The surface and near-surface composition in perovskite-based electroceramics is analysed at the atomic scale using highly surface sensitive low-energy ion scattering (LEIS).

Stainless steels are used in countless diverse applications for their corrosion resistance. Although they have extremely good general resistance, they are nevertheless susceptible to pitting corrosion. This localized dissolution of an oxide-covered metal in specific aggressive environments is one of the most common and catastrophic causes of failure of metallic structures. The pitting process has been described as random, sporadic and stochastic and the prediction of the time and location of events remains extremely difficult. Many contested models of pitting corrosion exist, but one undisputed aspect is that manganese sulphide inclusions play a critical role. Indeed, the vast majority of pitting events are found to occur at, or adjacent to, such second-phase particles. Chemical changes in and around sulphide inclusions have been postulated as a mechanism for pit initiation but such variations have never been measured. Here we use nanometre-scale secondary ion mass spectroscopy to demonstrate a significant reduction in the Cr:Fe ratio of the steel matrix around MnS particles. These chromium-depleted zones are susceptible to high-rate dissolution that 'triggers' pitting. The implications of these results are that materials processing conditions control the likelihood of corrosion failures, and these data provide a basis for optimizing such conditions.

No abstract

The chemical analysis of excavated glass fragments from dated archaeological contexts in Raqqa, Syria, has provided a detailed picture of the chemical compositions of artefacts deriving from eighth to ninth and 11th century glassmaking and glassworking activities. Evidence for primary glass production has been found at three excavated sites, of eighth to ninth, 11th and 12th century dates; the first two are discussed here. The 2 km long industrial complex at al‐Raqqa was associated with an urban landscape consisting of two Islamic cities (al‐Raqqa and al‐Rafika) and a series of palace complexes. The glass fused and worked there was presumably for local as well as for regional consumption. Al‐Raqqa currently appears to have produced the earliest well‐dated production on record in the Middle East of an Islamic high‐magnesia glass based on an alkaline plant ash flux and quartz. An eighth to ninth century late ‘Roman’/Byzantine soda–lime recipe of natron and sand begins to be replaced in the eighth to ninth century by a plant ash – quartz Islamic soda–lime composition. By the 11th century, this process was nearly complete. The early Islamic natron glass compositional group from al‐Raqqa shows very little spread in values, indicating a repeatedly well‐controlled process with the use of chemically homogeneous raw materials. A compositionally more diffuse range of eighth to ninth century plant ash glass compositions have been identified. One is not only distinct from established groups of plant ash and natron glasses, but is believed to be the result of experimentation with new raw material combinations. Compositional analysis of primary production waste including furnace glass (raw glass adhering to furnace brick) shows that contemporary glasses of three distinct plant ash types based on various combinations of plant ash, quartz and sand were being made in al‐Raqqa during the late eighth to ninth centuries. This is a uniquely wide compositional range from an ancient glass production site, offering new insights into the complexity of Islamic glass technology at a time of change and innovation.

No abstract