In the frame of future exploration missions such as Solar Probe Plus (NASA) and PHOIBOS (ESA), research was carried out to study pyrolytic BN material envisaged as coating for their heat shields. The physico-chemical behavior of CVD pBN at very high temperature with or without hydrogen ions and VUV (Vacuum Ultra-Violet) irradiations was studied in high vacuum together with the in situ measurement of the thermal radiative properties conditioning the thermal equilibrium of the heat shield. Experimental results obtained on massive pBN samples are presented through in situ mass spectrometry and mass loss rate, and post-test microstructural characterization by XRD, SEM, AFM and nano-indentation techniques, some of them leading to mechanical properties. It could be concluded that synergistic effect of high temperature, protons and VUV radiation has an impact on the emission of gaseous species, the mass loss rate and the mechanical properties of the material.