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Abstract: Simple n-alcohols, such as 1-dodecanol, show anomalous film-forming and friction behaviors under elastohydrodynamic lubrication (EHL) conditions, as found inside bearings and gears. Using tribometer, diamond anvil cell (DAC), and differential scanning calorimetry (DSC) experiments, we show that liquid 1-dodecanol undergoes a pressure-induced solidification when entrained into EHL contacts. Different solid polymorphs are formed inside the contact depending on the temperature and pressure conditions. Surprisingly, at a moderate temperature and pressure, 1-dodecanol forms a polymorph that exhibits robust macroscale superlubricity. The DAC and DSC experiments show that superlubricity is facilitated by the formation of lamellar, hydrogen-bonded structures of hexagonally close-packed molecules, which promote interlayer sliding. This novel superlubricity mechanism is similar to that proposed for the two-dimensional materials commonly employed as solid lubricants, but it also enables the practical advantages of liquid lubricants to be maintained. When the pressure is increased, 1-dodecanol undergoes a polymorphic transformation into a phase that gives a higher friction. The DAC and DSC experiments indicate that the high-friction polymorph is an orthorhombic crystal. The polymorphic transformation pressure coincides with the onset of a dimple formation in the EHL films, revealing that the anomalous film shapes are caused by the formation of rigid orthorhombic crystals inside the contact. This is the first demonstration of a macroscale superlubricity in an EHL contact lubricated by a nonaqueous liquid that arises from bulk effects rather than tribochemical transformations at the surfaces. Since the superlubricity observed here results from phase transformations, it is continuously self-replenishing and is insensitive to surface chemistry and topology. This discovery creates the possibility of implementing superlubricity in a wide range of machine components, which would result in enormous improvements in efficiency and durability.

Open Access

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Abstract: Hydroxide perovskite solid solutions along the CuxZn1−xSn(OH)6 join have been investigated at ambient conditions. Two compositions, Cu0.4Zn0.6Sn(OH)6 (cubic) and CuSn(OH)6 (tetragonal), have also been studied at pressures up to 17 GPa. In both ambient and high-pressure experiments, samples were characterised using powder X-ray diffraction. Bulk compositions between 0 ≤ XCu ≤ 0.4 are metrically cubic (space group Pn 3 ¯ 3¯ ), whereas those with XCu = 0.9 and 1 produced single-phase tetragonal Cu0.9Zn0.1Sn(OH)6 and CuSn(OH)6 (space group P42/n). The products of syntheses with 0.5 ≤ XCu ≤ 0.8 contain coexisting cubic and tetragonal phases. The cubic → tetragonal transformation is rationalised in terms of being driven by local strain associated with the accumulation of Cu-rich domains in the cubic phase. The high-pressure studies of cubic Cu0.4Zn0.6Sn(OH)6 and tetragonal CuSn(OH)6 phases showed contrasting behaviour. The compression curve of the cubic phase is smooth without inflexion or discontinuity to 17 GPa. The derived bulk modulus of Cu0.4Zn0.6Sn(OH)6 is K0 = 75.8(4) GPa (K′ = 4). For CuSn(OH)6, compression data cannot be fitted by a single equation-of-state over the entire pressure range to 17 GPa, as there is a clear discontinuity between 7 and 10 GPa that corresponds to an increase in compressibility at higher pressures. Compression data for CuSn(OH)6 to 7 GPa are: K0 = 59.7(9) GPa, Ka0 = 79(2) GPa, and Kc0 = 38.0(3) GPa (K′ = 4 for all). It is shown that the strong Jahn–Teller distortion associated with the Cu(OH)6 octahedron is primarily responsible for the discontinuous and highly anisotropic compressional behaviour of the unit cell of CuSn(OH)6 hydroxide perovskite.

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Abstract: Siidraite, Pb2Cu(OH)2I3, is a new mineral from the Broken Hill deposit in New South Wales, Australia. It occurs as an extremely rare secondary phase alongside marshite, other lead and copper secondaries and supergene cuprite on a single specimen, BM 84642 preserved in the collection of the Natural History Museum, London. Siidraite is yellow and occurs in crystalline grainy aggregates up to 0.3 mm around relict galena. The mineral is translucent with a vitreous lustre and yellow streak, no cleavages or forms have yet been observed. It is non-fluorescent in mixed-wavelength UV light. The calculated density is 6.505 g cm−3. Siidraite is orthorhombic, space group Fddd, a = 16.7082(9) Å, b = 20.846(1) Å, c = 21.016(1) Å, V = 7320.0(8) Å3 and Z = 32. The empirical formula derived from a combination of electron-microprobe analysis and structure determination is Pb2.06Cu0.89(OH)2I2.97, the ideal formula has (in wt%) 8.01 Cu2O, 50.01 PbO, 42.65 I and 2.02 H2O. The five strongest lines in the calculated X-ray powder diffraction pattern are [(hkl), dobs (Å), I/Imax (%)]: [(246), 2.746, 100], [(404), 3.270, 81], [(264), 2.738, 77], [(315), 3.312, 76], [(351), 3.296, 69]. The crystal used for structure determination had minor pseudomerohedral twinning on [011] and the structure was refined taking this into account to R1 = 0.037, wR2 = 0.052, GooF = 1.016, based upon 1368 unique reflections having I > 2σ(I). The structure of siidraite is a framework comprising an alternation of two structural elements, a cubane-like [Pb4(OH)4] 4+ group and a [Cu2I6]4 dimer of edge-sharing CuI4 tetrahedra with non-equivalent Cu. Six halocuprate groups surround each [Pb4(OH)4]4+ nucleus, and each halocuprate group is shared between six adjacent [Pb4(OH)4]4+ groups, five long Pb–I bonds are required to complete the co-ordination of each Pb atom. The resulting Pb(OH)3I5 polyhedra are centred on a tetrahedron of O atoms to form a Pb4(OH)4I16 cluster. Siidraite has a unique composition and structure. It is the third naturally occurring halocuprate(I) after marshite and nantokite. A compositionally similar synthetic compound Pb2Cu2(OH)2I2Br has been described that has cubane and CuI4 groups, but a very different structural topology from that of siidraite. Bideauxite, Pb2Ag(OH)FCl3, which has the [Pb4(OH)4]4+ group, shares some topological features with siidraite.

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Abstract: Pb2Cu(OH)2I3 is a new type of halocuprate(I) that is a framework of alternating [Pb4(OH)4]4+ and [Cu2I6]4− units. The structure has been determined in orthorhombic space group Fddd to R1=0.037, wR2=0.057, GoF=1.016. Unit cell parameters are a=16.7082(9) Å, b=20.8465(15) Å, c=21.0159(14) Å, V=7320.0(8) Å3 (Z=32). There is no synthetic counterpart. The structure is based upon a cubane-like Pb4(OH)4 nucleus that is coordinated to sixteen iodide ions. Cu+ ions are inserted into pairs of adjacent edge-sharing tetrahedral sites in the iodide motif to form [Cu2I6]4− groups. The Raman spectrum of Pb2Cu(OH)2I3 has two O-H stretching modes and as such is consistent with space group Fddd, with two non-equivalent OH groups, rather than the related space group I41/acd which has only one OH group. Consideration of the 18-electron rule implies that there is a Cu=Cu double bond, which may be consistent with the short Cu…Cu distance of 2.78 Å, although the dearth of published data on the interpretation of Cu…Cu distances in halocuprate(I) compounds does not allow a clear-cut interpretation of this interatomic distance. The orthorhombic structure is compared with that of the synthetic halocuprate(I) compound Pb2Cu(OH)2BrI2 with space group I41/acd and having chains of corner-linked CuI4 tetrahedra rather than isolated Cu2I6 pairs. The paired motif found in Pb2Cu(OH)2I3 cannot be achieved in space group I41/acd and, conversely, the chain motif cannot be achieved in space group Fddd. As such, the space group defines either a chain or an isolated-pair motif. The existence of Pb2Cu(OH)2I3 suggests a new class of inorganic halocuprate(I)s based upon the Pb4(OH)4 group.

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Abstract: The effect of pressure on the naturally occurring hydroxide-perovskite stottite, FeGe(OH)(6), has been studied in situ by micro-Raman spectroscopy to 21 GPa at 300 K. The ambient spectrum contains six OH-stretching bands in the range 3064-3352 cm(-1). The presence of six non-equivalent OH groups is inconsistent with space group P4(2)/n. In view of this inconsistency a new ambient structure determination of stottite from Tsumeb was carried out, but this did not allow the clear rejection of P4(2)/n symmetry. However, a successful refinement was also carried out in space group P2/n, a subgroup of P4(2)/n, which allows for six non-equivalent 0 atoms. The two refinements are of comparable quality and do not allow a choice to be made based purely on the X-ray data. However, taken with the ambient and 150 K Raman spectra, a good case can be made for stottite having P2/n symmetry at ambient conditions. On this basis, the pressure induced spectroscopic changes are interpreted in terms of a reversible phase transition P2/n <-> P4(2)/n.