Endothermic fillers

Owens-Corning claimed the use of ammonium fluoroborate or potassium fluoroborate as smoke suppressant in isocyanurate-urethane.107 It was believed that the fluoroborate decomposition products such as BF3, KF, or NH4F act as free radical chain stopper and add across double bounds of olefinic decomposition products. NASA reported that both ammonium fluoroborate and potassium fluoroborate are the effective endothermic fillers of ablative intumescent coating.108... 

Sawko, PM. and Salvatore, R. 1978. Intumescent ablator using endothermic filler. U.S. Patent 4,088,806. 

The authors of [99] proposed a calorimetric method for determining the degree of the polymer-filler interaction the exothermal effect manifests itself in the high energy of the polymer-filler adhesion, the endothermal effect is indicative of a poor, if any, adhesion. The method was used to assess the strength of the PVC-Aerosil interaction with Aerosil surface subjected to different pre-treatments... 

Using calorimetry to estimate the degree of filler-polymer interaction as described in [99] the authors of [318, 319] determined that the filler reaction with PVC is exothermic, which is indicative of a stronger bond in the polymer-filler system. No thermal effect was noted for mechanical mixtures, except for a few cases where it was endothermal. 

Prior to the chemical reaction of the silane with the silanol-groups on the sUica surface, the silane molecule has to make contact with the sUica surface by adsorption. Then the chemical reaction of silica with an alkoxy-silyl moiety of the coupling agent takes place in a two-step, endothermic reaction. The primary step is the reaction of alkoxy-groups with silanol-groups on the silica filler surface [4]. Two possible mechanisms are reported ... 

Aluminium hydroxide is essentially non-toxic, but does require high addition levels to be effective. As a result, the physical properties of the compound usually suffer. Its fire retardancy action results from the endothermic reaction which releases water under fire conditions and produces a protective char . The endothermic reaction draws heat from the rubber/filler mass and thus reduces the thermal decomposition rate. The water release dilutes the available fuel supply, cooling the rubber surface and mass. 

The performance of aluminium hydroxide/magnesium hydroxide-filled systems can be enhanced by incorporation of zinc hydroxystannate in halogen-free rubbers giving reduced smoke and toxic gas emission, coupled with higher flame retardancy. This action will be complimentary to the water release and endothermic effects of aluminium hydroxide/magnesium hydroxide filler systems. 

One of the emerging technologies that is showing great promise is the use of hydrated mineral fillers such as aluminium and magnesium hydroxides, as such materials can provide high levels of flame retardancy without the formation of smoke or corrosive and potentially toxic fumes. The use of fillers as flame retardants has recently been reviewed by Rothon [23]. Essentially the key features are an endothermic decomposition to reduce the temperature, the release of an inert gas to dilute the combustion gases and the formation of an oxide layer to insulate the polymer and to trap and oxidise soot precursors. 

It is self evident that mineral fillers need to be stable at the temperatures (up to 350 °C) experienced in processing thermoplastics. Most fillers are stable to much higher temperatures and so this is not usually an issue. However, it is a very important topic for flame retardant fillers which function by decomposing endothermically with the release of inert gasses. To be effective, this decomposition must occur near to the temperature at which the polymer begins to decompose and release flammable volatiles. This is usually not too much above the processing temperature in the case of thermoplastics and hence the exact temperature at which decomposition commences is of great importance. The size and position of the endotherm and the rate at which the inert gas is released are also of importance to the flame retardant effect itself [23]. 

Aluminium hydroxide has a Moh hardness of about 3 and a specific gravity of 2.4. It decomposes endothermically with the release of water at about 200 °C and this makes it a very useful flame retardant filler, this being the principal reason for its use in polymers. The decomposition temperature is in fact too low for many thermoplastics applications, but it is widely used in low smoke P VC applications and finds some use in polyolefins. For these applications low aspect ratio particles with a size of about 1 micron and a specific surface area of 4-10 m g are preferred. The decomposition pathway can be diverted through the mono-hydrate by the application of pressure, and this may reduce the flame retardant effect [97]. This effect can be observed with the larger sized particles. Although it is chemically the hydroxide, it has for many years been known as alumina trihydrate and by the acronym ATH. 

FIGURE 7.2 (See color insert following page 530.) Endothermic decomposition of hydrated fillers. (From Camino, G. et al., Polym. Deg. Stab., 74, 457, 2001. With permission.)... 

Filler coke is formed by the same general mechanism as that already described for binder coke. However, the feedstocks used are various petroleum residual fractions, instead of coal tar. Temperatures of 400-500°C convert these resids into green coke within a day. A complex series of endothermic pyrolysis reactions produce liquid-crystal mesophase which is transformed to a carbon polymer of generally graphitic structure. However, there are varying amounts of... 

Flame-retardants are used as additives in the preparation of fire retardant paints. They are decomposed by heat to produce nonflammable components, which are able to blanket the flames. Both inorganic and organic types of flame-retardants are available in the market. The most widely used inorganic flame-retardants are aluminum trihydroxide, magnesium hydroxide, boric acid, and their derivatives. These substances have a flame-retardant action mainly because of their endothermic decomposition reaction and their dilution effect. The disadvantage of these solids is that they are effective in very high filler loads (normally above 60 percent). 

The physical properties of some fillers play a role in their function as stabilizers. A1(OH)3 undergoes endothermic decomposition which lowers temperature of material. Loss of water from MgiOH), may increase stability in some cases. In others, it may cause degradation. This is discussed below. The platelet structure of some fillers (e.g., talc or mica) contributes to an increased thermal stability because the degradation rate is increased as oxygen concentration increases. The structure formed by the platelets reduces the diffusion rate of oxygen. 

Since the decomposition reaction occurs at a specific temperature, the performance of these fillers depends on the properties of the polymers in which they are used. For example, Mg(0H)2 performs better in polyethylene than AlfOI I) because it remains stable during compounding and decomposes at a temperature closer to the decomposition of PE (300-400 C). In unsaturated polyesters, Al(0H)3 starts to release water at 200°C. The major endothermic peak occurs at 300°C with a heat of decomposition of 300 kJ/mol. About 90% of the water is released between 200 and 400 C. A considerable amount of heat is absorbed before the polymer is affected. The water also dilutes combustible gases and hinders the access of oxygen to the polymer surface. Figure 12.8 shows the difference between talc and a fire retardant filler in PP." Talc causes an increase in the combustion rate as its concentration increases, whereas Mg(OH)2, used at a sufficient concentration (above 20%), decreases the rate of combustion. 

Miscellaneous. These approaches include dilution of the polymer with nonflammable materials (for example, inorganic fillers), incorporation of materials that decompose to nonflammable gases such as carbon dioxide, and formulation of products that decompose endothermically. A typical example of such a flame retardant is aluminum oxide trihydrate (AI2O3.3H2O). This type of material acts as a thermal sink to increase the neat capacity of the combusting system, lower the polymer surface temperature via endothermic events, and dilute the oxygen supply to the flame, thereby reducing the fuel concentration needed to sustain the flame. 

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