Effect of ball milling on the mechanical properties and crystallization of graphene nanoplatelets reinforced short chain branched-polyethylene

Short-chain-branched-polyethylene (SCB-PE) is extensively used in domestic hot and cold piping systems. SCB-PE nanocomposites using graphene nanoplatelets (GNPs) as a filler, were prepared in this work. The effect of ball-milling as a premixing technique prior to melt-mixing, on the crystallization and the nanomechanical properties of the composites has been studied. Two sets of SCB-PE/GNPs nanocomposites with various filler loadings were prepared; one with and one without the ball-milling step. The dispersion of the filler was evaluated by optical microscopy while the crystallization process was studied using differential scanning calorimetry. The nonisothermal crystallization's experimental data were analyzed using various methods. The materials' nanomechanical behavior was investigated by conducting nanoindentation tests. A finite element analysis process was developed to extract the composites' stress–strain behavior. The composites prepared with ball-milling presented improved dispersion of GNPs in the SCB-PE matrix, which affected the crystallization, while nanoindentation tests showed significantly enhanced mechanical properties.     

Properties of poly(lactic acid)/montmorillonite/carbon nanotubes nanocomposites: determination of percolation threshold

Incorporation of rigid nanoparticles is the most effective means of improving polymer properties. Montmorillonite (MMT) and multi-walled carbon nanotubes (MWCNTs) are legendary in this field for their individual exceptional properties. A synergistic phenomenon is induced between these two particles when they are simultaneously incorporated into polymers. At a definite nanofillers concentration, called the percolation threshold, there is a sudden change in nanocomposite properties due to the formation of a 3D-structured network of the nanoparticles within the matrix. In this work, the properties of poly(lactic acid) (PLA) nanocomposites filled with different fractions of MMT/MWCNTs hybrid (0.5–2.0 wt%) were analyzed. In particular, the percolation threshold of the MMT/MWCNTs hybrid was uniquely identified by differential scanning calorimetry, thermogravimetric analysis and dynamic mechanical thermal analysis. The structural studies by X-ray diffraction and Fourier-transform infrared spectroscopy were also associated with the percolation threshold of MMT/MWCNTs in PLA. At 1.0 wt% MMT/MWCNTs concentration, the complete exfoliation of the particles was maintained, and the thermal characteristics such as glass transition, crystallization and melting temperatures reached their plateau at this hybrid concentration. Moreover, the thermal degradation and viscoelastic parameters showed their peak values at this critical point, which is correlated with the formation of the percolation threshold within the matrix. The morphological studies confirmed the homogeneous dispersion of MMT/MWCNTs in PLA up to a concentration of 1.0 wt%. At 2.0 wt% MMT/MWCNTs, few aggregations occurred in the PLA-based composite, confirming that the percolation threshold was formed at a lower concentration of MMT/MWCNTs nanoparticles.

     

β-nucleated propylene–ethylene random copolymer filled with multi-walled carbon nanotubes: Mechanical,thermal and rheological properties

Nanocomposites of a β-nucleated propylene–ethylene random copolymer filled with different amounts of multi-walled carbon nanotubes (ΜWCNTs) were prepared by a melt mixing process. The complex crystalline structure that the samples exhibited was attributed to the strong α-nucleating effect of MWCNTs and the presence of calcium pimelate, as it was revealed by X-ray diffraction. It was found that the presence of MWCNTs at concentrations higher than 2.5 wt.% practically diminishes the effect of the β-nucleating agent, and this was also reflected on the mechanical properties of the samples. The quality of MWCNT dispersion in the polymer matrix was evaluated by transmission electron microscopy. Mechanical and thermal properties of the nanocomposites were studied as a function of the crystalline structure and the filler content by tensile and impact testing, thermogravimetric analysis and differential scanning calorimetry. A crystallization kinetics study was also performed in order to export conclusions regarding the rates and parameters of crystallization.     

Modified Crystalline Structure of Silane‐Crosslinked Polyethylene in the Proximity of Nanodiamonds

The introduction of nanodiamond particles (NDs) in silane‐crosslinked polyethylene is found to lead to a notable and systematic deformation of the polymer unit cell. X‐ray diffraction evidence of the existence of a modified crystalline structure in the bulk of the polymer due to the presence of NDs is reported here for the first time. The covalent bonding between NDs and the surrounding macromolecular chains may support that the excessive local stress field ultimately distorts the polymer conformation, yielding a new distorted but still crystalline interface. Supporting data from solid‐state NMR experiments confirm the existence of a modified crystalline interface of about 1–2 nm in all the nanocomposite materials.

     

Effect of evolved interactions in poly(butylene succinate)/fumed silica biodegradable in situ prepared nanocomposites on molecular weight,material properties,and biodegradability

Poly(butylene succinate) (PBSu)/fumed silica nanocomposites were prepared in situ by condensation polymerization. TEM micrographs verified that the dispersion of the nanoparticles was homogeneous in the PBSu matrix, while some small agglomerates were also formed at a higher SiO₂ content. ¹³C NMR spectra affirmed that the hydroxyl end groups of PBSu could form covalent bonds with the surface silanol groups of SiO₂. These interactions affected the molecular weight of the prepared nanocomposites. At low concentrations the SiO₂ nanoparticles acted as chain extenders, increasing the molecular weight of PBSu, while at higher loadings they resulted in extended branching and crosslinking reactions, leading to gradually decreased molecular weights. Silica nanoparticles acted as nucleating agents, increasing the crystallization rate of PBSu. However, the degree of crystallinity was slightly reduced. Tensile strength and Young's modulus were significantly increased with increasing SiO₂ content. The presence of the nanoparticles resulted in reduced enzymatic hydrolysis rates compared to pure PBSu, attributed to the smaller available organic surface, due to the incorporation of SiO₂, and to the existence of branched and crosslinked macromolecules. Dynamic mechanical and rheological properties were also extensively studied. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical properties and viscoelastic behavior of basalt fiber‐reinforced polypropylene

In the present article, a series of commercial‐grade polypropylenes (PP) filled with different contents of short basalt fibers were studied. This composite material presented deterioration of both mechanical characteristics, for example, stress and strain at yield with increasing of the fiber content. On the other hand, the impact strength was fourfold higher than that of unfilled PP. A poor adhesion between the PP matrix and the basalt fibers was detected. This is why interfacial interactions were promoted by the adding of poly(propylene‐g‐maleic anhydride) (PP‐g‐MA). It was observed that the tensile properties of the obtained materials and their impact strengths increased significantly with increasing of the amount of PP‐g‐MA in the blend. The adhesion improvement was confirmed by scanning electron microscopy as well. Fourier transform infrared spectroscopy was applied to assess if any chemical interactions in the system PP/PP‐g‐MA/basalt fibers exist. Dynamic mechanical thermal analysis data showed an increase of the storage modulus with increasing fiber content. The conclusion was made that the modification of the PP matrix led to a higher stiffness but its value remained constant, irrespective of the PP‐g‐MA content. With increasing fiber content, damping in the β‐region decreased, but increase of the coupling agent content restored its value back to that of PP. The loss modulus spectra presented a strong influence of fiber content on the α‐relaxation process of PP. The position of the peaks of the above‐mentioned relaxation processes are discussed as well. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 523–531, 1999     

Properties of fatty-acid esters of starch and their blends with LDPE

In the present study, starch octanoates OCST1.8 and OCST2.7 with degrees of substitution (d.s.) of 1.8 and 2.7, respectively, and dodecanoate DODST2.7 (d.s. = 2.7), were prepared by esterification of native starch with fatty acid chlorides. Our analyses, including elemental analysis, FTIR, contact angle, DSC, and TGA measurements confirmed the esterification reaction of starch and the degree of substitution. The ester group was found to act like an internal plasticizer, with an increase in the number and the size of fatty acyl chains grafted onto starch. These starch esters were mixed with low density polyethylene (LDPE) at various proportions in a Haake Rheomixer. Water and moisture absorption, thermal and mechanical properties, and biodegradation were investigated as a function of blend composition. The DODST2.7/LDPE blends showed, in general, better thermal stability and higher elongation, but lower tensile strength and water absorption, than did corresponding OCST/LDPE blends. The addition of starch esters to LDPE led to a very slow rate of biodegradation of these blends. © 1997 John Wiley & Sons, Inc. J Appl Polym 65: 705–721, 1997     

Dynamic thermomechanical and tensile properties of chain-extended poly(ethylene terephthalate)

A series of chemically modified poly(ethylene terephthalate) (PET) samples was received after chain extension of a virgin sample at different reaction times with a new diepoxide as chain extender. These samples showed different intrinsic viscosity and degrees of branching or crosslinking. The effect of this differentiation on thermal properties was studied by dynamic mechanical thermal analysis and the determined T_g values were found to be in good agreement with those obtained by differential scanning calorimetry and thermomechanical analysis. Also, the branching or crosslinking exhibited significant improvement in tensile mechanical properties, which were studied, and the results are discussed. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 797–803, 1998     

Dissolution enhancement of flavonoids by solid dispersion in PVP and PEG matrixes: A comparative study

Polyvinylpyrrolidone (PVP) and poly(ethylene glycol) (PEG) solid dispersion systems with flavanone glycosides, naringin and hesperidin, and their aglycones, naringenin and hesperetin, were prepared, using solvent evaporation method, to enhance their dissolution rates that may affect their bioavailability. Drug release of both flavanone glycosides and their aglycones was directly affected by the physical state of solid dispersions. Powder‐XRD technique in combination with scanning and transmission electron microscopy revealed that PVP polymer formed amorphous nanodispersion systems with flavanone aglycones, while such systems could not be formed with their glycosides, which are bulkier molecules. Fourier transform infrared spectra suggest the presence of hydrogen bonds between PVP carbonyl groups and hydroxyl groups of both flavanone aglycones. These interactions prevent the crystallization of naringenin and hesperetin aglycones in PVP matrix. On the other hand, the ability of PEG carrier to form hydrogen bonds with flavanone glycosides or aglycones was limited, and as a result both flavanone glycosides and their aglycones remain in the crystalline form. For this reason, the solubility enhancement of PEG solid dispersions was lower than when PVP was used as drug carrier. At pH 6.8, the % release of naringenin and hesperetin from PVP/naringenin–hesperetin (80/20 w/w) solid dispersion was 100% while in PEG solid dispersions, it was not higher than 60–70%. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 460–471, 2006     

Novel miscible poly(ethylene sebacate)/poly(4-vinyl phenol) blends: Miscibility, melting behavior and crystallization study

High molecular weight samples of the novel biodegradable polyester poly(ethylene sebacate) (PESeb) were synthesized. Miscible poly(ethylene sebacate)/poly(4-vinyl phenol) semicrystalline/amorphous blends were prepared by applying the solvent casting method. Miscibility was proved by the single composition dependent glass transition temperature over the entire composition range observed in DSC traces of the quenched blend samples and also by the melting point depression. The Flory-Huggins interaction parameter was found to be x₁₂ = −1.3. Also, FTIR spectra supported the hypothesis of intermolecular interactions due to hydrogen bonding. The crystallization of PESeb in blends was studied. As expected, isothermal crystallization rates decreased in the blends with increasing the PVPh content. The Lauritzen-Hoffman analysis was tested. The values of nucleation constant K_g did not show any substantial variation. The non-isothermal crystallization of the blends was also tested. It was found that the crystallization is retarded in the case of blends, compared to the neat PESeb.