Ignition. In order for most materials to be ignited they should be in a gaseous or vapor state.

A few materials may burn directly in a solid state or glowing form of combustion including some forms of carbon and magnesium. These gases or vapors should then be present in the atmosphere in sufficient quantity to form a flammable mixture. Liquids with flash points below ambient temperatures do not require additional heat to produce a flammable mixture. The fuel vapors produced should then be raised to their ignition temperature. The time and energy required for ignition to occur is a function of the energy of the ignition source, the thermal inertia (k, p, c) of the fuel, and the minimum ignition energy required by that fuel and the geometry of the fuel. If the fuel is to reach its ignition temperature, the rate of heat transfer to the fuel should be greater than the conduction of heat into or through the fuel and the losses due to radiation and convection. A few materials, such as cigarettes, upholstered furniture, sawdust, and cellulosic insulation, are permeable and readily allow air infiltration. These materials can burn as solid phase combustion, known as smoldering. This is a flameless form of combustion whose principal heat source is char oxidation. Smoldering is hazardous, as it produces more toxic compounds than flaming combustion per unit mass burned, and it provides a chance for flaming combustion from a heat source too weak to directly produce flame.

The term smoldering is sometimes inappropriately used to describe a nonflaming response of a solid fuel to an external heat flux. Solid fuels, such as wood, when subjected to a sufficient heat flux, will degrade, gasify, and release vapors. There usually is little or no oxidation involved in this gasification process, and thus it is endothermic. This is more appropriately referred to as forced pyrolysis, and not smoldering.

Ignition of Solid Fuels For solid fuels to burn with a flame, the substance should either be melted and vaporized (like thermoplastics) or be pyrolyzed into gases or vapors (i.e., wood or thermoset plastic). In both examples, heat must be supplied to the fuel to generate the vapors. High-density materials of the same generic type (woods, plastics) conduct energy away from the area of the ignition source more rapidly than low-density materials, which act as insulators and allow the energy to remain at the surface. For example, given the same ignition source, oak takes longer to ignite than a soft pine. Low-density foam plastic, on the other hand, ignites more quickly than highdensity plastic.

The amount of surface area for a given mass (surface area to mass ratio) also affects the quantity of energy necessary for ignition. It is relatively easy to ignite one pound of thin pine shavings with a match, while ignition of a one-pound solid block of wood with the same match is very unlikely. Because of the higher surface area to mass ratio, corners of combustible materials are more easily burned than flat surfaces. These are good estimates for ignition of wood by an existing fire. These temperatures are not to be used to estimate the temperature necessary for the first item to ignite. The absence of the pilot flame requires that the fuel vapors of the first item ignited be heated to their autoignition temperature. In An Introduction to Fire Dynamics, Dougal Drysdale reports two temperatures for wood to autoignite or spontaneously ignite. These are heating by radiation, 600C (1112F), and heating by conduction, 490C (914F).

For spontaneous ignition to occur as a result of radiative heat transfer, the volatiles released from the surface should be hot enough to produce a flammable mixture above its autoignition temperature when it mixes with unheated air. With convective heating on the other hand, the air is already at a high temperature and the volatiles need not be as hot. When exposed to their ignition temperature, thin materials ignite faster than thick materials (e.g., paper vs. plywood).

Ignition of Liquids In order for the vapors of a liquid to form an ignitible mixture, the liquid should be at or above its flash point. The flash point of a liquid is the lowest temperature at which it gives off sufficient vapor to support a momentary flame across its surface based on an appropriate ASTM test method. The value of the flash point may vary depending on the type of test used. Even though most of a liquid may be slightly below its flash point, an ignition source can create a locally heated area sufficient to result in ignition.

Atomized liquids or mists (those having a high surface area to mass ratio) can be more easily ignited than the same liquid in the bulk form. In the case of sprays, ignition can often occur at ambient temperatures below the published flash point of the bulk liquid provided the liquid is heated above its flash point and ignition temperature at the heat source.

Ignition of Gases. Combustible substances in the gaseous state have extremely low mass and require the least amount of energy for ignition.

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