Transport properties have been measured transverse to the plane of sheared and un-sheared thin-film nanocomposites of isotactic Polypropylene (iPP) and multiwall carbon nanotubes (MWCNTs) at various MWCNT concentrations. The sheared samples were processed in the melt at 200 0C at 1 Hz in a Linkan microscope shearing hot stage. The thermal and electrical conductivity measurements were performed on the same cell arrangement with the transport perpendicular to the thin-film plane using a DC method. The thermal and electrical conductivity perpendicular to the surface of the films are higher for the un-sheared as compared to the sheared samples. Interestingly, the percolation threshold appears smeared in both conductivity measurements likely due to pressing and shear treatment of the films, or the spacing between the data points. Important for electronics packaging and materials for which those anisotropic properties are highly desired this work presents important advances in understanding the structure-transport property relations.

The internal micro/nano-structure of anisotropically oriented polymer/CNTs composites determines their macroscopic properties. However, the connections between the two are not fully understood. The varying of CNT concentration, preparation method, and a thermodynamic parameter (e.g. temperature) can all play interconnected role. In this work, the macroscopic electrical conductivity was measured perpendicular to the film thickness of an insulating polymer (isotactic PolyPropylene, iPP) and a nano-composite of iPP with 5 weight percent of CNT. The thin films studied were sheared (anisotropically nano-structured) and non-sheared (with random internal structure). In general the effect of melt shearing induces anisotropy on the electrical transport properties of the iPP/CNT films in directions parallel and perpendicular to the direction of orientation. Our results show that for the pure iPP, resistivity slightly increases with shear at higher temperatures. When CNTs are introduced, there is a large difference between the resistivity of the sheared and non-sheared nanocomposite. The sheared PNCs when the CNTs are aligned parallel to each other, have higher resistivity, which is possibly due to the higher concentration at which the percolation threshold occurs in this arrangement. The resistivity decreases overall, as the temperature increases from 0 to 50 °C. These results show that CNTs can be used to control and fine tune the desired macroscopic physical properties of nanocomposites, by concentration and orientation, such as electrical conductivity, for applications where such properties are necessary.

Transport properties of polymer nanocomposites become increasingly important for range applications with many outstanding questions remaining. Thermal conductivity is especially important in applications like temperature sensing and packaging. We chose isotactic PolyPropylene (iPP) as one of the most widely used polymers and created nano-colloidal dispersions at different weight percent concentration of carbon nanotubes (CNTs). We oriented the thin-film samples using melt-shear at 200°C and 1Hz in a Linkam microscope shearing hot stage. Thermal conductivity measurements were performed at room temperature on two iPP/CNT sheared thin-film samples (1% and 5% CNT content) both parallel and perpendicular to the shear direction as well as a pure iPP sheared thin-film, prepared using the same process. Our findings indicate that the CNTs enhance kappa by 12% for the 1% CNT sample and 35% by the 5% CNT sample compared to that measured for pure iPP. Additionally, the CNTs under shear induce a novel anisotropy to the thermal conductivity in iPP/CNTs nano-composites. We introduce an approach to extract the shear induced orientational order of thermal conductivity by the dispersed CNTs.

We present a hybrid structure of Isotactic Polypropylene (iPP) nanocomposite with multiwall carbon nanotubes (MWCNTs). The polymer component contributes to the optical properties, flexibility and integrity of the polymer film while the carbon nanotubes change the thermal and mechanical stability, electrical and thermal conductivity and sensitivity. The multifunctional characteristics of this nanocomposite material are enhanced by anisotropic organization of the nanotubes and polymer through melt shearing which provides organization of the structural constituents at the molecular, nano, and micro length scales. This results in anisotropy of the macroscopic composite film properties parallel and perpendicular to the direction of shearing. On the molecular scale, the CNTs control the arrangement of the polymer molecules in a crystal lattice. On the nanometer scale, the CNTs couple to and align with the smectic normal of the liquid crystal phase of iPP. On the micron scale and larger, the secondary polymer crystal structure is rearranged due to the pinning of the polymer at the CNT surface to form fibrillar rather than spherulitic structures. These multi-scale rearrangements affect the optical, thermal, electrical, mechanical and chemical properties of the nanocomposite film. Our findings indicate that the CNTs under shear induce a novel anisotropy to the various thermo-physical properties of the iPP/CNTs films. We introduce an approach to extract the shear induced orientational order from the thermal conductivity of the dispersed CNTs. The index of refraction of the nanocomposites was also estimated via ellipsometry and was found to decrease slightly when CNTs were added and also showed shear induced anisotropy. The comparison between the results from the different experiments methods for probing induced anisotropy by melt shearing shows that orientation in iPP/CNTs nanocomposites induces anisotropy in multiple macroscopic properties.

Optical transport through Isotactic Polypropylene (iPP) and multiwall carbon nanotubes (MWCNTs) nanocomposite thin films is important to many applications where optical transmission or polarization are used. Especially interesting is the case where the optical properties are anisotropic as in oriented thin films and the optical transport is different in the direction of orientation and perpendicular to it. Changing the orientation of the film or the polarization of the light can change the way in which the nanocomposite film interacts with light. Our polymer of choice, Isotactic Polypropylene, is one of the most widely used polymers which will increase the applicability of our results. We blended iPP with different concentration of carbon nanotubes (CNTs): 1%, 2% and 5% and oriented the thin film samples using melt-shear at 200°C and 1Hz in a Linkam microscope sharing hot stage. We measured that the index of refraction of the nanocomposites slightly decreased when CNTs are added and that when nanocomposites were shear-oriented at low loading of CNTs the index of refraction showed small difference in directions parallel and perpendicular to the direction of orientation. The extinction coefficient increased therefore it’s tuning in the nanocomposite films by the content of the carbon nanotubes can help devise new materials with the desired values of this property.

We report the preparation and characterization of binary blend films of poly(vinylidene fluoride) (PVDF) and poly(1- ethyl-3-vinylimidazolium trifluoromethylsulfonylimide) (PVIm+TFSI-) derived from ionic liquid imidazolium monomers and doped with TFSI- salt. The potential utility of such materials in capacitive electronic devices and in proton exchange membrane fuel cells is of particular interest. Thin PVDF/ PVIm+TFSI- films were fabricated from solutions of dimethly formamide (DMF) by doctor blading. The nature of the PVDF crystalline polymorph and degree of crystallinity were evaluated as a function of the volume fraction of imidazolium polymer and thermal treatment. The morphology, thermal and mechanical characteristics and crystallinity of PVDF, in semicrystalline blend films was studied by wide angle X-ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetry, and dynamic mechanical analysis. In these materials, conditions such as choice of solvent, drying conditions, and thermal treatment affect the crystal phase, crystallite size, and degree of crystallinity of PVDF as well as the distribution of the minor component, the vinylimidazolium polymer. The polar beta phase of PVDF crystals dominates in as-cast films, while the non-polar alpha phase is observed after cooling from the melt. PVDF imparts mechanical strength and chemical stability to the composite films, and because of its high crystal melting point (Tm > 160 °C), serves to improve the high temperature stability of resulting films.

A new family of A-B di-block copolymers based on the amino acid sequences of Nephila clavipes major ampulate dragline spider silk, which have a strong potential for applications in tissue regeneration and drug delivery, was synthesized and characterized. The morphology was assessed by SEM: HBA3 formed fibrillar structure and 2 μm diameter hollow micelles, while HBA4 and HBA6 formed hollow micelles in water solution. The secondary structures of water-cast spider silk-like block copolymer films were assessed by FTIR. The crystallinity was determined by Fourier self-deconvolution of the amide I spectra and confirmed by wide angle X-ray diffraction. Results indicate that the self-assembled morphology and the crystallinity can be varied by changing the length of A-block, and a minimum of 3 A-blocks are required to form β sheet crystalline regions in water-cast spider silk block copolymers. A theoretical model was used to predict the specific reversing heat capacity, Cp(T), which is crucial to the design of smart biomaterials. Excellent agreement was found between the theoretical value and the Cp(T) determined by temperature modulated differential scanning calorimetry. This method can serve as a standard by which to assess the thermal properties for other biologically inspired block copolymers, and then be further applied to control the biological interactions for use in drug delivery and smart biomaterials applications.

Polymer and carbon nanotubes (CNTs) nanocomposites exhibit many properties that are not present in either the pure polymer or CNTs. The polymer crystallization kinetics and crystal forms are greatly changed by dispersion of CNTs nanotubes. In addition to various thermophysical properties, CNTs are metallic or semiconductive and highly anisotropic while the polymer hosts are typically excellent insulators and isotropic. In this work, measurements of the electrical conductivity, σ, of thin-film nanocomposites of isotactic polypropylene (iPP) and CNTs as a function of CNT concentration (0, 1, 2, and 5% by weight of CNT) and melt-shearing induced anisotropy in σ between parallel and perpendicular to the shearing axis is presented and compared them with analogous data for their thermal transport properties. The iPP host is itself one of the most widely used polymers, has liquid crystalline phases, and it is expected that iPP/CNT nanocomposites will be widely used in many polymer applications, some of which are for flexible electrodes, medical and electronics packaging and chemical sensors. The effect of melt-shearing is expected to induce anisotropy in the various properties of the iPP/CNT thin film that should be particularly apparent in the electrical conductivity of the polymer films, higher in the direction of the alignment and lower in the direction perpendicular to it. With increasing CNT content, the average conductivity 〈σ〉 increases slightly from 0 to 2% CNT then dramatically increases by eight orders of magnitude for 5%. The shear induced property of anisotropy, δσs = (σ‖ − σ┴) / 〈σ〉, overall increases with CNT content, revealing a large spike for the 1% sample, indicating the possibility of enhanced δσs due to optimized orienting procedures.

Multiwall Carbon Nanotubes (MWCNT) align by coupling to the liquid crystals’ (LC) nematic director in LC/MWCNT dispersions. This coupling is so strong that the LC molecules act as molecular motors to reorient the MWCNTs when an electric field is applied across oriented electro optic cells. On the other hand, MWCNTs also improve the LC order and modify the crystal phase of LCs. We investigate the physical reasons for those strong effects by studying the molecular interactions between a host LC and MWCNTs. It has been predicted theoretically that the aromatic rings could stack with their π orbitals in 4-Cyano-4’-pentylbiphenyl (5CB) and MWCNT nanocomposites. Experimentally 5CB modifies the MWCNTs Raman breathing modes in the same nanocomposites. In turn, we look for evidence of this interaction between MWCNTs and LCs at the 5CB molecules. Using FTIR spectroscopy we found that the modes corresponding to 5CB aromatic rings vibrations are affected in the presence of MWCNTs which confirms that π-π stacking of 5CB’s biphenyl rigid core to the carbon rings on the MWCNTs’ surface may indeed be major mechanism for MWCNT/LC nematic coupling. It shows also that the Raman breathing mode effects on MWCNTs can be due to this π-π stacking interaction with 5CB. Further investigations of the MWCNTs interactions with 5CB can lead to developing of a complete model of this phenomenon and help applications for electro optic cells, nanoswitches, new crystal forms for optics, communication technology and others.

Carbon nanotubes (CNTs) exhibit liquid crystalline order and their nematic director couples to the one of low molecular weight liquid crystals. Here we explore the interactions between CNTs and the smectic liquid crystal phase of a polymer and the possibility for a similar coupling in this system. Isotactic Polypropylene (iPP) and iPP/CNTs nanocomposites were made in solution with varying CNT concentrations and hot pressed into 50-100μm thick films. The pure iPP and iPP/CNT films were then sheared at one rotation per second in the melt state. Shearing continued as the temperature was decreased from 200°C to 145°C to induce a smectic liquid crystal phase. The sheared samples were analyzed using polarized optical microscopy, Two Dimensional Microscopic Transmission Ellipsometry (2D-MTE) and Two Dimensional Wide Angle X-Ray Scattering (2D-WAXS). During shearing we detected a sudden increase of birefringence at 151°C in the samples, higher than the iPP crystallization temperature, indicating liquid crystalline ordering. The samples were then crystallized at 135°C for 30 minutes. We measured anisotropic 2D-WAXS patterns of the samples that contained CNTs, indicating strong ordering of the crystals. Upon reheating, we measured birefringence at temperatures higher than the melting endotherm for the iPP crystals, using polarized microscopy, which indicates that some smectic order still persists in the samples, even after crystallization and complete melting of all crystals. Our results indicate that CNTs couple to the smectic phase of iPP, improve its order upon shearing and the crystals created after the formation of the oriented smectic phase are strongly aligned parallel to the direction of shearing.

The largest commercial application of carbon nanotubes (CNT) are their polymer nanocomposites (PNCs). This motivates detailed studies of the interactions between CNTs and polymers and the ways the CNTs influence the crystallization behavior and structure of PNCs. We have chosen isotactic polypropylene (iPP) as one of the best model systems because of its ability to form a smectic liquid crystal phase. We studied iPP/CNT nanocomposites with CNT concentrations ranging from 0.01 to 5% per weight. We prepared films by compression molding and quenching in a mixture of isopropyl alcohol and dry ice. Some of the formed smectic liquid crystalline (LC) phase of iPP/CNT PNCs persisted to temperatures higher than the last melting temperature for iPP crystals. By means of differential scanning calorimetry we corroborated the existence of the LC phase in the nanocomposites and studied the impact of multi-walled carbon nanotubes on its melting and re-crystallization. We used a polarizing optical microscopy to reconfirm our DSC data.

Polymer nanocomposites are the largest commercial application for carbon nanotubes (CNTs) which determines the interest in their effect on crystallization processes of polymers. We chose Isotactic Polypropylene (iPP) as one of the most widely used polymers. Nanocomposites with multiwall carbon nanotubes (MWCNTs) 0-5% by weight were studied, using differential scanning Calorimetry to measure the crystal nucleation and kinetics effects of MWCNTs. Isothermal crystallization at 138°C was performed and the data were analyzed using Avrami analysis. We obtained results for the effect of MWCNTs on the crystallization kinetics. The Avrami analysis showed a dramatic increase in the crystallization rate constant and constancy of the Avrami exponent with increase of the CNTs concentration. The full width at half maximum (FWHM) of the heat flow exotherm and the peak time for crystallization (tp) change dramatically. The crystallinity shows a slight variation with the CNTs concentration dipping at 2% CNTs which can be explored further at higher concentrations.

Multiwall Carbon Nanotubes (MWCNTs) form a nematic liquid crystalline (LC) phase in their lyotropic form, enabling their mixing and coupling of their director to that of nematic LCs. An important aspect of this LC/MWCNT interaction, for applications other than display technology, is looking at the ways the MWCNTs affect the physical properties of the LCs. We study the effect of MWCNTs on the nematic to crystal (N-C) phase transition of 4-cyano-4-npentylbiphenyl (5CB). Our Differential Scanning Calorimetry (DSC) results show a dramatic increase in N-C phase transition temperature of 14°C for only 0.1% and of 20°C for 1% MWCNT, due to the crystal nucleation activity of the nanotubes. Using Polarized Microscopy we observe a change in the crystalline order of 5CB from spherulitic at 0% MWCNTs to a multidomain in presence of MWCNTs. The new crystals resemble those formed by a smectic LC 4- Decyloxybenzoic acid. This is in line with predictions from simulations, that the MWCNTs form smectic order in nematic 5CB at their interface. MWCNTs induced modifications of the crystal phase of 5CB promise to create controlled novel crystal forms for the purposes of optical transmission and other applications.

Smart Materials are those which can undergo a reversible property change in response to an external influence. An important polymeric Smart Material is poly(vinylidene fluoride), or PVF2, which is piezoelectric. The structure of PVF2 determines which crystal phases will be electrically active. Recent research has shown that the electrically active beta phase of PVF2 grows preferentially in nanocomposites of PVF2 mixed with organically modified silicates (OMS) ‘1-4’. These nanocomposite Smart Materials offer a new processing strategy for PVF2 piezo-films. Using PVF2 nanocomposites as the research focal point, a summer internship program was developed for deaf and hard of hearing (DHH) undergraduate students [5,6]. This paper describes the program and presents research results achieved by the interns. It is written from the perspective of the Principal Investigator, Cebe, on behalf of all the co-authors.

We studied the effects of multiwalled carbon nanotubes (MWCNTs) on the Freedericksz transition of a liquid crystal (LC) and calibrated the altitudinal angle of CNTs as a function of the electric field. In addition, we directed the azimuthal angle which gave us complete control of the 3D orientation of the CNTs. We constructed anti-parallel electro-optic cells using a nanocomposite at a concentration of 0.01% CNTs with 4-Cyano-4'-pentylbiphenyl (5CB) liquid crystal. This low concentration was necessary to achieve maximum transmission of electromagnetic radiation through the cell and to minimize the Van der Waals attraction between the CNTs responsible for their aggregation. We chose two dimensional microscopic transmission ellipsometry (2D-MTE) to measure the phaseshift of the polarized electromagnetic radiation through the cell and to derive from it the altitudinal angle of the CNTs. Our results show that in the presence of CNTs the Freedericksz transition occurs at 55% of the transitional electric field as compared to the control electro-optic cell without CNTs. The width of the Freedericksz transition narrows by a similar factor. The switching time of the cell decreased in the presence CNTs by 18.5%.

Isotactic Polypropylene (iPP) nanocomposites with low concentrations of multiwall carbon nanotubes (CNTs) 0-1% were studied, using differential scanning calorimetry and Avrami analysis. The nanocomposites were isothermally crystallized at 135°C, in order to measure the effect of nanotubes on the kinetics of crystallization. In our study there is a great effect of the CNTs on the iPP crystallization kinetics. The Avrami analysis shows increase in the crystallization rate constant and constancy the Avrami exponent with increase of the CNTs concentration. The full width at half maximum (FWHM) of the heat flow exotherm and the peak time for crystallization (tp) change dramatically. For iPP, the carbon nanotubes serve as nucleation agents to speed up the crystallization process.

In our previous work [1] we investigated the impact of cold-crystallization on the structure of nanocomposites of PVDF with Lucentite STN™ OMS and observed the crossover composition in which the crystallographic beta phase dominated over alpha phase. Here, melt crystallization of PVDF/OMS nanocomposites was studied in the range of 0 to 1.0 wt% of OMS. In crystallization from melt, a decrease in crystallinity index occurs as a result of an increase in OMS. While beta phase fraction increased with an increase of OMS content in the range of interest, the amount of alpha crystals was found to be dominant even at high OMS compositions. At 1.0 wt% of OMS, beta crystals had reached at most 30% of the total crystallinity. Polarizing optical microscopy (POM) studies showed smaller, less birefringent spherulites with higher melting temperature compared to alpha spherulites appeared with OMS addition. Growth rate of these weakly birefringent spherulites is smaller than that of the strongly birefringent alpha spherulites. The increase in size and amount of the weakly birefringent spherulites with an increase of OMS and their higher melting point suggests these spherulites may be in the beta crystallographic phase.

Phase separation into controllable patterned microstructures was observed for Bombyx mori silkworm silk and poly(ethylene oxide) (PEO) (900,000 g/mol) blends cast from aqueous solution. Solution blending was used to incorporate water-soluble PEO into silk to enhance elasticity and hydrophilicity. The sizes of the globule fibroin phase ranged from 3.1±0.9 μm to 18.2±2.1 μm depending on the ratio of silk/PEO. Optical microscopy and SEM analysis confirmed the micro-phase separation between PEO and silk. Surface properties were determined by contact angle. The PEO can be easily extracted from the films with water to generate silk matrices with definable porosity and enhanced surface roughness. These blend films formed from two biocompatible polymers provide new potential tissue engineering scaffolds and controlled release drug delivery materials.

In this paper we report a synchrotron small angle x-ray scattering (SAXS) study of development of structure in semicrystalline Poly(Ether Ether Ketone), (PEEK) and an 80/20 blend with amorphous Poly(Ether Imide) (PEEK/PEI). Samples were treated to dual stage melt crystallization scheme involving initial isothermal crystallization at T1 followed by a second isothermal period at T2 (T1 < T2). Intensity of small angle scattering was measured in real-time. Structural parameters characterizing the lamellar thickness, 1c, long period, L, and SAXS invariant were deduced from the one-dimensional electron density correlation function assuming an ideal, two-phase structural model.