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For high-voltage components, the measurement of partial discharge (PD) is a useful tool for performance assessment of electrical insulation. In this study, experimental measurements of PD activity for different spherical cavity sizes and material temperatures have been performed. A simulation model representing PD behaviour within spherical cavities in homogeneous dielectric materials has also been developed. The model has been used to study the influence of cavity size and material temperature on PD activity. Comparison of measurement and simulation results has been undertaken. The model uses a finite element analysis (FEA) method along with MATLAB code. It has been found that certain parameters in the model are both cavity size and temperature dependent. Thus, critical parameters influencing PD behaviour for different cavity sizes within the material and material temperatures can be identified; these are the charge decay time constant, cavity surface conductivity, electron generation rate (EGR), PD inception and extinction fields and the cavity temperature decay time constant.