Etching Morphology

In order to discuss the correlation between etching kinetics and etching morphology, let us first reconsider the current-potential characteristics of III-V semiconductors, as depicted in Fig. 1. For the sake of clarity, the behavior in alkaline solutions (Fig. 1 (b)) is treated first. As announced, the discussion is mainly based on experimental results obtained from GaP single crystals. 

However, the peculiar attack morphology of a deep, localized area of corrosion surrounded by lightly etched areas was not characteristic of acid corrosion. 

Fig. 3. Wedge test crack length as a function of maximum Cu buildup at the oxide-metal interface. The adhesive was Cytec FM-123. The surfaces were prepared with the Forest Products Laboratory etch. The oxide morphology was kept constant. Data are from Ref. 115].

Fig. 6. Top Morphology of FPL surface following fluorine contamination. This is to be compared to the standard FTL morphology of Fig. 14. Middle Climbing drum peel (CDP) strength as a function of F surface concentration. Bottom F concentration on FPL surfaces following doping the FPL etch solution and the rinse water with NaF. The dotted line corresponds to the surface concentration with which the CDP strength began to decrease. Adapted from Ref. [37].

A more recent process, the P2 etch [60], which uses ferric sulfate as an oxidizer in place of sodium dichromate avoids the use of toxic chromates, but still provides a similar oxide surface morphology (Fig. 15) allowing a mechanically interlocked interface and strong bonding [9]. The P2 treatment has wide process parameter windows over a broad range of time-temperature-solution concentration conditions and mechanical testing confirms that P2-prepared surfaces are, at a minimum, equivalent to FPL-prepared specimens and only slightly inferior to PAA-prepared surfaces [61]. 

Fig. 29. Phosphoric acid etched A606. steel surface showing smut-free, smooth-walled crevice morphology [54].

As with chemical etches, developing optimum conversion coatings requires assessment of the microstructure of the steel. Correlations have been found between the microstructure of the substrate material and the nature of the phosphate films formed. Aloru et al. demonstrated that the type of phosphate crystal formed varies with the orientation of the underlying steel crystal lattice [154]. Fig. 32 illustrates the different phosphate crystal morphologies that formed on two heat-treated surfaces. The fine flake structure formed on the tempered martensite surface promotes adhesion more effectively than the knobby protrusions formed on the cold-rolled steel. 

Fig. 36. Pari of a Morphology Catalog illustrating the unacceptable morphologies resulting from incorrect surface treatment (a) Turco alkaline clean with no FPL etch, and (b) Amchem deoxidizer with no FPL etch [169. ...

The present review shows how the microhardness technique can be used to elucidate the dependence of a variety of local deformational processes upon polymer texture and morphology. Microhardness is a rather elusive quantity, that is really a combination of other mechanical properties. It is most suitably defined in terms of the pyramid indentation test. Hardness is primarily taken as a measure of the irreversible deformation mechanisms which characterize a polymeric material, though it also involves elastic and time dependent effects which depend on microstructural details. In isotropic lamellar polymers a hardness depression from ideal values, due to the finite crystal thickness, occurs. The interlamellar non-crystalline layer introduces an additional weak component which contributes further to a lowering of the hardness value. Annealing effects and chemical etching are shown to produce, on the contrary, a significant hardening of the material. The prevalent mechanisms for plastic deformation are proposed. Anisotropy behaviour for several oriented materials is critically discussed. 

Morphology of the cured samples was analyzed by SEM of the fractured samples etched with tetrohydrofuran (THE), which is a solvent for the rubber. Figure 11.24 shows the fracture surfaces of the PWE and PNE specimens. Whereas the PWE fracture surface presents an essentially homogeneous surface with only a few small voids present, small yet uniformly distributed cavities are seen in PNE samples. The PWE morphology is consistent with the high degree of intermolecular link between rubber and epoxy macromolecules. The PNE morphology indicates incomplete reaction between epoxy and rubber. 

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