In cement based systems, the residual stresses are created by internal expansion. This provides toughening by the release of the residual stresses as the macro-crack propagates. While circumstantial evidence of the residual stresses exist (e.g. micro-crack formation leading to permanent deformation in flexural tests), it is very difficult to observe the mechanism in action. The quantitative estimate of the changes occurring in such cement-based systems is challenging due to the anisotropy and complexity of the material. Non-Destructive Testing (NDT) techniques were used in this research to observe the mechanism in action. An ultrasound technique is used to examine strength development and an acoustic emission (AE) technique is used to examine micro-structural changes, micro-cracks, crack initiation, crack propagation, crack arrests and crack bridging in plain concrete samples including samples containing admixtures and waste materials. The NDT techniques were found to be accurate in being able to measure compressive strength, with good correlation between both standard mechanical testing and NDT techniques. It was shown that admixtures could be effectively used to alter the properties of a curing cement mortar. This work has also demonstrated that ultrasound can be successfully used to determine the compressive strength of concrete from an early age. The ability to pre-determine the strength of concrete through correlation with NDT test parameters may reduce the time spent waiting on concrete to set and to obtain results using standard mechanical testing methods. The findings in this research present the effect admixtures had on the curing process of the cement based material. The introduction of certain additives into mortars have demonstrated an increase in both the rate of initial hardening and the magnitude of the compressive strength attained over the curing period depending on the mixture specification. The additives considered have been shown to actively alter and enhance the chemical process of curing from the start of hydration. Some additives that accelerate the curing process (accelerators) were found to lower the compressive strength of concrete using the ultrasound technique. Additives that caused an increase in the final strength of mortar also increased its toughness. The significant contributions in this research enabled observation of micro-structural changes and failure behaviour under compressive and flexural loading conditions on an on-line basis. The results obtained are encouraging and lead to increased understanding of cracking mechanisms in concrete containing various types of additives and aggregates. The application of the AE technique allowed the failure of interfacial bonding to be observed. The variation of the aggregate size and its effect on the monitored waveforms was established and the parameters in the AE signals are directly related to crack propagation (grain bridging/micro-mechanism) and strength of interfacial bonding. These findings have greatly contributed to the understanding of the concrete behaviour under complex conditions where no other technique could provide such valuable information on an online basis