Thermal Behaviour of Poly(propylene) Layered Silicate Nanocomposites

The thermal degradation behaviour of nanocomposites based upon poly(propylene)/organoclay, modified with protonated octadecyl amine (C18) in comparison to that of non‐exfoliated microcomposites based upon organoclay, modified with protonated butyl amine (C4), was studied by thermogravimetry. In the case of the nanocomposite, the temperature at which volatilisation occurs increases as compared of the microcomposite. Moreover, the thermal oxidation process of the polymer is strongly slowed down in the nanocomposite with high char yield both by a physical barrier effect, enhanced by ablative reassembling of the silicate, and by a chemical catalytic action due to the silicate and to the strongly acid sites created by thermal decomposition of the protonated amine silicate modifier.     

Polyhedral oligomeric silsesquioxanes (POSS) thermal degradation

The mechanism of thermal degradation of several substituted polyhedral oligomeric silsesquioxanes (POSS) cages is studied in this work.Hydrogen POSS and methyl POSS shows incomplete sublimation on heating, both in inert atmosphere and in air. Isobutyl and octyl substituted POSS undergo an almost complete evaporation when heated in inert atmosphere. In air, oxidation competes with volatilization, producing a considerable amount of silica-like residue on heating up to 800 °C.Phenyl POSS shows a higher thermal stability than saturated aliphatic POSS and limited volatility, producing a ceramic residue at high yield on heating in nitrogen, composed of a silica containing a considerable amount of free-carbon. A lower amount of residue is shown after heating in air, corresponding to the POSS Si-O fraction.A vinyl POSS cage/network resin is also studied, in comparison to above materials, showing the highest ceramic yield.     

Quantitative extraction of uranium(VI) in aqueous solutions with n-alkylamine intercalates of γ-titanium phosphate

The intercalation compounds Ti(C₃H₇NH₂)(HPO₄)₂·H₂O (18.4 Å) (-TiP/n-Pr) and Ti(C₄H₉NH₂)(HPO₄)₂·H₂O (20.5 Å) (-TiP/n-Bu) have been prepared using -titanium phosphate, Ti(HPO₄)₂·2H₂O (11.6 Å), as precursor. The retention of UO ₂ ²⁺ , in aqueous solutions by -TiP is very low being only a superficial adsorption phenomenon. When the intercalated materials are used, the retention is quantitative until 95% of the cation exchange capacity in the -TiP/n-Pr case (c.e.c.=6.30 mequiv./g), and over 80% for the -TiP/n-Bu compound (c.e.c.=6.04 mequiv./g).     

Thermal degradation of polymer-fire retardant mixtures: Part III—Degradation products of polypropylene-chlorinated paraffin mixtures

When polypropylene is thermally degraded in mixtures with a highly chlorinated fire retardant chloroparaffin, a smaller amount of the lighter hydrocarbon fraction, which is also modified in composition, is evolved compared with that evolved from pure polypropylene. A corresponding increase in the amount of high boiling chain fragments is obtained from the mixtures. This effect can be explained in terms of the interactions which occur between degrading polymer and additive.     

Metal functionalized POSS as fire retardants in polypropylene

This paper deals with the study of the combustion properties of dimeric and oligomeric Al-and Zn-isobutyl silsesquioxane (POSS)/polypropylene (PP) composites, in comparison with neat PP and PP/octaisobutyl POSS.The presence of Al-POSS leads to a decrease in combustion rate with respect to PP, resulting in a decrease of Heat Release Rate (−43% at 10 wt% POSS loading) as well as reduction in CO and CO₂ production rates, whereas a negative effect on the above parameters is obtained with octaisobutyl POSS. Zn-POSS does not significantly affect the PP combustion behaviour.The effect of Al-POSS is most likely related to its chemical activity, which favours the formation of a moderate amount of char residue, by catalysing secondary reactions in the polymer during combustion.     

Performance and mechanisms of fire retardants in polymers—A review

The fundamental mechanisms by which fire retardant additives can interrupt the self-sustained combustion cycle of organic polymers are reviewed. Evaluation of fire retardant performance and methods used for mechanism assessment are discussed. Examples are given of recent mechanistic studies of halogen-based and intumescent systems indicating that some previous generalisations should be revised. It is shown that a deeper understanding of fire retardance mechanisms acquired through detailed thermal degradation studies is the only way to answer the ever increasing demand for polymeric materials characterised by minimised overall fire hazard.     

Study of the mechanism of intumescence in fire retardant polymers: Part V—Mechanism of formation of gaseous products in the thermal degradation of ammonium polyphosphate

On heating, ammonium polyphosphate eliminates ammonia and water in two successive steps. The first (T = 165–280°C) involves a limited weight loss (ca. 3%) and the formation of some branched structures. The transition from one crystalline form of ammonium polyphosphate to another, more stable, form, may prevent further elimination of NH₃ and H₂O which occurs in the second step (T > 280°C). The final product of degradation is characterised by a crosslinked POP structure formed by elimination of H₂O between POH groups freed by the evolution of NH₃.     

Thermal degradation of fire retardant chloroparaffin-metal compound mixtures—Part I: Antimony oxide

The main characteristics of the evolution of HCl and SbCl₃ during the thermal degradation of chloroparaffin-Sb₂O₃ mixtures, which are typical fire retardant additives for polymers, have been studied.Sb₂O₃ reacts with HCl evolved from the chloroparaffin without any apparent effect on the dehydrochlorination process itself. Evolution of SbCl₃ occurs at a maximum rate between 300 and 350°C and is somewhat delayed in the earlier stage of reaction, depending on the composition of the mixture.     

Thermal decomposition of antimony oxyhalides

The thermal decomposition of SbOCl, Sb₄O₅Cl₂ and Sb₈O₁₁Cl₂ has been studied by thermogravimetry with identification of the products resulting in the condensed phase by X-ray diffraction and infrared technique. It is shown that in nitrogen SbOCl undergoes progressive stepwise thermal disproportionation to Sb₂O₃ and SbCl₃ with formation of Sb₄O₅Cl₂ and Sb₈O₁₁Cl₂ and as intermediates. It is thus confirmed that Sb₃O₄Cl, suggested to be formed instead of Sb₈O₁₁Cl₂, is not an intermediate of this process. An identical mechanism is observed in air but with oxidation of Sb₂O₃ to Sb₂O₄.

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Zusammenfassung Mittels TG wurde die thermische Zersetzung von SbOCl, Sb₄O₅Cl₂ und Sb₈O₁₁Cl₂ untersucht und die entstehenden Produkte der kondensierten Phase mittels Röntgendiffraktionsuntersuchungen und IR-Spektroskopie identifiziert. Es wurde gezeigt, daß SbOCl in Stickstoff einer stufenweise thermische Disproportionierung unterliegt, bei der über die Zwischenprodukte Sb₄O₅Cl₂ und Sb₈O₁₁Cl₂ zuletzt Sb₂O₃ und SbCl₃ entstehen. Es wurde weiterhin bewiesen, daß das anstelle von Sb₈O₁₁Cl₂ vorgeschlagene Sb₃O₄C_l kein Zwischenprodukt dieses Zersetzungsvorganges ist. Ein ähnlicher Mechanismus gilt für die Zersetzung in Luft, jedoch mit der Oxidation von Sb₂O₃ zu Sb₂O₄.

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This work was carried out with the financial support of the Progetto Finalizzato Chimica Fine II del Consiglio Nationale delle Ricerche.     

Synthesis and Characterization of α‐Titanium Phosphate/Propylamine Intercalation Compounds Containing Transition‐Metal Ions

Polycrystalline intercalated TiM_xH_2−nx(PO₄)₂· yC₃H₇NH₂·wH₂O compounds with transition metal (TM) ions (Mⁿ⁺ = Co²⁺, Ni²⁺, Fe³⁺ or Cr³⁺) have been prepared by means of an indirect route and characterised using X-ray diffraction, scanning electron microscopy, chemical and thermal analysis, X-ray absorption and magnetic measurements. These novel pillared layered materials, which were obtained from the monoclinic (P2₁/c space group) α-Ti(HPO₄)₂·H₂O phase, lose its crystallinity after intercalation. However all the TM ions are octahedrally surrounded by 6 oxygen atoms, although the X-ray absorption spectra evidence a clear dependence on the temperature. Surprisingly, all the materials behave as paramagnetic down to 1.5 K, but they exhibit different colours, what means that they are optically active (Co²⁺: violet; Ni²⁺: pale green; Fe³⁺: yellow; Cr³⁺: dark green).