Scale nucleation

The importance of flocculating ions is borne out by Midkiff (282, 283) who found that cooling water containing more than 300 ppm silica did.not deposit a scale if calcium ions were first converted to soluble chelates otherwise, a deposit of colloidal silica, associated with calcium carbonate, was formed. At the concentration involved, over half of the silica in solution must have been colloidal and the particles quite small. The rate of deposition was over 100 times faster than would be possible if monomeric silica alone were involved. Wohlberg and Bucholz (246) reported that if the silica concentration exceeded about 240 ppm (at which point colloidal silica would be expected to be nucleated), scale formation occurred when calcium was present. 

In principle, nucleation should occur for any supersaturation given enough time. The critical supersaturation ratio is often defined in terms of the condition needed to observe nucleation on a convenient time scale. As illustrated in Table IX-1, the nucleation rate changes so rapidly with degree of supersaturation that, fortunately, even a few powers of 10 error in the preexponential term make little difference. There has been some controversy surrounding the preexponential term and some detailed analyses are available [33-35]. 

For these sequences the value of Gj, is less than a certain small value g. For such sequences the folding occurs directly from the ensemble of unfolded states to the NBA. The free energy surface is dominated by the NBA (or a funnel) and the volume associated with NBA is very large. The partition factor <6 is near unify so that these sequences reach the native state by two-state kinetics. The amplitudes in (C2.5.7) are nearly zero. There are no intennediates in the pathways from the denatured state to the native state. Fast folders reach the native state by a nucleation-collapse mechanism which means that once a certain number of contacts (folding nuclei) are fonned then the native state is reached very rapidly [25, 26]. The time scale for reaching the native state for fast folders (which are nonnally associated with those sequences for which topological fmstration is minimal) is found to be... 

Guo Z and Thirumalai D 1995 Kinetics of protein folding nucleation mechanism, time scales and pathways Biopolymers 36 83-103... 

Another approach, the so-called seeding technique, provides preferential sites for the nucleation of scale, which permits the heat-transfer surfaces to remain clean of scale. Extensive studies of this technique have been conducted, and field use was reported ia the former USSR as early as the mid-1960s (42). The use of ion-exchange methods is another possible approach. Eor calcium, the exchange can be represented as... 

Scaling is not always related to temperature. Calcium carbonate and calcium sulfate scaling occur on unheated surfaces when their solubiUties are exceeded in the bulk water. Metallic surfaces are ideal sites for crystal nucleation because of their rough surfaces and the low velocities adjacent to the surface. Corrosion cells on the metal surface produce areas of high pH, which promote the precipitation of many cooling water salts. Once formed, scale deposits initiate additional nucleation, and crystal growth proceeds at an accelerated rate. 

In contrast to chrysotile fibers, the atomic crystal stmcture of amphiboles does not inherentiy lead to fiber formation. The formation of asbestiform amphiboles must result from multiple nucleation and specific growth conditions. Also, whereas the difference between asbestiform and massive amphibole minerals is obvious on the macroscopic scale, the crystalline stmctures of the two varieties do not exhibit substantial differences. Nonfibrous amphiboles also exhibit preferential cleavage directions, yielding fiber-shaped fragments. 

Highest heat-transfer coefficients are obtained in FC evaporators when the liquid is aUowed to boil in the tubes, as in the type shown in Fig. 11-122 7. The heating element projects into the vapor head, and the hquid level is maintained near and usuaUy slightly below the top tube sheet. This type of FC evaporator is not well suited to salting solutions because boiling in the tubes increases the chances of salt deposit on the waUs and the sudden flashing at the tube exits promotes excessive nucleation and production of fine ciystals. Consequently, this type of evaporator is seldom used except when there are headroom hmitations or when the hquid forms neither salt nor scale. 

The failure of conventional criteria may be due to the fact that it is not only one mixing process which can be limiting, rather for example an interplay of micromixing and mesomixing can influence the kinetic rates. Thus, by scaling up with constant micromixing times on different scales, the mesomixing times cannot be kept constant but will differ, and consequently the precipitation rates (e.g. nucleation rates) will tend to deviate with scale-up. 

The model is able to predict the influence of mixing on particle properties and kinetic rates on different scales for a continuously operated reactor and a semibatch reactor with different types of impellers and under a wide range of operational conditions. From laboratory-scale experiments, the precipitation kinetics for nucleation, growth, agglomeration and disruption have to be determined (Zauner and Jones, 2000a). The fluid dynamic parameters, i.e. the local specific energy dissipation around the feed point, can be obtained either from CFD or from FDA measurements. In the compartmental SFM, the population balance is solved and the particle properties of the final product are predicted. As the model contains only physical and no phenomenological parameters, it can be used for scale-up. 

Garside, J. and Davey, R.J., 1980. Secondary contact nucleation Kinetics, growth and scale-up. Chemical Engineering Communications, 4, 393. 

Garside, J. and Jancic, S.J., 1979. Measurement and scale-up of secondary nucleation kinetics for the potash alum-water system. American Institute of Chemical Engineers Journal, 25, 948. 

A pre-factor 1/r contains a time scale r or a frequency which for instance corresponds to the hard phonon or to an atomic frequency. The growth rate of the crystal is proportional to this rate (23). As will be shown later, the nucleus once formed expands in a time scale shorter than the one necessary for nucleation. If the process consists of a series of sequential subprocesses, the global velocity is governed by the slowest one. Therefore, this nucleation process determines the growth rate of a faceted surface. 

Generally, the most important reaction is that of tantalum with oxygen, since it tends to form oxides when heated in air. Reaction starts above 300°C and becomes rapid above 600°C . The scale is not adherent, and if the oxidised material is heated above 1000°C oxygen will diffuse into the bulk of the material and embrittle it. At 1200°C catastrophic oxidation attack takes place at a rate of about 150 mm/h Oxygen is not driven off by heating alone, but in vacuum above 2300°C it is removed as a suboxide. The first step of the conversion mechanism of tantalum into oxide was shown to occur by the nucleation and growth of small plates along the 100) planes of the BCC metaP. ... 

Small additions of Ce have been shown to have a favourable influence on oxide growth of several Fe-Cr alloys by improving scale adherence and acting as nucleation sites for CrjO, . Levels of Ce as low as 0.024% reduce the carbon uptake of steels in carbonaceous atmospheres by several orders of magnitude. Trace concentrations of As and Sn have been found to improve the breakaway properties of mild and low alloy steels in CO/COj, whereas Cu has been found to be detrimental. ... 

In sulphur dioxide linear kinetics are generally observed due to control by phase boundary reactions, i.e. adsorption of SOj. RahmeF suggested that this is one of the conditions which favours simultaneous nucleation of sulphide and oxide at the gas/scale interface. The main reaction products are NiO, NijSj, Ni-S,j, and NiS04, depending on the temperature and gas pressure for example, according to the following reaction ... 

The effect of nucleating sources is important when attempting to scale studies with models tO full-size components. A common practice in model tests is to expose the fluid to a high static pressure prior to testing in order to drive free gas into solution. In contrast the seeding of water tunnels is considered to improve scaling particularly in high-speed propeller applications . 

The precipitation of calcium carbonate in the boiler involves a number of discrete processes, including nucleation, followed by the formation of microcrystals which compete to grow into larger crystals (accretion) that eventually form layers of dense, crystalline scale on the heat exchange surface. 

Characteristic features of a—time curves for reactions of solids are discussed with reference to Fig. 1, a generalized reduced-time plot in which time values have been scaled to t0.s = 1.00 when a = 0.5. A is an initial reaction, sometimes associated with the decomposition of impurities or unstable superficial material. B is the induction period, usually regarded as being terminated by the development of stable nuclei (often completed at a low value of a). C is the acceleratory period of growth of such nuclei, perhaps accompanied by further nucleation, and which extends to the... 

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