Preparation and characterization of calcium carbonate/low‐density‐polyethylene nanocomposites

Calcium carbonate/low‐density‐polyethylene (LDPE) nanocomposites have been prepared by melting blend with twin‐screw extruder. The mechanical properties of composites and the dispersion of the nanoparticles were studied. The reinforcement mechanism was discussed. The results show that not only the tensile property but also the flexural modulus of the system have been evidently increased by the addition of calcium carbonate. The calcium carbonate particles have been dispersed in the matrix in the nanometer scale. The reinforcement mechanism of the calcium carbonate lies on that the calcium carbonate particles, acting as hetero‐nuclei, can induce higher crystallinity at the matrix‐particle interface compared to regions away from the interface. Consequently, in the process of the tensile test, the nanocomposites have better tensile yield strength. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Formation and Characterization of Nano‐sized RDX Particles Produced Using the RESS‐AS Process

It has been shown that nano‐sized particles of secondary explosives are less sensitive to impact and can alter the energetic performance of a propellant or explosive. In this work the Rapid Expansion of a Supercritical Solution into an Aqueous Solution (RESS‐AS) process was used to produce nano‐sized RDX (cyclo‐1,3,5‐trimethylene‐2,4,6‐trinitramine) particles. When a saturated supercritical carbon dioxide/RDX solution was expanded into neat water, RDX particles produced from the RESS‐AS process agglomerated quickly and coarsened through Ostwald ripening. However, if the pH level of the suspension was changed to 7, particles were metastably dispersed with a diameter of 30 nm. When the supercritical solution was expanded into air under the same pre‐expansion conditions using the similar RESS process, RDX particles were agglomerated and had an average size of approximately 100 nm. Another advantage of using a liquid receiving solution is the possibility for coating energetic particles with a thin layer of polymer. Dispersed particles were formed by coating the RDX particles with the water soluble polymers polyvinylpyrrolidone (PVP) or polyethylenimine (PEI) in the RESS‐AS process. Both PVP and PEI were used because they have an affinity to the RDX surface. Small and well‐dispersed particles were created for both cases with both PVP and PEI‐coated RDX particles shown to be stable for a year afterward. Several benefits are expected from these small polymer coated RDX particles such as decreased sensitivity, controlled reactivity, and enhanced compatibility with other binders for fabrication of bulk‐sized propellants and/or explosives.     

Properties of New Composite Materials Based on Hydroxyapatite Ceramic and Cross-Linked Gelatin for Biomedical Applications

The main aim of the research was to develop a new biocompatible and injectable composite with the potential for application as a bone-to-implant bonding material or as a bone substitute. A composite based on hydroxyapatite, gelatin, and two various types of commercially available transglutaminase (TgBDF/TgSNF), as a cross-linking agent, was proposed. To evaluate the impacts of composite content and processing parameters on various properties of the material, the following research was performed: the morphology was examined by SEM microscopy, the chemical structure by FTIR spectroscopy, the degradation behavior was examined in simulated body fluid, the injectability test was performed using an automatic syringe pump, the mechanical properties using a nanoindentation technique, the surface wettability was examined by an optical tensiometer, and the cell viability was assayed by MTT and LDH. In all cases, a composite paste was successfully obtained. Injectability varied between 8 and 15 min. The type of transglutaminase did not significantly affect the surface topography or chemical composition. All samples demonstrated proper nanomechanical properties with Young’s modulus and the hardness close to the values of natural bone. BDF demonstrated better hydrophilic properties and structural stability over 7 days in comparison with SNF. In all cases, the transglutaminase did not lead to cell necrosis, but cellular proliferation was significantly inhibited, especially for the BDF agent.     

Impact Strength and Crystallization Behavior of Nano‐SiOx/Poly(phenylene sulfide) (PPS) Composites with Heat‐Treated PPS

The effects of heat treatment on the crystal structure and impact strength of poly(phenylene sulfide) (PPS) and nano‐SiO_x/ PPS nanocomposites were studied. The molecular weight of heat‐treated neat PPS was increased by 28% due to the crosslinking reaction that changed its crystal morphology. Also, the crystallinity was reduced by 18%, leading to an improvement of the Izod impact strength by 66%. Nano‐SiO_x/PPS composites were manufactured by intensive compounding with 3 wt.‐% nano‐SiO_x particles treated by an epoxy functional group. Test results showed that the Izod impact strength of nano‐SiO_x/heat‐treated PPS composites was 91% better and the crystallinity 27% less compared to the same properties of “as received” neat PPS. Nano‐SiO_x has a high specific surface area and a high surface energy; its grafted epoxy group promotes interfacial adhesion with the PPS matrix, hence increasing the Izod impact strength of the nanocomposites.

TEM micrograph of NHTM‐PPS with 3 wt.‐% nano‐SiO_x.     

Preparation of Novel Fluoroalkyl End‐Capped Oligomer/Hydroxyapatite Nanocomposites

Novel fluoroalkyl end‐capped oligomer/hydroxyapatite nanocomposites have been easily prepared by the reaction of disodium hydrogenphosphate and calcium chloride in the presence of self‐assembled molecular aggregates formed by fluoroalkyl end‐capped oligomers in aqueous media. The fluorinated hydroxyapatite nanocomposites thus obtained were found to exhibit a good dispersibility in a variety of media, and were applied to the surface modification of glass.

     

Curing Viscosity of HTPB‐Based Binder Embedding Micro‐ and Nano‐Aluminum Particles

Aluminum is used as a metal fuel in energetic materials for the improvement of propulsion performance and density. Both nano‐sized and micrometer‐sized activated powders represent valuable options in order to improve metal combustion properties, each possessing advantages and drawbacks. These ingredients bear peculiar properties (namely, higher specific surface, coatings, or surface characteristics) which generate high mixing viscosity once suspended in a polymer as well as altered mechanical properties of the final product. Four different powders dispersed in a polymer binder are taken into consideration and the evolution of viscosity in time during the curing process is investigated. The suspending medium is represented by a mixture of hydroxyl‐terminated polybutadiene (HTPB), isophorone diisocyanate (IPDI) and dioctyl adipate (DOA). Viscosity was measured for 5 h on samples under isothermal curing at 60 °C. Non‐isothermal DSC kinetic analyses were also performed using the Kissinger method. It was found that, for the test conditions, a size reduction of metal particles slowed down the increment rate of curing viscosity while some peculiar coatings, such as fatty acids, introduced opposite trends.     

Nano‐scaled ordering of hyperbranched and star‐hyperbranched polymers

Hyperbranched polystyrenes (HPS) were prepared by living radical polymerization of 4‐vinylbenzyl N,N‐diethyldithiocarbamate (VBDC) as an inimer under UV irradiation. These HPS exhibited large amounts of photofunctional diethyldithiocarbamate (DC) groups on their outside surfaces. We derived star‐HPS (SHPS) by grafting from such HPS macroinitiator with methyl methacrylate (MMA) or ethyl methacrylate (EMA). The ratios of radius of gyration to hydrodynamic radius R_g/R_h for HPS and SHPS in tetrahydrofuran (THF) were in the range of 0.74–0.90 and 1.05–1.12, respectively. HPS and SHPS behaved in a good solvent as hard and soft spheres, respectively. We demonstrated the structural ordering of both branched polymers in THF through small‐angle X‐ray scattering (SAXS), by varying the polymer concentration. As a result, HPS and SHPS formed face‐centered‐cubic (fcc) and body‐centered‐cubic (bcc) structures, respectively, near the overlap threshold (C*). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3340–3345, 2006     

Hydroxyapatite (n‐HA)/unsaturated poly(ester‐amide) nanocomposites for bone fixation material

A new type of unsaturated poly(ester‐amide) viz maleic anhydride‐phthalic anhydride‐ethylene glycol‐neopentylene glycol‐glycin copolymer was prepared by melt polycondensation. The copolymer was characterized by FT‐IR, gel permeation chromatography, and thermal gravimetric analysis. The molecular structure of crosslinked unsaturated poly(ester‐amide) was determined by wide‐angle X‐ray diffraction. Hydroxyapatite (n‐HA) was used to boost up the new unsaturated poly (ester‐amide), the flexural properties of n‐HA/unsaturated poly(ester‐amide) nanocomposites with different n‐HA content were measured. Studies of degradation behavior were carried out in simulated body fluid at pH 7.4 and 37°C, the flexural strength changes and cumulative mass loss of n‐HA/ unsaturated poly(ester‐amide) nanocomposites were measured at different degradation times. The n‐HA/unsaturated poly(ester‐amide) nanocomposites was hydrolyzed in 1M NaOH standard solution at room temperature to study the mass loss with different n‐HA contents. All the preliminary results suggested that n‐HA/unsaturated poly(ester‐amide) nanocomposites might be potentially used as a new type of bone fixation material. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of High‐Energy Vibromilling on Interfacial Interaction and Mechanical Properties of PVC/Nano‐CaCO3 Composites

Summary: The effects of interfacial interaction between nano‐CaCO₃ and PVC on mechanical properties and morphology of PVC/nano‐CaCO₃ composites were studied. Nano‐CaCO₃ was treated with vibromilling in the presence of PVC and coupling agents. The mechanical properties of PVC/treated nano‐CaCO₃ are remarkably improved. Transmission electron microscopy results revealed that vibromilled nano‐CaCO₃ particles are well dispersed in PVC matrix with good homogeneity and well adhered to PVC matrix. Molau test indicated that chemical reaction between newly formed surface of nano‐CaCO₃ and PVC or coupling agent took place. Theoretical calculation results show that the interfacial interaction between PVC and nano‐CaCO₃ are substantially improved through vibromilling treatment of nano‐CaCO₃ in the presence of PVC and coupling agent.

Molau test results of the samples in THF.     

A Solvent‐Assisted Compression Molded of Poly(L‐lactide)/Hydroxyapatite Electrospun Fibers for Robust Engineered Scaffold Systems

In an attempt to enhance the biocompatibility and mechanical strength of fibrous polymeric scaffold systems, nanocrystalline hydroxyapatite (HAp) particles were incorporated into the electrospun poly(L ‐lactide) (PLLA) fibers and then mechanically interlocked using a vapor‐phase solvent adsorption method. The solvent‐assisted compression molding substantially increased the tensile strength (from 4.61 to 12.63 MPa) and mechanical modulus (from 50.6 to 627.7 MPa) of the fibrous scaffold, which maintained the interstitial space between the fibers to allow the facile transport of nutrients and waste during cell growth and polymer biodegradation. Macrometer‐sized pores (ca. 100–400 µm) were introduced into the scaffolds in a controlled fashion using the salt leaching/gas forming technique to give desired space for a facile cell implantation and growth. Overall, the developed methodology allows the polymer‐based scaffold systems to be tailored for various applications in light of surface characteristics, mechanical strength, and pore size of engineered scaffolds.

     

Synthesis of Small‐Scale Boron‐Rich Nano‐Size Particles

The synthesis times required to produce high energy density compounds (C₂B₄H₂)_n and (C₂B₁₀H₄)_n by gas phase pyrolysis of the carboranes C₂B₄H₆ and C₂B₁₀H₁₂, respectively, have been measured at 1150–2000 K and carborane pressures of (0.3–3.0)⋅10⁻³ MPa. Kinetic model simulations of the synthesis have been performed. The temperatures, carborane pressures, and synthesis times required to produce small‐scale (C₂B₄H₂)_n and (C₂B₁₀H₄)_n particles of 10 to 30 nm diameter are determined.     

In‐situ Preparation of a Porous Copper Based Nano‐Energetic Composite and Its Electrical Ignition Properties

In this paper, the in‐situ preparation and characterization of a porous copper‐sodium perchlorate energetic nano‐composite (PCu/NaClO₄) and its electrical ignition properties are presented. Porous copper was in‐situ produced by electro‐deposition on a Ni/Cr alloy wire, which acts as a cathode during the electro‐deposition. The PCu/NaClO₄ nano‐composite was produced by dipping the bridge with porous copper into a saturated sodium perchlorate acetone solution. SEM, EDS, and XRD were used to characterize the composite and DSC was used to study the thermal decomposition of the composite. The copper grain size was reduced by using additives such as CTAB in the electrolyte. The PCu/NaClO₄ nano‐composite on the bridge can be ignited by feeding a current through the bridge and the ignition delay time and electrical ignition sensitivity were measured.     

Mechanical and flame‐retarding properties of styrene–butadiene rubber filled with nano‐CaCO3 as a filler and linseed oil as an extender

A nanosize CaCO₃ filler was synthesized by an in situ deposition technique, and its size was confirmed by X‐ray diffraction. CaCO₃ was prepared in three different sizes (21, 15, and 9 nm). Styrene–butadiene rubber (SBR) was filled with 2–10 wt % nano‐CaCO₃ with 2% linseed oil as an extender. Nano‐CaCO₃–SBR rubber composites were compounded on a two‐roll mill and molded on a compression‐molding machine. Properties such as the specific gravity, swelling index, hardness, tensile strength, abrasion resistance, modulus at 300% elongation, flame retardancy, and elongation at break were measured. Because of the reduction in the nanosize of CaCO₃, drastic improvements in the mechanical properties were found. The size of 9 nm showed the highest increase in the tensile strength (3.89 MPa) in comparison with commercial CaCO₃ and the two other sizes of nano‐CaCO₃ up to an 8 wt % loading in SBR. The elongation at break also increased up to 824% for the 9‐nm size in comparison with commercial CaCO₃ and the two other sizes of nano‐CaCO₃. Also, these results were compared with nano‐CaCO₃‐filled SBR without linseed oil as an extender. The modulus at 300% elongation, hardness, specific gravity, and flame‐retarding properties increased with a reduction in the nanosize with linseed oil as an extender, which helped with the uniform dispersion of nano‐CaCO₃ in the rubber matrix. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2563–2571, 2005     

Preparation of Nano‐Structured Polyaniline Composite Film via “Carbon Nanotubes Seeding” Approach and its Gas‐Response Studies

Summary: Polyaniline composite film with nano‐structure was prepared through a chemical oxidation method by adding carbon nanotubes (CNTs) as nano‐fiber seeds. Spin‐coating or casting method was employed on the interdigital electrodes of carbon and the composite film was formed with an in‐situ polymerization approach. The gas‐response to trimethylamine was also examined at room temperature. It was found that the difference was not only in the morphology, but also in the value of gas‐sensitivity. Comparing with films without the CNTs, the value of gas‐sensitivity decreased dramatically, while the baseline current of the sensor increased remarkably. This method can be an effective way to adjust the gas‐sensitivity of sensors made from polyaniline composite film by adding a small amount of carbon nanotube. XRD data showed that the degree of orientation of polyaniline was increased greatly with the addition of CNTs.

Morphology and reproducibility (inset) of polyaniline composite film containing carbon nanotubes.     

Tannin‐Tethered Gelatin Hydrogels with Considerable Self‐Healing and Adhesive Performances

Hydrogels, especially the ones with self‐recovery and adhesive performances, have attracted more and more attention owing to their wide practical potential in the biomedical field involving cell delivery, wound filling, and tissue engineering. Tannic acid (TA), a nature‐derived gallol‐rich polyphenol, exhibits not only unique chelating properties with transition metal cations but also desirable anti‐oxidation properties and strong bonding capability to proteins and gelatin. Thus, taking advantage of the versatility of TA, a one‐pot method is proposed herein to produce TA‐modified gelatin hydrogels with the aid of NaIO₄ under basic conditions. By changing the amount of NaIO₄ used, the obtained hydrogels are covalently cross‐linked to different degrees and consequently exhibit diversity in their self‐healing and adhesive properties. The gelling time, viscoelasticity, and morphology of hydrogels are investigated, and when the feed molar ratio of NaIO₄ to TA is adjusted to 15:1, the fabricated hydrogel shows optimum self‐healing efficiency of 73% and adhesive strength of 36 kPa. Additionally, considering the completely natural origin of TA and gelatin, this study offers an original way for the fabrication of biocompatible self‐healing and adhesive materials.     

Improvement of Tribological Performance of Epoxy by the Addition of Irradiation Grafted Nano‐Inorganic Particles

To develop wear resistant nanocomposite coating materials, the authors of the present work treated nanosilica first by introducing a certain amount of grafting polymers onto the particles in terms of an irradiation technique. Through irradiation grafting, the nanoparticle agglomerates turn into a nanocomposite microstructure (comprised of the nanoparticles and the grafted, homopolymerized secondary polymer), which in turn built up a strong interfacial interaction with the surrounding epoxy matrix through chain entanglement and chemical bonding during the subsequent mixing and consolidation. The experimental results indicated that the addition of the grafted nanosilica into epoxy significantly reduced wear rate and frictional coefficient of the matrix at low filler loading. Compared with the cases of microsized silica and untreated nanosilica, the employment of grafted nanosilica provided composites with much higher tribological performance enhancement efficiency. Unlike the approaches for manufacturing of other types of nanocomposites, the current method is characterized by many advantages, such as simple, low cost, easy to be controlled, and broader applicability.     

Preparation and Properties of PVC Ternary Nanocomposites Containing Elastomeric Nanoscale Particles and Exfoliated Sodium‐Montmorillonite

Summary: A novel rigid PVC ternary nanocomposite containing NBR‐ENP and untreated Na‐MMT has been fabricated. X‐ray diffraction XRD, TEM and SEM observations revealed that the untreated Na‐MMT was exfoliated and most NBR‐ENPs (about 90 nm) were separately dispersed in the PVC matrix. DMTA and TGA demonstrated that the PVC ternary nanocomposites had a higher glass transition temperature and a higher decomposition temperature than neat PVC, while the toughness increased simultaneously. Combustion tests showed that the exfoliated clay in the PVC/NBR‐ENP/MMT ternary nanocomposites did not improve the flame retardancy after ignition under strong heat flux.

Schematic diagram of the fabrication procedure of PVC/NBR‐ENP/Na‐MMT ternary nanocomposites.     

Preparation of nano‐structured pig bone hydroxyapatite for high‐efficiency adsorption of Pb2+ from aqueous solution

The nano‐structured hydroxyapatite was prepared from pig bone materials by mineralization. The obtained nano‐structured bone was much better compared to the bone without nanostructure for removing Pb²⁺. The process was investigated under different conditions including contact time, initial Pb²⁺ concentration, and pH. The pseudo‐second‐order kinetic model and Langmuir isotherm model were suitable for describing adsorption process. Moreover, the maximum adsorption capacities of nano‐structured bone and bone without nanostructure were 312.5 and 96.1 mg/g, respectively. Overall, the advantages of excellent adsorption capacity and simple mineralization together with low cost make nano‐structured bone an attractive material for removal of Pb²⁺ from aqueous solution.     

Preparation of the composite consisting of nano‐sized gold particles and nylon‐11 oligomer

Nylon‐11 oligomer was utilized as a matrix to prepare a composite containing nano‐sized gold particles. Nylon‐11 oligomer was prepared by a thermal degradation of a commercial nylon‐11 in vacuum. Weight‐average molecular weight of the oligomer was in a range from 500 to 800. Nylon‐11 oligomer was formed into a film, and then gold was vapor‐deposited onto the oligomer film. The gold‐colored oligomer film turned a transparent red after a heat treatment at 120°C. Transmission electron microscopy showed an isolated distribution of nano‐sized gold particles in the red film of the oligomer. The gold particles were stable in the oligomer for more than a year, and they were dissolved in CH₂Cl₂ to produce a stable colloidal solution. These results suggest that the gold particles were not only dispersed in the oligomer film, but they were stabilized by the nylon‐11 oligomer to form a composite. IR spectrum of the composite showed that N H groups of the nylon‐11 oligomer were responsible for the interaction between the gold particles and the oligomer. Pulse ¹H‐NMR measurement suggested that an active molecular motion of the nylon‐11 oligomer caused the dispersion of the gold particles. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1654–1661, 1999