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Exposure of pressure vessels to fire can result in catastrophic explosion and escalation of accidents. The safe transportation of cargo in pressure vessels therefore requires knowledge of what will happen to the cargo in the event of a vehicle derailment or rollover resulting in fire exposure. The chapter presents an overview of selected testing and modelling work undertaken to understand the thermohydraulic processes within a vessel that drive pressurization during fire. A series of experiments highlighting the importance of adequate design and selection of protection systems are summarized. It is concluded that pressure relief alone is typically insufficient to prevent vessel rupture, but the combination of relief and thermal coatings can be effective.