Sol-Gel Synthesis of Protoenstatite and a Study of the Factors That Affect Crystallization

Three different magnesium silicate sols were prepared from Mg(OMe)₂ and TEOS for which hydrolysis with H₂O₂ and H₂O was under stoichiometric, stoichiometric, or over stoichiometric. Xerogels were prepared from the sols by simple evaporation, spray-drying, or freeze-drying. The freeze-dried precursor formed mostly protoenstatite, a high-temperature polymorph of enstatite (MgSiO₃) that is generally not stable at room temperature; the other precursors formed mixtures of protoenstatite and clinoenstatite. The three xerogels and their calcined products were studied with XRD, HTXRD, BET, carbon analysis, TG/DTA and²⁹ Si-NMR. Residual carbon was found to be an important factor in the crystallization, and ²⁹Si-NMR spectroscopy was found to be a better tool than XRD to assess the phase purity of protoenstatite.     

Low-temperature heat capacity of monoclinic enstatite

Synthetic enstatite MgSiO₃ was crystallized from a melt, quenched into water, and then annealed at 873 K. The product is the monoclinic polymorph with the unit cell parameters of a=0.9619(7), b=0.8832(3), c=0.5177(4) nm, β=108.27(5)°. Heat capacity was measured from 6 to 305 K using an adiabatic vacuum calorimeter. Thermodynamic functions for clinoenstatite differ by about 5% from those predicted after a thermodynamic model in the literature, but are very close to those measured for orthorhombic enstatite.     

The influence of exchangeable cation on thermal behaviour of ground vermiculite

Grinding and contact with water or salt solution increased the specific surface (ssa) but lowered the first dehydration effect (escaping up to 150°C) and increased the second dehydration effect (150 to 500°C). The dehydroxylation was moved to lower temperatures and was only ΔM(500-1100°C)=3.7±0.3 % as compared to 5.5% in the parent vermiculite (V). Except ΔM(20-150°C), the mass losses measured at the remaining T ranges, were consistent in the ground samples, thus the grinding for 2 min caused the homogenization of the crystal structure of vermiculite [ΔM(150-500°C)=7.6±0.7%]. DTA curves after grinding and cation exchange indicate an important exothermal peak at 795-870°C, its temperature depending on exchangeable cation. It indicates the formation of high temperature phases (enstatite, forsterite, spinel). The lowest temperature of the peak (795°C) was observed in V-gr-Li, here lithium silicate was formed. The highest peak temperature (870°C) was found in V-gr-K, where almost only forsterite developed. These exothermal peaks were very weak in unground V with various exchangeable cations. This revised version was published online in July 2006 with corrections to the Cover Date.     

Stabilities of some silicate minerals under approximate venusian surface conditions

Stability field diagrams have been constructed for forsterite, enstatite, wollastonite, and their precursors and reaction products under 90 atm CO₂ at 427°C, approximating the environment on Venus. The compounds were also studied experimentally under similar conditions. The results show that forsterite and enstatite are stable but that wollastonite is not. Periclase and magnesite undergo reaction, the former to magnesite and the latter to synthetic forsterite. Calcite is stable.     

The Incorporation of Indigo Molecules in Sepiolite Tunnels

Evidence for access of molecules the size of acetone or pyridine to the intracrystalline tunnels of nanofibre clay (sepiolite) has indicated formation of a new type of organic–inorganic nanocomposites. However, the introduction of larger molecules has been a recurring problem. It is now agreed that for indigo, the molecules are located on the external surface and at the ends of the fibres, thus blocking access to internal tunnels. We claim, however, that it is possible for indigo molecules to access the internal channels of sepiolite. FTIR and XRD analyses have provided evidence for folding of the sepiolite structure preheated at high temperature (above 350 °C). By comparison, we have shown that for indigo/sepiolite mixtures treated in the same conditions, no change in the crystalline structure of the sepiolite is observed, and that blue samples, related to Maya blue, with indigo molecules incorporated deeply enough into sepiolite to prevent folding of the tunnels, can be obtained. NMR, FTIR and thermal analysis confirm the interaction of indigo with the water coordinated to magnesium(II) and located inside the internal and external channels of sepiolite. Two other hypotheses are excluded; we show both that zeolitic water is not blocked in the tunnels by indigo, and that if thermal decomposition products of indigo can be formed, they are in a minority.     

Effect of interlayer cations on high-temperature phases of vermiculite

Static and dynamic heating of vermiculite samples from Santa Olalla, Huelva, Spain, saturated with different cations, i.e. Na⁺, Cs⁺, NH₄ ⁺, Mg²⁺, 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.     

Study of raw and thermally treated sepiolite from the Mantoudi area,Euboea, Greece

Raw and thermally treated sepiolites from the Mantoudi area, Euboea, Greece, were investigated by means of X-ray diffraction (XRD) in combination with thermo-gravimetric analysis (TG/DTG) and differential thermal analysis (DTA), as well as Fourier transform (FTIR) spectroscopy, in order to study the collapse of the sepiolite structure with increasing temperature. The main mineral constituent (>95%) is a well crystallized sepiolite. Quartz and dolomite occur in minor amounts. Calcination of the samples was carried out up to 350, 720 and 820°C, for 2 h, and ‘sepiolite dihydrite’, ‘sepiolite anhydrite’ and ‘enstatite’ were formed, respectively, as magnesium co-ordinated water and octahedrically co-ordinated hydroxyl groups, are removed and the dehydroxylated phase recrystallize to enstatite (MgSiO₃). These structural and textural changes play an important role to the properties and uses of the studied sepiolites.     

Preparation and characterization of porous cordierite for potential use in cellular ceramics

Cordierite porous ceramics Z, X, and K were prepared using three mixtures of clay minerals: Z from kaolinite, talc, and aluminum hydroxide, X from kaolinite, talc, vermiculite, and aluminum hydroxide, and K from kaolinite, talc, and magnesium oxide. Ceramics were different in porosity, specific surface area, cordierite polymorphs, and secondary crystalline phases. Vermiculite influenced textural architecture of calcined cordierite ceramics X and predestinated crystallization of the high-temperature hexagonal α-cordierite with secondary minerals enstatite, spinel and corundum. Ceramics Z contained low-temperature orthorhombic β-cordierite, enstatite, and corundum, K was diphase of β-cordierite and forsterite. Total pore area (TPA) and specific surface area (SSA) of X, in spite of the higher porosity and the pore size distribution in the range of 300–1000 nm, were smaller in comparison with TPA and SSA of Z. Ceramics K retained high porosity, two maxima at 300–1000 nm and 50–200 nm in the pores size distribution, and the highest TPA and SSA compared to those observed in ceramics Z and X. Presented at the 8th Conference on Solid State Chemistry, 6-11 July 2008, Bratislava, Slovak Republic.     

The effect of halloysite nanotubes and N,N′-ethylenebis (stearamide) on morphology and properties of polylactide nanocomposites with crystalline matrix

Poly(lactide)/halloysite nanotubes (PLA/HNT) nanocomposites with crystalline matrix were obtained by cold crystallization and examined. Neat HNT and HNT treated with N,N′- ethylenebis(stearamide) (EBS) were used as nanofillers. Reference materials, PLA and PLA/EBS blend, prepared in the same way, were also considered. The influence of HNT and/or EBS content on the crystallinity and morphology of PLA matrix, as well as on the dynamic mechanical and optical properties of the materials, was determined.The nanocomposites contained well-distributed HNT, with only occasional agglomerates. HNT, EBS-treated HNT and EBS influenced the morphology of the crystalline PLA matrix and the amounts of the disorder α’ (termed also δ) and order α crystallographic forms of PLA. Crystallinity increased stiffness of the materials compared to their counterparts with the amorphous matrix. Owing to the crystallinity and the presence of the nanofillers, the storage modulus at 20 °C and 60 °C increased by up to 30 and 60%, respectively, compared to neat amorphous PLA. Interestingly, at lower nanofiller content the crystalline nanocomposites with EBS were more transparent than neat crystalline PLA.     

Non-isothermal crystallization kinetics of some aventurine decorative glaze

Thermal and structural properties of three clays (sepiolite and two kaolinites) from Turkey were studied by thermal analysis (TG–DTA), X-ray diffraction (XRD), X-ray fluorescence (XRF), Fourier transform infrared (FT-IR), and surface area measurement techniques The adsorption of sulfur dioxide (SO₂) gas by these clays was also investigated. SO₂ adsorption values of K1, K2, and S clay samples were measured at 20 °C and pressures up to 106 kPa. Sepiolite sample (S) primarily consists of pure sepiolite, only dolomite present as accompanying mineral. Both kaolinite samples, K1 and K2, mainly contain kaolinite as the major clay mineral and quartz as impurity. In K2 sample, muscovite phase is also present. Simultaneous TG–DTA curves of all clay samples were obtained at three different heating rates 10, 15, and 20 °C min⁻¹ over the temperature range 30–1200 °C. It was found that the retention value of SO₂ by S clay (2.744 mmol/g) was higher than those of K1 (0.144 mmol/g) and K2 (0.164 mmol/g) samples.     

The changes of crystalline structure of cellulose during dissolution in 1-butyl-3-methylimidazolium chloride

The morphology and crystalline structure changes of cellulose during dissolution in 1-butyl-3-methylimidazolium chloride [(BMIM)Cl] were investigated by optical microscopy and synchrotron radiation wide-angle X-ray diffraction (WAXD). Neither swelling nor dissolution of cellulose was observed under the melting point of [BMIM]Cl. While the temperature was elevated to 70 °C, the swelling phenomenon of cellulose happened with the interplanar spacing of ( _boxclose_boxclose_boxclose0 1\bar{1}0 ) and (020) planes increased slightly. With the temperature further going up to 80 °C, cellulose was dissolved gradually with the crystallinity (W _c,x) and crystalline index (CrI) of cellulose decreased rapidly, which indicated the crystalline structure of cellulose was destroyed completely and transformed into amorphous structure.     

Controlled rate thermal analysis of sepiolite

Controlled rate thermal analysis (CRTA) technology offers better resolution and a more detailed interpretation of the decomposition processes of a clay mineral such as sepiolite via approaching equilibrium conditions of decomposition through the elimination of the slow transfer of heat to the sample as a controlling parameter on the process of decomposition. Constant-rate decomposition processes of non-isothermal nature reveal changes in the sepiolite as the sepiolite is converted to an anhydride. In the dynamic experiment two dehydration steps are observed over the ~20–170 and 170–350 °C temperature range. In the dynamic experiment three dehydroxylation steps are observed over the temperature ranges 201–337, 337–638 and 638–982 °C. The CRTA technology enables the separation of the thermal decomposition steps.     

Preparation of Forsterite by the Geopolymer Technique—Gel Compositions as a Function of pH and Crystalline Phases

Mg-bearing silicate precursor gels have been prepared by mixing 0.74 mol/L sodium metasilicate and 1.48 mol/L magnesium nitrate solutions. Caustic soda solution of 1.0 mol/L concentration was introduced to regulate pH. The magnesium nitrate solution was added dropwise to the sodium silicate solution in equi-volume at various pH values. Raw and heat-treated gels were characterized by XRF, TG-DTA, XRD and FE-SEM. As a result, gel compositions were dependent on pH values of mixing solutions. The pH value yielding stoichiometric forsterite composition, MgO/SiO₂ = 2 was reached at pH 9.3. In addition, this value was pH 8.4 for stoichiometric enstatite composition, MgO/SiO₂ = 1. With decreasing pH from 9.3, the ratio became less than 2 and forsterite and enstatite precipitated by heating the gels. With increasing pH from 9.3, the ratio became more than 2 and forsterite and periclase precipitated by heating the gels. DTA curves showed a characteristic exothermic peak centered at 700–900^∘C, indicating relatively low temperature formation of crystalline phases due to the presence of polycondensed frame works of silicates in the precursor gels.     

Photoluminescence spectral reliance on aggregation order of 1,1-Bis(2'-thienyl)-2,3,4,5-tetraphenylsilole

1,1-Bis(2'-thienyl)-2,3,4,5-tetraphenylsilole (1) was prepared and characterized crystallographically. Silole 1 exhibited aggregation-induced emission (AIE) behavior like other 2,3,4,5-tetraphenylsiloles. Unexpectedly, aggregates formed in water/acetone (6:4 by volume) mixture emitted a blue light that peaked at 474 nm, while aggregates formed in the mixtures with higher water fractions emitted green light that peaked at 500 nm. Transmission electron microscopy demonstrated that the aggregates formed in the mixture with water fraction of 60% were single crystals, while aggregates that formed in the mixture with water fraction of 90% were irregular and poorly ordered particles. The unusual PL spectral reliance on aggregation order was further confirmed by PL emissions of macroscopic crystal powders and amorphous powders of the silole in the dry state. PL spectral blue shifting was observed upon aging of the poorly ordered aggregates formed in mixtures with water fractions of 70-90%, and they finally exhibited the same blue emission as the crystalline aggregates. The as-deposited thin solid film was amorphous and it could be transformed to a transparent crystalline film upon treatment in the vapor of an ethanol/water (1:1 by volume) mixture, along with PL spectral blue shifting due to changing of aggregation order. It was also found that the crystalline film showed a blue-shifted absorption spectrum relative to the amorphous film and the shift of the absorption edge of the spectra could match that of corresponding PL spectra. The FT-IR spectrum of crystal powders of 1 displayed more vibration modes compared with that of amorphous powders, suggesting the existence of different pi-overlaps or different molecular conformations. The crystals of 1-methyl-1,2,3,4,5-pentaphenylsilole and hexaphenylsilole also showed blue-shifted PL emissions of their amorphous solids, with a comparable PL spectral shift of 1. Developing of a silole solution on a TLC plate readily brought about an amorphous thin layer. Our results suggest that crystalline films of AIE-active siloles are potential emissive layers for efficient blue OLEDs with stable color and long lifetime.     

The synergetic effect of phenylphosphonic acid zinc and microfibrillated cellulose on the injection molding cycle time of PLA composites

This study evaluates the effects of nucleants phenylphosphonic acid zinc (PPA-Zn) and talc, mold temperature, and microfibrillated cellulose (MFC) reinforcement in the acceleration of injection molding cycle of polylactic acid (PLA). PLA was dissolved in an organic solvent, mixed with nucleant and MFC, and dried compounds were injection molded into molds at temperatures ranging from 40 °C to 95 °C and holding times from 10 s to 120 s. Our results showed that PPA-Zn is more effective nucleating agent compared to talc. The addition of 1 wt% PPA-Zn and the mold temperature of 95 °C exhibited the fastest crystallization rates for the molded PLA, however, at this temperature the parts could not be quickly ejected without distortion. Addition of 10 wt% MFC increased the stiffness of PLA at high temperatures and allowed ejection of parts without distortion at a holding time of just 10 s. At this holding time, the crystallinity of the PLA composite was 15.3% but the storage modulus above T _g was superior to that of fully crystallized neat PLA due to MFC reinforcement, retaining the shape of the molded part during demolding. The mechanical properties of the composite at room temperature were also higher than those of fully crystallized neat PLA.     

Thermo-mechanical properties of microfibrillated cellulose-reinforced partially crystallized PLA composites

Polylactic acid (PLA) in a crystallized state has mechanical properties at high temperatures superior to PLA in an amorphous state. However, a long annealing time is required to fully crystallize PLA. In this study, microfibrillated cellulose (MFC)-reinforced partially crystallized PLA composites were produced, with the goal of reducing the time required to fabricate PLA parts. A series of PLA/MFC composites at a fiber content of 10 wt% from degree of crystallinity (Xc) 0 to 43% was obtained by annealing at 80 °C. Although the annealing time required to obtain a composite (Xc: 17%) was only around one-seventh of the 20 min needed to fully crystallize neat PLA (Xc: 41%), both materials had comparable rigidity above the glass transition temperature (T _g) and creep deformation at around T _g. These results showed that partially crystallized PLA/MFC composite can replace fully crystallized neat PLA.     

Micro- to macroscopic observations of MnAlPO-5 nanocrystal growth in ionic-liquid media

Micro‐ and macroscopic studies of nucleation and growth processes of MnAlPO‐5 nanosized crystals under ionothermal synthesis conditions are reported herein. The samples treated at 150 °C were extracted from the reaction mixture at various stages of crystallization, and characterized by XRD; SEM; thermogravimetric analysis (TGA); ³¹P and ²⁷Al solid‐state magic angle spinning (MAS) NMR, Raman, UV/Vis, and X‐ray fluorescence spectroscopy (XRF). The starting raw materials (alumina, manganese, and phosphorous) were dissolved completely in the ionic liquid and transformed into an amorphous solid after 5 h of ionothermal treatment. This amorphous solid then undergoes structural changes over the following 5–25 h, which result in an intermediate phase that consists of octahedral Al species linked to the manganese and phosphate species. The first MnAlPO‐5 nuclei on the surface of the intermediate can be observed after 50 h ionoheating. These nuclei further grow, as the surface of the intermediate is in full contact with the ionic liquid, to give crystalline MnAlPO‐5 nanoparticles with a mean diameter of 80 nm. The crystals become fully detached from the intermediate and are then liberated as discrete particles after 90 h heating. The transformation process from amorphous to intermediate and then to the crystalline MnAlPO‐5 nanoparticles shows that nucleation starts at the solid–liquid interface and continues through surface‐to‐core reversed‐growth until the entire amorphous solid is transformed into discrete nanocrystals.     

Nanotailoring of sepiolite clay with poly [styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene]: structure–property correlation

Poly [styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS)/sepiolite clay nanocomposites are prepared by solvent casting method. Two types of schemes have been adopted to establish the compatibility between nonpolar polymer (SEBS) and needle‐like inorganic filler (sepiolite), either by polar modification of the nonpolar polymer or organic modification of the inorganic filler. Structure–property correlation of nanocomposites derived from two different approaches is compared. Structural and morphological analysis of nanocomposites has been investigated by Fourier transform infrared spectroscopy, X‐ray diffraction, field emission scanning electron microscopy and transmission electron microscopy. Fourier transform infrared result shows better compatibility between SEBS and modified sepiolite clay compared to maleic anhydride grafted SEBS and pristine sepiolite in their nanocomposites. Tensile strength and % elongation are found to increase by 32 and 105%, respectively, with the addition of just 3 parts per hundred parts of resin (phr) modified sepiolite clay to pristine SEBS matrix. Moreover, thermal stability has also improved by 96°C with similar loading. This work provides a new insight into the structure and thermo‐mechanical properties of novel SEBS–sepiolite clay nanocomposites. Copyright © 2017 John Wiley & Sons, Ltd.     

Multiaxial deformation of polyethylene and polyethylene/clay nanocomposites: in situ synchrotron small angle and wide angle X‐ray scattering study

A unique in situ multiaxial deformation device has been designed and built specifically for simultaneous synchrotron small angle X‐ray scattering (SAXS) and wide angle X‐ray scattering (WAXS) measurements. SAXS and WAXS patterns of high‐density polyethylene (HDPE) and HDPE/clay nanocomposites were measured in real time during in situ multiaxial deformation at room temperature and at 55 °C. It was observed that the morphological evolution of polyethylene is affected by the existence of clay platelets as well as the deformation temperature and strain rate. Martensitic transformation of orthorhombic into monoclinic crystal phases was observed under strain in HDPE, which is delayed and hindered in the presence of clay nanoplatelets. From the SAXS measurements, it was observed that the thickness of the interlamellar amorphous region increased with increasing strain, which is due to elongation of the amorphous chains. The increase in amorphous layer thickness is slightly higher for the nanocomposites compared to the neat polymer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Synthesis and characterization of novel poly(propylene terephthalate-co-adipate) biodegradable random copolyesters

Novel aromatic/aliphatic poly(propylene terephthalate-co-adipate) (PPTAd) random copolymers were synthesized. Copolymer composition varied over the whole range from that of neat poly(propylene terephthalate) (PPT) to that of neat poly(propylene adipate) (PPAd). Interestingly, the copolymers showed that they can degrade via hydrolysis, especially in presence of enzymes, even for a terephthalate content as high as 66 mol%. Thermal behaviour and solid state as well as mechanical properties were studied. In contrast to hydrolysis rates, mechanical properties increase with terephthalate content. WAXD patterns indicate some extent of co-crystallization of both comonomers, especially for intermediate compositions. The thermodynamic analysis of the melting point depression showed that some portion of the adipate comonomer units participate in the formation of crystals, although the major portion of them is rejected from crystals and remain in the amorphous phase. WAXD patterns showed that even for a 60 mol% or more adipate content, the copolymers form PPT like crystals. Thus, the amorphous phase is enriched in adipate units, as is also shown by a lowering of the glass transition temperature of the crystallized copolymer samples, compared to glassy ones. Finally, multiple melting behaviour of the melt crystallized copolymer samples, as well as, banded spherulitic morphology was observed.