Alloy surface analysis

Chemical analysis of the metal can serve various purposes. For the determination of the metal-alloy composition, a variety of techniques has been used. In the past, wet-chemical analysis was often employed, but the significant size of the sample needed was a primary drawback. Nondestmctive, energy-dispersive x-ray fluorescence spectrometry is often used when no high precision is needed. However, this technique only allows a surface analysis, and significant surface phenomena such as preferential enrichments and depletions, which often occur in objects having a burial history, can cause serious errors. For more precise quantitative analyses samples have to be removed from below the surface to be analyzed by means of atomic absorption (82), spectrographic techniques (78,83), etc. 

X-ray scattering studies at a renewed pc-Ag/electrolyte interface366,823 provide evidence for assuming that fast relaxation and diffu-sional processes are probable at a renewed Sn + Pb alloy surface. Investigations by secondary-ion mass spectroscopy (SIMS) of the Pb concentration profile in a thin Sn + Pb alloy surface layer show that the concentration penetration depth in the solid phase is on the order of 0.2 pm, which leads to an estimate of a surface diffusion coefficient for Pb atoms in the Sn + Pb alloy surface layer on the order of 10"13 to lCT12 cm2 s i 820 ( p,emicai analysis by electron spectroscopy for chemical analysis (ESCA) and Auger ofjust-renewed Sn + Pb alloy surfaces in a vacuum confirms that enrichment with Pb of the surface layer is probable.810... 

The salient features of surface analysis by ESCA of the oxidized ternary alloys are In general agreement with the results In the case of the binary Nl Th system. NIO, FCjO, and Th02 are the predoml-... 

Comparison of the surface analysis and methanatlon activity of (Nl Th ) alloys (Figure 6) shows that there Is some Interdependence betweeK the surface concentration of Nl and activity high Nl surface concentration generally results In greater methanatlon activity. 

EQCM Analyses It was suggested by XPS analysis that the nonprecious metals were leached out from the alloy surface during CVs in acidic electrolyte solution. Therefore, we used an EQCM to measure the mass change at the electrode. The resolution and stability of our 10 MHz EQCM was +0.1 Hz, i.e., +0.44ngcm without any signal averaging. 

Environmental tests have been combined with conventional electrochemical measurements by Smallen et al. [131] and by Novotny and Staud [132], The first electrochemical tests on CoCr thin-film alloys were published by Wang et al. [133]. Kobayashi et al. [134] reported electrochemical data coupled with surface analysis of anodically oxidized amorphous CoX alloys, with X = Ta, Nb, Ti or Zr. Brusic et al. [125] presented potentiodynamic polarization curves obtained on electroless CoP and sputtered Co, CoNi, CoTi, and CoCr in distilled water. The results indicate that the thin-film alloys behave similarly to the bulk materials [133], The protective film is less than 5 nm thick [127] and rich in a passivating metal oxide, such as chromium oxide [133, 134], Such an oxide forms preferentially if the Cr content in the alloy is, depending on the author, above 10% [130], 14% [131], 16% [127], or 17% [133], It is thought to stabilize the non-passivating cobalt oxides [123], Once covered by stable oxide, the alloy surface shows much higher corrosion potential and lower corrosion rate than Co, i.e. it shows more noble behavior [125]. 

Surface alloys, micro structure of, 14 451 Surface analysis, 10 428... 

Ion-beam thinning is usually used for dense bulk specimens where particular regions must be analyzed. It can be useful in AEM for thinning the same single crystals used in surface analysis to make direct comparisons with results from AES, XPS, etc. Ion-beam thinning can also be useful in analysis of interfaces and defects within bulk metallic catalysts such as Pt and Pd and their alloys. 

A.H. Deutchman and R.J. Partyka (Beam Alloy Corporation observe, "Characterization and classification of thin diamond films depend both on advanced surface-analysis techniques capable of analyzing elemental composition and microstructure (morphology and crystallinity), and on measurement of macroscopic mechanical, electrical, optical and thermal properties. Because diamond films are very thin (I to 2 micrometers or less) and grain and crystal sizes are very small, scanning electron microscopy... 

A common observation in most cases is that the surface of amorphous alloys, especially those containing Ti, Zr and Mo, is largely covered with inactive oxides which impart low electrocatalytic properties to the material as prepared [562, 569, 575], Activation is achieved by removing these oxides either by prepolarization or, more commonly and most efficiently, by leaching in HF [89, 152, 576]. Removal of the passive layer results in a striking enhancement of the electrocatalytic activity [89], but surface analysis has shown [89, 577] that this is due to the formation of a very porous layer of fine particles on the surface (Fig. 32). A Raney type electrode is thus obtained which explains the high electrocatalytic activity. Therefore, it has been suggested [562, 578] that some amorphous alloys are better as catalyst precursors than as catalysts themselves. However, it has been pointed out that the amorphous state appears to favor the formation of such a porous layer which is not effectively formed if the alloy is in the crystalline state [575]. 

In the past ten years the number of chemistry-related research problems in the nuclear industry has increased dramatically. Many of these are related to surface or interfacial chemistry. Some applications are reviewed in the areas of waste management, activity transport in coolants, fuel fabrication, component development, reactor safety studies, and fuel reprocessing. Three recent studies in surface analysis are discussed in further detail in this paper. The first concerns the initial corrosion mechanisms of borosilicate glass used in high level waste encapsulation. The second deals with the effects of residual chloride contamination on nuclear reactor contaminants. Finally, some surface studies of the high temperature oxidation of Alloys 600 and 800 are outlined such characterizations are part of the effort to develop more protective surface films for nuclear reactor applications. ... 

This present paper discusses in more detail three separate nuclear-related studies where surface analysis has been used extensively borosilicate glass leaching, surface chloride contamination, and gas phase oxidation of some nickel alloys. 

Coupons of Type 304 stainless steel were prepared by mechanical abrasion and rinsed with methanol. Each sample was analyzed by XPS prior to treatment to ensure that no detectable casually-introduced chlorine was present. Two separate series of laboratory experiments were done one series (a) followed the effects of short-term contact between chlorocarbon and the alloy surface, a second series (b) investigated the effects of prolonged vapor and liquid contact with the alloy in a glass refluxer. In series (a) the clean alloy surface was swabbed using trichloroethane-soaked tissue and immediately inserted into the vacuum chamber of an XPS spectrometer for analysis. After analysis, the same coupon was exposed to the atmosphere for periods of 72 and 336 hours... 

Surface Analysis of Silicon-Alloyed and Unalloyed LTI Pyrolytic Carbon," in this volume. 

The empirical approach adopted here integrates classical electrochemical methods with modem surface preparation and characterization techniques. As described in detail elsewhere, the actual experimental procedure involves surface analysis before and after a particular electrochemical process the latter may vary from simple inunersion of the electrode at a fixed potential to timed excursions between extreme oxidative and reductive potentials. Meticulous emphasis is placed on the synthesis of pre-selected surface alloys and the interrogation of such surfaces to monitor any electrochemistry-induced changes. The advantages in the use of electrons as surface probes such as in X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), high-resolution... 

Little can be gleaned about the nature of the alloy interface from only the cyclic current-potential curves. An important question that needs to be addressed is whether or not the cychc vol-tammograms are accompanied by changes in the surface composition of the alloy while a qualitative solution to this problem can easily be obtained from multiple voltammetric scans, a quantitative answer is fundamentally necessary. In fact, a more critical matter involves the stability the PtsCo alloy under fuel-cell operating conditions that is, after prolonged use at the OCP in an 02-saturated solution. All of these issues can be simultaneously tackled if the surface composition of the PtsCo alloy is monitored as a function of time at a given applied potential. For such measurements, the alloy electrode is withdrawn from the 02-saturated electrolyte at the test potential and, prior to transfer into the surface analysis chamber, rinsed in deaerated ultrapure (Millipore) water to remove emersed sulfuric acid. The results are shown in Fig. 11. 

This reversal of the sequence from TMS/HFE to HFE/TMS is the most important issue. The second major issue is the effect of the O2 plasma treatment on the fluorine-containing contaminants. The XPS analysis of an initial sample revealed virtually no silicon on the alloy surface beneath the lifted primer but did indicate a rather substantial fluorine presence. The appearance of a strong silicon signal on the interface side of the removed primer indicated that the entire plasma film had likely delaminated at the interface with the alloy. Analysis of additional samples confirmed that the entire film and primer system had delaminated from the alloy panels. 

Other complications that arise are (a) that the surface compositions of glassy metals to be used as electrocatalysts are rarely identical with the corresponding bulk compositions, as was shown in recent Auger surface analysis experiments by Vracar and Conway (134), and (b) that when such alloys are used as anodes for O2 evolution in water electrolysis an oxide film of appreciable thickness is formed, and the distribution of elements of the alloy in the film is not usually the same as in the parent metal owing to some preferential anodic leaching of any base-metal components that are present in the alloy. 

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