The deintercalation of a low-defect kaolinite intercalated with hydrazine was studied by X-ray diffraction, diffuse reflectance infrared spectroscopy (DRIFT), and Raman microscopy over 30 d. X-ray diffraction showed that the kaolinite was fully intercalated. More than 120 h were required for the hydrazine-intercalate to decompose. The Raman spectra of the hydrazine intercalate showed only a single band at 3620 cm−1, which was attributed to the innerhydroxyl group. Upon deintercalation, additional Raman bands were observed at 3626 and 3613 cm−1. These bands decreased in intensity with further deintercalation. As deintercalation proceeded, the bands assigned to the inner-surface hydroxyl groups at 3695, 3682, 3670, and 3650 cm−1 occurred and increased in intensity. DRIFT spectra showed two bands at 3620 and 3626 cm−1 for the fully intercalated kaolinite only. Upon deintercalation, an additional band assigned to intercalated water was observed at 3599 cm−1 and increased in intensity at the expense of the 3626-cm−1 band. Bands attributed to the innersurface hydroxyl groups increased in intensity with deintercalation. Both the Raman and DRIFT spectra showed complexity in the NH-stretching region with two sets of NH-symmetric and antisymmetric stretching bands. Deintercalation was followed by the loss of intensity of these bands. Significant changes were also observed in the hydroxyl deformation and water-bending modes as a result of deintercalation. A model of hydrazine intercalation of kaolinite based on the insertion of a hydrazine-water unit is proposed. The hydrated end of the hydrazine molecule hydrogen bonds with the innersurface hydroxyl groups resulting in the formation of a band at 3626 cm−1 in the DRIFT spectra.

Kaolinite hydroxyls in dimethylsulphoxide-intercalated (DMSO-intercalated) kaolinites have been determined using Raman spectroscopy at 298 and 77 K. The inner surface hydroxyl frequencies at 3650, 3670, 3684 and 3693 cm-1 move to higher wavenumbers upon cooling to 77 K and are observed at 3659, 3676, 3692 and 3702 cm-1. The inner hydroxyl frequency is at 3620 cm-1 at 298 K and is at 3615 cm-1 at 77 K. Upon intercalation with DMSO, additional bands are found at 3660, 3536 and 3501 cm-1 for the low-defect kaolinite and at 3664, 3543 and 3509 cm-1 for the high-defect kaolinite at 298 K. The 3660 cm-1 band at 298 K is resolved into two bands at 3658 and 3663 cm-1 at 77 K for the low-defect kaolinite and these bands are assigned to the inner surface hydroxyl groups, hydrogen-bonded to the DMSO molecule. It is proposed that the DMSO molecule exists with two different orientations in the intercalate and these two molecular forms are differentiated by the OH-stretching bands of the inner surface hydroxyl groups. This band for the high-defect kaolinite is found at 3664 cm-1 at 298 K and resolves into two bands at 3664 and 3673 cm-1 at 77 K.

The Raman spectrum of holmquistite, a Li-containing orthorhombic amphibole from Bessemer City, USA has been measured. The OH-stretching region is characterized by bands at 3661, 3646, 3634 and 3614 cm−1 assigned to 3 Mg–OH, 2 Mg + Fe2+–OH, Mg + 2Fe2+–OH and 3 Fe2+–OH, respectively. These Mg and Fe2+ cations are located at the M1 and M3 sites and have a Fe2+/(Fe2+ + Mg) ratio of 0.35. The 960–1110 cm−1 region represents the antisymmetric Si–O–Si and O–Si–O stretching vibrations. For holmquistite, strong bands are observed around 1022 and 1085 cm−1 with a shoulder at 1127 cm−1 and minor bands at 1045 and 1102 cm−1. In the region 650–800 cm−1 bands are observed at 679, 753 and 791 cm−1 with a minor band around 694 cm−1 attributed to the symmetrical Si–O–Si and Si–O vibrations. The region below 625 cm−1 is characterized by 14 vibrations related to the deformation modes of the silicate double chain and vibrations involving Mg, Fe, Al and Li in the various M sites. The 502 cm−1 band is a Li–O deformation mode while the 456, 551 and 565 cm−1 bands are Al–O deformation modes.

The presence of a magnesian vivianite (Fe2+)2.5(Mg,Mn,Ca)0.5(PO4)2·8H2O, has been identified in a soil sample from a Roman camp near Fort Vechten, The Netherlands, using a combination of Raman microscopy and scanning electron microscopy. An unsubstituted vivianite and baricite were characterised for comparative reasons. The split phosphate-stretching mode is recognised around 1115, 1062 and 1015 cm−1, while the corresponding bending modes are found around 591, 519, 471 and 422 cm−1. The substitution of Mg and Mn for Fe2+ in the crystal structure causes a shift towards higher wavenumbers compared to pure vivianite. As shown by the baričite sample substitution causes a broadening of the bands. The observed broadening however is larger than can be explained by substitution alone. The low intensity of the water bands, especially in the OH-stretching region between 2700 and 3700 cm−1 indicates that the magnesian vivianite is partially dehydrated, which explains the much larger broadening than the observed broadening caused by substitution of Mg and Mn in vivianite and baričite.

This paper describes the Raman and infrared spectroscopy of SrSO4 or celestine from the Muschelkalk of Winterswijk, The Netherlands. The infrared absorption spectrum is characterised by the SO42-modes V1 at 991 cm-1, v3 at 1201, 1138 and 1091 cm-1, and v4 at 643 and 611 cm-1. An unidentified band is observed at 1248 cm-1. In the Raman spectrum at 293 K the V1 mode is found at 1000 cm-1 and is split in two bands at 1001 and 1003 cm-1 upon cooling to 77 K.The v2 mode, not observed in the infrared spectrum, is observed as a doublet at 460 and 453 cm-1. The v3 mode is represented by four bands in the Raman spectrum at 1187, 1158, 1110 and 1093 cm-1 and the v4 mode as three bands at 656, 638 and 620 cm-1. Cooling to 77 K results in a general decrease in bandwidth and a minor shift in frequencies. A decrease in intensities is observed upon cooling to 77 K due to movement of the Sr atom towards one or more of the oxygen atoms in the sulfate group.

Megalithic art is a well-known feature of the Neolithic chambered tombs of Atlantic Europe. The surviving evidence consists largely of carved motifs, and, until recently, painted megalithic art was thought to be restricted to western Iberia. Recent discoveries have expanded that distribution, assisted by new methods of detection, recording and analysis. The discovery of painted motifs at Barnenez in Brittany, reported here, marks a breakthrough and raises the possibility that many megalithic tombs in north-west Europe were once coloured as well as carved. Similarities in motifs and techniques also point to the likelihood of direct connections with Iberia.

It is shown that star disclinations can be a significant source of stress in chemical vapor deposited (CVD) diamond. This purely geometrical origin contrasts with other sources of stress that have been proposed previously. The effectiveness is demonstrated of the use of electron irradiation using a transmission electron microscope (TEM) to displace atoms from their equilibrium sites to investigate intrinsic defects and impurities in CVD diamond. After irradiation, the samples are studied by low temperature photoluminescence microscopy using UV or blue laser illumination. Results are given that are interpreted as arising from isolated <100> split self-interstitials and positively charged single vacancies. Negatively charged single vacancies can also be revealed by this technique. Nitrogen and boron impurities may also be studied similarly. In addition, a newly developed liquid gallium source scanned ion beam mass spectrometry (SIMS) instrument has been used to map out the B distribution in B doped CVD diamond specimens. The results are supported by micro-Raman spectroscopy.