The thermal shrinkage and weight loss of a systematic series of geopolymers with nominal composition of NaAlO2(SiO2) (z) center dot 5.5H(2)O (1.15 <= z <= 2.15) made by activation of metakaolin with sodium silicate solutions are presented. The thermal behaviour of Na-geopolymers are varied, but may be categorised into four regions of behaviour exhibited by all specimens. This investigation explores the effect of nominal Si/Al on the processes and mechanisms of thermal shrinkage and weight loss throughout constant heating of Na-geopolymer. The overall thermal shrinkage of Na-geopolymer increases with increasing nominal Si/Al, with the onset temperature of structural densification occurring at lower temperature with increasing Si/Al. Thermal shrinkage is observed to result from capillary strain, dehydroxylation and viscous sintering in different temperature regions, and is explored by use of dilatometry, thermogravimetry, nitrogen porosimetry and use of different constant heating rates.