Performance of clinoptilolite zeolite after milling as a pretreatment on hydration kinetics, shrinkage, and alkali-silica reaction of cementitious materials

Natural clinoptilolite zeolite has been a popular supplementary cementitious material (SCM) due to its acceptable pozzolanic performance and the overall lower environmental footprint. Previous research established that milling is an effective pretreatment technique to further increase the pozzolanic reactivity of zeolitic tuffs leading to an increased specific surface area and amorphous contents. Therefore, the present study characterized the zeolite particles after ball milling for 1 and 3 h using phase analysis by X-ray diffraction (XRD), particle size distribution by laser diffraction, microstructural analysis by scanning electron microscopy (SEM), moisture absorption rate, and relative chemical dissolution. The performance of milled clinoptilolite zeolite as a SCM with the replacement of up to 20% portland cement was evaluated through hydration kinetics (heat of hydration, setting time, chemical shrinkage, degree of hydration), workability, compressive strength, autogenous shrinkage, drying shrinkage, and alkali-silica reaction (ASR). Results revealed that 1 and 3 h of milling led to an increased specific surface area, moisture absorption capacity, and relative dissolution of particles, but had no visible effects on the crystalline structure of zeolite particles compared to the unmilled zeolite particles. For the hydrated system, both 1 and 3-h milled zeolite increased the overall heat of hydration leading to an increased silicate and aluminate reaction along with the acceleration effects in the setting time. The compressive strength of up to 20% milled (1 and 3 h) zeolite samples was increased by about 20 to 25% compared to the unmilled zeolite samples at an early age which suggested an increasing pozzolanic response of milled zeolite particles in the system due to an increased volume of hydrated phases and degree of hydration. Milling slightly decreased the workability by demanding a higher content of fresh water which was released at a later age leading to a higher drying and autogenous shrinkage. In addition, milling reduced the internal curing capacity leading to damage to the porous structure of zeolite particles. The use of up to 20% 3-h milled zeolite reduced the deleterious expansion by about 80% due to ASR compared to the control sample and the overall performance of milled clinoptilolite zeolite as the SCM was satisfactory in the hydrated system.