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Further increase in the grinding times to 6 (for PAL-6, PAL-8 and PAL- 10 samples), the intensity of the characteristic diffraction peak at 2¦È=8.38¡ã (d=10.6 Å [24] remarkably decreased and the otherpeaks had no obvious change, indicating that the repeated grinding treatment with high intensity would affect the crystal structure of PAL to certain extent and slightly reduced its order¨Cdisorder structural degree [26], which was an advantageous property for well-defined adsorbents [27], as validated by the following adsorption results for MB. The intensity of the peak at 2¦È=8.38¡ã (d=10.6 Å [24] forPAL-6 was lowest, increased for PAL-8 and decreased for PAL-10. This may be according to following reasons: for PAL-6, the crystal aggregates were dissociated and crystal rods were shortened, thusleading to large degree of destructiveness in crystal structure; for PAL-8, more stressing force acted on the sample, and then crystal structure was further affected. The crystal rods would rearrange due to minimum energy principle, leading to the crystal structure was recovered to a certain extent; whereas for PAL-10, superabundant stressing force operated on the sample, and then crystal structure was affected so serious that it was difficult to be recovered 3.4. Effect of grinding treatment on specific surface area Specific surface area is one of the most crucial physical-chemical properties of an adsorbent as to remove heavy metal ions and dyes. Liu et al. [28] found that the specific surface area of CTA+-REC had significant effect on the removal of anionic dye Congo red, and the similar results were reported by Chen et al. [29]. Thus, the effect of grinding times on specific surface area of PAL was investigated and shown in Table 1. SBET and Smicro of PAL-0 were only 153 and 28 m2/g, respectively. The SBET was greatly enhanced after grinding treatment. The SBET firstly increased to 229 m2/g for PAL-2, and then decreased to 184 m2/g for PAL-6. With further increasing the grinding times to 8, the SBET increased to 213 m2/g and kept constant. Furthermore, the tendency of Sext/SBET ratio versus grinding times was quite the reverse of the SBET and only little change in the value of Sext can be found. For PAL samples with grinding treatment, the Sext/SBET ratio increased until PAL-6 and then decreased with increasing grinding times due to the change in the SBET, indicating grinding treatment had insignificant effect on the Sext. The tendencies in Smicro and the Smicro/SBET ratio with grinding timeswere in linewith the obtained for SBET. Itwas also clearly observed that Smicro increased with the grinding times until PAL-2 and then decreased until PAL-6 and finally increased. The Smicro of PAL with grinding treatment was higher than that initial PAL-0 value. In all, the SBET of grinding treated PAL was obviously higher than that of PAL-0 due to the increase in Smicro. This was attributed to that the rod-like crystals of PAL become shorter after grinding treatment as validated by FESEMimages, which led to the increase inmicroparticles, and then resulted in the increase of Smicro 3.5. Effect of grinding treatment on pore-size distribution The pore size of an adsorbent material exhibits great influence on the adsorption capacity for dyes or metal ions, especially for adsorbates with large and complex molecular structures. In this case, the effect of grinding treatment on pore-size distribution for PAL samples was studied and illustrated in Fig. 4. As shown in the inset of Fig. 4, the first peak at about 3.5 nm for PAL-0, 3.6 nm for PAL-2 and PAL- 4, 3.8 nm for PAL-6, PAL-8 and PAL-10 was ascribed to the mesopores between layers of PAL and furthermore, as pore size was in the range of 0 and 8.0 nm, the peak area was in the order of PAL-4>PAL-2> PAL-0>PAL-6>PAL-8>PAL-10, suggesting the mesopore volume had the same sequence except PAL-0 and PAL-4. It was clear from Fig. 4 that another peak at 30 nm for PAL-0 and 28 nm for PAL-2, PAL-4, PAL-6 and PAL-8 and 29 nm for PAL-10 was corresponding to non-structural pores between microparticles of PAL. In addition, the first set of peaks were small and narrow attributed to the inner surface area, while the second set of peaks were large and broad attributed to the outer surface area of PAL. This means that the pores present an irregular size distribution [30,31]. Furthermore, the results suggested that the non-structural pores among microparticles of PAL were dominant and responsible for the large proportion of the pore volume and specific surface area. It can be also seen from Fig. 4 the non-structural pore of PAL-2, PAL-4, PAL-6, PAL-8 and PAL-10 was a little smaller than that of PAL-0. This may be due to that the change of crystal aggregates and the break of rod-like crystals of PAL. The strong compression and shearing action resulting from the stone miller disc led to the rearrangement of crystal bundles and the stack of crystals became compact, which caused a small decrease in nonstructural pores of PAL-2, PAL-4, PAL-6, PAL-8 and PAL-10 and thechange in structure of crystal aggregates. Due to strong shearing forces induced by the stone miller operating on the PAL, crystal aggregates, bundles were dissociated and part of single crystals were shortened. According to the Van der Waals forces and hydrogen bonds, part of dissociated crystal aggregates, bundles and single crystals would rearrange and part of the interstitial spaces between the crystal aggregates would change according to minimum energy principle. Under these conditions, shortened crystals would be more compact. A slight decrease of intensity in the second peak set and the increase of intensity in the first peak set with grinding treatment were observed. Thus there was a slight change in pore volume of PAL after grinding treatment and the extent in change depended on the decreasing extent in the second set of peak and increasing extent in the first set of peak |
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