Analyst Insight

Despite a bullish trends ruling the market for the bulk of the period, the North American market had mixed sentiments in the fourth quarter of 2021. This was mostly due to the adequate pushback from the supply-demand imbalance, which was further compounded by rising natural gas prices, which had taken a proper toll on the future production of numerous minerals, including titanium dioxide. An increase in COVID instances had prompted concerns in ore feedstock. As a result, during the fourth quarter of 2021, the FD UGSC (USA) quarterly average negotiations for the chemical CP Rutile Grade were finalised at USD 4434 per tonne.

Data availability statement

The basic scenario of resistive switching in TiO₂ (Jameson et al., 2007) assumes the formation and electromigration of oxygen vacancies between the electrodes (Baiatu et al., 1990), so that the distribution of concomitant n-type conductivity (Janotti et al., 2010) across the volume can eventually be controlled by an external electric bias, as schematically shown in Figure 1B. Direct observations with transmission electron microscopy (TEM) revealed more complex electroforming processes in TiO₂ thin films. In one of the studies, a continuous Pt filament between the electrodes was observed in a planar Pt/TiO₂/Pt memristor (Jang et al., 2016). As illustrated in Figure 1C, the corresponding switching mechanism was suggested as the formation of a conductive nanofilament with a high concentration of ionized oxygen vacancies and correspondingly reduced Ti³⁺ ions. These ions induce detachment and migration of Pt atoms from the electrode via strong metal–support interactions (Tauster, 1987). Another TEM investigation of a conductive TiO₂ nanofilament revealed it to be a Magnéli phase Ti_nO_2n−1 (Kwon et al., 2010). Supposedly, its formation results from an increase in the concentrations of oxygen vacancies within a local nanoregion above their thermodynamically stable limit. This scenario is schematically shown in Figure 1D. Other hypothesized point defect mechanisms involve a contribution of cation and anion interstitials, although their behavior has been studied more in tantalum oxide (Wedig et al., 2015; Kumar et al., 2016). The plausible origins and mechanisms of memristive switching have been comprehensively reviewed in topical publications devoted to metal oxide memristors (Yang et al., 2008; Waser et al., 2009; Ielmini, 2016) as well as TiO₂ (Jeong et al., 2011; Szot et al., 2011; Acharyya et al., 2014). The resistive switching mechanisms in memristive materials are regularly revisited and updated in the themed review publications (Sun et al., 2019; Wang et al., 2020).