Authors:G. Colón, M. Avilés, J. Navío and P. Sánchez-Soto
A microcomposite powder in the system TiO2—ZrO2 as a precursor of zirconium titanate (ZT) materials has been studied by thermal methods (DTA-TG) and X-ray diffraction (XRD). The microcomposite powder has been prepared by chemical processing of crystalline TiO2 (rutile, 10 mass% anatase),as inner core, coated with in situ precipitated amorphous hydrated zirconia gel, asouter core. The morphology and chemical composition of the resultant powders has been examined by SEM-EDX (Scanning electron microscopy-energy dispersive X-ray spectroscopy). Thermal behaviour of the microcomposite powder was reported, showing the dehydration and dehydroxylation of the zirconia gel, the crystallization into metastable cubic/tetragonal zirconia at temperatures 400—470°C, and the feasibility of preparing ZT powder materials by progressive reaction of TiO2 and ZrO2 at higher temperatures (1400°C).
Authors:Ewa Stepkowska, M. Aviles, J. Blanes and J. Perez-Rodriguez
The low temperature
of decomposition of some calcium carbonates and the bending of the TG curves
of hydrated cement between 500 and 800°C suggested the presence of some
complex compound(s), which needed complementary investigation (XRD, TG). Stepwise
transformation of portlandite (and/or lime) into calcium carbonate, with intermediate
steps of calcium carbonate hydroxide hydrates (CCH-1 to CCH-5), was indicated
by the previous study of two OPC.
This was checked here on four
cements ground for tg=15,
20, 25 and 30 min and hydrated either in water vapour, successively at RH=1.0,
0.95 and 0.5 for 2 weeks each (WR1, WR2 and WR3, respectively) or as mortars
in liquid water (1m), followed by WR as above. The d spacing of portlandite
was confirmed to vary: here between the lowest and the highest standard values.
The diffractograms of n=32 different samples
were analyzed for presence of standard CCH peaks, generally slightly displaced.
These were: CCH-1 [Ca3(CO3)2(OH)2]: N=11 peaks, of three different d[hkl] spacings, CCH-2 [Ca6(CO2.65)2(OH657)7(H2O)2]: N=10 for two d[hkl], CCH-3 [Ca3(CO3)2(OH)2·1.5H2O]: N=14 for five d[hkl], CCH-4,
ikaite [CaCO3(H2O)6]: N=13 for six d[hkl], CCH-5[CaCO3(H2O)]: N=15 for five d[hkl]. Thus the most probable is the presence of the
last three. The stepwise transformation of Ca(OH)2
into CaCO3 was confirmed:
portlandite (varying d)→CCH-1→CCH-2→CCH-3→CCH-4→CCH-5→CaCO3
The content of CCH was the highest at tgr=15
min, decreasing down to tgr=25
min and increasing slightly at 30 min, as inferred from the number of the
peaks observed. After cement powder hydration at RH=1.0 (WR1) peak number
increased gradually from CCH-1 to CCH-5, whereas in the hydrated mortar (1m)
the peak number decreased from CCH-1 to CCH-5, indicating the respective progress
of the carbonation reaction.
Authors:P. Sánchez-Soto, M. Villacampa, J. Ginés, A. Ruiz-Conde, M. Avilés and M. Arias
Several derivatives containing a new organic ring system, the tropane-6-spiro-5′-hydantoin structure (namely 8-alkyl-8-azabicyclo
[3.2.1.] octane-6-spiro-5′-imidazoline-2′,4′-diones) have been characterized by thermal (DSC and simultaneous DTA-TG-DTG)
and spectroscopic techniques (IR,1 H-NMR,13 C-NMR). X-ray powder diffraction and elemental analysis were applied for structural and molecular characterization. All the
compounds melt in the range 160–250°C and undergo decomposition with progressive mass loss after the solid-liquid thermal
transition with molecular degradation. It was found that tropane-6-spiro-5′-hydantoin derivatives with the hydantoin ring
in β position are thermally less stable than those containing this ring in α position.
Authors:E.T. Stepkowska, J. Perez-Rodriguez, M. Aviles, M. Jimenez de Haro and M. Sayagues
Specific surface, S, of CSH-gel particles of disordered layered structure, was studied by water sorption/retention in two cement pastes differing
in strength, i.e. C-33 (weaker) and C-43 (stronger), w/c=0.4. Hydration time in liquid phase was th=1 and 6 months, followed by hydration in water vapour either on increasing stepwise the relative humidity, RH=0.5→0.95→1.0 (WS) or on its lowering in an inverse order (WR). Specific surface was estimated from evaporable (sorbed) water
content, EV (110C), assuming a bi- and three-molecular sorbed water layer at RH=0.5 or 0.95, respectively (WS). On WR it was three- and three- to four-molecular (50 to 75%), respectively, causing a hysteresis
of sorption isotherm. At RH=0.5 the S increased with cement strength from 146 m2 g-1 (C-33, 1 m) to 166 m2 g-1 (C-43, 1 m) and with hydration time to 163 (C-33, 6 m) and to 204 m2 g-1 (C-43, 6 m). At RH=1.0 (and 0.95), higher S-value were measured but these differences were smaller: S amounted to 190-200 m2 g-1 in C-33 (1 and 6 m) and 198-210 m2 g-1 in C-43 (1 and 6 m). Thus no collapse occurred on air drying of paste C-43 (6 m).
Authors:E. T. Stepkowska, J. M. Blanes, A. Justo, M. A. Aviles and J. L. Perez-Rodriguez
Summary Two hydrated and aged cement pastes from India (NCB), w/c=0.4, of a similar chemical composition but of a different specific surface and different strength (OPC, C-33 and C-43), hydrated at w/c=0.4 for 1 month, were studied by XRD after 1 year and 5-6 year ageing on contact with air. They were tested by static heating (SH) in fresh state, and by DTA/DTG/TG, IR and mass spectrometry (MS), after ageing, presented elsewhere. The main XRD peaks of (i) portlandite were decreasing with T and disappearing about 450°C, (ii) calcite peak at room T was small and broad, it increased gradually, especially after portlandite disappearance; above 600°C it was lowered and it was lost above 700°C. Important variation in the d(001) of portlandite with ageing was observed, exceeding the standard value of d(001)=4.895 Å (72-0156). It was higher in the paste C-33 (4.925-4.936 Å), containing more carbonates, than in the paste C-43 (4.916-4.927 Å). Small variations only were found in the value of d(101), i.e. 2.627-2.635 Å (nominally 2.622 Å), whereas the d(104) of calcite could be used as internal standard and other calcium carbonates (vaterite and aragonite) showed a small variation only. The increase ind(hkl) with temperature was straight linear (in portlandite ?d(001)=0.095 Å, at 30-400°C) and the thermal expansion coefficient estimated thereform was high (4.75-4.95·10-5 K-1). Close to the T of decomposition the ?d/?T became steeper. The thermal variation of d(104)=3.035 Å of calcite (?d=0.015 Å at 30-400°C) was smaller than that ofd(101) of portlandite (?d=0.025 Å at 30-400°C) and was similar in C-33 and C-43. The thermal expansion coefficient was 1.54 10-5 K-1, thus higher than the reported aa=0.65·10-5 K-1.
Authors:M. Avilés, J. Ginés, J. del Rio, J. Pascual, J. Pérez-Rodríguez and P. Sánchez-Soto
This paper examines the polymerization of acrylonitrile to poly(acrylonitrile)(PAN), and its cyclization, in bulk form and using N,N-dimethylformamide (DMF) as solvent in which both monomer and polymer are soluble. Thermal analysis of the resultant products after polymerization has been performed by DSC and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). Scanning electron microscopy has been used to study the morphology of the resultant products and after thermal treatments. The DSC thermal curve of PAN-DMF sample is quite different from the PAN bulk sample, showing a single sharp exothermic peak associated with nitrile group polymerization (cyclization) of PAN at lower temperature (240°C) than that of bulk PAN sample (314°C). Cyclization of PAN was confirmed by IR spectroscopy. It was found that the amide molecules are difficult to eliminate completely in the product obtained after the polymerization reaction, even after prolonged heating at 110°C, and remain occluded. The formation of a complex by dipolar bonding is also possible and it is discussed. It is concluded that the amount of heat evolved as well as the temperature interval over which it is released are influenced by the chemical processing of PAN when using DMF as solvent of both monomer and polymer. Pyrolysis of these PAN samples revealed the release of occluded molecules of DMF, and several compounds containing nitrogen produced from the thermal degradation processes. All these results are interesting to know the chemical processing of carbon fibres and activated carbon fibres from PAN modified precursors.
Authors:E. Stepkowska, J. Bijen, J. Perez-Rodriguez, A. Justo, P. Sanchez-Soto and M. Aviles
A simple water sorption/retention (WS/WR) test, followed by stepwise static heating, was applied to the study of cement quality and the reactivity of its grain surface.
The physically bound water and hence the specific surface both in the unhydrated and in the hydrated state were estimated
as a function of the hydration time. Rehydration after heating at 220°C and contact with air was different inWS from that inWR samples, which indicates a difference in microstructure. XRD proved the formation of portlandite during the sorption test
and eventual heating at 200°C, and its transformation into carbonates on contact with air, especially on heating at 400°C.
The contents of these compounds were estimated from the mass difference between 400 and 800°C, which was compatible with the
mass change between 220 and 400°C and this indicates surface reactivity. The test may serve for the routine study of cement.
Authors:V. Ramírez-Valle, M. Jiménez de Haro, M. Avilés, L. Pérez-Maqueda, A. Durán, J. Pascual and J. Pérez-Rodríguez
Static and dynamic heating
of vermiculite samples from Santa Olalla, Huelva, Spain, saturated with different
cations, i.e. Na+, Cs+,
Ca2+, Ba2+ and Al3+,
have been studied. The characterization of the phases formed during heating
has been carried out by X-ray diffraction. The phases formed depend on the
cation present in the interlamellar position and the heating process. The
phases identified in the vermiculite samples saturated with different cations
and heated at different temperatures are the following: enstatite, forsterite,
spinel, cordierite, anorthite, pollucite, nepheline, coesite, celsian and
others various mixed silicates; also some dehydrated and amorphous phases
have been observed. On static heating, at the maximum temperature reached
in this work, the phases formed appear mixed with a glassy phase.