Film resistance

Dry-Film Resists Based on Radical Photopolymerization. Photoinitiated polymerization (PIP) is widely practiced ia bulk systems, but special measures must be taken to apply the chemistry ia Hthographic appHcations. The attractive aspect of PIP is that each initiator species produced by photolysis launches a cascade of chemical events, effectively forming multiple chemical bonds for each photon absorbed. The gain that results constitutes a form of "chemical amplification" analogous to that observed ia silver hahde photography, and illustrates a path for achieving very high photosensitivities. 

One potential approach extends the idea of chemical amplification introduced in our preceding description of dry-film resists. In 1982, Ito and co-workers (37,38) recognized that if a photosensitizer producing an acidic product is photolyzed in a polymer matrix containing acid-labile groups, the acid will serve as a spatially localized catalyst for the formation or cleavage of chemical bonds. 

In situations where the gas film resistance is predominant (gas film-controlled situation), k Pis much smaller than and the tie line is very steep. approachesjy so that the overall gas-phase driving force and the gas-film driving force become approximately equal, whereas the Hquid-film driving force becomes negligible. From equation 7 it also follows that in such cases. The reverse is tme if the Hquid film resistance is controlling. Since the... 

Lujuid-Pha.se Transfer. It is difficult to measure transfer coefficients separately from the effective interfacial area thus data is usually correlated in a lumped form, eg, as k a or as These parameters are measured for the Hquid film by absorption or desorption of sparingly soluble gases such as O2 or CO2 in water. The Hquid film resistance is completely controlling in such cases, and kjji may be estimated as since x (Fig. 4). This... 

As illustrated ia Figure 6, a porous adsorbent ia contact with a fluid phase offers at least two and often three distinct resistances to mass transfer external film resistance and iatraparticle diffusional resistance. When the pore size distribution has a well-defined bimodal form, the latter may be divided iato macropore and micropore diffusional resistances. Depending on the particular system and the conditions, any one of these resistances maybe dominant or the overall rate of mass transfer may be determined by the combiaed effects of more than one resistance. 

External Fluid Film Resistance. A particle immersed ia a fluid is always surrounded by a laminar fluid film or boundary layer through which an adsorbiag or desorbiag molecule must diffuse. The thickness of this layer, and therefore the mass transfer resistance, depends on the hydrodynamic conditions. Mass transfer ia packed beds and other common contacting devices has been widely studied. The rate data are normally expressed ia terms of a simple linear rate expression of the form... 

In the case of a less soluble gas such as oxygen, diffusion occurs so slowly through the Hquid film that only a small concentration difference is required to overcome the resistance of the gas film. Thus the Hquid film at the interface is considered to be very close to oxygen saturation and it is not necessary to consider gas film resistance in the calculation (14). 

The second parameter, tear strength, describes the film resistance to tear propagation. It is measured with a special apparatus, the Ehnendorf Tear Tester (ASTM D1922), and defined as the weight of a loaded pendulum capable of tearing a notched piece of film. Two values are usually measured for each film sample. One determines tear propagation in the machine direction of the film, the other in the transverse direction. 

E] Based on oxygen transfer from water to air 77 F. Liquid film resistance controls. (Dwnei- 77 F = 2.4 X 10 ). Equation is dimensional. Data was for thin-waUed polyethylene Raschig rings. Correlation also fit data for spheres. Fit 25%. See Reiss for graph. 

E] Ammonia absorption into water from air at 70 F. Gas-film resistance controls. Thin-waUed polyethylene Raschig rings and 1-inch Intalox saddles. Fit 25%. See Reiss for fit. Terms defined as above. 

FIG. 14-78 Liqnid-film resistance in absorption of gases in wetted-wall columns. Theoretical lines are calculated for oxygen absorption in water at 55 F. To convert feet to meters, multiply by 0.3048 C = /9 ( F — 32). (Sheixuood and Vigfoid, Absorption and Extraction, 2d ed., McGraw-Hill, New York, 1952. )... 

In either equation, /c is given by Eq. (16-84) for parallel pore and surface diffusion or by Eq. (16-85) for a bidispersed particle. For nearly linear isotherms (0.7 < R < 1.5), the same linear addition of resistance can be used as a good approximation to predict the adsorption behavior of packed beds, since solutions for all mechanisms are nearly identical. With a highly favorable isotherm (R 0), however, the rate at each point is controlled by the resistance that is locally greater, and the principle of additivity of resistances breaks down. For approximate calculations with intermediate values of R, an overall transport parameter for use with the LDF approximation can be calculated from the following relationship for sohd diffusion and film resistance in series... 

Liquid-Film Coefficients (Physical) and (Reactive) The gas-side resistance can be eliminated by employing a pure gas, thus leaving the liquid film as the only resistance. Alternatively, after the gas-film resistance has been found experimentally or from corre-... 

Tubeside fouling Shellside fouling Tube metal wall Tubeside film resistance Shellside film resistance... 

For film coefficients many situations exist. Table 1 and Figure 1 give ballpark estimates of film resistance at reasonable design velocities. 

Typical film coefficients can be used to build rough overall heat transfer coefficients. This should suffice in most cases to establish that the design is within ballpark accuracy. Later, for final design, certain critical services will be checked in detail. Typical film resistances for shell and tube heat exchangers and overall heat transfer coefficients for air cooled heat exchangers are shown in Chapter 2, Heat Exchangers. 

With tube side condensation, coefficients are generally lower than for comparable shell side condensers. This phenomenon is attributed to (1) lower coolant velocities outside the tubes than are possible with tube side cooling, and (2) increased film thicknesses, namely, film resistance inside the tubes. 

Note that H is simply Henry s constant corrected for units. When the solute gas is readily soluble in the liquid solvent, Henry s law constant (H or H ) is small and Kj approximately equals k, and the absorption process is controlled by the gas film resistance. For systems where the solute is relatively insoluble in the liquid, H is large and K( approximately equals k, and the absorption rate is controlled by the liquid phase resistance. In most systems, the solute has a high solubility in the solvent selected, resulting in the system being gas film resistance controlled. 

Assume fouling resistances for shell side and tube side. Calculate the overall resistance, less shell-side film resistance ... 

The values of /"fh and ffc (the film resistances for the hot and cold fluids, respectively) can be calculated from the Dittus-Boelter equations previously described and the wall metal resistance / from the average metal thickness and thermal conductivity. The fouling resistances of the hot and cold fluids /"dh and are often based on experience, but a more detailed discussion of this will be presented later in this chapter. 

Equation 1.116 is ohmic (/ a r for constant film thickness) the term x/2AB can be regarded as the film resistance. The equation is identical to parabolic film growth, for which the film thickens with the square root of time at constant potential. 

Table 10.30 Current density to maintain passivity and film resistance of some metals and alloys in 67 wt% sulphuric acid (after Shock, Riggs and Sudbury )...

Metal or alloy Current density to maintain passivity (W Am- ) Total film resistance (flcm)... 

Later publications have been concerned with mass transfer in systems containing no suspended solids. Calderbank measured and correlated gas-liquid interfacial areas (Cl), and evaluated the gas and liquid mass-transfer coefficients for gas-liquid contacting equipment with and without mechanical agitation (C2). It was found that gas film resistance was negligible compared to liquid film resistance, and that the latter was largely independent of bubble size and bubble velocity. He concluded that the effect of mechanical agitation on absorber performance is due to an increase of interfacial gas-liquid area corresponding to a decrease of bubble size. 

Carbon dioxide is absorbed in water from a 25 per cent mixture in nitrogen. How will its absorption rate compare with that from a mixture containing 35 per cent carbon dioxide, 40 per cent hydrogen and 25 per cent nitrogen It may be assumed that the gas-film resistance is controlling, that the partial pressure of carbon dioxide, at the gas-liquid interface is negligible and that the two-lilm theory is applicable, with the gan film thickness the same in the two cases. 

Impedance spectroscopy is best suited for the measurement of electronic conductivities in the range 10 -7to 10 2S cm 1.145 In principle, it is perhaps the best method for this range, but it is often difficult to interpret impedance data for conducting polymer films. The charge-transfer resistance can make measurements of bulk film resistances inaccurate,145 and it is often difficult to distinguish between the film s ionic and electronic resistances.144 This is even more of a problem with chronoamperometry146 and chronopotentiometry,147 so that these methods are best avoided. 

---