Graduation Year


Document Type




Degree Name

Doctor of Philosophy (Ph.D.)

Degree Granting Department

Civil and Environmental Engineering

Major Professor

A. Zayed, Ph.D.

Committee Member

Manoj K. RAM, Ph.D.

Committee Member

Mahmood H. Nachabe, Ph.D.

Committee Member

Ajit Mujumdar, Ph.D.

Committee Member

Abdul Malik, Ph.D.


Portland Cement, Isothermal Calorimetry, Graphene Nan oplatelet, Statistical Analysis, Thermal Cracking


Heat of hydration is a property of Portland cement and a direct result of the chemical reaction between cement and water. The amount of heat released is dependent upon the cement mineralogical composition, curing temperature, water to cement ratio, and cement fineness. High temperature resulting from heat of hydration (thereon referred to as HOH) of cement can affect the hydration process, and consequently the kinetics of development of the mechanical properties of concrete. One of the main reasons triggering the interest in HOH of cement is its implication in thermal cracking of concrete. The high temperature gradient between the inner core and the outer surface of a concrete element is known to result in large tensile stresses that may exceed tensile strength, thus leading to early–age thermal cracking in mass concrete.

This dissertation initially addresses accurately predicting the heat of HOH of Portland cement at seven days based on the heat flow data collected from isothermal calorimetry for a time interval of 0-84 h. This approach drastically reduces the time required to identify the seven day HOH of Portland cement.

The second part of this study focuses on cement fineness and its critical role on the heat generated by Portland cement during hydration. Using a matrix of four commercially available Portland cements, representing a wide range of mineralogical composition, and subjecting each of the as-received cements to several grinding increments, a linear relationship was established between cement fineness and heat of hydration. The effect of cement fineness and mineralogical composition on HOH of Portland cement was then related through a mathematical expression to predict the HOH of Portland cement based on its mineralogical composition and fineness. Three expressions were proposed for the 1, 3 and 7 day HOH. The findings indicate that the equations developed, based on cement main phase composition and fineness, can be used to identify cements with high heat of HOH that may cause thermal cracking in mass concrete elements. Also, the equations can be used to correlate the HOH with the other properties of Portland cement for quality control and prediction of chemical and physical properties of manufactured Portland cement and concrete.

Restrained shrinkage experiments results on mortar specimens prepared with cements of variable phase composition and fineness indicate that interaction of C3A and sulfate source is the prime phenomenon followed by cement fineness as the second main factor influencing concrete cracking. In order to minimize this effect, the third part of this study focused on studying alternatives that can lower the heat generated by concrete on hydration through the incorporation of nanomaterials; namely, graphene nanoparticles. The results indicate that incorporation of graphene a as replacement for Portland cement improves thermal diffusivity and electrical conductivity of the cement paste. Consequently, the use of graphene can trigger improvement of the thermal conductivity of concrete elements thus reducing the cracking potential of concrete.

Measurements of HOH of graphene-cement paste, at w/c=0.5, using isothermal conduction calorimetry, indicate that incorporation of graphene up to 10% increases the length of the induction period while reduces the magnitude of the alite main hydration peak due to the filler effect. Furthermore, increasing the w/c ratio from 0.5 to 0.6 and graphene content from 1 % to 10% (as a partial replacement of cement) increases the 7 day HOH of Portland cement by 50 J/g. Isothermal conduction calorimetry heat flow curves show that incorporation of graphene particles up to 10% does not have significant effect on interaction of aluminates and sulfates sources since the time of occurrence of the C3A sulfate depletion peak is not affected by graphene substitution up to 10%.

Full factorial statistical design and analysis conducted on compressive strength data of mortar specimens prepared at two w/c ratios, using cements of different finenesses and graphene content indicates that the quantity of graphene and the physical interaction due to variable w/c, graphene and cement fineness, have the smallest P-value among all the samples, representing the most significant impact on compressive strength of mortar samples. It appears that in graphene cement paste composites, addition of 1% graphene results in 21% reduction of Young’s modulus. Increasing the graphene content from 1% to 5% and/or 10% does not show significant effect on Young’s modulus. Similar trends can be observed in the hardness of graphene cement paste samples.

In conclusion, partial replacement of Portland cement with graphene nanoparticles in concrete mixtures is a good alternative to lower the cracking potential in mass concrete elements.