Early Hydration and Strength Development in Polymer-Modified Cements Incorporating TEA–TIPA Blends

YahyaKaya1

VeyselKobya1

MurtedaUnverdi1

YunusKaya2

AliMardani1✉Emailali.mardani16@gmail.com

1Department of Civil EngineeringBursa Uludag UniversityBursaTurkey

2Department of ChemistryBursa Technical UniversityBursaTurkey

Yahya Kaya ¹, Veysel Kobya ¹, Murteda Unverdi ¹, Yunus Kaya ², Ali Mardani, ^1*

¹ Department of Civil Engineering, Bursa Uludag University, Bursa, Turkey

² Department of Chemistry, Bursa Technical University, Bursa, Turkey

^*ali.mardani16@gmail.com

Abstract

In this study, triethanolamine (TEA) and triisopropanolamine (TIPA) were combined at specific ratios to enhance the performance of amine-based grinding aids (GAs), which are commonly employed to achieve more economical and environmentally friendly cement production. The effects of TEA-TIPA blends, prepared in three different ratios, as well as TEA and TIPA used individually, were evaluated in terms of early hydration kinetics and early-age strength development. A total of 11 CEM I 42.5R cement samples, including a control sample without GA, were produced. The early hydration behavior of paste mix-tures prepared with these cements was thoroughly investigated using heat of hydration measurements, Scanning Electron Microscopy (SEM), X-Ray diffraction (XRD), Thermo-gravimetric analysis (TGA), and setting time tests. In addition, 1- and 3-day compressive strength developments of the corresponding mortar mixtures were compared. The results demonstrated that blending TIPA with TEA mitigated the low calcium hydroxide for-mation rate, delayed early hydration, and prolonged setting time associated with TEA. Moreover, the air-entraining effect typically observed with TIPA could be minimized by incorporating TEA. Among all formulations, the most favorable performance was ob-tained with a blend containing 25% TEA and 75% TIPA.

1. Introduction

Grinding aids (GAs) contribute to environmentally friendly production goals by re-ducing energy consumption and enhancing grinding efficiency. Their use also plays a significant role in lowering CO2 emissions during the cement manufacturing process ^1–5. Thus, the incorporation of GAs supports global efforts to reduce carbon emissions in the cement industry ^6–8. GAs promote sustainable practices and help mitigate the negative environmental impacts of cement production ^9–11.

The mechanism of action of GAs is primarily based on their ability to modify the surface properties of cement particles, thereby improving particle dispersion and reducing agglomeration. As a result, grinding efficiency increases, providing a significant contribu-tion to sustainable cement production ^12–15.

Among the most commonly used GAs are alkanolamines such as triethanolamine (TEA) and triisopropanolamine (TIPA). In addition to enhancing grinding efficiency, these alkanolamines also improve the hydration kinetics of cementitious systems ^14,16,17. The addition of TEA in cement production can significantly accelerate hydration by in-fluencing the reaction of C₃A, thereby improving strength development in cementitious systems. Furthermore, TIPA has been reported to affect the C₄AF reaction, enhancing hy-dration kinetics, leading to the formation of more stable hydration products and improved mechanical properties ^18–20. These effects of GAs on hydration kinetics underscore the critical importance of selecting an appropriate GA to improve both the efficiency of the production process and the performance of the cement ^9,21,22.

The hydration behavior of cementitious systems can vary depending on the dosage of TEA used. While low dosages tend to enhance early strength, higher dosages may lead to undesirable effects such as flash setting ^23–26. Therefore, determining the optimal GA dosage is crucial to balancing performance characteristics such as workability and setting time ^27,28.

The effect of TIPA on compressive strength has been observed to vary depending on the mineralogical composition of the cement, highlighting the need for careful selection based on cement type ²⁹. The interaction between GAs and hydration variables is of vital importance for both optimizing cement performance and minimizing environmental im-pact ²⁸. In conclusion, the proper selection and application of GAs such as TEA and TIPA at optimal dosages can yield significant improvements in both the efficiency and sustainability of cement production processes ^21,30,31.

There has been a growing interest in the combined use of GAs at specific dosages to enhance the performance of cementitious systems. These studies highlight the potential benefits of such combinations in terms of both hydration kinetics and strength develop-ment ^16,22,30,32. The synergistic effects arising from the use of different GAs together can accelerate hydration rates and significantly improve mechanical properties, thereby enabling the optimization of cement performance ^13,21,31. Selected examples from the literature on amine-based GAs are summarized in Table 1.

Table 1
Selected studies from the literature
Reference	Waste material or product used	GA	Dosage of grinding aids (cement%)	Properties studied	Observations
⁹	Natural pozzolan	TEA, TIPA	0.012, 0.032, 0.048, 0.060, 0.080, 0.096, 0.128 & 0.140	Blaine values, compressive strength	Higher Blaine value reflects an increased degree of fineness, compressive strength increased by 15%
³³	Glucose	TIPA	0.05	Hydration, pore structure	TIPA and glucose enhance the hydration at 28 days, TIPA accelerate the hydration particularly after 7 days, had a relatively small specific surface area at 3 days, increased average pore diameter
³⁴	-	TEA	0.02, 0.2, 2, 4, 6 & 8	Hydration, pore solution, setting time	TEA (0.2%) accelerates the reaction of C₃A with calcium sulfate, enhancing the formation of calcium sulfoaluminate hydrate (AFt) and its conversion to AFm, particularly at higher dosages, improve the hydration heat during the initial period, exhibits a retarding effect on the hydration of C₃S
¹⁴	-	TEA, TIPA	0.02 & 0.04	Setting time, compressive strength, hydration, pore structure	TEA (0.02%), accelerated the hydration, improved early strength and a reduction in setting time at low dosages; TIPA increases the hydration and strength but provides a lower early strength due to its air-entraining effects
²⁰	SO3	TIPA	0.5	Compressive strength, hydration,	TIPA enhances the hydration of the ferrite phase of clinker and improve strength after 7 days, promotes the hydration degree of silicates in the early ages
³⁵	-	TEA	0.1 & 0.5	Hydration, pore solution	TEA (0.1%) accelerates the aluminate reaction during the hydration and enhances the initial dissolutions of key clinker phases
¹¹	Superplasticizer	TEA	0.1	Setting time, compressive strength, reology, hydration	TEA resulting in a 20-minute delay in setting, enhances early strength, increased viscosity, after 41 hours approximately 20% higher heat
³⁶	Phosphorous slag (PS) and steel slag (SS)	TIPA	0.03, 0.06 & 0.09	Compressive strength, hydration, pore structure	TIPA (0.06%) enhances the compressive strength containing PS and SS cementitious system with improvements of 12% and 18% at 28 days, accelerates the dissolution of aluminum in PS and iron in SS, refines the pore structure in the later stages of hydration

As shown in Table 1, the individual use of TEA and TIPA results in variations in set-ting time as well as early and late strength development of cementitious systems, de-pending on dosage ^{9,14,34,36,37}. In this regard, polymers such as polycarbox-ylate-based (PCE) water-reducing admixtures have also been employed as GAs to opti-mize cementitious system interactions and enhance fluidity ³⁷. However, their use has been associated with delayed early hydration of cementitious systems ³⁸.

Previous studies have predominantly focused on the individual effects of TEA and TIPA. This highlights the need for further investigation into the combined effects and po-tential synergistic benefits of amine-based GAs on hydration kinetics. While several stud-ies have explored interactions between different Gas ^{14,28,39–41}, research addressing their joint effects on hydration kinetics and early strength development remains limited. Additional studies are necessary to identify optimal combinations and dosages that maximize performance while minimizing potential drawbacks.

This study aims to systematically examine the interactions between TEA and TIPA and to evaluate their combined effects on the hydration kinetics and early mechanical properties of cementitious systems. Although TEA and TIPA are not polymers in the con-ventional high-molecular-weight sense, they are polyhydroxy organic molecules contai-ning multiple functional groups that can simultaneously interact with ionic species in cementitious environments. These multifunctional frameworks enable them to form polymer-like adsorption networks with Ca²⁺ ions, promoting surface complexation and modifying hydration pathways. From this perspective, their behavior parallels that of polymeric dispersants, where multiple anchoring sites facilitate extended ion-binding in-teractions and improved particle dispersion.

Furthermore, the combined use of TEA and TIPA enhances this polymer-like effect. With its three hydroxyl groups and tertiary amine functionality, TEA exhibits strong coor-dination with Ca²⁺ ions. In contrast, with its bulkier isopropanol groups, TIPA introduces steric effects that alter adsorption geometry and surface coverage. These molecules gene-rate cooperative interaction networks that resemble the multifunctional binding and spa-tial organization typically observed in polymeric systems when used together. This sy-nergistic interaction increases the density of available coordination sites, stabilizes Ca²⁺–ligand complexes, and improves the homogeneity of ion distribution on particle surfaces.

Such cooperative molecular behavior mimics the multivalent binding characteristics of comb-like PCEs, albeit at a smaller molecular scale, resulting in polymer-inspired per-formance benefits. Therefore, TEA–TIPA blends can be regarded as low-molecular-weight polymer analogues, whose combined effects not only improve grinding efficiency and hydration kinetics but also bridge the conceptual link between classical amine-based grinding aids and polymeric admixtures in cement science. Thus, the study of TEA–TIPA blends contributes not only to the understanding of grinding aids but also to the broader field of polymer-inspired admixtures in sustainable cement composites.

In this study, a series of cement pastes was prepared using various TEA–TIPA com-binations at different ratios. The synergistic effects of these GAs on hydration behavior and strength development were assessed. The hydration kinetics of the prepared mixtures were analyzed using isothermal calorimetry, X-ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). In addition, particle size dis-tribution (PSD) analysis was conducted to investigate the influence of GAs on cement par-ticle morphology. Furthermore, FTIR spectroscopy and calcium ion (Ca²⁺) adsorption modeling were employed to explore the chemical interactions between GAs and cement components. Finally, compressive strength tests at 1 and 3 days were performed to evalu-ate early strength development.

2. Materials and Methods

2.1. Materials

In this study, the cements were produced by grinding a mixture of 96% clinker and 4% gypsum in a laboratory-scale ball mill until the target Blaine fineness of 3900 ± 100 cm²/g was achieved. The resulting cements conform to the CEM I 42.5R type specified in the EN 197-1 ⁴² standard. The physical and chemical properties of the clinker and gyp-sum used are presented in detail in Table 2.

Table 2
Some properties of the clinker and gypsum
Product	Chemical composition (%)
	Clinker	Gypsum
SiO₂	21.52	4.98
Al₂O₃	5.43	1.21
Fe₂O₃	3.31	0.83
CaO	65.38	28.94
MgO	1.04	0.83
SO₃	0.38	39.67
Na₂O + 0.658 K₂O	0.83	0.37
Cl	0.01	-
C₃S	56.51
C₂S	19.06
C₃A	8.79
C₄AF	10.07
Loss on ignition	0.52

The mixing ratios of the GAs used in this study are presented in Table 3.

Table 3
The mixing ratios of the GAs used in the study
Nomenclature	TEA dosage (%)	TIPA dosage (%)
Kontrol	0	0
TEA	100	0
75TEA	75	25
50TEA	50	50
25TEA	25	75
TIPA	0	100

For the preparation of mortar mixtures, washed river sand with a particle size of 0–4 mm was used in accordance with the EN 196-1 ⁴³ standard. The aggregate’s saturated sur-face dry specific gravity was determined as 2.64, and its water absorption capacity was measured as 1.2%, both values obtained following the EN 1097-6 ⁴⁴ standard.

2.2. Methods

2.2.1. Experimental procedures and analyses of cementitious systemss

The mixtures were prepared with a water-to-cement (w/c) ratio of 0.35, selected based on guidelines from previous studies. The effects of the GAs on hydration reactions were evaluated through setting time measurements, heat flow curves of hydration, and analy-ses of hydration products. Setting times were determined using an automatic Vicat appa-ratus in accordance with the EN 196-3 ⁴⁵ standard, while hydration temperature was measured using a UTCM-0347 cement calorimeter following the EN 196-8 ⁴⁶ standard.

Mortar mixtures were prepared with a Hobart-type mixer according to ASTM C109 ⁴⁷. Flow (workability) values were determined based on ASTM C1437 ⁴⁸. The w/c ratio, sand-to-binder ratio, and target flow value were fixed at 0.485, 2.75, and 190 ± 20 mm, respectively. Compressive strengths of the mixtures prepared to achieve the specified flow values were evaluated in accordance with ASTM C109 ⁴⁷.

2.2.2. Analyses on Hydrated Samples

To investigate the effects of the GA on cement hydration and microstructure, TGA, XRD, and SEM analyses were conducted. The w/c for the mortar mixtures was set to 0.35 in accordance with previous studies ²⁵. Samples at different hydration ages (6 hours, 12 hours, 24 hours, and 3 days) were cut into approximately 1 cm pieces and immersed in isopropanol for 48 hours to halt hydration ⁴⁹. Subsequently, the samples were either ground to ≤ 90 µm for TGA and XRD analyses or dried at 40°C for 48 hours for SEM ob-servations. The powdered samples were subjected to TGA and XRD, while the intact spe-cimens were used for SEM imaging.

2.2.3. Modelling

Within the scope of this study, the molecular structures of TEA, TIPA, TEA-Al, TEA-Ca, TIPA-Al, and TIPA-Ca were modeled using GaussView 5.0 software. Geometry optimizations and frequency calculations for all molecules were performed with the Ga-ussian 09 program ⁵⁰. The absence of negative frequencies in the obtained frequency calculations indicates that the molecules were optimized at the most probable geometries. All optimization procedures were carried out using the semi-empirical PM6 basis set.

2.2.4. Nomenclature

of Cement and Mixtures

In the nomenclature of the cements, the type and dosage of the GA used in cement production were taken into consideration. For example, a cement containing a grinding aid mixture of 75% TEA and 25% TIPA at a dosage of 0.05% was designated as 75TEA-0.05. The same naming convention was applied to the paste and mortar mixtures.

3. Results and Discussion

3.1. FTIR Spectroscopy

The FTIR spectra of TIPA, TEA, and their mixtures at different ratios are presented in Fig. 1. Both molecules contain triol groups as well as aliphatic CH groups, which is ref-lected in their similar FTIR spectra. As observed in both spectra, the OH stretching vibra-tions appear as broad bands in the range of 3600–3200 cm-1. The aliphatic CH stretching vibrations are observed below 3000 cm-1, specifically in the 2880–2750 cm-1 region for both molecules. Bands with a maximum near 1600 cm-1 correspond to OH bending vibrations. In the fingerprint region (1600–400 cm-1), in-plane and out-of-plane CH bending vibrati-ons, as well as C–O and C–C stretching vibrations, are detected. The most notable diffe-rence between TIPA and TEA in this region is observed between 850 and 800 cm-1. The C–H bending vibrations seen at 800 cm-1 in TIPA appear at lower intensity and around 850 cm-1 in the TEA molecule. In solutions prepared with different ratios of the two compo-nents − 75% TIPA + 25% TEA, 50% TIPA + 50% TEA, and 25% TIPA + 75% TEA- the band observed at 800 cm-1 is dominant in the first two mixtures, whereas in the last solution, this band significantly diminishes and the intensity of the band at 850 cm-1 increases.

Fig. 1

FTIR spectra of TIPA, TEA, and their mixtures at 25%, 50%, and 75% TEA compositions.

3.2. Computational Calculations

The optimized structures of TEA, TIPA, TEA-Al, TEA-Ca, TIPA-Al, and TIPA-Ca mo-lecules, calculated using the semi-empirical PM6 method, are presented in Fig. 2, while the calculated optimized energies and interaction energies are listed in Table 4. Examina-tion of Fig. 2 reveals that both TEA and TIPA molecules adopt a trigonal pyramidal geometry centered around the nitrogen atom, with hydroxyl groups positioned to maximize their mutual distances. In the interactions of the TEA molecule with Al and Ca ions, all hydroxyl oxygen atoms and the nitrogen atom participate, forming a tetracoordi-nated complex. For TIPA, a tetracoordinated interaction is observed with the Al ion, whe-reas with the Ca ion, a more stable tricoordinated structure is favored. The positivity of all calculated vibrational frequencies confirms that all structures were properly optimized. Comparing the energy differences between the interacting and non-interacting TEA and TIPA molecules, it was found that Al ions exhibit stronger interactions with TEA than with TIPA. Conversely, despite TIPA forming a tricoordinated complex with Ca ions, the shorter interaction distances result in stronger binding compared to TEA. These computa-tional findings are consistent with the experimental results.

Fig. 2

Optimized structures of TEA, TIPA, TEA-Al, TEA-Ca, TIPA-Al, and TIPA-Ca molecules.

Table 4
Optimized energies and interaction energies of TEA, TIPA, TEA-Al, TEA-Ca, TIPA-Al, and TI-PA-Ca molecules obtained using the semi-empirical PM6 method.
Compound	Energy (a.u.)	ΔE_interaction (a.u)
TEA	-0.223505
TEA-Al	0.823222	0.104673
TEA-Ca	0.231966	0.455471
TIPA	-0.269355
TIPA-Al	0,730465	0.999820
TIPA-Ca	0,198363	0.467718

3.3. Particle Size Distribution

Particle size distributions of cements ground to the same Blaine fineness (3900 ± 100 cm²/g) are presented in Fig. 3.

Fig. 3

Particle size distributions of all mixtures.

An examination of Fig. 3 reveals that the particle size distribution of the cements is significantly influenced by the type and dosage of the GA used. Notably, the particle size range between 3 and 32 microns is known to be of great importance for the hydration re-actions of cement ^51–53. In this context, TIPA demonstrates a stronger effect in reducing the proportion of larger particles. This is critically important for improving hydration ki-netics and strength development in cementitious systems ^3,10,54,55.

Among the GAs, the use of 0.1% TIPA resulted in the most pronounced reduction in particle size, decreasing the proportion of particles larger than 45 µm from 18% to 7.54%, and the fraction above 60 µm from 2.24% to 0.44%, while simultaneously increasing the proportion of fine particles below 10 µm. Compared to the control cement, the TIPA-0.1 cement showed a reduction in coarse particles. Furthermore, the combined use of TEA and TIPA led to a decrease in the percentage of particles larger than 45 µm from 18% to between 10% and 14%, relative to the control mixture. Additionally, a significant increase in the percentage of particles in the 10–32 µm range was observed when GAs were used in combination, indicating a synergistic grinding effect. Overall, the TIPA-0.1 cement exhibi-ted the narrowest particle size distribution. These positive effects are thought to result par-ticularly from the three-dimensional structure and high polarity of TIPA, which facilitates effective dispersion during the cement grinding process ⁵⁶.

3.4. Heat of Hydration

The 24-hour hydration heat flow curves of the control, TEA, TIPA, and 50TEA mix-tures are presented in Fig. 4.

Fig. 4

Heat of hydration of mixtures.

The first peak observed in Fig. 4 is attributed to the sudden heat release caused by the initial contact of water with the cement particles. During this stage, ions from the most reactive aluminate phases in the cement diffuse into the mixing water. The formation of ettringite occurs through the reaction of dissolved gypsum with C₃A, resulting in the ini-tial peak, followed by an induction period until ion equilibrium is established in the mixture ⁵⁷. During this period, a thin layer consisting of ettringite forms around C₃A, while Portlandite and C-S-H develop around C₃S, causing the hydration heat to reach a minimum. The moment immediately after this stage can be defined as the initial setting time, which is critical for the workability period of concrete ⁵⁸. As seen in Fig. 4, no significant difference was observed in the initial setting times among the GA-containing mixtures. However, the control mixture without GA exhibited a delayed initial setting ti-me. This can be attributed to the accelerated dissolution of ions from mixed oxides by TEA and TIPA admixtures, which leads to earlier ion equilibrium ⁷.

Regarding the second peak, regardless of the GA type, the use of GA shortens the time to reach the second (main) peak of cement hydration. This effect is linked to both physical and chemical influences of GAs. Cement particles produced with GAs are finer (Fig. 3), and physically smaller particles react faster by ionizing more rapidly, thus reaching the main peak earlier ^11,39,53. Moreover, the accelerated hydration kinetics due to the redu-ced particle size results in a higher main peak compared to the control. Chemically, the presence of TEA is known to particularly promote C₃A hydration ⁵⁹, which shortens the duration and narrows the width of the main peak. Conversely, TIPA, characterized by the finest particle size, accelerates both silicate and aluminate phases, leading to an increase in both the height and the width of the main peak. Additionally, a third peak appears alongside the main peak with TIPA use, which is thought to result from TIPA’s stronger influence on the C₄AF phase compared to C₃A ⁷, and its delayed conversion of ettringite to monosulfate due to delayed sulfate and C₃A reactivity relative to TEA. In the final stage of the deceleration reactions, sharper transitions are observed in the presence of TEA, whereas in the control cement, this stage lasts longer due to combined physical and che-mical effects.

3.5. XRD Analysis

The data obtained from XRD analyses of paste mixtures prepared with the control cement and cements containing 0.05% GA at 6, 12, and 24 hours are presented in Table 5, while the diffraction peaks between 0° and 80° 2θ are shown in Fig. 5.

Table 5
Peak results at selected Ɵ values from the XRD analysis of the mixtures.
	Ettringite (11,6Ɵ*)			Monosulfate (12,2Ɵ)			C₃A (32,2Ɵ)			C₄AF (32,6Ɵ)			CH (18,2Ɵ)
	6h	12h	24h	6h	12h	24h	6h	12h	24h	6h	12h	24h	6h	12h	24h
Control	2,8625	2,3653	2,2403	2,4361	2,4667	2,6771	8,5444	7,6083	6,1063	6,6194	5,7847	4,6299	1,4639	3,4167	3,9097
TEA	3,3243	2,3188	2,2604	2,4819	2,6801	2,7942	7,8556	5,5139	5,17	7,041	5,8417	3,9354	1,4833	2,9493	3,4646
75TEA	3,2333	2,3486	2,2868	2,3708	2,4882	2,6264	7,9806	6,6125	5,0167	6,7278	5,2264	4,2021	1,4639	2,9042	3,5333
50TEA	3,0472	2,5792	2,2875	2,4375	2,574	2,6854	10,8243	7,6375	6,1868	7,9292	5,8528	4,8514	1,5826	3,8903	4,4646
25TEA	3,1806	2,4479	2,2535	2,375	2,5118	2,6486	9,8507	6,4604	4,916	6,3951	4,6472	4,2611	1,4931	2,3014	3,5757
TIPA	2,9167	2,475	2,3028	2,391	2,4486	2,6924	10,9669	6,0938	5,0951	6,3278	4,059	3,47882	1,4875	2,416	4,0063

*Ɵ value at which the peak is observed.

Fig. 5

XRD peaks of the mixtures at a) 6 h, b) 12 h, and c) 24 h.

During the early stages of hydration (0–6 hours), C₃A and sulfates are consumed most effectively, leading to the formation of ettringite. In addition, the reactions of silicate phases also begin during this period. At later stages (6–12 hours), the transformation of ettringite into monosulfate becomes evident, while Portlandite (CH), formed as a result of silicate phase hydration, becomes more prominent. Furthermore, during this period, the consumption of C₃A and C₄AF phases and their transformation processes play a signifi-cant role depending on the GA content. As seen in Table 5, after 6 hours of hydration, the highest ettringite peak intensity was observed in the mixture containing 100% TEA, while the lowest ettringite content was found in the GA-free control mixture. Similarly, with increasing reaction time (from 6 to 12 hours), the TEA-containing cement exhibited the most pronounced conversion of ettringite into monosulfate. As previously discussed, this is likely due to TEA accelerating the reaction of aluminate phases.

Fig. 6

Changes in the C₃A and C₄AF phases of a) Control, b) TIPA, and c) TEA cements.

To more clearly observe the changes in the quantities of C₃A and C₄AF over time in the presence of TEA and TIPA, the time-dependent peak intensities of these crystalline phases are shown in Fig. 6. After 6 hours of hydration, the lowest C₃A content was fo-und in the TEA-containing mixture, while the lowest C₄AF content was observed in the mixture with TIPA. As the hydration time progressed, the greatest decrease in C₃A content was again observed with TEA, confirming its strong influence on aluminate phases. In contrast, the most significant reduction in C₄AF content was associated with TIPA, high-lighting its effectiveness on the ferrite phase. These trends are also reflected in the hydra-tion heat flow curves.

3.6. TGA Analysis

In the literature, the peaks observed within the 50–200°C range are attributed to the dehydration of ettringite (Aft), monosulfoaluminate (AFm) phases, and C–S–H gel ^35,60,61. On the other hand, the peaks observed around 400–550°C are generally attri-buted to the decomposition of calcium hydroxide (CH). However, these hydration phases cannot be distinctly separated by TGA, as the peaks occurring in these temperature ranges often overlap, making it difficult to differentiate between them ⁶¹.

Mass losses of the prepared samples within the 50–200°C and 400–500°C ranges were calculated separately. Furthermore, based on the data recorded in the 400–550°C range from the TGA curves, the amount of CH was estimated using the mass loss within this range and the formula given in Eq. 1 ^62–64:

W_CH = W_{loss,400−550} ×

$\:\frac{{M}_{CH}}{{M}_{W}}$

× 100 + W_{loss,600−800} ×

$\:\frac{{M}_{CH}}{{M}_{W}}$

× 100 (1)

In this context, WCH represents the amount of CH in the cement paste; Wloss refers to the mass loss observed during the decomposition of CH in the TGA analysis; while MCH and MW denote the molecular weights of CH and water, respectively. The relative molecu-lar weights of CH and water were taken as 74 and 18, respectively ⁶⁵.

Non-evaporable water (NEW) refers to the amount of chemically bound water present in hydration products such as C–S–H gel and ettringite. Unlike free water, these water molecules can only be removed from the system through structural degradation occurring at elevated temperatures. NEW is considered a key parameter in determining the degree of hydration and the long-term durability of cementitious materials ⁶⁶. In this study, NEW was calculated using the Eq. 2:

$\:\text{W}\text{n}\:=\:\frac{W1-W2\:}{W2}-\:\frac{{r}_{fc}}{1-{r}_{fc}}$

The amount of NEW is denoted by Wn, where W1 represents the mass of the sample after drying at 105°C, and W2 is the residual mass after heating up to 950°C. Additionally, rfc refers to the loss on ignition of the cement.

The weight losses, CH contents, and NEW values of the control and GA-containing mixtures (with 0.05% dosage) at 6, 12, and 24 hours of hydration are presented in Table 6.

Table 6
Weight losses, CH contents, and NEW values of the mixtures at 6, 12, and 24 hours.
		Time	Control	TEA	75TEA	50TEA	25TEA	TIPA
Weight loss (%)	50–200°C	6-hr	2,44	2,59	2,76	2,84	2,95	2,72
		12-hr	4,04	3,76	3,87	3,92	4,02	3,84
		24-hr	4,53	4,30	4,48	4,78	4,97	4,41
	400–550°C	6-hr	2,02	1,84	1,97	2,05	2,27	2,37
		12-hr	3,27	2,94	3,16	3,47	3,61	3,93
		24-hr	3,72	3,27	3,57	3,86	4,06	4,38
CH content (%)		6-hr	10,71	9,75	10,44	10,87	12,03	12,56
		12-hr	17,33	15,58	16,75	18,39	19,13	20,83
		24-hr	19,72	17,33	18,92	20,46	21,52	23,21
NEW values (%)		6-hr	5,14	4,98	5,23	5,32	5,47	5,84
		12-hr	8,22	8,14	8,42	8,37	9,01	9,76
		24-hr	10,74	9,82	10,94	11,02	11,76	12,24

As shown in Table 6, the weight losses of the TEA-containing mixtures within the 50–200°C and 400–550°C ranges were lower than those of the control mixture. This is attributed to TEA’s accelerating effect on the hydration of the C₃A phase while delaying the hydration of the C₃S phase. Moreover, TEA is known to form complexes with Ca²⁺ ions, increasing the saturation degree of the solution, which in turn delays the nucleation and crystal growth of Ca(OH)₂ ⁷. As discussed earlier, the peaks observed between 50–200°C correspond to ettringite, monosulfoaluminate, and C–S–H phases. As shown in Table 6, the weight losses in this temperature range were not as low as those in the 400–550°C range -associated with the CH phase- when compared to the control. This can be explai-ned by the increased formation of ettringite due to the enhanced C₃A hydration in the pre-sence of TEA. This finding is also consistent with the XRD results (Fig. 5).

Improvement in both temperature ranges (50–200°C and 400–550°C) was observed as the TEA content decreased and the TIPA content increased. Starting from the 50TEA mixture, weight losses in these temperature intervals began to exceed those of the control, which is attributed to the ability of TIPA to promote the hydration of both C₄AF and C₃S phases ^7,67. To better visualize the changes in CH and NEW contents in the GA-containing mixtures compared to the control, the relative differences in CH and NEW contents are presented in Fig. 7.

(a)

(b)

Figure 7. Relative changes in a) CH content and b) NEW content of GA-containing mixtures compared to the control.

As shown in Fig. 7, the CH and NEW contents of the TEA mixture decreased by up to 12% and 9%, respectively, compared to the control. The reduction in CH content was less pronounced in the 75TEA mixture, where it decreased to 4%, while the NEW content did not show a significant increase relative to the control. TEA can promote the rapid for-mation of the ettringite phase, which may cover the surface of C₃S and hinder its hydra-tion ⁷. Since CH formation results from the hydration of the C₃S phase, and TEA can de-lay this hydration, the observed decrease in CH content persisted. However, as the amount of NEW is associated not only with the hydration of the C₃S phase (formation of C–S–H gel) but also with the hydration of C₃A (ettringite formation), the increased formation of the ettringite phase compensated for the decrease in CH content. On the other hand, as the TIPA dosage in the mixture increased, both CH and NEW contents showed an increase, becoming notably apparent starting from the 25TEA mixture (Fig. 7). In this context, the synergistic effect of the TEA-TIPA mixture clearly exhibits positive outcomes in terms of hydration kinetics. The increase in hydration products, especially in the 25TEA mixture compared to the control, is particularly remarkable.

3.7. Product Morphology

To compare the morphology of the products formed in mixtures containing GA, SEM images of the control and mixtures with 0.05% GA after 1 day of hydration are presented in Fig. 8.

Fig. 8

1-day SEM images of the mixtures: a) Control, b) TEA, c) 75TEA, d) 50TEA, e) 25TEA, f) TIPA.

In the literature, it is reported that cement particles produced without grinding aids (GAs) tend to have sharp edges and irregular shapes, which can negatively affect hydra-tion efficiency. In contrast, GAs such as TEA and TIPA contribute to the formation of more rounded and finer particles, enabling better particle dispersion and faster hydration ^11,39,53,68.

As seen in Fig. 8b, the TEA mixture exhibits a dense presence of needle-like ettrin-gite phases. An increase in the dosage of TIPA corresponds with a higher density of CH and C–S–H phases (Figs. 8d–f). Moreover, especially in Figs. 8e and 8f, the product density increases with increasing TIPA content. This effect is likely due to TIPA promoting the hydration of not only C₄AF but also C₃S phases. Consistent with XRD and TGA results, the synergistic effect of the TIPA–TEA mixture clearly mitigates the adverse impact that TEA alone can have on C–S–H formation. In this context, the product morphology results further support the combined use of these mixtures, indicating that an optimal perfor-mance is achieved with a blend ratio of 75% TIPA and 25% TEA.

3.8. Setting Time and Compressive Strength

The water demand, initial and final setting times of all mixtures are presented in Fi-gure 9, while the 1- and 3-day compressive strength results are shown in Fig. 10.

*Water demand was determined as the weight ratio of the water required to achieve the desired consistency to the weight of the cement.

Figure 9. Setting times and water demand of all mixtures.

Fig. 10

Compressive strengths of all mixtures.

As seen in Fig. 9, the use of GAs led to an increase in the water demand of the mixtures. However, this increase was not found to be significant. The rise in water de-mand can be attributed to the narrower particle size distribution of the mixtures contai-ning GAs (Fig. 3) and the accelerated hydration rates (Fig. 4). A narrower particle si-ze distribution may increase the water or superplasticizer demand of the cement ^54,69.

When comparing the initial and final setting times, all GA-containing mixtures exhi-bited shorter setting times compared to the control mixture. This has been associated with the physically finer particle size distribution caused by GA usage and the chemically en-hanced hydration kinetics detailed in the hydration kinetics section. The initial and final setting times of the TEA-0.05 mixture were reduced by approximately 16% and 19%, res-pectively, compared to the control. The magnitude of this reduction decreased with incre-asing TIPA concentration in the system at the same GA dosage. For the TIPA mixture, no significant change was observed in the initial setting time relative to the control, while the final setting time decreased by about 10%.

The effect of increasing the dosage of TEA-TIPA mixtures on setting times followed the same trend, with changes becoming more pronounced at higher dosages. For example, the initial setting time of the 75TEA mixture at 0.05 dosage was 17% lower than the cont-rol, while at 0.1 dosage, this reduction decreased to 11%. This can be attributed to the hig-her TIPA concentration at increased dosages balancing the accelerating effect of TEA on setting.

Regarding compressive strength results, all GA-containing mixtures except TIPA showed increases ranging between 6% and 20% at 1 day compared to the control (Fig. 10). The TIPA mixtures at 0.05 dosage showed no significant difference from the control, while at 0.1 dosage, a 7% decrease was observed. Although TIPA improved hydration ki-netics, the reduction in 1-day strength is linked to the air-entraining effect of TIPA ^14,67, which increases porosity and can reduce early age strength. At 0.05 dosage, this air entra-inment effect was balanced by TIPA’s hydration-enhancing properties, whereas at 0.1 do-sage, air entrainment dominated, leading to strength loss.

At 3 days, in contrast to 1-day results, higher TIPA concentrations yielded higher compressive strengths compared to the control (Fig. 10). The ongoing hydration reacti-ons during the 3-day curing period outweighed TIPA’s air-entraining effect. On the other hand, TEA mixtures showed a decrease in 3-day strength by about 4% (TEA-0.05) and 7% (TEA-0.01) compared to the control. Although TEA initially accelerated C₃A hydration, leading to rapid early hydration and higher initial strength, a delayed C-S-H formation caused strength reduction over the 3-day period, as previously discussed (see Section 3.6 TGA Analysis).

In conclusion, the hydration kinetics results demonstrated that TIPA mitigates the adverse effects caused by TEA. Compressive strength data showed that TEA counterba-lanced the strength loss caused by TIPA’s air entrainment. Overall, the synergistic effect of the TEA-TIPA mixture alleviated some of the issues encountered when using these ad-mixtures individually. Accordingly, the mixture containing 75% TIPA and 25% TEA (25TEA) emerged as the most advantageous in terms of the evaluated properties.

4. Conclusions

In this study, the combined use of TEA and TIPA admixtures aimed to improve both early hydration and early strength performance. The main findings obtained from the experiments are summarized as follows:

Mixtures containing TEA alone exhibited high early hydration heat, rapid setting, and reduced CH formation, which posed certain challenges. The synergistic effect achieved by combining TEA with TIPA was found to effectively address these issues.

While the use of TIPA alone yielded positive results regarding early hydration and CH formation, its air-entraining effect led to lower 1-day strength performance. The combination of TIPA with TEA resulted in improved 1-day compressive strength.

Among the various ratios of TEA and TIPA admixtures, the mixture containing 75% TIPA and 25% TEA demonstrated the best performance in terms of early hydration kinetics and early-age strength.

The combined application of TEA and TIPA admixtures was shown to eliminate some of the drawbacks encountered when these admixtures are used individually, enabling the production of more sustainable and durable cementitious materials.

Author Contribution

Conceptualization, Y.K., V.K., M.Ü., Yunus, K., and A.M.; methodology, Y.K., V.K., M.Ü., Yunus, K., and A.M.; soft-ware, Y.K., V.K., M.Ü., Yunus, K., and A.M.; validation, Y.K., V.K., M.Ü., Yunus, K., and A.M.; formal analysis, Y.K., V.K., M.Ü., Yunus, K., and A.M.; investigation, Y.K., V.K., M.Ü., Yunus, K., and A.M.; resources, Y.K., V.K., M.Ü., Yunus, K., and A.M.; data curation, Y.K., V.K., M.Ü., Yunus, K., and A.M.; writing—original draft preparation, Y.K., V.K., M.Ü., Yunus, K., and A.M.; writing—review and editing, Y.K., V.K., M.Ü., Yunus, K., and A.M.; visualization Y.K., V.K., M.Ü., Yunus, K., and A.M.; supervision, A.M.; project administration, A.M. All au-thors have read and agreed to the published version of the manuscript.

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.

Funding

They extend their appreciation to the Bursa Uludağ University Science and Technology Centre (BAP) for their contributions under grant number FGA-2025-2048.

Acknowledgement

The authors gratefully acknowledge the Scientific and Technological Research Council of Turkey (TÜBİTAK) for its support through project grant number 222M245. They also appreciate the con-tributions of the Bursa Uludağ University Science and Technology Centre (BAP) via grant num-bers FGA-2024-1754 and FDK-2024-1960. The first author further extends his gratitude to TÜ-BİTAK for the 2211A scholarship awarded during his doctoral studies. The corresponding author also thanks the Turkish Academy of Sciences (TÜBA) for its support.

Data Availability

Data is provided within the manuscript.

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Table 1. Selected studies from the literature

Reference	Waste material or product used	GA	Dosage of grinding aids (cement%)	Properties studied	Observations
⁹	Natural pozzolan	TEA, TIPA	0.012, 0.032, 0.048, 0.060, 0.080, 0.096, 0.128 & 0.140	Blaine values, compressive strength	Higher Blaine value reflects an increased degree of fineness, compressive strength increased by 15%
³³	Glucose	TIPA	0.05	Hydration, pore structure	TIPA and glucose enhance the hydration at 28 days, TIPA accelerate the hydration particularly after 7 days, had a relatively small specific surface area at 3 days, increased average pore diameter
³⁴	-	TEA	0.02, 0.2, 2, 4, 6 & 8	Hydration, pore solution, setting time	TEA (0.2%) accelerates the reaction of C₃A with calcium sulfate, enhancing the formation of calcium sulfoaluminate hydrate (AFt) and its conversion to AFm, particularly at higher dosages, improve the hydration heat during the initial period, exhibits a retarding effect on the hydration of C₃S
¹⁴	-	TEA, TIPA	0.02 & 0.04	Setting time, compressive strength, hydration, pore structure	TEA (0.02%), accelerated the hydration, improved early strength and a reduction in setting time at low dosages; TIPA increases the hydration and strength but provides a lower early strength due to its air-entraining effects
²⁰	SO3	TIPA	0.5	Compressive strength, hydration,	TIPA enhances the hydration of the ferrite phase of clinker and improve strength after 7 days, promotes the hydration degree of silicates in the early ages
³⁵	-	TEA	0.1 & 0.5	Hydration, pore solution	TEA (0.1%) accelerates the aluminate reaction during the hydration and enhances the initial dissolutions of key clinker phases
¹¹	Superplasticizer	TEA	0.1	Setting time, compressive strength, reology, hydration	TEA resulting in a 20-minute delay in setting, enhances early strength, increased viscosity, after 41 hours approximately 20% higher heat
³⁶	Phosphorous slag (PS) and steel slag (SS)	TIPA	0.03, 0.06 & 0.09	Compressive strength, hydration, pore structure	TIPA (0.06%) enhances the compressive strength containing PS and SS cementitious system with improvements of 12% and 18% at 28 days, accelerates the dissolution of aluminum in PS and iron in SS, refines the pore structure in the later stages of hydration

Table 2. Some properties of the clinker and gypsum

Product	Chemical composition (%)
	Clinker	Gypsum
SiO₂	21.52	4.98
Al₂O₃	5.43	1.21
Fe₂O₃	3.31	0.83
CaO	65.38	28.94
MgO	1.04	0.83
SO₃	0.38	39.67
Na₂O + 0.658 K₂O	0.83	0.37
Cl	0.01	-
C₃S	56.51
C₂S	19.06
C₃A	8.79
C₄AF	10.07
Loss on ignition	0.52

Table 3. The mixing ratios of the GAs used in the study

Nomenclature	TEA dosage (%)	TIPA dosage (%)
Kontrol	0	0
TEA	100	0
75TEA	75	25
50TEA	50	50
25TEA	25	75
TIPA	0	100

Table 4. Optimized energies and interaction energies of TEA, TIPA, TEA-Al, TEA-Ca, TIPA-Al, and TI-PA-Ca molecules obtained using the semi-empirical PM6 method.

Compound	Energy (a.u.)	ΔE_interaction (a.u)
TEA	-0.223505
TEA-Al	0.823222	0.104673
TEA-Ca	0.231966	0.455471
TIPA	-0.269355
TIPA-Al	0,730465	0.999820
TIPA-Ca	0,198363	0.467718

Table 5. Peak results at selected Ɵ values from the XRD analysis of the mixtures.

	Ettringite (11,6Ɵ*)			Monosulfate (12,2Ɵ)			C₃A (32,2Ɵ)			C₄AF (32,6Ɵ)			CH (18,2Ɵ)
	6h	12h	24h	6h	12h	24h	6h	12h	24h	6h	12h	24h	6h	12h	24h
Control	2,8625	2,3653	2,2403	2,4361	2,4667	2,6771	8,5444	7,6083	6,1063	6,6194	5,7847	4,6299	1,4639	3,4167	3,9097
TEA	3,3243	2,3188	2,2604	2,4819	2,6801	2,7942	7,8556	5,5139	5,17	7,041	5,8417	3,9354	1,4833	2,9493	3,4646
75TEA	3,2333	2,3486	2,2868	2,3708	2,4882	2,6264	7,9806	6,6125	5,0167	6,7278	5,2264	4,2021	1,4639	2,9042	3,5333
50TEA	3,0472	2,5792	2,2875	2,4375	2,574	2,6854	10,8243	7,6375	6,1868	7,9292	5,8528	4,8514	1,5826	3,8903	4,4646
25TEA	3,1806	2,4479	2,2535	2,375	2,5118	2,6486	9,8507	6,4604	4,916	6,3951	4,6472	4,2611	1,4931	2,3014	3,5757
TIPA	2,9167	2,475	2,3028	2,391	2,4486	2,6924	10,9669	6,0938	5,0951	6,3278	4,059	3,47882	1,4875	2,416	4,0063

*Ɵ value at which the peak is observed.

Table 6. Weight losses, CH contents, and NEW values of the mixtures at 6, 12, and 24 hours.

		Time	Control	TEA	75TEA	50TEA	25TEA	TIPA
Weight loss (%)	50–200°C	6-hr	2,44	2,59	2,76	2,84	2,95	2,72
		12-hr	4,04	3,76	3,87	3,92	4,02	3,84
		24-hr	4,53	4,30	4,48	4,78	4,97	4,41
	400–550°C	6-hr	2,02	1,84	1,97	2,05	2,27	2,37
		12-hr	3,27	2,94	3,16	3,47	3,61	3,93
		24-hr	3,72	3,27	3,57	3,86	4,06	4,38
CH content (%)		6-hr	10,71	9,75	10,44	10,87	12,03	12,56
		12-hr	17,33	15,58	16,75	18,39	19,13	20,83
		24-hr	19,72	17,33	18,92	20,46	21,52	23,21
NEW values (%)		6-hr	5,14	4,98	5,23	5,32	5,47	5,84
		12-hr	8,22	8,14	8,42	8,37	9,01	9,76
		24-hr	10,74	9,82	10,94	11,02	11,76	12,24

Yes