Alloy films evaporation

Thus nickel and nickel-copper alloy films evaporated in vacuo onto the inner walls of the reaction vessel have been chosen for further investigations. The films were deposited onto the inner wall of a glass tube kept at 450°C their thickness amounted to approximately 2000 A. After annealing at the same temperature in vacuo they were transferred into the side-arm of the Smith-Linnett apparatus in order for the recombination coefficients to be determined. The bulk homogeneity of alloy films prepared in this way was confirmed by X-ray diffraction (65, 65a, 66). 

Table IV shows X-ray data (55) on the homogeneity of Pd-Ag films prepared by simultaneous evaporation from separate sources, either in conventional vacuum or in UHV, with the substrate maintained at 0°C. The second group of films was prepared using a stainless steel system incorporating a large (100 1/sec) getter-ion pump, sorption trap, etc., but deposited inside a glass vessel. By the tests of homogeneity adopted, alloy films evaporated in conventional vacuum were not satisfactory, i.e., the lattice constants were generally outside the limits of the experimental error, 0.004 A, and the X-ray line profiles were not always symmetrical. In contrast, alloy films evaporated in UHV were satisfactorily homogeneous. Further, electron micrographs showed that these latter films were reasonably unsintered and thus, this method provides clean Pd-Ag alloy films with the required characteristics for surface studies.

R. Van Hardeveld and F. Hartog Adsorption and Catalysis on Evaporated Alloy Films... 

It is reasonable to ask two questions in relation to studies using evaporated alloy films, viz, why work with alloys and why prepare alloy catalysts in this particular form ... 

The pure metals are readily available to try out as catalysts, whereas the alloys are not, if a moderate surface area is required. Methods for preparing alloys as high-area powders, etc., raise questions about the unwanted introduction of promoters, e.g., chloride ions. Here, again, evaporated alloy films recommend themselves for the exploration of a whole new territory of alloy systems as catalysts in a variety of reactions. 

There are a variety of options available for the preparation of evaporated alloy films and, indeed, suggested methods of preparation can be traced back over many years (9). Nevertheless, it is possible to distinguish some general methods for the preparation of binary alloys as follows ... 

Finally, with respect to successive evaporation, Pd-Rh films used for CO oxidation (34) are an example of preparing alloy films where a miscibility gap exists and interdiffusion rates are slow. These Pd-Rh films were prepared by depositing layers of palladium and rhodium at 0°C, followed by annealing in 50 Torr hydrogen at 400°C for 21 hr. The apparent surface compositions, evaluated from the CO oxidation rate as described in Section IV, and information on film structure obtained by X-ray diffraction (XRD) are recorded in Table II. 

Evaporation from an alloy source largely avoids the problems of source geometry which may be encountered in simultaneous evaporation from separate pure metal sources. The success of the method depends on the relative vapor pressures of the component metals in the alloy source because one component metal with a substantially higher vapor pressure will evaporate preferentially. The alloy film will then be rich in the more volatile component compared with the composition of the source and may also be stratified into layers of different composition. Evaporation from alloy sources is discussed in detail by Dushman (43) and Holland (44) on the basis of Raoult s law, and it is possible to predict which metal pairs... 

Fig. 4. Sliding cathode phototube (41) showing evaporation sources (1, 2) for depositing the alloy film on the photocathode (3), shielded partly as required by the glass screen (4). A quartz window (5) faces the cathode and connection is made to a gold film anode evaporated from (6).

According to the data in Table III, the value of the ratio P)Mm is approximately the same for the metals Au, Fe, Co, Ni, and Pd. Binary alloys formed from any pair of these metals can therefore be expected to evaporate without substantial fractionation. On the other hand, films evaporated from Ag-Pd and Cu-Ni alloys can be expected to be enriched in Ag and Cu, respectively. These predictions are largely confirmed by experiment. For example, the composition of Pd-Au films was found to be the same as the wires which were evaporated (46), but in the case of Pd-Ag, evaporation of a 30% Ag-Pd alloy ware yielded a 50% Ag-Pd alloy film (47)- Alexander and Russell evaporated a number of alloys from pellets in the reaction vessel as shown in Fig. 5 (48) The alloy pellet was placed in a small quartz cup with its surface equidistant from the hemispherical top of the reaction vessel. The pellet was evaporated by... 

Fig. 5. Reaction vessel, in the dome of which, alloy films are deposited by evaporation from an alloy pellet subjected to induction heating (.48).

In discussing the principles involved in alloy film formation, reference had to be made to alloy systems which are uncommon or unused in studies of adsorption and catalysis. This section is specifically concerned with the characterization of alloy films prepared for such purposes. However, the various aspects of alloy film structure mentioned in Section II have to be kept in mind when discussing results of catalytic experiments using evaporated alloy films. 

The characterization of evaporated alloy films can be carried out at widely different levels of sophistication. At the very least, it is necessary to determine the bulk composition, probably after the film has been used for an adsorption or catalytic experiment. Then various techniques can be applied, e.g., X-ray diffraction, electron diffraction, and electron microscopy, to investigate the homogeneity or morphology of the film. The measurement of surface area by chemisorption presents special problems compared with the pure metals. Finally, there is the question of the surface composition (as distinct from the bulk or overall composition), and a brief account is given of techniques such as Auger electron spectroscopy which might be applied to alloy films. 

With due regard to the lateral variations in composition which can arise as a consequence of source geometry and positioning (discussed in Section II), it is vise to analyze the alloy film at a number of representative points. For example, if a catalytic reaction was carried out over an alloy film deposited inside a spherical vessel maintained at a constant temperature over its entire area, then the mean alloy composition (and the uniformity of composition) is required. A convenient procedure is to cut glass reaction vessels carefully into pieces at the end of the experiment and to determine the composition by X-ray fluorescence analysis of a number of representative pieces. Compositions of Pd-Ag alloy films (40) determined at 12 representative parts of a spherical vessel from the intensities of the AgK 12 and PdKau fluorescent X-ray emissions are shown in Table V mean compositions are listed in the first column. (The Pd and Ag sources were separate short concentric spirals.) In other applications of evaporated alloy films to adsorption and catalytic studies, as good or better uniformity of composition was achieved. Analyses of five sections of a cylindrical... 

Alloy films are commonly sintered during preparation by deposition on substrates heated to, say, 400°C or by subsequent annealing at such temperatures, and, consequently, rather small surface areas have to be measured, perhaps in vessels of substantial volume. Krypton adsorption at liquid nitrogen temperature was used with induction-evaporated Cu-Ni, Fe-Ni, and Pd-Ni films, and BET surface areas of 1000-2000 cm2 were recorded (48), after correction for bare glass. The total area of Cu-Ni films was measured by the physical adsorption of xenon at — 196°C (70) in addition, the chemisorption of hydrogen on the same samples enabled the quantity a to be determined where... 

Further progress in the study of the Cu-Ni system awaited the preparation and careful characterization of alloy films of known bulk and surface composition. The essential step was taken by Sachtler and his co-workers 28, 88, 114) who prepared Cu-Ni alloy films by successive evaporation of the component metals in UHV. After evaporation the films were homogenized by heating in vacuum at 200°C. The bulk composition of the alloys was derived from X-ray diffraction, and the photoelectric work function of the films was also measured. A thermodynamic analysis, summarized by Fig. 13, indicated that alloy films sintered at 200°C should consist, at equilibrium, of two phases, viz., phase I containing 80% Cu and phase II containing 2% Cu. Evidence was presented that alloys within the... 

In one of the earliest reports of the use of clean evaporated alloy films in surface studies, Stephens described the preparation and characterization of Pd-Au films and presented some results for the adsorption of oxygen on them 46). Films of pure Pd and 60% Au were evaporated directly from wires, while films of 80% Au and pure Au were evaporated from a pre-outgassed tungsten support wire. The films were evaporated in a UHV system and the pressure was kept below PC8 Torr during evaporation. After evaporation, the films were stabilized by cycling between —195° and 30°C four times. They w ere characterized by X-ray diffraction and chemical analysis surface areas were measured by the BET method using krypton adsorption. 

The decomposition of formic acid over evaporated Pd-Au alloy films has been studied by Clarke and Rafter (69) the same reaction on Pd-Au alloy wires was studied by Eley and Luetic (128). The alloy films were prepared in a conventional high vacuum system by simultaneous evaporation of the component metals from tungsten hairpins. The alloy films were characterized by X-ray diffraction and electron microscopy. The X-ray diffractometer peaks were analyzed by a method first used by Moss and Thomas (SO). It was found that alloys deposited at a substrate temperature of 450°C followed by annealing for one hour at the same temperature were substantially homogeneous. Electron microscopy revealed that all compositions were subject to preferred orientation (Section III). 

There have been few studies of chemisorption on alloys, particularly where the surface has been prepared under very clean conditions, although such studies should help us to understand the catalytic process. It has been shown that homogeneous Pd-Ag alloy films can be prepared without extensive sintering 54) by simultaneous evaporation in UHV with the substrate cooled to 0°C, and so it is now possible to study chemisorption on Pd-Ag alloy films. Surface potentials accompanying CO chemisorption were measured 126) by the diode method. Comparisons of surface potentials were made after exposure to CO at 0°C at a pressure of 2 X 10-< Torr for 10 min. 

A few results were reported by Campbell and Emmett 29) for the hydrogenation of ethylene on Ni-Au alloys. Two alloy films containing 45 and 84% Ni were prepared by simultaneous evaporation followed by... 

There is now available a substantial amount of information on the principles and techniques involved in preparing evaporated alloy films suitable for adsorption or catalytic work, although some preparative methods, e.g., vapor quenching, used in other research fields have not yet been adopted. Alloy films have been characterized with respect to bulk properties, e.g., uniformity of composition, phase separation, crystallite orientation, and surface areas have been measured. Direct quantitative measurements of surface composition have not been made on alloy films prepared for catalytic studies, but techniques, e.g., Auger electron spectroscopy, are available. 

The subject of Adsorption and Catalysis on Evaporated Alloy Films is reviewed and Moss and Whalley conclude that phase separation caused a variety of complications which makes it difficult to define the nature of catalytic activity. 

Alloy films (continued) nucleation and growth of, 22 131 preparation of, 22 117-134 evaporation... 

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