Surface chemistry materials

George M. Whitesides is Mallinckrodt Professor of Chemistry at Harvard University. He received his A.B. from Harvard College in 1960 and his Ph.D. from the California Institute of Technology in 1964. His research areas are Materials Science and Organic Chemistry, with specific focus in surface chemistry, materials science, self-assembly, capillary electrophoresis, organic solid state, molecular virology, directed ligand discovery, and protein chemistry. He is a member of the National Academy of Sciences, and he received the U.S. National Medal of Science in 1998. 

In recent years, advances in experimental capabilities have fueled a great deal of activity in the study of the electrified solid-liquid interface. This has been the subject of a recent workshop and review article [145] discussing structural characterization, interfacial dynamics and electrode materials. The field of surface chemistry has also received significant attention due to many surface-sensitive means to interrogate the molecular processes occurring at the electrode surface. Reviews by Hubbard [146, 147] and others [148] detail the progress. In this and the following section, we present only a brief summary of selected aspects of this field. 

A very important but rather complex application of surface chemistry is to the separation of various types of solid particles from each other by what is known as flotation. The general method is of enormous importance to the mining industry it permits large-scale and economic processing of crushed ores whereby the desired mineral is separated from the gangue or non-mineral-containing material. Originally applied only to certain sulfide and oxide ores. 

This chapter concludes our discussion of applications of surface chemistry with the possible exception of some of the materials on heterogeneous catalysis in Chapter XVIII. The subjects touched on here are a continuation of Chapter IV on surface films on liquid substrates. There has been an explosion of research in this subject area, and, again, we are limited to providing just an overview of the more fundamental topics. 

Students and instructors). Each chapter presents first the basic surface chemistry of the topic, with optional material in small print. Derivations are generally given in full and this core material is reinforced by means of problems at the end of the chapter. A solutions manual is available to instructors. It is assumed that students have completed the usual undergraduate year course in physical chemistry. As a text for an advanced course, the basic material is referenced to fundamental, historical sources, and to contemporary ones where new advances have been incorporated. There are numerous examples and data drawn from both the older and from current literature. 

Cluster research is a very interdisciplinary activity. Teclmiques and concepts from several other fields have been applied to clusters, such as atomic and condensed matter physics, chemistry, materials science, surface science and even nuclear physics. Wlrile the dividing line between clusters and nanoparticles is by no means well defined, typically, nanoparticles refer to species which are passivated and made in bulk fonn. In contrast, clusters refer to unstable species which are made and studied in the gas phase. Research into the latter is discussed in the current chapter. 

The definition above is a particularly restrictive description of a nanocrystal, and necessarily limits die focus of diis brief review to studies of nanocrystals which are of relevance to chemical physics. Many nanoparticles, particularly oxides, prepared dirough die sol-gel niediod are not included in diis discussion as dieir internal stmcture is amorjihous and hydrated. Neverdieless, diey are important nanoniaterials several textbooks deal widi dieir syndiesis and properties [4, 5]. The material science community has also contributed to die general area of nanocrystals however, for most of dieir applications it is not necessary to prepare fully isolated nanocrystals widi well defined surface chemistry. A good discussion of die goals and progress can be found in references [6, 7, 8 and 9]. Finally, diere is a rich history in gas-phase chemical physics of die study of clusters and size-dependent evaluations of dieir behaviour. This topic is not addressed here, but covered instead in chapter C1.1, Clusters and nanoscale stmctures, in diis same volume. 

Unlike melting and the solid-solid phase transitions discussed in the next section, these phase changes are not reversible processes they occur because the crystal stmcture of the nanocrystal is metastable. For example, titania made in the nanophase always adopts the anatase stmcture. At higher temperatures the material spontaneously transfonns to the mtile bulk stable phase [211, 212 and 213]. The role of grain size in these metastable-stable transitions is not well established the issue is complicated by the fact that the transition is accompanied by grain growth which clouds the inteiyDretation of size-dependent data [214, 215 and 216]. In situ TEM studies, however, indicate that the surface chemistry of the nanocrystals play a cmcial role in the transition temperatures [217, 218]. 

The properties of fillers which induence a given end use are many. The overall value of a filler is a complex function of intrinsic material characteristics, eg, tme density, melting point, crystal habit, and chemical composition and of process-dependent factors, eg, particle-si2e distribution, surface chemistry, purity, and bulk density. Fillers impart performance or economic value to the compositions of which they are part. These values, often called functional properties, vary according to the nature of the appHcation. A quantification of the functional properties per unit cost in many cases provides a vaUd criterion for filler comparison and selection. The following are summaries of key filler properties and values. 

Chemical appHcations of Mn ssbauer spectroscopy are broad (291—293) determination of electron configurations and assignment of oxidation states in stmctural chemistry polymer properties studies of surface chemistry, corrosion, and catalysis and metal-atom bonding in biochemical systems. There are also important appHcations to materials science and metallurgy (294,295) (see Surface and interface analysis). 

Other applications of REELM include monitoring variations like oxidation, segregation, and hydration in the surface chemistry of polycrystalline materials. Differences of 1 /10 of a monolayer in oxygen coverage due to variations in grain... 

The most useful application of ISS is in the detection and identification of sur-fece contamination, which is one of the major causes of product failures and problems in product development. The surface composition of a solid material is almost always different than its bulk. Therefore, surface chemistry is usually the study of unknown surfaces of solid materials. To better understand the concept of surface analysis, which is used very loosely among many scientists, we must first establish a definition for that term. This is particularly Important when considering ISS... 

Applications of ISS to polymer analysis can provide some extremely useful and unique information that cannot be obtained by other means. This makes it extremely complementary to use ISS with other techniques, such as XPS and static SIMS. Some particularly important applications include the analysis of oxidation or degradation of polymers, adhesive failures, delaminations, silicone contamination, discolorations, and contamination by both organic or inorganic materials within the very outer layers of a sample. XPS and static SIMS are extremely comple-mentar when used in these studies, although these contaminants often are undetected by XPS and too complex because of interferences in SIMS. The concentration, and especially the thickness, of these thin surfiice layers has been found to have profound affects on adhesion. Besides problems in adhesion, ISS has proven very useful in studies related to printing operations, which are extremely sensitive to surface chemistry in the very outer layers. 

One of the most common modes of characterization involves the determination of a material s surface chemistry. This is accomplished via interpretation of the fiag-mentation pattern in the static SIMS mass spectrum. This fingerprint yields a great deal of information about a sample s outer chemical nature, including the relative degree of unsaturation, the presence or absence of aromatic groups, and branching. In addition to the chemical information, the mass spectrum also provides data about any surface impurities or contaminants. 

In a molded polymer blend, the surface morphology results from variations in composition between the surface and the bulk. Static SIMS was used to semiquan-titatively provide information on the surface chemistry on a polycarbonate (PC)/polybutylene terephthalate (PBT) blend. Samples of pure PC, pure PBT, and PC/PBT blends of known composition were prepared and analyzed using static SIMS. Fn ment peaks characteristic of the PC and PBT materials were identified. By measuring the SIMS intensities of these characteristic peaks from the PC/PBT blends, a typical working curve between secondary ion intensity and polymer blend composition was determined. A static SIMS analysis of the extruded surface of a blended polymer was performed. The peak intensities could then be compared with the known samples in the working curve to provide information about the relative amounts of PC and PBT on the actual surface. 

The synthesis of the packing materials is done by experienced polymer chemists using standardized equipment and procedures. PSS takes special care in cleaning the sorbents after polymerization to achieve constant quality and surface chemistry characteristics. Each production step is checked separately for quality control conformity. 

Apart from manifold structures, carbons can have various shapes, forms, and textures, including powders with different particle size distributions, foams, whiskers, foils, felts, papers, fibers [76, 77], spherical particles [76] such as mesocarbon microbeads (MCMB s) [78], etc. Comprehensive overviews are given, for example in [67, 71, 72], Further information on the synthesis and structures of carbonaceous materials can be found in [67, 70, 72, 75, 79]. Details of the surface composition and surface chemistry of carbons are reviewed in Chapter II, Sec. 8, and in Chapter III, Sec. 6, of this handbook. Some aspects of surface chemistry of lithiated carbons will also be discussed in Sec. 5.2.2.3. 

The SEI is formed by parallel and competing reduction reactions and its composition thus depends on i0, t], and the concentrations of each of the electroactive materials. For carbon anodes, (0 also depends on the surface properties of the electrode (ash content, surface chemistry, and surface morphology). Thus, SEI composition on the basal plane is different from that on the cross—section planes. 

Models of chemical reactions of trace pollutants in groundwater must be based on experimental analysis of the kinetics of possible pollutant interactions with earth materials, much the same as smog chamber studies considered atmospheric photochemistry. Fundamental research could determine the surface chemistry of soil components and processes such as adsorption and desorption, pore diffusion, and biodegradation of contaminants. Hydrodynamic pollutant transport models should be upgraded to take into account chemical reactions at surfaces. 

The formation of ordered two- and three-dimensional microstructuies in dispersions and in liquid systems has an influence on a broad range of products and processes. For example, microcapsules, vesicles, and liposomes can be used for controlled drug dehvery, for the contaimnent of inks and adhesives, and for the isolation of toxic wastes. In addition, surfactants continue to be important for enhanced oil recovery, ore beneficiation, and lubrication. Ceramic processing and sol-gel techniques for the fabrication of amorphous or ordered materials with special properties involve a rich variety of colloidal phenomena, ranging from the production of monodispersed particles with controlled surface chemistry to the thermodynamics and dynamics of formation of aggregates and microciystallites. 

The use of ordered supramolecular assemblies, such as micelles, monolayers, vesicles, inverted micelles, and lyotropic liquid crystalline systems, allows for the controlled nucleation of inorganic materials on molecular templates with well-defined structure and surface chemistry. Poly(propyleneimine) dendrimers modified with long aliphatic chains are a new class of amphiphiles which display a variety of aggregation states due to their conformational flexibility [38]. In the presence of octadecylamine, poly(propyleneimine) dendrimers modified with long alkyl chains self-assemble to form remarkably rigid and well-defined aggregates. When the aggregate dispersion was injected into a supersaturated... 

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