The hydrothermal synthesis of Mg-beidellite in which limited amounts of Ga and Cr are clearly shown to be incorporated into nonexchangeable positions in the clay layer framework is reported for the first time. Elemental analyses indicate that, up to at least 15 mole percent, Ga can replace Al virtually completely; Cr incorporation is more difficult. It appears that the Ga that is incorporated into the beidellite is located primarily in the octahedral sheet. Pillaring of the synthesized beidellite by replacing the Mg2+ with large AlO4Al12(OH)24(H2O)127+ ions showed that approximately 5.5 meq Al3+ was required per g of beidellite to achieve complete pillaring. This amount is very similar to that required for montmorillonite, and suggests that the cation exchange capacity (CEC) of the beidellite is about 98 meq/g.

A direct comparison between electron transparent transmission electron microscope (TEM) samples prepared with gallium (Ga) and xenon (Xe) focused ion beams (FIBs) is performed to determine if equivalent quality samples can be prepared with both ion species. We prepared samples using Ga FIB and Xe plasma focused ion beam (PFIB) while altering a variety of different deposition and milling parameters. The samples’ final thicknesses were evaluated using STEM-EELS t/λ data. Using the Ga FIB sample as a standard, we compared the Xe PFIB samples to the standard and to each other. We show that although the Xe PFIB sample preparation technique is quite different from the Ga FIB technique, it is possible to produce high-quality, large area TEM samples with Xe PFIB. We also describe best practices for a Xe PFIB TEM sample preparation workflow to enable consistent success for any thoughtful FIB operator. For Xe PFIB, we show that a decision must be made between the ultimate sample thickness and the size of the electron transparent region.

The transformation of unstable austenite to ferrite or α′ martensite as a result of exposure to Xe+ or Ga+ ions at room temperature was studied in a 304 stainless steel casting alloy. Controlled Xe+ and Ga+ ion beam exposures of the 304 were carried out at a variety of beam/sample geometries. It was found that both Ga+ and Xe+ ion irradiation resulted in the transformation of the austenite to either ferrite or α′ martensite. In this paper, we will refer to the transformation product as a BCC phase. The crystallographic orientation of the transformed area was controlled by the orientation of the austenite grain and was consistent with either the Nishiyama–Wasserman or the Kurdjumov–Sachs orientation relationships. On the basis of the Xe+ and Ga+ ion beam exposures, the transformation is not controlled by the chemical stabilization of the BCC phase by the ion species, but is a result of the disorder caused by the ion-induced recoil motion and subsequent return of the disordered region to a more energetically favorable phase.

Gallium (Ga) and germanium (Ge) are technologically important critical elements. Lead blast furnace slags from Tsumeb, Namibia, comprise over two million metric tons of material that contains high levels of Ga (135–156 ppm) and Ge (128–441 ppm) in addition to significant Zn concentrations (up to 11 wt.%) and represent a potential resource for these elements. A combination of mineralogical and chemical methods (PXRD, FEG-SEM-EPMA and LA-ICP-MS) indicated different partitioning of Ga and Ge within the individual slag phases. Gallium is predominantly bound in small euhedral crystals of Zn–Fe–Al spinels (<10 μm in size), exhibiting concentrations in the range of 480–1370 ppm (up to 0.004 atoms per formula unit, apfu). Concentrations of Ga in other phases (e.g. melilite) are systematically below 90 ppm. The principal host of Ge is the silicate glass and, to a lesser extent, silicates (melilite and olivine group phases). Concentrations of Ge in glass attained a concentration of 470 ppm (EPMA), but the LA-ICP-MS analysis of glass matrix containing submicrometre spinel crystallites indicated that average Ge levels vary in the range of 113–394 ppm. In the potential extraction of Ga and Ge, the results indicate that ultrafine milling is needed to liberate the Ga- and Ge-hosting phases prior to metallurgical processing of the slag.

The composition of topaz from different granites and greisen in the Krušné Hory/Erzgebirge area was investigated using electron microprobe analysis (EMPA) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). All topaz grains are rich in F (17.9 19.8 wt.%, 1.73 1.90 a.p.f.u.) and the most important minor/trace elements are P, Ge and Ga. Contents of P up to 1 wt.% P2O5 (0.025 a.p.f.u.) were found in topaz from the strongly peraluminous P-rich magmatic systems at Podlesí. Regardless of genetic type, topaz from granites typically contains 50 100 ppm Ge. The greatest amounts (up to 204 ppm Ge) were found in topaz from quartz-topaz-apatite greisen in Krásno. In fractionated granites and greisens, topaz is calculated to contain 23 87% of the bulk Ge content in the rock. In contrast, topaz does not concentrate Ga. The Ga content of topaz (typically 5 35 ppm in S-type granites, <10 ppm Ga in A-type granites) is usually smaller than the bulk Ga content of the rock. In addition, up to 16 ppm Sc, 23 ppm Sn and >400 ppm Fe may be present.

Gallium abundances, determined by laser ablation-inductively coupled plasma-mass spectrometry, are presented for phenocrysts and glassy matrices from a metaluminous trachyte and five peralkaline rhyolites from the Greater Olkaria Volcanic Complex, Kenya Rift Valley. Abundances in the glasses range from 28.9 to 33.3 ppm, comparable with peralkaline rhyolites elsewhere. Phenocryst Ga abundances (in ppm) are: sanidine 31.5–45.3; fayalite 0.02–0.22; hedenbergite 3.3–6.3; amphibole 12; biotite 72; ilmenite 0.56–0.72; titanomagnetite 32; chevkinite-(Ce) 364. The mafic phases and chevkinite-(Ce) are enriched in Ga relative to Al, whereas Ga/Al ratios in sanidine are smaller than in coexisting glass. Apparent partition coefficients range from <0.01 in fayalite to 12 in chevkinite-(Ce). Coefficients for hedenbergite, ilmenite and titanomagnetite decrease as melts become peralkaline. The sharp increase in Ga/Al in the more fractionated members of alkaline magmatic suites probably results from alkali feldspar-dominated fractionation. Case studies are presented to show that the Ga/Al ratio may be a sensitive indicator of such petrogenetic processes as magma mixing, interaction of melts with F-rich volatile phases, mineral accumulation and volatile-induced crustal anatexis.

Ga-rich plumbogummite, (Pb0.87,Ca0.13)Σ1.00H(Al1.95,Ga1.05)Σ3.00(PO4)2(OH)6, from Tsumeb, Namibia, has rhombohedral symmetry, space group Rm, with the cell parameters a = 7.0752(19) Å, c = 16.818(4) Å and V = 729.1(3) Å3. The crystal structure has been refined to R1 = 2.05%. Ga-rich plumbogummite has an alunite-type structure comprised of a rhombohedral stacking of (001) composite layers of corner-shared (Al,Ga)O6 octahedra and PO4 tetrahedra, with Pb atoms occupying icosahedrally coordinated sites between the layers. The Pb and H positions are discussed. Ga-rich plumbogummite is nonpleochroic, uniaxial (+), with indices of refraction, ε = 1.742(3) and ω = 1.722(3), determined in white light. The five strongest powder-diffraction lines [d in Å, (I/I°), (hkl)] are: 2.995, (100), (113); 5.766, (95), (101); 2.236, (43), (107, 122); 3.539, (38), (110); 1.919 (32), (303, 033).

The Kabwe Zn-Pb deposit (central Zambia) consists of a cluster of mixed sulfide and non-sulfide orebodies. The sulfide ores comprise sphalerite, galena, pyrite, chalcopyrite and accessory Ge-sulfides (±Ga and In). The non-sulfide ores comprise: (1) willemite-dominated zones encasing massive sulfide orebodies and (2) oxide-dominated alteration bands, overlying both the sulfide and Zn-silicate orebodies. This study focuses on the Ge, In and Ga distribution in the non-sulfide mineralization, and was carried out on a suite of Kabwe specimens, housed in the Natural History Museum Ore Collection (London). Petrography confirmed that the original sulfides were overprinted by at least two contrasting oxidation stages dominated by the formation of willemite (W1 and W2), and a further event characterized by weathering-related processes. Oxygen isotopic analyses have shown that W1 and W2 are unrelated genetically and furthermore not related to supergene Zn-Pb-carbonates in the oxide-dominated assemblage. The δ18O composition of 13.9–15.7‰ V-SMOW strongly supports a hydrothermal origin for W1. The δ18O composition of W2 (−3.5‰ to 0‰ V-SMOW) indicates that it precipitated from groundwaters of meteoric origin in either a supergene or a low-T hydrothermal environment. Gallium and Ge show a diversity of distribution among the range of Zn-bearing minerals. Gallium has been detected at the ppm level in W1, sphalerite, goethite and hematite. Germanium occurs at ppm levels in W1 and W2, and in scarcely detectable amounts in hemimorphite, goethite and hematite. Indium has low concentrations in goethite and hematite. These different deportments among the various phases are probably due to the different initial Ga, In and Ge abundances in the mineralization, to the different solubilities of the three elements at different temperatures and pH values, and finally to their variable affinities with the various minerals formed.

Molecular dynamics simulations are performed to model milling via a focused ion beam (FIB). The goal of this investigation is to examine the fundamental dynamics associated with the use of FIBs, as well as the phenomena that govern the early stages of trench formation during the milling process. Using a gallium beam to bombard a silicon surface, the extent of lateral damage (atomic displacement) caused by the beam at incident energies of both 2 and 30 keV is examined. These simulations indicate that the lateral damage is several times larger than the beam itself and that the mechanism responsible for the formation of a V-shaped trench is due to both the removal of surface material, and the lateral and horizontal migration of subsurface silicon atoms toward the vacuum/crater interface. The results presented here provide complementary information to experimental images of trenches created during milling with FIBs.