Clays thermal stability

PLA/PCL-OMMT nano-composites were prepared effectively using fatty amides as clay modifier. The nano-composites shows increasing mechanical properties and thermal stability (Hoidy et al, 2010c). New biopolymer nano-composites were prepared by treatment of epoxidized soybean oil and palm oil, respectively plasticized PLA modified MMT with fatty nitrogen compounds. The XRD and TEM results confirmed the production of nanocomposites. The novelty of these studies is use of fatty nitrogen compoimds which reduces the dependence on petroleum-based surfactants (Al-Mulla et al., 2011 Al-Mulla et ah, 2011 Al- Mulla et ah, 2010c). 

Polyimide-clay nanocomposites constitute another example of the synthesis of nanocomposite from polymer solution [70-76]. Polyimide-clay nanocomposite films were produced via polymerization of 4,4 -diaminodiphenyl ether and pyromellitic dianhydride in dimethylacetamide (DMAC) solvent, followed by mixing of the poly(amic acid) solution with organoclay dispersed in DMAC. Synthetic mica and MMT produced primarily exfoliated nanocomposites, while saponite and hectorite led to only monolayer intercalation in the clay galleries [71]. Dramatic improvements in barrier properties, thermal stability, and modulus were observed for these nanocomposites. Polyimide-clay nanocomposites containing only a small fraction of clay exhibited a several-fold reduction in the... 

A fluid loss additive for hard brine environments has been developed [1685], which consists of hydrocarbon, an anionic surfactant, an alcohol, a sulfonated asphalt, a biopolymer, and optionally an organophilic clay, a copolymer of N-vinyl-2-pyrrolidone and sodium-2-acrylamido-2-methylpropane sulfonate. Methylene-bis-acrylamide can be used as a crosslinker [1398]. Crosslinking imparts thermal stability and resistance to alkaline hydrolysis. 

Singh, I.B., Chaturvedi, K., Singh, D.R., and Yegneswaran, A.H., Thermal stabilization of metal finishing waste with clay, Environmental Technology, 26 (8), 877-884, 2005. 

The thermal stability of PMI with additives is not changed by the introduction of clay, charcoal, AI2O3. These additives were quite stable over the temperature range under study (up 900°C). The lower thermal stability observed for the cases of ZnCl2 and NiC12 as additives may have resulted from a change in the degradation mechanism. 

The aluminium content of the two samples is comparable, when referred to the silica content of the original clay, and the two PILC have comparable surface areas after calcination at 300°C. The ACH bentonite was formed into small extrudates and flash-dried, whereas sample G5 was dried in a thin cake. In both cases, crushing to a fine powder was easy. Sample G5 retains a higher surface area at 800°C in spite of a higher potassium content. Therefore the K O content of the PILC is not the predominant factor for the thermal stability. 

Table 6 Influence of the K O content on the thermal stability of clays. (1) this work original clay and sample G5.

Lithium introduced in the structure of the clay allows to control the density of the pillars and the strength of interaction between the pillar and the clay layer. At low calcination temperature, the interlayer distances and the surface area increased. The thermal stability of the clay, calcined at temperature higher than 400°C, drastically decreases. 

Brindley and Sempels (1), Vaughan et al. (2) and Shabtai (3) have shown that the experimental conditions of Al intercalation influences the physicochemical properties of the clay. The nature, amount and spacial distribution of the pillars change the thermal stability, texture and acidity of the pillared clays. For example, Rausch and Bale (4) have reported that the OH/Al ratio modifies the structure of the Al complex and that monomeric [Al(0H)x(H20)6-x] " or polymeric [A1i304(0H)24(H20)i2] species can be obtained. Clearfield (5) demonstrated that the polymerisation state of Zr species depends on the temperature, concentration and pH of the solutions. In any case, the height of pillars is largely controlled by the polymerisation state of the intercalated complexes. However, in order to maintain the accessibility of the inner surface, the density or spacial distribution of the pillars has to be controlled. This parameter has been studied by Flee et al (5), and Shabtai et al (7) for Al pillared clays and Farfan-Torres et al (8) for zirconium. 

A small increase of the (d 001) basal spacing is observed for the Li containing Zr pillared clays. However, the thermal stability of these solids drastically decrease. At high temperature, the collapse of the strucutre is also supported by the decrease of the surface area which is, at 700°C, almost identical to those measured for the montmorillonite. Different hypothesis may be proposed to explain the increase of the interlayer distance at low temperature (i) a better polymerization of the intercalated complex (ii) a modification of the distribution of the pillars (iii) a lower interaction between the pillar and the silica layer. The first hypothesis may easily be eliminated since the small variation of the height of the pillars (less than 1 A) cannot be explained by structural changes of the... 

However, the thermal stability of the Li-Zr pillared clays is drastically influenced after calcination at temperatures higher than 400°C. This is mainly due to Li acting as flux. 

Vidal, O. 1997. Experimental study of the thermal stability of pyrophyllite, paragonite and clays in a thermal gradient. European Journal of Mineralogy, 9, 123-140. 

In rubber-plastic blends, clay reportedly disrupted the ordered crystallization of isotactic polypropylene (iPP) and had a key role in shaping the distribution of iPP and ethylene propylene rubber (EPR) phases larger filler contents brought about smaller, less coalesced and more homogeneous rubber domains [22]. Clays, by virtue of their selective residence in the continuous phase and not in the rubber domains, exhibited a significant effect on mechanical properties by controlling the size of rubber domains in the heterophasic matrix. This resulted in nanocomposites with increased stiffness, impact strength, and thermal stability. 

In the case of 34NBR, the polymer chains have H-bonding interactions with the clay along with van der Waals interactions. These in turn improve the thermal stability of the nanocomposite. 

Compatibility of NA with organic polymer is much inferior to the compatibility of , 15A, and SP. Thus, Sl-NA-4 has inferior thermal stability as compared to the other three clays. Moreover, the intergallery spacing of NA is very small (only 1.22 nm, obtained from XRD results, Fig. 26a). Only a few chains of HNBR (with 34% acrylonitrile content), being bulky in nature, can find their way into such a small gallery space, which results in poor polymer-filler interaction. This is confirmed by both XRD and (Fig. 26a, b). 

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