  (Abridged) The observed presence of pure CO2 ice in protostellar envelopes is
attributed to thermally induced ice segregation, but a lack of quantitative
experimental data has prevented its use as a temperature probe. Quantitative
segregation studies are also needed to characterize diffusion in ices, which
underpins all ice dynamics and ice chemistry. This study aims to quantify the
segregation mechanism and barriers in different H2O:CO2 and H2O:CO ice mixtures
covering a range of astrophysically relevant ice thicknesses and mixture
ratios. The ices are deposited at 16-50 K under (ultra-)high vacuum conditions.
Segregation is then monitored at 23-70 K as a function of time, through
infrared spectroscopy. Thin (8-37 ML) H2O:CO2/CO ice mixtures segregate
sequentially through surface processes, followed by an order of magnitude
slower bulk diffusion. Thicker ices (>100 ML) segregate through a fast bulk
process. The thick ices must therefore be either more porous or segregate
through a different mechanism, e.g. a phase transition. The segregation
dynamics of thin ices are reproduced qualitatively in Monte Carlo simulations
of surface hopping and pair swapping. The experimentally determined
surface-segregation rates for all mixture ratios follow the Ahrrenius law with
a barrier of 1080[190] K for H2O:CO2 and 300[100] K for H2O:CO mixtures. During
low-mass star formation H2O:CO2 segregation will be important already at 30[5]
K. Both surface and bulk segregation is proposed to be a general feature of ice
mixtures when the average bond strengths of the mixture constituents in pure
ice exceeds the average bond strength in the ice mixture.
