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The role of calorimetry in the structural study of mesophases and their glass states

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Abstract

Four mesomorphic states of matter are known: liquid crystal, plastic crystal, condis phase, and rotator phase, all of them are solid phases, except liquid crystal, which is fluid. Plastic crystal (also called ODIC, orientational disordered crystal), rotator phase, and even condis phase have been considered the same phase by many authors. Differences between them will be established to define their own characteristics. Two organic salts series have been used for discussion in this presentation: (1) thallium(I) alkanoate series, that presents a condis mesophase, and (2) lead(II) alkanoate series, that present a rotator one, both forming a smectic A-like liquid crystal phase. Based in the literature data of the alkyl ammonium bromide series it can be established that the short chain length members would present a rotator phase, and, the large chain ones, a condis phase. Five different glass states are known (four with partial crystalline order), corresponding with the above mentioned mesophases, and the ordinary (amorphous) glass state.

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References

  1. Duruz J, Michels HJ, Ubbelohde AR. Molten fatty acid salts as model ionic liquids I. Thermodynamic and transport parameters of some organic sodium salts. Proc R Soc Lond Ser A. 1971;322:281–99.

    Article  CAS  Google Scholar 

  2. Ramos Riesco M, Martínez Casado FJ, López-Andrés S, García Pérez MV, Redondo Yélamos MI, Torres MR, Garrido L, Rodríguez Cheda JA. Monotropic polymorphism in copper(II) decanoate. Cryst Growth Des. 2008;8:2547–54.

    Article  CAS  Google Scholar 

  3. Earle MJ, Seddon KR. Ionic liquids Green solvents for the future. Pure Appl Chem. 2000;72:1391–8.

    Article  CAS  Google Scholar 

  4. Rao CNR, Natarajan S, Vaidhyanathan R. Metal carboxylates with open architectures. Angew Chem Int Ed. 2004;43:1466–96.

    Article  CAS  Google Scholar 

  5. Patrick Stahly G. A survey of cocrystals reported prior to 2000. Cryst Growth Des. 2009;9:4212–29.

    Article  Google Scholar 

  6. Klimusheva G, Koval’Chuk A, Volynets N, Vakhnin A. Electrooptical properties of metal organic ionic liquid crystals. Opto-Electron Rev. 2002;10(1):39–42.

    CAS  Google Scholar 

  7. Sánchez Arenas A, García Pérez MV, Redondo MI, Cheda JAR, Roux MV, Turrión C. Thermophysical study of lead(II) n-alkanoates by DCS, optical microscopy, FTIR, and Raman spectroscopy. Liq Cryst. 1995;18(3):431–41.

    Article  Google Scholar 

  8. Martínez Casado FJ, García Pérez MV, Redondo Yélamos MI, Cheda JAR, Sánchez Arenas A. Intermediate rotator phase in lead(II) alkanoates. J Phys Chem C. 2007;111(18):6826–31.

    Article  Google Scholar 

  9. Cheda JAR, Redondo MI, García MV, López de la Fuente FL, Fernández-Martín F, Westrum EF Jr. A thermophysical study of the melting process in alkyl chain metal n-alkanoates: the thallium(I) series. J Chem Phys. 1999;111:3590–8. And all of our references therein.

    Article  CAS  Google Scholar 

  10. Lindau J, Diele S, Kruger H, Dorfler HD. Thermal phase-behavior of thallium (I) salts of aliphatic carbonic-acids. Z Phys Chem Leipzig. 1981;262:775–84.

    CAS  Google Scholar 

  11. Lindau J, Konig HJ, Dorfler HD. Systemization of the low-temperature modifications of homologous thallium(I) salts of aliphatic carbonic-acids through their mixability relationships. Colloid Polym Sci. 1983;261:236–40.

    Article  CAS  Google Scholar 

  12. Orientational disorders in crystals. In: Rudman R, Smith GW, editors. ODIC Newsletter. 1976;1:1–4.

  13. Gregoryanz E, Goncharov AF, Hemley RJ, Mao H, Somayazulu M, Shen G. Raman, infrared, and x-ray evidence for new phases of nitrogen at high pressures and temperatures. Phys Rev B. 2002;66:224108.

    Article  Google Scholar 

  14. Binnemans K. Ionic liquid crystals. Chem Rev. 2005;105:4148–204.

    Article  CAS  Google Scholar 

  15. Wunderlich B, Moller M, Grebowicz J, Baur H. Conformational motion and disorder in low and high molecular mass crystals. London: Springer–Verlag; 1988. (Advances in Polymer Science, vol no. 87).

  16. Wunderlich B. Thermodynamic description of condensed phases. J Therm Anal Calorim. 2010;102:413–24.

    Article  CAS  Google Scholar 

  17. Lacouture F, Francois M, Didierjean C, Rivera JP, Rocca E, Steinmetza J. Anhydrous lead(II) heptanoate. Acta Crystallogr. 2001;C57:530–1.

    CAS  Google Scholar 

  18. Ryckaert JP, Klein ML, McDonald IR. Disorder at the bilayer interface in the pseudohexagonal rotator phase of solid n-alkanes. Phys Rev Lett. 1987;58:698–701.

    Article  Google Scholar 

  19. Marbeuf A, Brown R. Molecular dynamics in n-alkanes: premelting phenomena and rotator phases. J Chem Phys. 2006;124:054901.

    Article  Google Scholar 

  20. Shinohara Y, Kawasaki N, Ueno S, Kobayashi I, Nakajima M, Amemiya Y. Observation of the transient rotator phase of n-hexadecane in emulsified droplets with time-resolved two-dimensional small- and wide-angle X-ray scattering. Phys Rev Lett. 2005; 94:097801(1-4).

    Google Scholar 

  21. Spitalsky Z, Bleha T. Energetics of stretching of conformational defects in extended poly(methylene) chains. Macromol Theory Simul. 2001;10(9):833–41.

    Article  CAS  Google Scholar 

  22. Wunderlich BJ. Thermal properties of aliphatic nylons and their link to crystal structure and molecular motion. J Therm Anal Calorim. 2008;93:1–17.

    Article  Google Scholar 

  23. Corkery RW. Metal organic framework (MOF) liquid crystals. 1D, 2D and 3D ionic coordination polymer structures in the thermotropic mesophases of metal soaps, including alkaline earth, transition metal and lanthanide soaps. Curr Opin Colloid Interface Sci. 2008;13:288–302.

    Article  CAS  Google Scholar 

  24. Martínez-Casado FJ, Sánchez Arenas A, García Pérez MV, Redondo Yélamos MI, López de Andrés S, Cheda JAR. Short chain lead (II) alkanoates as ionic liquids and glass formers: a DSC, X-ray diffraction and FTIR spectroscopy study. J Chem Thermdyn. 2007;39(3):455–61.

    Article  Google Scholar 

  25. Martínez Casado FJ, Ramos Riesco M, Sánchez Arenas A, García Pérez MV, Redondo MI, López-Andrés S, Garrido L, Cheda JAR. A novel rotator glass in lead(II) pentanoate: calorimetric and spectroscopic study. J Phys Chem B. 2008;112(51):16601–9.

    Article  Google Scholar 

  26. Nagle JF. Theory of biomembrane phase transitions. J Chem Phys. 1973;58:252–3.

    Article  CAS  Google Scholar 

  27. Nagle JF. Theory of the main lipid bilayer phase transition. Annu Rev Phys Chem. 1980;31:157–96.

    Article  CAS  Google Scholar 

  28. Nagle JF, Goldstein M. Decomposition of entropy and enthalpy for the melting transition of polyethylene. Macromolecules. 1985;18:2643–52.

    Article  CAS  Google Scholar 

  29. Flory PJ. Statistical mechanics of chain molecules. New York: Wiley; 1969.

    Google Scholar 

  30. García Pérez MV, Redondo Yélamos MI, López de la Fuente FL, Cheda JAR, Westrum EF Jr, Fernández-Martín F. Temperature dependence of the vibrational spectra of thallium(I) alkanoates. Appl Spectrosc. 1994;48:338–44.

    Article  Google Scholar 

  31. Kurik MV, Lavrentovich OD. Defects in liquid crystals: homotopy theory and experimental studies. Sov Phys Uspekhi. 1988;31:196–224.

    Article  Google Scholar 

  32. Gray GW, Goodby JWG. Smectic liquid crystals textures and structures. Glasgow & London: Leonard Hill; 1984. p. 23–44.

    Google Scholar 

  33. Martínez Casado FJ, Ramos Riesco M, García Pérez MV, Redondo Yélamos MI, López-Andrés S, Cheda JAR. Structural and thermodynamic study on short metal alkanoates: lithium propanoate and pentanoate. J Phys Chem B. 2009;113(39):12896–902.

    Article  Google Scholar 

  34. Martínez Casado FJ, Ramos Riesco M, Da Silva I, Labrador A, Redondo MI, García Pérez MV, López-Andrés S, Cheda JAR. Thermal and structural study of the crystal phases and mesophases in the lithium and thallium(I) propanoates and pentanoates binary systems: formation of mixed salts and stabilization of the ionic liquid crystal phase. J Phys Chem B. 2010;114(31):10075–85.

    Article  Google Scholar 

  35. Martínez Casado FJ, Ramos Riesco M, Da Silva I, Redondo MI, Labrador A, Cheda JAR. Lithium and lead(II) butyrates binary system. Pure compounds and an intermediate salt: from 2D to 3D coordination polymers. Cryst Growth Des. 2011;11(3):759–67.

    Article  Google Scholar 

  36. Martínez Casado FJ, Ramos Riesco M, Da Silva I, Redondo MI, Cheda JAR. Lithium-thallium (I) butyrates binary system: an intermediate salt and liquid crystal from non-mesogenic compounds. RSC Adv. 2011;1:147–55.

    Article  Google Scholar 

  37. Strobl G, Ewen B, Fischer EW, Piesczek W. Defect structure and molecular motion in the four modifications of n -tritriacontane. I. Study of defect structure in the lamellar interfaces using small angle x-ray scattering. J Chem Phys. 1974;61(12):5257–64.

    Article  Google Scholar 

  38. Busico V, Ferraro A, Vacatello M. Polymorphism and liquid-crystalline behavior of lithium n-hexadecanoate. J Phys Chem-US. 1984;88(18):4055–8.

    Article  CAS  Google Scholar 

  39. Busico V, Ferraro A, Vacatello M. A study of the “rotator” phase of 16-hydroxy-lithlum-hexadecanoate. J Chem Phys. 1986;84(1):471–5.

    Article  CAS  Google Scholar 

  40. Sirota EB. Remarks concerning the relation between rotator phases of bulk n-alkanes and those of Langmuir monolayers of alkyl-chain surfactants on water. Langmuir. 1997;13(14):3849–59.

    Article  CAS  Google Scholar 

  41. Vollhardt D. Effect of unsaturation in fatty acids on the main characteristics of Langmuir monolayers. J Phys Chem C. 2007;111(8):6805–12.

    Article  CAS  Google Scholar 

  42. Dorfler HD, Brandt A. X-ray diffraction studies on homologous thallium soaps below the temperature range of the neat phase 1. Calculation and comparison of the structure parameters of unit cells. Colloid Polym Sci. 1992;270(3):267–81.

    Article  Google Scholar 

  43. Dorfler HD, Brandt A, Kolbe A. X-ray diffraction studies on homologous thallium soaps below the temperature range of the neat phase 2. Structure models of crystalline modifications in the temperature range below the neat phase. Colloid Polym Sci. 1992;270(3):282–97.

    Article  Google Scholar 

  44. Bazuin CG, Guillon D, Skoulios A, Amorim da Costa AM, Burrows HD, Geraldes CFGC, Teixeira-Dias JJC, Blackmore E, Tiddy GJT. Thermotropic polymorphism in liquid-crystalline lead(II) alkanoates. Liq Cryst. 1988;3(12):1655–7.

    Article  CAS  Google Scholar 

  45. Busico V, Cernicchiaro P, Corradini P, Vacatello M. Polymorphism in anhydrous amphiphilic systems long-chain primary n-alkylammonium chlorides. J Phys Chem-US. 1983;87:1631–5.

    Article  CAS  Google Scholar 

  46. Iwai S, Hattori M, Nakamura ID, Ikeda R. Ionic dynamics in the rotator phase of n-alkylammonium chlorides (C-6-C-10), studied by H-1 nuclear-magnetic-resonance, electrical-conductivity and thermal measurements. J Chem Soc Faraday Trans. 1993;89(5):827–931.

    Article  CAS  Google Scholar 

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Acknowledgements

Partial support of this research by the DGICYT of the Spanish Ministerio de Ciencia e Innovación (Project CTQ2008-06328/BQU) and also the Beca de Especialización en Organismos Internacionales, ES-2006-0024, and the postdoctoral contract JAE-DOC 2010) is gratefully acknowledged. The authors wish to thank BM16 and BM25 (Spanish beamlines at the ESRF, in Grenoble, France) and the CAI (Centro de Asistencia a la Investigación) of XRD of the UCM for the use of their technical facilities.

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Authors and Affiliations

  1. Laboratorio de Estudios Cristalográficos, IACT (CSIC-UGR), Avenida de las Palmeras 4, Armilla, 18100, Granada, Spain

    F. J. Martínez Casado

  2. Departamento de Química Física I, Facultad de Ciencias Químicas, Universidad Complutense, 28040, Madrid, Spain

    M. Ramos Riesco, M. I. Redondo Yélamos & J. A. Rodríguez Cheda

  3. Sección Departamental de Física Aplicada I, Facultad de Veterinaria, Universidad Complutense, 28040, Madrid, Spain

    A. Sánchez Arenas

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Correspondence to J. A. Rodríguez Cheda.

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Martínez Casado, F.J., Ramos Riesco, M., Redondo Yélamos, M.I. et al. The role of calorimetry in the structural study of mesophases and their glass states. J Therm Anal Calorim 108, 399–413 (2012). https://doi.org/10.1007/s10973-011-1938-2

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