WAXD Results Research Articles

Triple shape memory effect in multiple crystalline polyurethanes

AbstractRemembering more than one permanent shape is an attractive research topic for shape memory materials (SMMs). In this paper, multiple crystalline shape memory polyurethanes (SMPUs) are prepared with PCL10000 and PTMG2900 by a three‐step polymerization method. DSC and WAXD results show that the obtained polyurethane contains, simultaneously and independently, two kinds of crystals. In addition, it is confirmed through DMA analysis that reversible soft phase and hard domains are formed in the PCL‐PTMG based SMPU system; and two‐step modulus decreases at low temperature range can be obtained in the SMPU with suitable mass proportion of PCL to PTMG, e.g., 1:7. Thus, shape memory effect (SME) can be achieved in this system. Moreover, it is found that the PTMG soft segment dominates the shape memory effect when the PCL mass is lower than that of PTMG; while the PCL soft segment dominates the SME when PCL mass is higher than that of PTMG; and a two‐step programing shape recovery can be achieved when the mass proportion of PCL/PTMG reaches a balance value, e.g., 3:5. Copyright © 2009 John Wiley & Sons, Ltd.

Polymorphic crystallization of fractionated microbial medium-chain-length polyhydroxyalkanoates

Abstract By focusing on a range of fractions of medium-chain-length polyhydroxyalkanoates (mcl-PHA), a more in-depth understanding of the thermal properties and the crystalline structure has been gained. Dual-mode melting was observed for all the fractionated samples. Further DSC analysis revealed that such phenomenon was due to the presence of two crystalline phases (phase I and phase II), forming at different temperatures. As noted, for the samples with higher 3-hydroxytetradecanoate (HTD) comonomer composition, the crystallization rate of phase II was much depressed, which made phase I dominant. The WAXD and FTIR results indicate that the two phases differ in the crystalline structure. The in situ IR and WAXD registrations indicate that phase I would transform into phase II through a melting-recrystallization process during heating. The high similarity of IR spectra in the range of 1500–900 cm−1 between phases I and II excludes the possibility of adopting different conformation. It is suggested that major differences between the two crystalline phases lie in the molecular packing.

Physical properties and biodegradation of acrylic acid grafted poly(ε-caprolactone)/chitosan blends

We blended films of acrylic acid grafted polycaprolactone (PCLgAA) and citosan (CS) with different compositions from aqueous acetic acid solution. DSC measurements showed that the melting temperatures and enthalpies of the blends decreased with increasing CS content. From FTIR results, we observe that the amino groups of CS form covalent bonds with the carboxylic groups of PCLgAA in addition to hydrogen bonds between the constituents in the blends. Though the crystal structure of the PCLgAA component was not changed, as proved by WAXD results, blending CS suppressed the crystallinity of the blends. Furthermore, the ductility of CS was increased during tensile testing in PCLgAA/CS blends due to enhanced affinity between the two components. However, PCLgAA/CS blends show greater resistance than PCL/CS blends to biodegradation in an enzymatic environment.

Skin Thickness and β-Crystals Development in Injection-Molded iPP Along the Flow Direction

In this study, iPP was injection molded at 180°C, 200°C, and 220°C. According to polarization optical microscopy (POM) results, for a given part, the skin thickness steadily decreases along the flow direction. However, at the same distance from the gate, the skin thickness of the parts molded at lower melt temperature is larger than that molded at higher melt temperature. It is found that flow time (here, the time taken for melt to pass the specific position along the flow direction) and melt temperature are two significant factors leading to this phenomenon, while the gate size is another one. The DSC and WAXD results show that the relative fraction of β-form crystals, for a specific part, decreases along the flow direction, which is mainly determined by flow time. However, for the parts molded at different molding temperatures, the fraction of the β-form crystals is mainly determined by the molding temperature, though this influence is very complex.

Influence of chain extension on the compatibilization and properties of recycled poly(ethylene terephthalate)/linear low density polyethylene blends

Polymeric methylene diphenyl diisocyanate (PMDI) was added as chain extender to a blend of recycled poly(ethylene terephthalate) (R-PET) and linear low density polyethylene (LLDPE) with compatibilizer of maleic anhydride- grafted poly(styrene–ethylene/butadiene–styrene) (SEBS- g-MA). Hydroxyl end groups of PET can react with both isocyanate groups of PMDI and maleic anhydride groups of SEBS- g-MA, which are competing reactions during reactive extrusion. The compatibility and properties of the blends with various contents of PMDI were systemically evaluated and investigated. WAXD results and SEM observations indicated that chain extension inhibits the reaction between PET and SEBS- g-MA. As the PMDI content increased, the morphology of dispersed phase changed from droplet dispersion to rodlike shape and then to an irregular structure. The DSC results showed that the crystallinity of PET decreased in the presence of PMDI, and the glass transition temperature ( T g) of PET increased with addition of 0–0.7 w% PMDI. The impact strength of the blend with 1.1 w% PMDI increased by 120% with respect to the blend without PMDI, accompanied by only an 8% tensile strength decrease. It was demonstrated that the chain extension of PET with PMDI in R-PET/LLDPE/SEBS- g-MA blends not only decreased the compatibilization effect of SEBS- g-MA but also hindered the crystallization of PET.

Structure and property of injection‐molded polypropylene along the flow direction

AbstractThe structure and mechanical properties of injection‐molded polypropylene along the flow direction were investigated in this article. A remarkable difference was found in morphology and mechanical properties of the injection‐molded parts along the flow direction. The three‐layered structure (namely the skin, subskin, and core layer) showed a gradient distribution along the flow direction. The IR and WAXD results showed that the orientation of the subskin layer in the gate part is much higher than that in the far part. DSC analysis results indicated that the two parts (gate part and far part) of injection‐molded bar has the same degree of crystallinity that should not be responsible for the mechanical difference of the two parts. According to the measurement of residual internal stress, there is large difference between the gate part and far part, which is the main reason leading to the difference of impact behavior. The annealing treatment eliminated the internal stress, so the mechanical difference between the two parts decreased and the fracture type of the far part changed from brittle to ductile. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers

Fine structure and physical properties of poly(buthylene terephthalate) sheets prepared by roller drawing method

Poly(butylene terephthalate) sheets were prepared by roller-drawing method with various draw ratio. The drawing temperature is 100 °C and draw ratios were varied 2, 2.5, 3, 3.5 and 4. The effect of draw ratio on the crystal structure, the molecular orientation, dynamic viscoelastic properties, sonic modulus and tensile properties of the roller-drawn PBT sheets were investigated. In WAXD results, with increasing of the draw ratio, (010) and (100) planes of preferred orientation have the strongest intensity on the equator. In the meridional scans, it was confirmed that α and β crystal co-existed in the roller drawn PBT sheets with various draw ratio. Uniaxially roller-drawn PBT sheets clearly increased orientation along the stretched direction at high draw ratio. And the four-methylene groups of PBT orient along the surface of the sheet. The mechanical properties of PBT sheets were improved by orientation-induced crystallization during roller drawing process at 100 °C.

Interactions between an Anticancer Drug and Polymeric Micelles Based on Biodegradable Polyesters

Interactions between the anticancer drug quercetin and biodegradable polyesters within micelles were investigated by DSC, WAXD, and UV analyses. For micelles based on poly(ethylene glycol) methyl ether-block-poly(epsilon-caprolactone) (MPEG-PCL), DSC analysis indicated that the interactions were between the hydrophobic core and the drug within the micelle. For micelles based on poly(ethylene glycol) methyl ether-block-poly(L-lactide) (MPEG-PLLA), the interactions were between the hydrophobic core and the drug and between hydrophilic segments and the drug. WAXD results indicated that no crystalline phase of the drug was found in either of the micelle types. Based on the DSC and WAXD results, two probable micelle structures were proposed. The UV spectra revealed the presence of hydrogen bonding as the main interaction between the drug and the polyesters. In vitro studies demonstrated that quercetin release from micelles was sustained and was affected by the polymer-drug interaction.

PEO/fatty acid blends for thermal energy storage materials. Structural/morphological features and hydrogen interactions

Application of poly(ethylene oxide)-based materials as efficient thermal energy storage systems requires understanding of structural and morphological issues that govern the thermal transitions of the blends. Poly(ethylene oxide)/lauric acid and poly(ethylene oxide)/stearic acid blends show high values of heat of melting and heat of crystallisation which exceed theoretically determined values – it is a synergistic effect that is advantageous in terms of energy storage. The PEO blends were investigated by PLM, SEM, AFM, WAXD, SAXS and 1H NMR techniques – PLM, SEM and AFM allows to observe regions, in which parallelly-packed crystals of fatty acid are present. WAXD results of PEO/fatty acid blends confirmed hindered crystallization of PEO in PEO/fatty acid blends and, finally, lower degree of polymer crystallinity. The NMR study shows that mixing of PEO and lauric acid results in an increase of PEO amorphous phase content in blends as compared to the pure PEO. From FTIR spectra, taken during melting and crystallization, it can be seen that for both investigated blends in the solid state there is only one maximum of band from ν(C O) (in position indicating that C O groups are engaged in formation of hydrogen bonds), while in the liquid state there are two maxima – position of the first maximum is characteristic for ν(C O) vibrations of C O groups that do not participate in formation of hydrogen bond, whereas position of the second maximum in the liquid state proves the presence of C O groups involved in formation of hydrogen bonds. Solid state NMR analysis reveals no esterification reactions between PEO and fatty acid.

Processing and characterization of electrospun poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) nanofibrous membranes

Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) nanofibrous membranes were first fabricated via electrospinning from chloroform (CHCl3) or CHCl3/dimethylformamide (DMF) polymer solutions. The electrospinning conditions such as the polymer concentration, the solvent composition, and the applied voltage were optimized in order to get smooth and nano-sized fibers. The crystalline structure, the melting behaviors and the mechanical properties of the obtained nanofibrous membranes were characterized. With pure CHCl3 as the solvent in the electrospinning process, the finest smooth PHBHHx fibers were about 1μm in diameter. When DMF is added to CHCl3 as a co-solvent, the conductivity and volatility of the solution increased and reduced, respectively, and the electrospinnability of the polymer solution increased as a result. The averaged diameters of PHBHHx fibers could be reduced down to 300–500nm when the polymer concentration was kept at 3wt%, the ratio of DMF/CHCl3 was maintained at 20/80 (wt%), and the applied voltage was fixed at 15kV during electrospinning. WAXD and DSC results indicated that the crystallization of the PHBHHx nanofibers was restricted to specific crystalline planes due to the molecular orientation along the axial direction of the fibers. The crystallization behaviors of the electrospun nanofibers were significantly different from that of the cast membranes because of the rapid solidification and the one-dimensional fiber size effect in the electrospinning process. Mechanically, the electrospun PHBHHx nanofibrous membranes were soft but tough, and their elongation at break averaged 240–300% and could be up to 450% in some cases. This study demonstrated how the size of electrospun PHBHHx fibers could be reduced by adding DMF in the solvent and gave a clue of the presence of oriented molecular chain packing in the crystalline phase of the electrospun PHBHHx fibers.

Poly(ethylene glycol) Octafunctionalized Polyhedral Oligomeric Silsesquioxane: WAXD and Rheological Studies

A homologous series of PEG (various chain length)-substituted octasilsesquioxanes prepared by the hydrosilylation of unsaturated PEGs (poly(ethylene glycol)s) with octa(dimethylsiloxy)silsesquioxane (Q8M8H) were studied by wide-angle X-ray diffraction WAXD and rheology. The WAXD results indicate that neat POSS is highly crystalline material, while its PEG hybrids show evidence of small, disordered POSS crystals. Rheological characterization shows largely Newtonian behavior of POSS−PEG materials, with an interesting interplay between attached PEG chain length and weight fraction of POSS, with regards to melt viscosity and activation energy of flow.

Probing nucleation and growth behavior of twisted kebabs from shish scaffold in sheared polyethylene melts by in situ X-ray studies

By utilizing synchrotron rheo-WAXD (wide-angle X-ray diffraction) and rheo-SAXS (small-angle X-ray scattering) techniques, the nucleation and growth behavior of twisted kebabs from the shear-induced shish scaffold in entangled high-density polyethylene (HDPE) melts were investigated. The evolution of the (110) reflection intensity in WAXD at the early stages of crystallization could be described by a simplified Avrami equation, while the corresponding long period of kebabs determined by SAXS was found to decrease with time. The combined SAXS and WAXD results indicate that the kebab growth in sheared HDPE melts consists of two-dimensional geometry with thermal (sporadic) nucleation. The WAXD data clearly exhibited the transformations of (110) reflection from equatorial 2-arc to off-axis 4-arc and of (200) reflection from off-axis 4-arc to meridional 2-arc, which can be explained by the rotation of crystallographic a-axis around the b-axis during twisted kebab growth. This observation is also consistent with the orientation mode changes from ‘Keller/Machin II’ to ‘intermediate’ and then to ‘Keller/Machin I’.

The anti‐static poly(ethylene terephthalate) nanocomposite fiber by in situ polymerization: The thermo‐mechanical and electrical properties

AbstractPoly(ethylene phthalate) (PET)/nano‐antimony doped tin oxide (ATO) composites prepared via in situ polymerization were spun into fiber by the melt‐spinning process. ATO were in the form of loose agglomeration dispersing in the PET fibers and the sizes of loose agglomeration were smaller than 150 nm. Comparing with the neat PET, the tenacity of PET/ATO hybrid fibers was improved, and PET/ATO hybrid fibers had a lower elongation at break by adding nano‐ATO. The percolation threshold of PET/ATO hybrid fibers at room temperature was as low as 1.05 wt %, much lower than that of the composites filled with conventional conductive particles. The PET/ATO hybrid fiber exhibited volume resistivity of 4.9 × 108 Ω cm when the contents of ATO were 1 wt %. The ATO nanoparticles improved the thermal stability of PET fiber. The WAXD and DSC results suggested that ATO nanoparticles increase the degree of crystallinity of PET acting as the nucleating agent, which prohibited the thermal shrinkage of PET fiber. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007

Synthesis and characterization of poly(ϵ‐caprolactone)‐b‐poly(ethylene glycol) block copolymers prepared by a salicylaldimine‐aluminum complex

AbstractA series of poly(ϵ‐caprolactone)‐b‐poly(ethylene glycol) (PCL‐b‐PEG) block copolymers with different molecular weights were synthesized with a salicylaldimine‐aluminum complex in the presence of monomethoxy poly(ethylene glycol). The block copolymers were characterized by 1H NMR, GPC, WAXD, and DSC. The 1H NMR and GPC results verify the block structure and narrow molecular weight distribution of the block copolymers. WAXD and DSC results show that crystallization behavior of the block copolymers varies with the composition. When the PCL block is extremely short, only the PEG block is crystallizable. With further increase in the length of the PCL block, both blocks can crystallize. The PCL crystallizes prior to the PEG block and has a stronger suppression effect on crystallization of the PEG block, while the PEG block only exerts a relatively weak adverse effect on crystallization of the PCL block. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007

Melt preparation and investigation of properties of toughened Polyamide 66 with SEBS-g-MA and their nanocomposites

Polyamide 66/SEBS-g-M alloys and their nanocomposites were prepared by melt compounding using a twin screw extruder. The mechanical properties, rheological behavior and morphology of these alloys and their nanocomposites were investigated. Morphological investigations with different methods show pseudo-one-phase type morphology for these prepared alloys at all percentage of rubber. Impact and tensile tests results showed that rubber toughened samples exhibit significantly more impact strength and elongation at break comparing to virgin Polyamide. Samples with 20% of rubber show impact strength about 15 times and elongation at yield several times more than those of virgin Polyamide. So, these rubbers modified polyamide can be consider as super toughened rubber. A general type organoclay at 4% and 8% has been used with rubber toughened samples to tolerate their modulus and tensile strength. Obtained results show that nanoclay could significantly increase modulus and tensile strength of rubber modified Polyamide 66 without considerable effects on impact strength. WAXD and SEM results show that the Polyamide 66 nanocomposites are better exfoliated in presence of SEBS-g-MA. Some investigation on viscosity and melt flow index of PA66 and their alloys show that shear viscosity of PA66 nonlinearly decrease with incorporation of SEBS-g-MA and organoclay into it.

Preparation of polyacrylate‐clay nanocomposites by in‐situ polymerization and heterocoagulation

AbstractPolyacrylate‐clay nanocomposites were prepared by an in situ polymerization method followed by heterocoagulation. In the heterocoagulation method, a cationic polyacrylate emulsion was prepared by emulsion polymerization using a cationic initiator in the presence/absence of free surfactant, cetyl trimethylammonium bromide (CTABr), followed by mixing with an aqueous clay slurry. WAXD results and TEM images suggest that morphologies of these nanocomposites depend on preparation method, mixing method, and the amount of free surfactant. TG‐DTG analyses demonstrate the improvement in thermal stability of these nanocomposites, while DSC results indicate no significant changes in glass transition temperature of these nanocomposites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3850–3855, 2006

Shear‐Induced Orientation and Structure Development in Isotactic Polypropylene Melt Containing Modified Carbon Nanofibers

The shear‐induced crystallization behavior of isotactic polypropylene (iPP) nanocomposite melt containing modified carbon nanofibers (MCNFs) was investigated by rheo‐SAXS (small‐angle X‐ray scattering) and rheo‐WAXD (wide‐angle X‐ray diffraction) techniques using synchrotron radiation. Under quiescent conditions, the nucleating effect of MCNFs on crystallization of iPP was pronounced and the system exhibited a remarkably low saturation point (ca. 0.05 wt% of MCNF). In‐situ SAXS and WAXD results showed the development of shear‐induced crystalline structures and lamellar morphology in nanocomposite melts. Under the same shear conditions, the filled system exhibited notably faster kinetics compared with the unfilled system. The oriented crystalline fraction was found to decrease with the MCNF loading, indicating the competition between oriented crystals (induced by shear) and unoriented crystals (due to the nucleating effect of MCNF). At the early stages of crystallization, the amount of the oriented crystals increased with the MCNF concentration, suggesting that the nanofiller hindered the motion of polymer chains after the cessation of flow resulting in the delayed relaxation of stretched polymer segments. Dedicated to Prof. Phillip H. Geil's seventy‐fifth birthday.

Thermal Stability of Shear-Induced Shish-Kebab Precursor Structure from High Molecular Weight Polyethylene Chains

In-situ rheo-SAXS (small-angle X-ray scattering) and rheo-WAXD (wide-angle X-ray diffraction) techniques were used to investigate repeated melting and re-formation of the flow-induced shish-kebab precursor structure in a once-sheared polyethylene (PE) bimodal blend at the confined quiescent state. The blend consisted of a noncrystallizing low molecular weight PE matrix (LMWPE, Mw = 53 000 g/mol, polydispersity = 2.2) and a small amount (2 wt %) of crystallizing high molecular weight PE (HMWPE, Mw = 1 500 000 g/mol, polydispersity = 1.1) under the chosen experimental temperature. After a step shear (shear rate = 125 s-1, shear duration = 20 s, temperature = 126.5 °C), combined SAXS and WAXD results confirmed that the shish-kebab structure was developed mainly from HMWPE chains, following a diffusion-controlled-like process. Although shish formed first followed by microkebabs and then macrokebabs, shish and microkebabs were melted simultaneously as an integrated entity after the macrokebab melting. Upon c...

Formation of a Unique Crystal Morphology for the Poly(ethylene glycol)−Poly(ε-caprolactone) Diblock Copolymer

The crystallization behaviors of the poly(ethylene glycol)-poly(epsilon-caprolactone) diblock copolymer with the PEG weight fraction of 0.50 (PEG(50)-PCL(50)) was studied by DSC, WAXD, SAXS, and FTIR. A superposed melting point at 58.5 degrees C and a superposed crystallization temperature at 35.4 degrees C were obtained from the DSC profiles running at 10 degrees C/min, whereas the temperature-dependent FTIR measurements during cooling from the melt at 0.2 degrees C/min showed that the PCL crystals formed starting at 48 degrees C while the PEG crystals started at 45 degrees C. The PEG and PCL blocks of the copolymer crystallized separately and formed alternating lamella regions according to the WAXD and SAXS results. The crystal growth of the diblock copolymer was observed by polarized optical microscope (POM). An interesting morphology of the concentric spherulites developed through a unique crystallization behavior. The concentric spherulites were analyzed by in situ microbeam FTIR, and it was determined that the morphologies of the inner and outer portions were mainly determined by the PCL and PEG spherulites, respectively. However, the compositions of the inner and outer portions were equal in the analysis by microbeam FTIR.

Monitoring elasticity and orientation in syndiotactic polypropylene

The effect of temperature on the elasticity and structure of syndiotactic polypropylene (sPP) is investigated using a combination of WAXD and rheo-optical FTIR spectroscopy. sPP has a rich crystal structure, which leads to unique mechanical behavior. Beyond yield point, it exhibits elastic response associated with deformation-induced structure–structure transformation. The structure and orientation were measured both during and after uniaxial tensile stretching of films (up to 200%) as a function of temperature (25–70 °C). Our WAXD and rheo-FTIR results suggest that as the temperature increases, there is a reduction in the extent of helical to trans-planar conformational change upon stretching. When the strain is released, there is partial transformation of trans-planar conformation back to helical. The presence and orientation of the trans-planar conformation plays a key role on the elastic behavior of sPP beyond the yield point. Rheo-optical FTIR dichroism studies provide further insights into the elasticity in syndiotactic polypropylene. Different proportions of helical and trans-planar conformations orient to different extents. The helical conformation does not orient appreciably at higher temperature though they are present beyond the yield point. In contrast, the trans-planar chains show a significant increase in dichroism beyond the yield point, suggesting that there is a difference in mobility (orientation) of the helical and trans-planar chains. This further supports the importance of trans-planar chains on the elastic behavior.