Bulk material

When a bulk material is submitted for analysis, the laboratory should be able to locate and identify very small quantities of asbestos within the sample matrix. Polarised light microscopy methods should be able to detect 0.01% (lOOmg/kg) asbestos if there are no interfering factors, however the majority of building materials or products contain concentrations ranging from virtually 100% asbestos down to around 1% and therefore it should not be difficult to correctly identify whether or not asbestos is present in the majority of routine samples. 

The idea of transforming light into mechanical energy has fascinated many researchers. In the early studies, reviewed by Irie [11], contraction/expansion behavior in conjunction with isomerization of photochromic entities either admixed to or chemically incorporated into polymer films was found. However, the dimensional changes were only marginal, amounting to 1% or less, and on scrutiny, turned out in many cases to be due to the local increase in temperature arising from non-radiative transitions rather than to isomerization of the chromophores. 

real effects, on the other hand, were observed with hydrogels. A typical result is presented in Fig. 5.12, which shows how a polyacrylamide gel containing 1.9 mol% triphenylmethane leucocyanide swells upon irradiation with UV light at 25 °C [49]. The swelling is correlated to a 18-fold increase in the relative weight. 

The possibility of converting light into mechanical energy has been impressively demonstrated with cross-linked liquid-crystalline polymeric systems containing azobenzene groups that were prepared by polymerizing previously aligned mixtures of acrylate 1-AC and diacrylate 2-AC (see Chart 5.10) [51]. 

Chart 5.10 Monomers used to prepare cross-linked polymeric systems exhibiting photomechanical effects. 

The phenomenon of light-induced dimensional alterations in polymer films has been exploited for the generation of regular surface structures in azobenzene-containing polymers. The technique employed is based on the fact that azobenzene groups undergo reorientation due to repeated trans-cis-trans isomerization upon 

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A tracer is a minute amount of matter similar to the bulk material which is added to a flow system without affecting the bulk flow and the concentration of which is measurable. Obtaining information of the tracer flow by measurements provides information about bulk flow properties. 

The limiting compression (or maximum v value) is, theoretically, the one that places the film in equilibrium with the bulk material. Compression beyond this point should force film material into patches of bulk solid or liquid, but in practice one may sometimes compress past this point. Thus in the case of stearic acid, with slow compression collapse occurred at about 15 dyn/cm [81] that is, film material began to go over to a three-dimensional state. With faster rates of compression, the v-a isotherm could be followed up to 50 dyn/cm, or well into a metastable region. The mechanism of collapse may involve folding of the film into a bilayer (note Fig. IV-18). 

The classic nucleation theory is an excellent qualitative foundation for the understanding of nucleation. It is not, however, appropriate to treat small clusters as bulk materials and to ignore the sometimes significant and diffuse interface region. This was pointed out some years ago by Cahn and Hilliard [16] and is reflected in their model for interfacial tension (see Section III-2B). 

Surfaces are found to exliibit properties that are different from those of the bulk material. In the bulk, each atom is bonded to other atoms m all tliree dimensions. In fact, it is this infinite periodicity in tliree dimensions that gives rise to the power of condensed matter physics. At a surface, however, the tliree-dimensional periodicity is broken. This causes the surface atoms to respond to this change in their local enviromnent by adjusting tiieir geometric and electronic structures. The physics and chemistry of clean surfaces is discussed in section Al.7.2. 

Although the structure of the surface that produces the diffraction pattern must be periodic in two dimensions, it need not be the same substance as the bulk material. Thus LEED is a particularly sensitive tool for studying the structures and properties of thin layers adsorbed epitaxially on the surfaces of crystals. 

With XRD applied to bulk materials, a detailed structural analysis of atomic positions is rather straightforward and routine for structures that can be quite complex (see chapter B 1.9) direct methods in many cases give good results in a single step, while the resulting atomic positions may be refined by iterative fitting procedures based on simulation of the diffraction process. 

One fiirther method for obtaining surface sensitivity in diffraction relies on the presence of two-dimensional superlattices on the surface. As we shall see fiirtlrer below, these correspond to periodicities that are different from those present in the bulk material. As a result, additional diffracted beams occur (often called fractional-order beams), which are uniquely created by and therefore sensitive to this kind of surface structure. XRD, in particular, makes frequent use of this property [4]. Transmission electron diffraction (TED) also has used this property, in conjunction with ultrathin samples to minimize bulk contributions [9]. 

A large number of ordered surface structures can be produced experimentally on single-crystal surfaces, especially with adsorbates [H]. There are also many disordered surfaces. Ordering is driven by the interactions between atoms, ions or molecules in the surface region. These forces can be of various types covalent, ionic, van der Waals, etc and there can be a mix of such types of interaction, not only within a given bond, but also from bond to bond in the same surface. A surface could, for instance, consist of a bulk material with one type of internal bonding (say, ionic). It may be covered with an overlayer of molecules with a different type of intramolecular bonding (typically covalent) and the molecules may be held to the substrate by yet another fomi of bond (e.g., van der Waals). 

As discussed in more detail elsewhere in this encyclopaedia, many optical spectroscopic methods have been developed over the last century for the characterization of bulk materials. In general, optical spectroscopies make use of the interaction of electromagnetic radiation with matter to extract molecular parameters from the substances being studied. The methods employed usually rely on the examination of the radiation absorbed. 

Metallic and semiconductor nanoparticles or nanocrystals —chunks of matter intennediate in size and physical properties between single atoms and tire macroscopic bulk materials—are of great interest botli for tlieir... 

Much of tire science of biocompatibility can be reduced to tire principles of how to detennine tire interfacial energies between biopolymer and surface. The biopolymer is considered to be large enough to behave as bulk material witli a surface since (for example) a water cluster containing only 15 molecules and witli a diameter of 0.5 nm already behaves as a bulk liquid [132] it appears tliat most biological macromolecules can be considered to... 

Silicon is used in many fonns, from high-purity tliin films to bulk material, which may be crystalline, multi- or poly crystalline and amorjDhous (usually hydrogenated). Silicon is the material discussed tire most in tliis article. Substitutional B and P are tire most common (of many) shallow acceptors and donors, respectively. 

For tire purjDoses of tliis review, a nanocrystal is defined as a crystalline solid, witli feature sizes less tlian 50 nm, recovered as a purified powder from a chemical syntliesis and subsequently dissolved as isolated particles in an appropriate solvent. In many ways, tliis definition shares many features witli tliat of colloids , defined broadly as a particle tliat has some linear dimension between 1 and 1000 nm [1] tire study of nanocrystals may be drought of as a new kind of colloid science [2]. Much of die early work on colloidal metal and semiconductor particles stemmed from die photophysics and applications to electrochemistry. (See, for example, die excellent review by Henglein [3].) However, the definition of a colloid does not include any specification of die internal stmcture of die particle. Therein lies die cmcial distinction in nanocrystals, die interior crystalline stmcture is of overwhelming importance. Nanocrystals must tmly be little solids (figure C2.17.1), widi internal stmctures equivalent (or nearly equivalent) to drat of bulk materials. This is a necessary condition if size-dependent studies of nanometre-sized objects are to offer any insight into die behaviour of bulk solids. 

The striking size-dependent colours of many nanocrystal samples are one of tlieir most compelling features detailed studies of tlieir optical properties have been among tire most active research areas in nanocrystal science. Evidently, tire optical properties of bulk materials are substantially different from Arose of isolated atoms of tire... 

Statistical mechanics is the mathematical means to calculate the thermodynamic properties of bulk materials from a molecular description of the materials. Much of statistical mechanics is still at the paper-and-pencil stage of theory. Since quantum mechanicians cannot exactly solve the Schrodinger equation yet, statistical mechanicians do not really have even a starting point for a truly rigorous treatment. In spite of this limitation, some very useful results for bulk materials can be obtained. 

The dielectric constant is a property of a bulk material, not an individual molecule. It arises from the polarity of molecules (static dipole moment), and the polarizability and orientation of molecules in the bulk medium. Often, it is the relative permitivity 8, that is computed rather than the dielectric constant k, which is the constant of proportionality between the vacuum permitivity so and the relative permitivity. 

Whether an adequate sampling of phase space is obtained Whether the system size is large enough to represent the bulk material Whether the errors in calculation have been estimated correctly... 

An area of great interest in the polymer chemistry field is structure-activity relationships. In the simplest form, these can be qualitative descriptions, such as the observation that branched polymers are more biodegradable than straight-chain polymers. Computational simulations are more often directed toward the quantitative prediction of properties, such as the tensile strength of the bulk material. 

The tests in the two previous paragraphs are often used because they are easy to perform. They are, however, limited due to their neglect of intermolecular interactions. Testing the effect of intennolecular interactions requires much more intensive simulations. These would be simulations of the bulk materials, which include many polymer strands and often periodic boundary conditions. Such a bulk system can then be simulated with molecular dynamics, Monte Carlo, or simulated annealing methods to examine the tendency to form crystalline phases. 

The molar volume is usually larger than the van der Waals volume because two additional influences must be added. The first is the amount of empty space in the bulk material due to constraints on how tightly together the chains can pack. The second is the additional space needed to accommodate the vibrational motion of the atoms at a given temperature. 

Smith, R. James, G. V. The Sampling of Bulk Materials. Royal Society of Chemistry London, 1981. 

Several factors affect the bandshapes observed ia drifts of bulk materials, and hence the magnitude of the diffuse reflectance response. Particle size is extremely important, siace as particle size decreases, spectral bandwidths generally decrease. Therefore, it is desirable to uniformly grind the samples to particle sizes of <50 fim. Sample homogeneity is also important as is the need for dilute concentrations ia the aoaabsorbiag matrix. 

Weighing is the operation of determining the mass of any material as represented by one or more objects or by a quantity of bulk material. Proportioning is the control, by weighing, of relative quantities of two or more ingredients according to a specific recipe in order to make a mixed product, or to prepare the ingredients for use in a chemical process. 

Nuclear. Mass can be determined directly by measuring changes in the absorption, reflection, or transmission of alpha- or beta-rays, which changes in proportion to the amount of material present. This method is primarily used to determine the mass of bulk material moving on a conveyor. The advantages include the following ... 

Tank and hopper scales weigh Hquids or bulk materials. The materials may be stored in the scale, or may be weighed while being transported for sale or for use in a process. The scale is usually part of a much larger material handling system. Capacities are mostly under 20 t, but can be as large as 200 t or more. 

Process industries frequently need to weigh and control the flow rate of bulk material for optimum performance of such devices as grinders or pulverizers, or for controlling additives, eg, to water suppHes. A scale can be installed in a belt conveyor, or a short belt feeder can be mounted on a platform scale. Either can be equipped with controls to maintain the feed rate within limits by controlling the operation of the device feeding the material to the conveyor. Direct mass measurement with a nuclear scale can also be used to measure and control such a continuous stream of material. 

Industrial appHcations often require that bulk materials or Hquids be weighed in hoppers, silos, tanks, or reactor vessels, referred to collectively as vessels. Because they come in such a wide variety of si2es, shapes, and capacities, scales using these vessels as load receivers are not typically available as standard products. Vessels are usually custom-fabricated to suit a particular appHcation, then mounted on a scale. Some can be mounted on a standard scale such as a bench, portable, or floor scale. More typically, a number of weigh modules are used to support the vessel. This offers the scale designer great flexibiHty but certain precautions are necessary in order to constmct an accurate scale. Some of the more important factors associated with the design of vessel scales are discussed herein. 

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