, \u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e]. The Z2 phase behaves similarly to the P phase (predominant M1 polymorph). However, the shoulder formed at 812cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and, the asymmetric stretching at 944cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e disappears, and the intensity of the peak at 880cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e is reduced. Phases Z2 and Z3 show similar spectra with predominant polymorphs at M1 and R with a peak reduction at 880cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The Z4 phase (predominant R polymorph) shows behavior similar to the Z5 phase with a slight increase in intensity at 880cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e with symmetrical stretching. However, the Z5 phase peaks with intensity at 400cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e with symmetrical bending of the ZnO corresponding to the excess dopant in the crystal structure.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e3.5. Calorimetry\u003c/h2\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e shows the heat flow and accumulated heat curves in the pure and doped C\u003csub\u003e3\u003c/sub\u003eS pastes during the first 72 hours of hydration. For all samples, the retardation effect occurs in comparison with the reference paste.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn the analysis of heat curves for the pastes, it becomes evident that the heat released by the pure C\u003csub\u003e3\u003c/sub\u003eS paste surpasses that of all other phases, accompanied by a shorter induction period within the initial 72 hours. Upon comparing doped pastes, an observable trend emerges: with increasing dopant content, there is a corresponding decrease in heat release and an extension of the induction period. Furthermore, the accumulated heat remains lower than that of the pure paste, indicative of a subdued hydration rate across all doped pastes, consistent with findings in the literature [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e, \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e, \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e, \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e, \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e, \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e, \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eThe rationale behind this phenomenon has been discussed by [\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e, \u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e54\u003c/span\u003e, \u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e55\u003c/span\u003e], who propose that zinc exerts a retarding influence owing to the formation of heavy metal hydroxide Ca[Zn(OH)\u003csub\u003e3\u003c/sub\u003eH\u003csub\u003e2\u003c/sub\u003eO]\u003csub\u003e2\u003c/sub\u003e or the emergence of amorphous Zn(OH)\u003csub\u003e2\u003c/sub\u003e on grain surfaces. Throughout the hydration process, this hydroxide undergoes conversion, consuming calcium ions and mitigating the supersaturation of the C-S-H solution, thereby impeding the precipitation of crystals. However, the authors refrain from establishing a direct correlation between the levels of introduced Zn into the C\u003csub\u003e3\u003c/sub\u003eS. This impact is pronounced at 8.0wt% and 10.0wt%, where no discernible hydration process is observed. The compounds outlined in the literature were not identified in this study. Under the synthesis conditions of C\u003csub\u003e3\u003c/sub\u003eS and paste production, there exists a saturation point in dopant content, resulting in excess deposition of ZnO on grain surfaces. A portion of this excess reacts with calcium, silicon, and oxygen ions, forming a CaO\u003csub\u003e6\u003c/sub\u003eSi\u003csub\u003e2\u003c/sub\u003eZn compound, while a percentage of CaO and C\u003csub\u003e3\u003c/sub\u003eS remains unreacted due to ZnO saturation, as illustrated in the XRD analysis depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eConcerning the hydration process of the polymorphs, it can be seen that the order of reactivity obtained in this work is that the triclinic polymorphs are more reactive than the monoclinic polymorphs, which in turn are more reactive than the rhombohedral polymorphs. This result is similar to that found by [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e], but it differs from what the literature shows: the monoclinic polymorphs are the most reactive [\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e, \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e, \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e, \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e, \u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e56\u003c/span\u003e]. However, this analysis can only be carried out by considering the effect of the dopant since its influence directly affects the hydration process and, depending on its content, inhibits the mechanism. Therefore, this technique cannot be used to classify the reactivity of polymorphs without considering the effect of the dopant.\u003c/p\u003e \u003c/div\u003e"},{"header":"4. Conclusion","content":"\u003cp\u003e \u003cdiv class=\"BlockQuote\"\u003e \u003cp\u003eThis study investigated the effect of high levels of ZnO doping on the polymorphism and reactivity of C\u003csub\u003e3\u003c/sub\u003eS using different techniques and analyzing its properties in the anhydrous and hydrated state. The results indicate that all the doping levels used in this work affected the behavior of C\u003csub\u003e3\u003c/sub\u003eS and its polymorphs about the pure phase.\u003c/p\u003e \u003cp\u003eStabilizing a single polymorph was only possible for the pure phase, and the phases doped with 8.0 and 10.0wt%. For the doped phases, two polymorphs of the three crystal systems (triclinic, monoclinic, and rhombohedral) were stabilized. Of the total seven polymorphs of C\u003csub\u003e3\u003c/sub\u003eS, this work stabilized four, these being T3, M1, M3, and R.\u003c/p\u003e \u003cp\u003eConcerning the dopant content, for the synthesis conditions used, the maximum dopant content of ZnO indicated is 4.0wt%; for levels above this, there was saturation of the solution with surface deposition of ZnO on the C\u003csub\u003e3\u003c/sub\u003eS grains.\u003c/p\u003e \u003cp\u003eThe techniques of Fourier transform infrared spectroscopy and Raman spectroscopy proved to be efficient for identifying the effect of the dopant on the polymorphism of C\u003csub\u003e3\u003c/sub\u003eS and identifying the saturation of the solid solution by the excess dopant used.\u003c/p\u003e \u003cp\u003eThe behavior of the polymorphs regarding the doping technique in the hydration process indicated that all the doped phases showed a low hydration rate with a more extended induction period, and the pastes with dopant contents were 8.0 and 10. 0wt% no hydration process was identified. This behavior was due to the excess deposit of ZnO on the surface of the C\u003csub\u003e3\u003c/sub\u003eS grains, which, when it came into contact with water, inhibited the formation of C-S-H and reacted with the Ca and Si ions to form a CaO\u003csub\u003e6\u003c/sub\u003eSi\u003csub\u003e2\u003c/sub\u003eZn compound.\u003c/p\u003e \u003cp\u003eIn terms of the reactivity of polymorphs in terms of the analysis of the hydration process, this study found that, unlike what has been found in the literature, the most reactive polymorphs are triclinic, followed by monoclinic and rhombohedral. However, to carry out this analysis, it is necessary to consider the effect of the dopant since its content will directly influence the speed of the hydration reaction and the inhibition of the process. Therefore, the isothermal calorimetry technique can only be used to classify the reactivity of polymorphs by considering the effect of the dopant.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eCRediT authorship contribution statement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eQueiroz, Luciana: Conceptualization, Investigation, Methodology, Writing \u0026ndash; original draft.\u003c/p\u003e\n\u003cp\u003eBarbosa, Waleska da Silva: \u0026nbsp;Methodology \u0026amp; Review.\u003c/p\u003e\n\u003cp\u003eBergmann, Carlos: Supervision.\u003c/p\u003e\n\u003cp\u003eKirchheim, Ana Paula: Writing - Review \u0026amp; Editing, Supervision.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDeclaration of competing interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors acknowledge the financial support of CAPES (Coordination for the Improvement of Higher Education Personnel). APK was sponsored by CNPq through the research fellowship 311893/2021-0. Thanks to Ms. Tailane Hauschild, Dr. Tania Basegio, and Dr. Marcia Machado from LACER - UFRGS for their help with the experiments. Thanks to Mr. Micael Rubens from LINCE \u0026ndash; UFRGS for their support a calorimetry.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eSupino S, Malandrino O, Testa M, Sica D (2016) Sustainability in the EU cement industry: the Italian and German experiences. 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J Phys Chem C 119:5074\u0026ndash;5079. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1021/jp510597e\u003c/span\u003e\u003cspan address=\"10.1021/jp510597e\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":true,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"materials-and-structures","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"maas","sideBox":"Learn more about [Materials and Structures](http://link.springer.com/journal/11527)","snPcode":"11527","submissionUrl":"https://www.editorialmanager.com/maas/default2.aspx","title":"Materials and Structures","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"C3S, polymorphism, dopant, reactivity","lastPublishedDoi":"10.21203/rs.3.rs-4745258/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4745258/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe doping technique is widely used to stabilise C\u003csub\u003e3\u003c/sub\u003eS polymorphs, combined with synthesis temperature and cooling techniques. This work studied the doping technique using ZnO as a dopant at contents of 1.5, 2.0, 4.0, 8.0, and 10.0wt% and evaluated its effect on the polymorphism and reactivity of C\u003csub\u003e3\u003c/sub\u003eS. The characterisation of the phases in the anhydrous state was carried out by X-ray diffraction (XRD), and the effect of doping on chemical bonds and displacements in the crystalline structure was identified by Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy (RAMAN). Hydration was assessed using isothermal calorimetry and X-ray diffraction (XRD) techniques. The results show a delay in the hydration process in all the doped pastes, a reduction in the average crystallite size with increasing dopant content, and changes in the displacements and symmetry of the polymorphs.\u003c/p\u003e","manuscriptTitle":"The use of ZnO for the stabilisation of C3S polymorphs","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-08-29 11:15:28","doi":"10.21203/rs.3.rs-4745258/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"reviewerAgreed","content":"","date":"2024-08-05T13:58:15+00:00","index":0,"fulltext":""},{"type":"reviewersInvited","content":"","date":"2024-08-02T23:11:15+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"Materials and Structures","date":"2024-08-01T22:08:37+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2024-07-17T17:43:15+00:00","index":"","fulltext":""},{"type":"submitted","content":"Materials and Structures","date":"2024-07-15T12:47:19+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"materials-and-structures","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"maas","sideBox":"Learn more about [Materials and Structures](http://link.springer.com/journal/11527)","snPcode":"11527","submissionUrl":"https://www.editorialmanager.com/maas/default2.aspx","title":"Materials and Structures","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"a2325210-1c7c-4ebc-8630-cbbcdbb44e59","owner":[],"postedDate":"August 29th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-05-19T16:02:49+00:00","versionOfRecord":{"articleIdentity":"rs-4745258","link":"https://doi.org/10.1617/s11527-025-02675-0","journal":{"identity":"materials-and-structures","isVorOnly":false,"title":"Materials and Structures"},"publishedOn":"2025-05-13 15:58:10","publishedOnDateReadable":"May 13th, 2025"},"versionCreatedAt":"2024-08-29 11:15:28","video":"","vorDoi":"10.1617/s11527-025-02675-0","vorDoiUrl":"https://doi.org/10.1617/s11527-025-02675-0","workflowStages":[]},"version":"v1","identity":"rs-4745258","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4745258","identity":"rs-4745258","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}