Fabrication and properties of poly(propylene carbonate)/calcium carbonate composites

Composites of poly(propylene carbonate) (PPC) reinforced with micrometric and nanometric calcium carbonate particles were prepared via melt mixing followed by compression molding. The morphology and mechanical and thermal behaviors of the composites were investigated. Static tensile tests showed that the tensile strength, stiffness, and ductility of the composites tended to increase with increasing contents of micrometric calcium carbonate particles. This improvement in the tensile properties was attributed to good interfacial adhesion between the fillers and matrix, as evidenced by scanning electron microscopy examination. However, because of the agglomeration of calcium carbonate nanoparticles during blending, those composites with nanoparticles exhibited the lowest tensile strength. Thermogravimetric measurements revealed that the incorporation of calcium carbonate into PPC resulted in a slight improvement in its thermooxidative stability. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1806–1813, 2003     

Partially pyrolyzed poly(dimethylsiloxane)‐based networks: Thermal characterization and evaluation of the gas permeability

In this investigation, the preparation and characterization of partially pyrolyzed membranes based on poly(dimethylsiloxane) (PDMS) are described. These membranes were obtained by the crosslinking of silanol‐terminated PDMS with multifunctional nanoclusters derived from the reaction of pentaerythritoltriacrylate with 2‐aminoethyl‐3‐aminopropyltrimethoxysilane and the in situ polycondensation of tetraethylortosilicate, followed by the thermal treatment of the resulting membranes at different temperatures. The partially pyrolyzed membranes were characterized with infrared spectroscopy, thermogravimetry, elemental analyses, dynamic mechanical analysis, small‐angle X‐ray scattering, and scanning electron microscopy. The membranes exhibited improvements in the thermal stability and mechanical strength. Even with distinct compositions with respect to the Si/O and Si/C ratios, the flexibility of these materials was maintained. The flux rates of the gases through the membranes were measured for N₂, H₂, O₂, CH₄, and CO₂, at 25 °C. The permeability of the membranes changed with increases in the pyrolysis and oxidation temperatures. These membranes could be described as PDMS chains separated by inorganic clusters. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 299–309, 2007.     

Influence of Film Structure and Precursor Composition on Rhodamine B Retention in Dye-Dopped Ormosils

The interplay between the chemical structure of the precursors, internal organization in the end materials and dye retention was investigated for composites (ormosils) doped with rhodamine B. Besides formulations with triethoxysilanes (RTES) only, we synthesized as well organic–inorganic hybrids with addition of titanium isopropoxide (TIP) and maleic anhydride (MA). The organic (R) functionality of RTES was changed from methyl (MeTES), to phenyl (PTES) and octyl (OTES). Atomic force microscopy and electron microscopy, coupled with thermogravimetric analysis prove that hydrophobicity increase stimulates the transition of film structure: from well-defined, compact particles (for MeTES), to a mixture of porous particles and non-granular material (for MeTES/PTES), with extreme results observed for octyl-based composites. For this latter, the apparent homogeneity comes from cluster-like organization, where the primary entities are pseudo—granules produced by hydrophobic interactions of oligomeric siloxanes. Controlling the composition and gelation procedure resulted in doped composites with good optical transparency and rhodamine B fluorescence emission bands at around 580 nm. Dye transport inside the inorganic structure is not facilitated when: (a) the particles have a compact (nonporous) inner structure and (b) the recipe does not contain the TIP/MA combination. For silica-based films, the dye is located in the macropores (between the granules) of the material and could be easy removed by washing with acetone. On the contrary, using TIP/MA changes not only the internal composition of the granular-like material (by creating a microporous titania-rich outer-shell of the particles) but also the affinity of the Rh-B to permeate and reside inside these new structures.     

单壁纳米碳管的纯化研究

A purification method to remove the metal catalysts and impurity carbon materials from arc-discharge-grown single-walled carbon nanotubes (SWCNTs) has been developed. Microporous membrane and the oxidation in the air for the crude SWCNTs were used to eliminate the coexisting metal catalysts nanoparticles，carbon nanoparticles and amorphous carbon. Then we used the high resolution transmission electron microscopy (HRTEM) to characterize the crude SWCNTs prepared by arc-discharge method and the purified SWCNTs. The Raman spectra and the thermogravimetric analysis (TGA) were also utilized to analyze the approach of our purification for SWCNTs. With this method the SWCNTs with the purity more than 95% could be obtained.     

The Study of Kinetics of Poly[(R,S)-3-hydroxybutyrate) Degradation Induced by Carboxylate

Summary: The carboxylate induced degradation of the poly[(R,S)-3-hydroxybutyrate] (PHB) has been investigated with non-isothermal measurements. The apparent activation energies for PHB degradation have been determined. Application of the Kissinger's and Flynn-Wall-Ozawa's method for TG and DSC derived data gave good correlation of the results proving applicability of the non-isothermal DSC measurements for the study. Moreover, dependence of the apparent activation energies on the activity of the carboxylate has been found.     

Molecular dynamics in bulk and surface species of cyanophenyl alkyl benzoates with 2, 3 and 7 carbon atoms in the alkyl chain: comparison in the whole homologous series

ABSTRACT

Molecular mobility of cyanophenyl alkylbenzoates (CPnBs) (n = 2, 3, 7 – number of carbon atoms in the alkyl chain) in the bulk and in composites with aerosil A380 is investigated by broadband dielectric spectroscopy, while thermal analysis and infrared spectroscopy were applied to characterise the molecular species. The work completes preliminary results obtained for the members with n = 4 … 6. An interaction by hydrogen bonding, between aerosil surface – OH groups and – CN or ester groups of the CPnB molecules takes place. It slows down the relaxation process as observed for related composites in comparison to the pure materials. The existence of two types of bonding might be the reason that Vogel temperature for the relaxation process in the surface layer does not show the odd-even effect. Temperature dependence of the relaxation rates for composites shows a crossover behaviour from a high to a low temperature regime. Moreover, the temperature dependence of the dielectric strength is unusual. As the loading degree is similar, comparison of the dielectric, spectroscopic and thermal data obtained here and with the results obtained for the composites with n = 4 … 6 can be directly done. Increasing the number of the members of the homologous series confirms and hardens the preliminary conclusions.     

Organic-Inorganic Hybrid Materials with the Ability to Bind Metal Ions: Calorimetric Properties and Thermostability

Organic-inorganic hybrid materials with excellent heavy metal ions chelating properties were synthesized by covalent bonding of multifunctional polymers of polyamidoamine (PAA) type onto silica. Two series of polyamidoamine-silica hybrid materials differing in the PAA chemical structure were prepared and their thermal properties were investigated. Differential Scanning Calorimetry was used to study the effects of chain immobilization and ion chelation on the glass-transition temperature (Tg) of the polymers. The Tg of PAA-hybrid materials was elevated with respect to ungrafted PAAs. Complex formation with metal ions such as Cu⁺⁺ or Co⁺⁺ caused total suppression of Tg for both linear polymers as well as the corresponding hybrid materials. Finally, the silica particles slightly influenced the decomposition temperatures of linear polymers increasing their thermal stability.     

Thermal Stability of Biodegradable Films Based on Soy Protein and Corn Starch

Summary: In this paper, films were prepared from soy protein and corn starch in different proportions and thermal stability and kinetic parameters were determined through degradation reactions in an inert atmosphere. Solid residues and decomposition products were identified by infrared spectroscopy. Films from corn starch were less thermally stable than soy protein films. The films containing both components had lower thermal stabilities when compared to those of the pure biopolymers. The mechanism of starch thermal degradation seems to occur in a single step, which can be confirmed by the constant E-values during the thermal degradation reaction. For the pure protein and its mixtures an increase in the activation energy was observed during the reaction. Solid residues for protein at different temperatures showed mainly bands related to CO stretching, angular deformation of N H and C H groups. For starch, absorptions related to free and bound O H, CO stretching of CO₂, CO and carbonyl compounds were observed. For the 50/50 mixture bands related to soy protein and corn starch were observed. The gaseous products for soy protein showed absorptions related to CO₂, CO, CO, NH₃ and C H stretching. For pure starch absorptions related to O H stretching from alcohol, CO from CO₂, CO and carbonyl compounds. The 50/50 mixture had the same characteristics as pure soy protein and corn starch.     

Influence of nanoparticle surface chemistry on the thermomechanical and magnetic properties of ferromagnetic nanocomposites

The effect of nanoparticle surface chemistry on the thermal, mechanical, and magnetic properties of poly(methyl methacrylate) (PMMA) nanocomposites with cobalt ferrite nanofillers was studied by comparing nanofillers coated with oleic acid (OA; which does not covalently bond to the PMMA matrix) and 3‐methacryloxypropyltrimethoxysilane (MPS, which covalently bonds to the PMMA matrix). Thermogravimetric analysis revealed an increase in the thermal degradation temperature of the nanocomposites compared with the neat polymer. The effect of cobalt ferrite nanofiller on the glass transition temperature (T_g) of the nanocomposite was evaluated by differential scanning calorimetry. The T_g value of the material increased when the particles were introduced. Dynamic mechanical analysis indicated an increase in the storage modulus of the nanocomposite because of the presence of nanofiller and a shift in the peak of loss tangent toward higher temperature. Magnetic measurements indicated that both nanocomposites had a small hysteresis loop at 300 K and no hysteresis at 400 K. However, estimates of the nanofiller's rotational relaxation times and measurements of the zero field cooled temperature‐dependent magnetization indicate that the observed lack of hysteresis at 400 K is likely because of particle rotation in the polymer matrix. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Kinetics of the Thermal and Thermo‐Oxidative Degradation of a Polystyrene–Clay Nanocomposite

Summary: Thermogravimetry and differential scanning calorimetry have been used to study the thermal and thermo‐oxidative degradation of polystyrene (PS) and a PS–clay nanocomposite. An advanced isoconversional method has been applied for kinetic analysis. Introduction of the clay phase increases the activation energy and affects the total heat of degradation, which suggests a change in the reaction mechanism. The obtained kinetic data permit a comparative assessment of the fire resistance of the studied materials.

The change in activation energy for the degradation of PS and the PS–clay nanocomposite with the extent of polymer conversion.     

Photo Polymerized Interpenetrating Polymer Network of Poly(antimony acrylate) and Poly(arsenic acrylate): Synthesis and Characterization

A series of IPN based on poly(antimony acrylate) and poly(arsenic acrylate) have been synthesized by a sequential mode of synthesis. Formation of complex based on “polymer solvent” method reflects the contraction of the polymer coils by determining the value of mutual interaction constant (k_AB) in different solvents such as dimethylsulphoxide (DMSO) (k_AB=0.60); dimethylformamide (DMF) (k_AB=0.42); dioxane (k_AB=0.26) predicting weak Vander Waal interaction. The scanning electron microscopy reveals dual phase morphology of both metal acrylates. The infrared spectrum indicates characteristic frequencies of (>C?O) at 1730 cm^?1,thus giving structural evidence for IPN. The properties namely percentage swelling, average molecular weight between crosslinks(M_c),Young's modulus, increases with concentrations of linear polymer(polyantimony acrylate) and initiator (benzoyl peroxide). However, it decreases with concentrations of monomer (arsenic acrylate) and crosslinker (divinyl benzene).The value of activation energy calculated from thermo gravimetric analysis is 15 KJ/mol.     

Properties of an organosilicon nanophase generated in a poly(amide imide) matrix by the sol‐gel technique

Poly(amide imide) (PAI) nanocomposites prepared by the in situ generation of crosslinked organosilicon nanophase (ON) through the sol‐gel process were characterized by wide‐angle and small‐angle X‐ray diffraction, thermogravimetric analysis, dynamic mechanical analysis and kinetics of water uptake. It was concluded that the polymer nanocomposite (PNC) were likely to possess a complex morphology on the nanoscale characterized by co‐existence of two mixed nanophases of different compositions. At low methyl triethoxysilane (MTS) contents the fractal‐like organization of paracrystalline nano‐domains of PAI chain fragments is destroyed by the randomly distributed ON particles, whereas on the increase of MTS content the spatial correlations between ON particles become stronger, giving rise to their own fractal‐like structure. The higher values of small‐angle X‐ray scattering (SAXS) invariant, apparent water diffusivity and limiting water uptake for the PNC compared to the pristine PAI were assumed to reflect the loose inner structures of PAI‐rich and ON‐rich nanophases, respectively. Copyright © 2005 John Wiley & Sons, Ltd.     

Determination of Volatile Organic Compounds by a Novel Polymer Spin-Coated Thin Film and Surface Plasmon Resonance

Here, the synthesis, characterization, and volatile organic compound (VOCs) sensing of a 1,3-dimethyl polyphenylene vinylene polymer is reported. The synthesis was performed by a Witting condensation through the reaction of 1,4-terphthaldehyde with the phosphonium chloride of meta-xylene. The material was characterized by infrared spectroscopy, elemental analysis, and thermogravimetric analyses. Thin films of the polymer were prepared by spin coating at speeds from 1000 to 5000?rpm. Ultraviolet–visible spectroscopy and surface plasmon resonance were used to characterize the spin-coated films. The thicknesses of the films were estimated by fitting the curves and were between 4.5 and 24.5?nm depending on the speed. The refractive index of the new polymer was 1.72. The polymer spin-coated films were exposed to volatile organic vapors to characterize their sensing properties by surface plasmon resonance as a function of time. The results showed that the new material responded rapidly, sensitively, and reversibly to VOCs.     

Preparation and characterization of nano‐platelet‐like hydroxyapatite/gelatin nanocomposites

Nature has succeeded in creating numerous bionanocomposites such as bones and teeth consisting of nano‐platelets and biopolymers. Understanding of the mechanisms of formation and of the relation between structure and properties is vital for development of new materials for biomedical and engineering applications. In this work, varying contents of nano‐platelet‐like hydroxyapatite (HAp) has been used to reinforce gelatin (Gel) to produce nanocomposites. The prepared HAp/Gel nanocomposites were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric (TG/DTG) analyses. XRD, TEM, and FTIR results confirm the synthesis of intercalated and exfoliated nanostructures depending on the amount of gelatin. TG results reveal that the intercalated HAp/gelatin nanocomposites show improved thermal properties as compared to pristine gelatin. The results reported here can be expanded to other HAp–polymer systems, thus paving a new way of designing and fabricating biomemitic nanocomposites for future engineering and particularly for biomedical applications. Copyright © 2010 John Wiley & Sons, Ltd.     

Unconventional cellulose products by fluorination of tosyl cellulose

The synthesis of novel deoxy-fluoro cellulose derivatives obtained by nucleophilic displacement reactions (SN) of p-toluenesulfonyl (tosyl) cellulose with tetrabutylammonium fluoride (TBAF) is described. Detailed studies concerning the influence of the reaction time and temperature as well as the water content of the TBAF on the composition of the products were carried out. The SN reaction occurs even at room temperature. The degree of substitution of deoxy-fluoro moieties (DSF) is in the range from 0.22 to 0.47. The polymers contain remaining tosyl groups. Preliminary 19F NMR measurements reveal the presence of the CH2F group. The degradation temperature of the deoxy-fluoro cellulose derivatives is increased compared to the starting tosyl cellulose, however, a distinct influence of the remaining tosyl groups appears.     

Ethylene glycol‐based ionic liquids via azide/alkyne click chemistry

A facile synthetic route for the preparation of dicationic ethylene glycol based‐ionic liquids (ILs) via the azide/alkyne “click” reaction is presented. The copper(I) catalyzed, microwave‐assisted azide/alkyne “click” reaction between diazido‐ethylene glycols and the corresponding alkyne containing IL‐head group enables a simple preparation of different sets of poly(ethylene glycol)‐based ILs. Beside tetra‐ and hexa(ethylene glycol)‐based ILs, also oligomeric (M_n = 400 g/mol) and polymeric ILs (M_n up to 1550 g/mol) could be prepared in good yield and with full conversion of the ionic head group. The prepared ILs were extensively characterized via NMR spectroscopy and ESI‐time‐of‐flight (TOF) mass spectroscopy, revealing the formation of multiply charged ions in the negative mode. Thermal stability proved to be exceptionally high (up to 300 °C) together with low glass‐transition temperatures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Poly(n‐alkylsilsesquioxane)s: Synthesis,characterization, and modification with poly(dimethylsiloxane)

Self‐supported translucent films constituted of poly(n‐octylsilsesquioxane) or poly(n‐dodecylsilsesquioxane) were obtained from the hydrolysis and condensation of n‐octyltriethoxysilane (OTES) or n‐dodecyltriethoxysilane (DTES), respectively. Dense films were obtained in the absence of organic solvents, with dibutyltin diacetate as catalyst. These films exhibited good optical transparency and thermal stability. The incorporation of oligomeric dimethylsiloxane units (D^Me,Me) in these materials, derived from silanol‐terminated poly(dimethylsiloxane) (PDMS) or 1,1,3,3‐tetramethyl‐1,3‐diethoxydisiloxane (TMDES), was carried out during the hydrolysis and condensation of OTES and DTES and was confirmed by solid‐state ²⁹Si NMR. Poly(n‐octylsilsesquioxane) showed a glass‐transition temperature at ?65 °C, due to the increase in the free volume, promoted by the bulky n‐octyl groups. The differential scanning calorimetric (DSC) curves of the polymer derived from DTES were characterized by first‐order transitions at temperatures ranging from ?15.8 to ?0.7 °C. Further studies of these networks by low‐temperature XRD evidenced narrowing of the diffraction halos suggesting a partial order–disorder transition for these materials at lower temperatures. Good thermal stability up to 350 °C and the solvent‐free production process make these polymers potential candidates for the development of self‐supported hydrophobic protective coatings. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1220–1229, 2010