| 1. |
- Persson, Per-Axel, et al.
(författare)
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High-pressure polymerized C60
- 1996
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Ingår i: Extended Abstracts of Carbon´96, European Carbon Conference, Newcastle-upon-Tyne 1996, volume 2. - : The British Carbon Group. ; , s. 746-747, s. 746-747
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Konferensbidrag (övrigt vetenskapligt/konstnärligt)
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| 2. |
- Persson, Per-Axel, et al.
(författare)
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NMR and Raman characterization of pressure polymerized C-60
- 1996
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Ingår i: Chemical Physics Letters. - : Elsevier BV. - 0009-2614 .- 1873-4448. ; 258:5-6, s. 540-546
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Tidskriftsartikel (refereegranskat)abstract
- Bulk C60 has been treated at 1.1 GPa and 550–585 K, producing a dense insoluble material which on heating to above 600 K reverts to normal C60. Raman and IR studies on modified material show a large number of new lines, and the Raman pentagon pinch mode shifts from 1469 to 1458 cm−1 as on photopolymerization. MAS NMR shows one broadened line at the original C60 shift 144 ppm and a small peak at about 77 ppm due to the bridging carbons. None of the new resonances observed for C60 polymerized by other methods were observed. The results verify previously suggested polymeric structures where the fullerence cages are connected by four-membered rings.
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| 3. |
- Persson, Per-Axel, et al.
(författare)
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Physical properties of pressure polymerized C60
- 1996
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Ingår i: High Pressure Science and Technology. - Singapore : World Scientific. - 9810225474 ; , s. 716-718
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Konferensbidrag (refereegranskat)abstract
- The properties of C60 have been studied after treatment at high temperature and high pressure (1.1 GPa and 565 K for 2 h). The treated material is insoluble in organic solvents. We present results obtained in NMR and Raman studies and measured data for the specific heat and the thermal expansion. Our results show clearly that there are no covalent bonds and no molecular rotation, but suggest that the molecules are slightly deformed and held together by weak pi-type bonds.
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| 4. |
- Persson, Per-Axel, et al.
(författare)
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The physical properties of high-pressure polymerized C60
- 1997
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Ingår i: Journal of Physics and Chemistry of Solids, volume 58, issue 11. - : Elsevier B.V.. ; 58:11, s. 1881-1885
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Konferensbidrag (refereegranskat)abstract
- We have studied the structural, thermophysical, and spectroscopic properties of polymeric C60 obtained by high pressure treatment at pressures and temperatures near 1 GPa and 600 K. We present here a brief overview of our results for the structural and thermophysical properties and a more detailed report on recent results obtained by Raman spectroscopy on both thin films, polycrystalline, and single crystal material. The results presented include a comparison between Raman results for photopolymerized and pressure polymerized thin films and a preliminary estimate of the binding energy of polymeric C60.
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| 5. |
- Soldatov, Alexander, et al.
(författare)
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Pressure polymerized C60 : Raman and NMR studies
- 1996
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Ingår i: Fullerenes and Fullerene Nanostructures. - Singapore : World Scientific. - 9810228538 ; , s. 344-348
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Konferensbidrag (refereegranskat)abstract
- The properties of bulk C60 have been studied after treatment at 1.1 GPa and 550-585 K. The treated material is insoluble in both toluene and 1,2-dichlorobenzene. Raman spectroscopy on modified aterial shows a large number of new lines, and the Raman pentagon pinch mode (Ag2) shifts from 1469 to 1458 /cm as on photopolymerization. MAS NMR shows one broadened line at the original C60 shift 144 ppm and a small peak at about 77 ppm due to the bridging carbons. The results verify previous suggested polymeric structures where the fullerene cages are connected by four-membered rings.
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| 6. |
- Sundqvist, Bertil, et al.
(författare)
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Physical properties of pressure polymerized C60
- 1996
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Ingår i: Fullerenes: Recent Advances in the Chemistry and Physics of Fullerenes and Related Materials, volume 3. - Pennington, NJ : The Electrochemical Society. - 1566771625 ; , s. 1014-1028
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Konferensbidrag (refereegranskat)abstract
- We present in this paper an overview of the physical properties of the high pressure polymerized C60 phase commonly known as "soft fcc". This phase has been studied by several methods over wide ranges in temperature T and/or pressure, p. We present here experimental information about the specific heat capacity, the thermal expansion coefficient, the lattice structure, and the thermal conductivity, and we also show results obtained by NMR and Raman spectroscopy. All data presented agree with the accepted model that the individual molecules in this phase are covalently bound to form linear molecular chains. In particular, the NMR data show clearly the presence of covalent bonds, and the Raman data exhibit several new lines at very low energies connected with chain vibrations. Thermal conductivity data obtained during polymerization show both the time dependence of the process and that polymerization occurs at lower p and T than observed previously for this phase.
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| 7. |
- Sundqvist, Bertil, et al.
(författare)
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Structural and physical properties of pressure polymerized C60
- 1998
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Ingår i: Carbon, vol. 36 issue 5-6. - : Elsevier B.V.. ; 36:5-6, s. 657-660
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Konferensbidrag (refereegranskat)abstract
- We discuss the structural and dynamic properties of C60 polymerized under low-P, low-T conditions, and suggest that the disordered mixed orthorhombic-tetragonal-rhombohedral phases produced under these conditions arise from nucleation of molecular chains in random directions because of the quasi-free molecular rotation under standard reaction conditions in the fcc phase of C60. Polymerization in He gives results qualitatively different from those obtained in other media.
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| 8. |
- Winter, Johannes, et al.
(författare)
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Charge transfer in alkali-metal-doped polymeric fullerenes
- 1996
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Ingår i: Physical Review B. Condensed Matter and Materials Physics. - 1098-0121 .- 1550-235X. ; 54, s. 17486-17492
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Tidskriftsartikel (refereegranskat)abstract
- We present room-temperature Raman measurements of pressure-polymerized C60 and compare them with the spectra of RbC60 in the orthorhombic phase. Although both materials were prepared according to two completely different routes the spectra show a surprising similarity with respect to mode positions and line splitting. We concluded from this that both materials, the uncharged pressure-polymerized C60 and the rubidium-doped orthorhombic compound, have the same overall structure and the AC60 compounds can be considered as the doped species of the C60, polymerized using moderate low pressure and high temperatures. From a detailed comparison between both spectra mode shifting and line broadening as a consequence of the charge transfer was determined and electron-phonon coupling constants were estimated for the high-frequency Hg(7) and Hg(8) modes. The low values for the coupling constants compared to the ones in the K3C60 can explain the lack of superconductivity in the AC60 compounds.
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| 9. |
- Wågberg, Thomas, et al.
(författare)
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A Raman study of polymerised C60
- 1997
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Ingår i: Applied Physics A. - : Springer Science and Business Media LLC. - 0947-8396 .- 1432-0630. ; 64:3, s. 223-226
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Tidskriftsartikel (refereegranskat)abstract
- Results of Raman scattering studies on high pressure polymerized and photo polymerized C60 are reported. Although prepared according to different routes the Raman spectra of the two polymeric phases of C60 show a quantitative agreement with respect to mode positions and intensity. We conclude from this that both materials have the same structure at least in the short range order, i.e. the same type of bonding and co-ordination between neighbouring C60 molecules. An investigation of the time dependence of the thermal decomposition of high pressure polymerised C60 is also presented. The rate of decomposition of the polymeric phase is found to be multi-exponential at all temperatures investigated. From an Arrhenius-type analysis of the short time data and the long time data, respectively, the activation energy for thermal dissociation of polymeric bonds was found to increase with time.
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| 10. |
- Wågberg, Thomas, et al.
(författare)
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Polymeric phases of C60
- 1997
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Ingår i: Fullerenes: Recent Advances in the Chemistry and Physics of Fullerenes and Related Materials, vol. 5. - Pennington, NJ : The Electrochemical Society. - 1566771927 ; , s. 674-679
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Konferensbidrag (refereegranskat)abstract
- We have investigated the "low" pressure region where C60 can be transformed into polymeric chains or clusters. To learn more about the polymerization process we have treated pristine C60 at several different temperatures under hydrostatic pressures in silicone oil. We found that the reaction rate varied with temperature. Above 520 K at 1.0 GPa similar and high polymer fractions were obtained in all samples, but at 497 K the polymer fraction was only 10% after three hours, as indicated by the shift of the intensity of the pentagonal pinch mode in the Raman spectrum. Also, samples treated at the same pressure and temperature but with different thermal pre-history showed different degrees of polymerization. We have also found a correlation between the shift of the pentagonal pinch mode in the Raman spectrum to 1463 /cm and the intermolecular vibrational mode at 97 /cm. We therefore make the conclusion that the shift of the pentagonal pinch mode to 1463 /cm corresponds to the presence of dimers in the sample.
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| 11. |
- Launois, Pascale, et al.
(författare)
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Pressure polymerized C60 single crystals: First x-ray diffraction results
- 1998
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Ingår i: Molecular Nanostructures. - Singapore : World Scientific. - 9789810232610 ; , s. 348-352
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Konferensbidrag (refereegranskat)abstract
- C60 single crystals compressed at approx. 1 GPa and heated at about 300 C are found to polymerize in one dimension without losing their crystalline order. The resulting structure is orthrhombic, with space group Pmnn and parameters a=9.14 Å, b=9.9 Å and c=14.66 Å. The X-ray single crystal results allow us to derive a polymerization mechanism, which may also, for instance, apply to one dimensional C60 polymers in the doped compounds. The new polymer phase is discussed with respect to the C60 pressure-temperature diagram. The comparison with the A1C60 polymers raises questions about the interchain and the alkali metal - fullerene interactins.
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| 12. |
- Moret, Roger, et al.
(författare)
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First X-ray diffraction analysis of pressure polymerized C60 single crystals
- 1997
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Ingår i: Europhysics letters. - : IOP Publishing. - 0295-5075 .- 1286-4854. ; 40:1, s. 55-60
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Tidskriftsartikel (refereegranskat)abstract
- It is shown that C60 single crystals can be polymerized under relatively modest pressure-temperature conditions. The resulting single crystals exhibit long-range order and they are made up of 12 orientation variants. The structure is orthorhombic with a short intermolecular distance along the chains (9.14 Å), characteristic of covalent bonding. We propose a structural mechanism for the polymerization of fullerene-based compounds; it involves a shift of one of the (111) cubic planes together with a shortening of the (111) spacing. The configuration of the polymer chains presents interesting relations with that found in the A1C60 polymer compounds.
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| 13. |
- Nagel, Peter, et al.
(författare)
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C60 one- and two-dimensional polymers, dimers, and hard fullerite: Thermal expansion, anharmonicity, and kinetics of depolymerization
- 1999
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Ingår i: Physical Review B. Condensed Matter and Materials Physics. - : American Physical Society. - 1098-0121 .- 1550-235X. ; 60:24, s. 16920-16927
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Tidskriftsartikel (refereegranskat)abstract
- We report on high-resolution thermal expansion measurements of high-temperature-pressure treated C60 [one-dimensional (1D) and (2D) polymers and “hard fullerite”], as well as of C60 dimers and single crystal monomer C60 between 10 and 500 K. Polymerization drastically reduces the thermal expansivity from the values of monomeric C60 due to the stronger and less anharmonic covalent bonds between molecules. The expansivity of the “hard” material approaches that of diamond. The large and irreversible volume change upon depolymerization between 400 and 500 K makes it possible to study the kinetics of depolymerization, which is described excellently by a simple activated process, with activation energies of 1.9±0.1 eV (1D and 2D polymers) and 1.75±0.05 eV (dimer). Although the activation energies are very similar for the different polymers, the depolymerization rates differ by up to four orders of magnitude at a given temperature, being fastest for the dimers. Preliminary kinetic data of C70 polymers are presented as well.
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| 14. |
- Nagel, Peter, et al.
(författare)
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High-resolution thermal expansion of high-pressure polymerized and 'normal' C60 from 10-500 K: Kinetics of depolymerization
- 1998
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Ingår i: Molecular Nanostructures. - Singapore : World Scientific. - 9810232616 ; , s. 365-368
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Konferensbidrag (refereegranskat)abstract
- High-resolution capacitance dilatometry was used to study the thermal expansion of both 'normal' and polymer phases of C60. The expansivity, alpha(T), of 'normal' C60 exhibits an unusual temperature dependence above the orientational disordering transition at 260 K; alpha(T) decreases by about 30% from 260 to 500 K and appears to reach a minimum near 500 K. Polymerized C60 has a much smaller expansivity than normal C60 due to the stronger covalent bonding between molecules. The polymerized state converts back to 'normal' C60 at temperatures between 450 and 500 K. We show that this is an activated process with a well-defined activation energy of 1.92 eV and a volume increase of about 2%.
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| 15. |
- Sundqvist, Bertil, et al.
(författare)
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Fullerenes under pressure : Structure, order, and disorder
- 1996
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Ingår i: High Pressure Science and Technology. - Singapore : World Scientific. - 9810225474 ; , s. 697-701
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Konferensbidrag (refereegranskat)abstract
- The weak intermolecular interactions in solid C60 and other fullerenes make crystal structures and other properties very sensitive to applied pressure. We review recent results on the properties and phases of fullerenes under pressure, concentrating on the low-p range up to about 1 GPa. Subjects discussed include compression and transport studies, orientational and rotational disorder, the glassy crystal transition, and pressure-induced polymerization.
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| 16. |
- Sundqvist, Bertil, et al.
(författare)
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Orientational disorder and the p-T phase diagram of fullerenes
- 1995
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Ingår i: Fullerenes: Recent Advances in the Chemistry and Physics of Fullerenes and Related Materials, volume 2. - Pennington, NJ : The Electrochemical Society. - 1566771048 ; , s. 891-905
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Konferensbidrag (refereegranskat)abstract
- The translational and orientational structures of fullerenes are very sensitive to pressure, p, because of the weak intermolecular potentials. We have recently carried out high-p studies of the thermal conductivity lambda and the bulk modulus B of C60 and C70, and we show here how the p-T phase diagrams of these materials can be mapped from data for B and lambda and a knowledge of the structures at zero pressure. We discuss how B and lambda are modified by translational, rotational and orientational disorder in the materials, mainly showing examples related to the orientational substructure and its evolution with T and p in C60. We also discuss briefly the structures and phase diagrams of C70 and C61H2, and we show preliminary experimental results suggesting that the structure of high-p, high-T treated C60 is probably not polymeric as recently suggested by several groups.
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| 17. |
- Wågberg, Thomas, et al.
(författare)
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Structural evolution of low-pressure polymerised C60 with polymerisation conditions
- 1999
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Ingår i: Journal of Physics and Chemistry of Solids. - : Elsevier B.V.. - 0022-3697 .- 1879-2553. ; 60:12, s. 1989-1994
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Tidskriftsartikel (refereegranskat)abstract
- We show in this paper that characteristic features in the Raman spectra, especially the frequency of the pentagonal pinch mode, can give information about the polymeric structure of pressure polymerised C60. High-pressure treatment at 1 GPa below 510 K for 3 h results in the formation of a low fraction of dimers only, while treatment at the same pressure and time above 540 K affords a fully polymerised material. In the latter case, different relative fractions of dimers and polymer chains are obtained depending on whether the final reaction conditions were reached by isobaric or isothermal path. We suggest that this difference results from different reaction dynamics in the two cases. The polymerisation rate depends on T and p and on the rotational and orientational states of the molecules. At 1 GPa no polymerisation is observed in sc C60, while in “hexagon” oriented sc C60 at 1.7 GPa dimers are already formed 175 K below the fcc–sc transition and a fully polymerised material is obtained just below the transition to the fcc phase.
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