Crystal colloidal

2 Colloidal crystals . At the end of Section 2.1.4, there is a brief account of regular, crystal-like structures formed spontaneously by two differently sized populations of hard (polymeric) spheres, typically near 0.5 nm in diameter, depositing out of a colloidal solution. Binary superlattices of composition AB2 and ABn are found. Experiment has allowed phase diagrams to be constructed, showing the crystal structures formed for a fixed radius ratio of the two populations but for variable volume fractions in solution of the two populations, and a computer simulation (Eldridge et al. 1995) has been used to examine how nearly theory and experiment match up. The agreement is not bad, but there are some unexpected differences from which lessons were learned. 

The importance of these pseudo-crystals is that their periodicities are similar to those of visible light and they can thus be used like semiconductors in acting on light beams in optoelectronic devices. 

Just like the lattice structures in atomic crystals, colloidal particles can form equilibrium crystal structures by minimizing their interparticle potentials. Opals are naturally occurring colloidal crystals. These semiprecious stones consist of a close-packed structure of silica spheres 

FIGURE 5.10 (a) Cluster growth by cluster-cluster aggregatlora. (b) Dis- 

FIGURE 5.11 A scanning electron microscopic image of 2-pm polystyrene beads densely packed into crystalline-like domains formed by sedimentation. 

FIGURE 5.12 Striking reflection colors can be seen in this white opal, a naturally occurring colloidal crystal. 

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The entropically driven disorder-order transition in hard-sphere fluids was originally discovered in computer simulations [58, 59]. The development of colloidal suspensions behaving as hard spheres (i.e., having negligible Hamaker constants, see Section VI-3) provided the means to experimentally verify the transition. Experimental data on the nucleation of hard-sphere colloidal crystals [60] allows one to extract the hard-sphere solid-liquid interfacial tension, 7 = 0.55 0.02k T/o, where a is the hard-sphere diameter [61]. This value agrees well with that found from density functional theory, 7 = 0.6 0.02k r/a 2 [21] (Section IX-2A). 

Due to the particle size, a colloidal crystal is much weaker than a nonnal solid material—the elastic moduli are... 

Experimentally, tire hard-sphere phase transition was observed using non-aqueous polymer lattices [79, 80]. Samples are prepared, brought into the fluid state by tumbling and tlien left to stand. Depending on particle size and concentration, colloidal crystals tlien fonn on a time scale from minutes to days. Experimentally, tliere is always some uncertainty in the actual volume fraction. Often tire concentrations are tlierefore rescaled so freezing occurs at ( )p = 0.49. The widtli of tire coexistence region agrees well witli simulations [Jd, 80]. 

The fonnation of colloidal crystals requires particles tliat are fairly monodisperse—experimentally, hard sphere crystals are only observed to fonn in samples witli a polydispersity below about 0.08 [69]. Using computer... 

Alexander S, Chaikin P M, Grant P, Morales G J, Pincus P and Hone D 1984 Charge renormalisation, osmotic pressure, and bulk modulus of colloidal crystals theory J. Chem. Phys. 80 5776-81... 

Grier, D.G. (editor) (1998) A series of papers on colloidal crystals, in MRS Bulletin, October 1998. 

Pusey, P.N. (2001) Colloidal Crystals, in Encyclopedia of Materials ed. K.H.J. Buschee et al. (Pergamon, Oxford) in press. 

Colloidal crystals can be grown by a templated approach too. Thus van Blaadcren and Wiltzius (1997) have shown that allowing colloidal spheres to deposit under gravity on to an array of suitably spaced artificial holes in a plate quickly generates a single crystalline layer of colloidal spheres, and a thick crystal will then grow on this basis. 

Comprehension of the interactions among microstructures composed of tethered chains is central to the understanding of many of their important properties. Their ability to impart stability against flocculation to suspensions of colloidal particles [52, 124, 125] or to induce repulsions that lead to colloidal crystallization [126] are examples of practical properties arising from interactions among tethered chains many more are conceivable but not yet realized, such as effects on adhesion, entanglement or on the assembly of new block copolymer microstructures. We will be rather brief in our treatment of interactions between tethered chains since a comprehensive review has been published recently of direct force measurements on interacting layers of tethered chains [127]. 

Chapter 8 presents evidence on how the physical properties of colloidal crystals organized by self-assembly in two-dimensional and three-dimensional superlattices differ from those of the free nanoparticles in dispersion. 

There are very many papers in the literature that address some aspect of gold nanospheres. In particular, their plasmon response (see Section 7.3.1.1) has been well studied, as has their agglomeration [50-52] and the manner in which they can be assembled into highly ordered colloidal crystals [50, 53, 54]. The latter are interesting and will be further discussed in Section 7.3.8.2. Conjugation of gold nanospheres with proteins and antibodies, for use as a stain in microscopy [55] or possibly, in medical applications [23], is another rich field. 

Figure 7.7 Colloidal crystal formed from oleylamine-stabilized gold nanoparticles, Reproduced with permission from Harris etal.

Compton, O.C. and Osterloh, F.E. (2007) Evolution of size and shape in the colloidal crystallization of gold nanopartides. Journal of the American Chemical Society, 129, 7793-7798. 

Sadakane, M., Asanuma, T., Kubo, J. et al. (2005) Facile procedure to prepare three-dimensionally ordered macroporous (3DOM) perovskite-type mixed metal oxides by colloidal crystal templating method, Chem. Mater. 17, 3546. 

If several sharp peaks of colloidal crystals are observed in the SAXS, the unit cell can be determined. 44In this case peak profile analysis can be carried out using the methods discussed in Sect. 8.2.5... 

Holtz J.H. and Asher S.A., Polymerized colloidal crystal hydrogel films as intelligent chemical sensing materials, Nature 1997 389 829-832. 

The concept is demonstrated for a simultaneous immunoassay of (32-microglobulin, IgG, bovine serum albumin, and C-reactive protein in connection with ZnS, CdS, PbS, and CuS colloidal crystals, respectively (Fig. 14.6). These nanocrystal labels exhibit similar sensitivity. Such electrochemical coding could be readily multiplexed and scaled up in multiwell microtiter plates to allow simultaneous parallel detection of numerous proteins or samples and is expected to open new opportunities for protein diagnostics and biosecurity. 

The method for selective chemical sensing using colloidal crystal films is depicted in Fig. 4.1. The steps for the fabrication of the colloidal crystal films and determination of selective chemical sensing response are summarized in Table 4.2. 

Fig. 4.1 Diagram of the method for selective vapor detection that includes fabrication of core (1) and core shell (2) materials, their assembly into a colloidal crystal film (3), exposure of the film to different vapors (4), measurements of the spectral response of the film (5), and multivariate analysis of the spectra (6) to obtain a vapor selective response of the colloidal crystal film...

Assemble colloidal crystal film with core/shell X/Y submicron spheres responsive to both... 

Expose colloidal crystal film to both classes of vapors... 

Measure differential reflectivity spectral response of the colloidal crystal film... 

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