Preparation and properties of nano‐CaCO3/acrylonitrile‐butadiene‐styrene composites

CaCO₃/acrylonitrile‐butadiene‐styrene (ABS) and CaCO₃/ethylene‐vinyl acetate copolymer (EVA)/ABS nanocomposites were prepared by melting‐blend with a single‐screw extruder. Mechanical properties of the nanocomposites and the dispersion state of CaCO₃ particles in ABS matrix were investigated. The results showed that in CaCO₃/EVA/ABS nanocomposites, CaCO₃ nanoparticles could increase flexural modulus of the composites and maintain or increase their impact strength for a certain nano‐CaCO₃ loading range. The tensile strength of the nanocomposites, however, was appreciably decreased by adding CaCO₃ nanoparticles. The microstructure of neat ABS, CaCO₃/ABS nanocomposites, and CaCO₃/EVA/ABS nanocomposites was observed by scanning electron microscopy. It can be found that CaCO₃ nanoparticles were well‐dispersed in ABS matrix at nanoscale. The morphology of the fracture surfaces of the nanocomposites revealed that when CaCO₃/EVA/ABS nanocomposites were exposed to external force, nano‐CaCO₃ particles initiated and terminated crazing (silver streak), which can absorb more impact energy than neat ABS. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Coincorporation of nano‐silica and nano‐calcium carbonate in polypropylene

In this study, various polypropylene (PP) nanocomposites were prepared by melt blending method. The effects of different spherical nanofillers, such as 50 nm CaCO₃ and 20 nm SiO₂, on the linear viscoelastic property, crystallization behavior, morphology and mechanical property of the resulting PP nanocomposites were examined. Rheological study indicated that coincorporation of nano‐SiO₂ and nano‐CaCO₃ favored the uniform dispersion of nanoparticles in the PP matrix. Differential scanning calorimeter (DSC) and polarizing optical microscopy (POM) studies revealed that the coincorporation of SiO₂ and CaCO₃ nanoparticles could effectively improve PP crystallizability, which gave rise to a lower supercooling temperature (ΔT), a shorter crystallization half‐life (t_1/2) and a smaller spherulite size in comparison with those nanocomposites incorporating only one type of CaCO₃ or SiO₂ nanoparticles. The mechanical analysis results also showed that addition of two types of nanoparticles into PP matrix gave rise to enhanced performance than the nanocomposites containing CaCO₃ or SiO₂ individually. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of poly(ϵ‐caprolactone‐co‐p‐dioxanone)–poly(ethylene glycol)–poly(ϵ‐caprolactone‐co‐p‐dioxanone)/bioactive inorganic particle nanocomposites

With an aim to develop injectable hydrogel with improved solution stability and enhanced bone repair function, thermogelling poly(ε‐caprolactone‐co‐p‐dioxanone)‐poly(ethylene glycol)‐poly(ε‐caprolactone–co‐p‐dioxanone) (PECP)/bioactive inorganic particle nanocomposites were successfully prepared by blending the triblock copolymer (PECP) with nano‐hydroxyapatite (n‐HA) or nano‐calcium carbonate (n‐CaCO₃). The hydrogel nanocomposites underwent clear sol–gel transitions with increasing temperature from 0 to 50°C. The obtained hydrogel nanocomposites were investigated by ¹H NMR, FT‐IR, TEM, and DSC. It was found that the incorporation of inorganic nanoparticles into PECP matrix would lead to the critical gelation temperature (CGT) shifting to lower values compared with the pure PECP hydrogel. The CGT of the hydrogel nanocomposites could be effectively controlled by adjusting PECP concentration or the content of inorganic nanoparticles. The SEM results showed that the interconnected porous structures of hydrogel nanocomposites were potentially useful as injectable scaffolds. In addition, due to the relatively low crystallinity of PECP triblock copolymer, the aqueous solutions of the nanocomposites could be stored at low temperature (5°C) without crystallization for several days, which would facilitate the practical applications. The PECP/bioactive inorganic particle hydrogel nanocomposites are expected to be promising injectable tissue engineering materials for bone repair applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Double‐hydrophilic polyether antiscalant used as a crystal growth modifier of calcium scales in cooling‐water systems

In this study, we synthesized a novel double‐hydrophilic poly(ethylene glycol) (PEG)‐based crystal growth modifier polyethylene glycol double‐ester of maleic anhydride/ acrylic acid named PEGDMA/AA, whose structure was still linear but also had some differences from a traditional chelating linear polymer, in which the PEG segment was incorporated. The scale inhibition behavior of PEGDMA/AA was evaluated by means of a static scale inhibition method. As the polymerization degree of PEG_nDMA was 8 (n = 8), the maximum inhibitory toward calcium carbonate (CaCO₃) and calcium sulfate (CaSO₄) were 89.0 and 98.8% at dosage levels of 12 and 3 mg/L, respectively. Comparisons with other inhibitors were also carried out. Characterization of the CaCO₃ and CaSO₄ scales with scanning electron microscopy and transmission electron microscopy proved that great changes in the size and morphology of the calcium scales took place under the influence of PEG₈DMA/AA. X‐ray diffraction and diffraction patterns further confirmed the impact of PEG₈DMA/AA as a crystal growth modifier. The three supposed mechanisms, (1) chelating solubilization, (2) multilayer type of adsorption, and (3) electrostatic repulsion function, are also described in detail. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39792.     

Polystyrene/calcium carbonate nanocomposites prepared by in situ polymerization in the presence of maleic anhydride

Polystyrene (PS)/calcium carbonate (CaCO₃) nanocomposites were prepared by in situ polymerization in the presence of maleic anhydride (MA). The composites were characterized by Fourier transform infrared spectra, gel permeation chromatography, differential scanning calorimetry, controlled stress rheometer, scanning electron microscope (SEM), small‐angle X‐ray scattering (SAXS), and mechanical test. Results show that the copolymer of styrene (St) and MA formed during the polymerization acts as a compatibilizer between PS and nanometer calcium carbonate (nano‐CaCO₃) particles, resulting in an increase in the glass transition temperature of the composite. The complex modulus and the impact strength of the PS/nano‐CaCO₃ composite show an increase with the addition of MA on account of the enhanced interfacial adhesion and the increased molecular weight. SEM and SAXS analyses indicate that a finer dispersion of nanoparticles and an increased homogeneity of the PS/nano‐CaCO₃ composites are obtained with application of a small amount of MA. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci., 2013     

Effects of nanoparticle treatment on the crystallization behavior and mechanical properties of polypropylene/calcium carbonate nanocomposites

Effects of nanoparticle surface treatment on the crystallization behavior and mechanical properties of polypropylene (PP)/CaCO₃ nanocomposites were investigated by using differential scanning calorimetry (DSC), polarized optical microscope (POM), X‐ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The results demonstrated that the interfacial interaction formed between PP and nanoparticles significantly influenced the thermal and mechanical properties of nanocomposites. It was found that CaCO₃ nanoparticles modified by a single aluminate coupling agent (CA‐1) could improve the onset crystallization temperature more effectively than that modified by a compound surface‐treating agent (CA‐2) could. However, there is no significant difference in total rate of crystallization for the two PP/CaCO₃ nanocomposites (PPC‐1 and PPC‐2), which contained CA‐1 and CA‐2, respectively. In contrast, CA‐2 modified nanoparticles could cause smaller spherulites and induce much more β‐phase crystal in nanocomposites than that of CA‐1 modified nanoparticles. This may be explained by a synergistic effect of aluminate coupling agent and stearic acid in CA‐2, which also resulted in an improved toughness for PPC‐2. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 3480–3488, 2006     

The influence of the different modifying agents on the synthesis of poly(methylmethacrylate)‐calcium carbonate nanocomposites via soapless emulsion polymerization

The synthesis of poly(methylmethacrylate)‐calcium carbonate nanocomposites via the soapless emulsion polymerization was investigated after the CaCO₃ nanoparticles were modified with different modifying agents. Such three kinds of modifying agents as sodium stearate (SS), oleic acid (OA), and PMMA were used to improve the surface property of CaCO₃ nanoparticles. What was the most important factor to improve the amount of nanoparticles in the composites is one of the general goals. As determined by Field‐emission scanning electron microscopy (FESEM), the nanocomposites size of the diluted polymer emulsion was over 250 nm, while the sample without CaCO₃ had a diameter of about 150 nm. It was worth pointing out that the surface morphology of polymer changed from slick to scraggy, when the nano‐CaCO₃ particles participated in the polymerization process. The increase of the droplet size and the change of the polymer morphology indicated that the CaCO₃ nanoparticles were present in the emulsion droplets. The X‐ray diffraction results of the nanocomposites showed the existence of typical calcite peaks. The results of the TGA, FTIR, and the contact angles indicated that the hydrophobic surface of CaCO₃ nanoparticles was crucial to improve the compatibility between the CaCO₃ and MMA monomer in emulsion system. The results of the TGA, FTIR, and the contact angles indicated that the hydrophobic surface of CaCO₃ nanoparticles was crucial to improve the compatibility between the CaCO₃ and MMA monomer in emulsion system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Phase characterization and mechanical and flame‐retarding properties of nano‐CaSO4/polypropylene and nano‐Ca3(PO4)2/polypropylene composites

An in situ deposition approach was used for the synthesis of nano‐CaSO₄ and nano‐Ca₃(PO₄)₂. The nanosize particles were confirmed with an X‐ray diffraction technique. Composites of polypropylene (PP) with 0.1–0.5 wt % nano‐ or commercial CaSO₄ or nano‐Ca₃(PO₄)₂ were prepared. The transition from the α phase to the β phase was observed for 0.1–0.3 wt % nano‐CaSO₄/PP and nano‐Ca₃(PO₄)₂/PP composites. This was confirmed by Fourier transform infrared. A differential scanning calorimetry analysis was carried out to determine the thermal behavior of the nanocomposites with increasing amounts of the nano‐CaSO₄ and nano‐Ca₃(PO₄)₂ fillers. Increases in the tensile strength and Young's modulus were observed up to certain loading and were followed by a decrease in the tensile strength. A continuous decrease in the elongation at break (%) was also observed for commercial CaSO₄ and larger nano‐Ca₃(PO₄)₂. A decrease in the mechanical properties after a certain loading might have been due to the agglomeration and phase transition of PP in the composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 670–680, 2007     

Microcellular foaming of low‐density polyethylene using nano‐CaCo3 as a nucleating agent

In this study, microcellular foaming of low‐density polyethylene (LDPE) using nano‐calcium carbonate (nano‐CaCO₃) were carried out. Nanocomposite samples were prepared in different content in range of 0.5–7 phr nano‐CaCO₃ using a twin screw extruder. X‐ray diffraction and scanning electron microscopy (SEM) were used to characterize of LDPE/nano‐CaCO3 nanocomposites. The foaming was carried out by a batch process in compression molding with azodicarbonamide (ADCA) as a chemical blowing agent. The cell structure of the foams was examined with SEM, density and gel content of different samples were measured to compare difference between nanocomposite microcellular foam and microcellular foam without nanomaterials. The results showed that the samples containing 5 phr nano‐CaCO₃ showed microcellular foam with the lowest mean cell diameter 27 μm and largest cell density 8 × 10⁸ cells/cm³ in compared other samples. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Kinetics of thermal degradation of nanometer calcium carbonate/linear low‐density polyethylene nanocomposites

To improve the thermal properties of linear low‐density polyethylene (LLDPE), the CaCO₃/LLDPE nanocomposites were prepared from nanometer calcium carbonate (nano‐CaCO₃) and LLDPE by melt‐blending method. A series of testing methods such as thermogravimetry analysis (TGA), differential thermogravimetry analysis, Kim‐Park method, and Flynn‐Wall‐Ozawa method were used to characterize the thermal property of CaCO₃/LLDPE nanocomposites. The results showed that the CaCO₃/LLDPE nanocomposites have only one‐stage thermal degradation process. The initial thermal degradation temperature T₀ increasing with nano‐CaDO₃ content, and stability of LLDPE change better. The thermal degradation activation energy (E_a) is different for different nano‐CaCO₃ content. When the mass fraction of nano‐CaCO₃ in nanocomposites is up to 10 wt %, the nanocomposite has the highest thermal degradation E_a, which is higher (28 kJ/mol) than pure LLDPE. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of alkali‐soluble photosensitive polysiloxane urethane acrylate

A new negative temperature coefficient of resistor (NTCR) thermistors based on nitrile butadiene rubber/magnetite (NBR/Fe₃O₄) nanocomposites were successfully fabricated by conventional roll milling technique. X‐ray diffraction and transmission (TEM) analysis showed that the product is mainly magnetite nanoparticles with diameter of 10‐13 nm. The microstructure of (NBR/Fe₃O₄) nanocomposites were examined by scanning electron microscopy (SEM) and FTIR spectroscopy. The dispersion of magnetite nanoparticles in the NBR rubber matrix and interfacial bonding between them were rather good. The thermal stability of nanocomposites was also obviously improved with the inclusion of the magnetite nanoparticles. The thermal conductivity, thermal diffusivity and specific heat of nanocomposites were investigated. The electrical conductivity of the NBR/Fe₃O₄ increases with the rise in temperature exhibiting a typical negative temperature coefficient of resistance (NTCR) behavior like a semiconductor. The nature of the temperature variation of electrical conductivity and values of activation and hopping energy, suggest that the transport conduction process is controlled by hopping mechanism. Values of characteristics parameters of the thermistors like thermistor constant, thermistor sensitivity and thermistor stability is quite good for practical application as NTCR devices at high temperature. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polymerization properties of polyamide in bottom‐up prepared polyamide‐calcium carbonate composites

Polyamide/calcium carbonate composites (CaCO₃) were prepared by bottom‐up process, using a precipitated CaCO₃ with polyamide monomers followed by the polymerization of the polyamide. The composites before and after the polymerization treatment were studied by gel permeation chromatography, differential scanning calorimetry, X‐ray powder diffraction, and attenuated total reflectance—Fourier transform infrared spectroscopy. A van der Waals interaction between monomer molecules and CaCO₃ surface, which was suggested by the blue shift in IR absorption band of NH₂ and CH₂, restricted the molecular motions of monomers on the CaCO₃ surfaces to inhibit the proceeding of polymerization reactions. A resembled blue shift was also observed in the polyamide/CaCO₃ composites. Besides the hydrophilic; hydrogen bonding and ionic, interactions, the van der Waals interaction should not be ignored and had a significant effect on the polymerization reactions. POLYM. COMPOS., 35:1132–1139, 2014. © 2013 Society of Plastics Engineers     

Mechanical and thermal properties of bio‐based CaCO3/soybean‐based hybrid unsaturated polyester nanocomposites

Bio‐based calcium carbonate nanoparticles (CaCO₃) were synthesized via size reduction of eggshell powder using mechanical attrition followed by high intensity ultrasonic irradiation. The transmission electron microscopic (TEM) and BET surface area measurements show that these particles are less than 10 nm in size and a surface area of ～44 m²/g. Bio‐based nanocomposites were fabricated by infusion of different weight fractions of as‐prepared CaCO₃ nanoparticles into Polylite® 31325‐00 resin system using a non‐contact Thinky® mixing method. As‐prepared bio‐nanocomposites were characterized for their thermal and mechanical properties. TEM studies showed that the particles were well dispersed over the entire volume of the matrix. Thermal analyses indicated that the bio‐nanocomposites are thermally more stable than the corresponding neat systems. Nanocomposite with 2% by weight loading of bio‐CaCO₃ nanoparticles exhibited an 18°C increase in the glass transition temperature over the neat Polylite 31325 system. Mechanical tests have been carried out for both bio‐nanocomposites and neat resin systems. The compression test results of the 2% Bio‐CaCO₃/Polylite 31325 nanocomposite showed an improvement of 14% and 27% in compressive strength and modulus respectively compared with the neat system. Details of the fabrication procedure and thermal and mechanical characterizations are presented in this article. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1442–1452, 2013     

Effect of dendrimer‐like PAMAM grafted attapulgite on the microstructure and morphology of Nylon‐6

The effect of dendrimer‐like polyamidoamine grafted attapulgite (ATP‐PAMAM) on the microstructure and morphology of Nylon‐6 (PA6) was investigated. The ATP‐PAMAM nanoparticles were prepared by treating attapulgite (ATP) with heat and acid followed by grafting with polyamidoamine (PAMAM) molecules, which was confirmed by Fourier transform infrared spectroscopy (FT‐IR), thermogravimetric analysis (TGA), and dispersion state in formic acid. The X‐ray diffraction (XRD) analysis result indicated that the grafting modification was occurred on the surface of fibrous crystals and did not shift the crystal structure of ATP. PA6/ATP‐PAMAM (G_2.0) nanocomposites with different modified ATP content were prepared by melt compounding in a twin screw extruder. XRD measurements suggested that the intensity of diffraction peak of α crystalline form of PA6 decreased gradually as the inclusion of ATP‐PAMAM(G_2.0) into the PA6 matrix, while that of γ crystalline form increased gradually. The results of molau experiment and scanning electron microscopy (SEM) observation showed not only a uniform dispersion of ATP‐PAMAM(G_2.0) in the PA6 matrix but also a strong interfacial adhesion between them. Mechanical investigation (by tensile test) showed an obvious improvement in the presence of surface modified ATP. POLYM. COMPOS., 35:627–635, 2014. © 2013 Society of Plastics Engineers     

Improving polypropylene microcellular foaming through blending and the addition of nano‐calcium carbonate

This article reports an attempt to improve polypropylene (PP) microcellular foaming through the blending of PP with high‐density polyethylene (HDPE) as a minor component and the incorporation of nano‐calcium carbonate (nano‐CaCO₃) into PP and its blends with HDPE. Three HDPEs were selected to form three blends with a viscosity ratio less than, close to, or greater than unity. Two concentrations of nano‐CaCO₃, 5 and 20 wt %, were used. The blends and nanocomposites were prepared with a twin‐screw extruder. The foaming was carried out by a batch process with supercritical carbon dioxide as a blowing agent. The online shear viscosity during compounding and the dynamic rheological properties of some samples used for foaming were measured. The cell structure of the foams was examined with scanning electron microscopy (SEM), and the morphological parameters of some foams were calculated from SEM micrographs. The rheological properties of samples were used to explain the resulting cell structure. The results showed that the blend with a viscosity ratio close to unity produced a microcellular foam with the minimum mean cell diameter (0.7 μm) and maximum cell density (1.17 × 10¹¹ cells/cm³) among the three blends. A foamed PP/nano‐CaCO₃ composite with 5 wt % nano‐CaCO₃ exhibited the largest cell density (8.4 × 10¹¹ cells/cm³). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Mechanical properties and morphology of polypropylene‐calcium carbonate nanocomposites prepared by dynamic packing injection molding

In this article, dynamic packing injection molding (DPIM) technology was used to prepare injection samples of Polypropylene‐Calcium Carbonate (PP/CaCO₃) nanocomposites. Through DPIM, the mechanical properties of PP/nano‐CaCO₃ samples were improved significantly. Compared with conventional injection molding (CIM), the enhancement of the tensile strength and impact strength of the samples molded by DPIM was 39 and 144%, respectively. In addition, the tensile strength and impact strength of the PP/nano‐CaCO₃ composites molded by DPIM increase by 21 and 514%, respectively compared with those of pure PP through CIM. According to the SEM, WAXD, DSC measurement, it could be found that a much better dispersion of nano‐CaCO₃ in samples was achieved by DPIM. Moreover, γcrystal is found in the shear layer of the DPIM samples. The crystallinity of PP matrix in DPIM sample increases by 22.76% compared with that of conventional sample. The improvement of mechanical properties of PP/nano‐CaCO₃ composites prepared by DPIM attributes to the even distribution of nano‐CaCO₃ particles and the morphology change of PP matrix under the influence of dynamic shear stress. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Impact‐toughening mechanisms of calcium carbonate‐reinforced polypropylene nanocomposite

The impact fracture mechanisms of polypropylene (PP), containing 9.2 vol % of calcium carbonate (CaCO₃) nanoparticles, were investigated using optical microscopy and transmission electron microscopy. The incorporation of CaCO₃ nanoparticles reduces the size of spherulites and induces the formation of β‐phase crystallites, which leads to a more ductile PP matrix. Double‐notch four‐point bending (DN‐4PB) Charpy impact specimens and notched Izod impact specimens were utilized to study the fracture mechanism(s) responsible for the observed toughening effect. A detailed investigation reveals that the CaCO₃ nanoparticles act as stress concentrators to initiate massive crazes, followed by shear banding in PP matrix. These toughening mechanisms are responsible for the observed, improved impact strength. A comparison of the fracture mechanisms observed between DN‐4PB Charpy and Izod impact tests is also made to show the effectiveness of DN‐4PB for investigation of impact fracture mechanisms of polymeric systems. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3070–3076, 2006     

The effects of polymer‐nanofiller interactions on the dynamical mechanical properties of PMMA/CaCO3 composites prepared by microemulsion template

We prepared novel poly(methyl methacrylate) (PMMA)/CaCO₃ nanocomposites by using reverse micelle as a template. The nanoparticles of CaCO₃ were prepared by the reverse microemulsion with functional monomer, methyl methacrylate (MMA) as oily phase, and the PMMA/CaCO₃ nanocomposite was obtained via polymerization of MMA monomer. The SEM image showed that the nanoparticles of CaCO₃ were dispersed in the polymer matrix. Dynamic mechanical analysis (DMTA) was performed to investigate the interaction between the nanoparticles and the polymer chains. In the low‐temperature ripening process, two tan δ peaks were observed in the nanocomposite, corresponding to the glass transitions of the matrix and the interface layer. In the high‐temperature ripening process, only one tan δ peak was observed, suggesting that the interface layer forms a continuous phase. The nanoparticles behave as a physical crosslinker in the interface layer. Modification of the surface of nanoparticles with polyacrylamide and poly(N,N′‐methylenedisacrylamide) in the nanocomposite did not show an appreciable effect on the interaction of nanoparticles with the matrix. Upon removal of the aqueous phase around the nanoparticles, we obtained surface‐capped nanoparticles by using an improved reverse microemulsion technique. Another PMMA/CaCO₃ nanocomposite was also obtained with these modified nanoparticles. DMTA analysis of this nanocomposite demonstrated that the aqueous phase layer around the nanoparticles does not significantly affect the interaction between the nanoparticles and the polymer chains. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2739–2749, 2004     

Properties of particulate resin‐luting agents with phosphate and carboxylic functional methacrylates as coupling agents

This study investigated properties of resin‐luting agents using silane [3‐(trimethoxysilyl)propyl methacrylate (TSPM)], phosphoric acid methacrylate (PAM) [mono/bis(methacryloyloxyethyl (di)hydrogen phosphate)], or carboxylic acid methacrylate (CAM) [mono‐2‐(methacryloyloxy)ethyl maleate] as coupling agents between the inorganic and organic phases. Ba‐B‐Al‐Si microparticles (3 μm) and SiO₂ nanoparticles (7 nm) were coated with TSPM, PAM, or CAM (control = no filler coating). A Bis‐GMA/triethyleneglycol dimethacrylate comonomer was loaded with 60% mass of inorganic fillers. The properties evaluated were degree of C?C conversion (DC), flexural strength (σ), and modulus (E_f), Knoop hardness number (KHN), and film thickness (FT). Dispersion/interaction of the particles with the resin phase was assessed by scanning electron microscopy (SEM). No significant differences in DC were observed. For σ and E_f, TSPM > CAM > Control > PAM. For KHN, TSPM > CAM > PAM = Control. For FT, TSPM < Control < CAM < PAM. The SEM analysis revealed clustering of nanoparticles for all groups and better organic–inorganic phases interaction for TSPM and CAM. The use of TSPM generated agents with improved properties as compared with the acidic methacrylates, with CAM showing better performance than PAM. The use of PAM generated agents with properties usually poorer compared with the material with no coupling agent. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Investigation into sulfur release in reductive decomposition of calcium sulfate oxygen carrier by hydrogen and carbon monoxide

Chemical looping combustion (CLC) is a promising technology with the inherent property of separating CO₂ from flue gas. For calcium sulfate (CaSO₄) oxygen carrier, the inhibition of the produced sulfurous gases in the reduction of CaSO₄, including sulfur dioxide (SO₂), hydrogen sulfide (H₂S) and carbonyl sulfide (COS), is the key for a CLC system. In this paper, the sensitivities of reacting temperature, oxygen ratio number (defined in this paper) and the mole fraction of both carbon monoxide (CO) and hydrogen(H₂) in the syngas to the sum of the amounts of released SO₂, H₂S and COS are discussed respectively. Thermo-gravimetric analysis (TGA) tests demonstrated that the amount of the produced sulfurous gases is greatly dependent on the partial pressure of H₂ or CO in the reduction of CaSO₄. When the partial pressure of H₂ or CO is higher than 40 kPa, the production of sulfurous gases, indicating the deterioration of the recyclability of CaSO₄, can be prevented completely even if the reacting temperature is as high as 1000 °C. A new kind of CaSO₄/CaCO₃ oxygen carrier is prepared using a mechanical mixing method. The addition of CaCO₃ nanoparticles largely improves the recyclability of the oxygen carrier in comparison with the fresh CaSO₄ oxygen carrier, without CaCO₃ nanoparticles, in a multi-cycle TGA test.