2017, Socher, Robert, Krause, Beate, Pötschke, Petra

The aim of this study was to decrease the electrical percolation threshold of multiwalled carbon nanotubes (MWCNTs) in a polyamide 12 matrix by the use of additives. Different kinds of additives were selected which either interact with the π-system of the MWCNTs (imidazolium based ionic liquid (IL) and perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA)) or improve the MWCNT wettability (cyclic butylene terephthalate, CBT). The composites were melt mixed using a DACA microcompounder. The electrical percolation threshold for PA12/MWCNT without additives, measured on compression molded plates, was found between 2.0 and 2.25 wt%. With all used additives, a significant reduction of the electrical percolation threshold could be achieved. Whereas the addition of IL and CBT resulted in MWCNT percolation at around 1.0 wt%, a slightly higher percolation threshold between 1.0 and 1.5 wt% was found for PTCDA as an additive. Interestingly, the electrical resistivity at higher loadings was decreased by nearly two decades when using CBT and one decade after application of PTCDA, whereas IL did not contribute to lower values in this range. In all cases macrodispersion as assessed by light microscopy was not improved and even worse as compared to non-modified composites. In summary, the results illustrate that these kinds of additives are able to improve the performance of PA12 based MWCNT nanocomposites.

2016, Hopmann, C., Windeck, C., Cohnen, A., Onken, J., Krause, Beate, Pötschke, Petra, Hickmann, T.

Bipolar plates constitute the most important structural component in fuel cell stacks. Highly filled thermoplastic composites with high electrical conductivity obtain an increasing importance in the design of bipolar plates as alternative to conventional metallic systems. Thermoplastics (e.g. PP) have suitable properties such as a good processability, chemical resistance, light weight and low production costs. As thermoplastics have low electrical conductivities, conductive fillers have to be included in the matrix. A high content of such fillers (e.g. graphite) in excess of 80 wt.-% is necessary to achieve the desired electrical properties. However, materials with such high filler contents embrittle readily. The workability in injection and compression molding is difficult and the mechanical stability is insufficient in case of strain deformation. As consequence, material failure and an inacceptable amount of damaged goods can be observed during the processing. As no suitable thermoplastic system is available for better mechanical properties, the induction and dispersion of a rubber phase in the thermoplastic matrix can be used to increase the impact strength of the conductive composite. In this research work a ternary composite, based on PP as matrix, EPDM as impact modifier and synthetic graphite as conductive filler, was developed. The material was produced using a 26 mm co-rotating, intermeshing twin-screw extruder. The amounts of PP, EPDM and graphite were varied systematically and a process window was defined that enables improved impact strength and high electrical conductivity of the new material. The results indicate that impact strength can be enhanced by about 99 % with an EPDM content of 30 wt.-% in the PP matrix. The electrical conductivity decreases in a small range with increasing content of EPDM, but the conductivity is still excellent for producing bipolar plates.

2018, Liebscher, Marco, Domurath, Jan, Krause, Beate, Saphiannikova, Marina, Heinrich, Gert, Pötschke, Petra

Electrical and melt rheological properties of melt-mixed polycarbonate (PC) and co-continuous PC/poly(styrene–acrylonitrile) (SAN) blends with carbon nanotubes (CNTs) are investigated. Using two sets of mixing parameters, different states of filler dispersion are obtained. With increasing CNT dispersion, an increase in electrical resistivity near the percolation threshold of PC–CNT composites and (PC + CNT)/SAN blends is observed. This suggests that the higher mixing energies required for better dispersion also result in a more severe reduction of the CNT aspect ratio; this effect was proven by CNT length measurements. Melt rheological studies show higher reinforcing effects for composites with worse dispersion. The Eilers equation, describing the melt viscosity as function of filler content, was used to fit the data and to obtain information about an apparent aspect ratio change, which was in accordance with measured CNT length reduction. Such fitting could be also transferred to the blends and serves for a qualitatively based discussion. © 2017 Wiley Periodicals

2017, Arjmand, Mohammad, Mirkhani, Seyyed Alireza, Pötschke, Petra, Krause, Beate, Sundararaj, Uttandaraman

Carbon nanotubes (CNTs) were synthesized by chemical vapor deposition technique at a broad range of temperatures, i.e. 550°C to 950°C (at 100°C intervals). CNTs were synthesized by flowing source and carrier gases (ethane, argon, and hydrogen) over Fe catalyst in a quartz tubular reactor. CNTs were melt mixed with a polyvinylidene fluoride (PVDF) matrix in a miniature mixer. The resulting nanocomposites were then compression molded, and electrically and morphologically characterized. Moreover, a wide range of characterization techniques were employed to obtain detailed information about the physical and morphological characteristics of CNTs. It was surprisingly observed that, despite the ascending trend of powder conductivity with the synthesis temperature, the nanocomposites made with (CNT)650°C had significantly lower percolation threshold (around 0.4wt.%) and higher electromagnetic interference shielding (20.3dB over the X-band for 1.1mm thickness) compared to the other temperatures. The characterization of nanofillers showed that the synthesis yield and quality of (CNT)650°C were highly superior to the other types of CNTs. At 850°C and 950°C, most of the synthesized carbonaceous materials formed graphitic structures around the sintered catalyst particles. It was also observed that the dispersion state of (CNT)650°C within the PVDF matrix was much better than that of CNTs synthesized at the other temperatures. Superior electrical properties of (CNT)650°C nanocomposites can be attributed to a combination of high synthesis yield, low diameter and decent quality of CNTs coupled with good state of dispersion within the PVDF matrix.

2017, Krause, Beate, Cohnen, A., Pötschke, Petra, Hickmann, T., Koppler, D., Proksch, B., Kersting, T., Hopmann, C.

In this study, composites based on polypropylene (PP) and different graphite fillers were melt mixed using small scale microcompounder Xplore DSM15 as well as lab-scale co-rotating twin screw extruder Coperion ZSK26Mc. The measurements of the electrical and thermal conductivity as well as mechanical properties of the composites were performed on pressed plates. It was found that the addition of graphite powders having different particle size distributions leads to different increases of the thermal conductivity. For synthetic graphite, the PP composites filled with TIMCAL Timrex® KS500 reached the highest value of thermal conductivity of 0.52 W/(m·K) at 10 vol% loading, whereas this composite was not electrical conductive. Furthermore, the influence of a styrene-ethylene-butylene-styrene block copolymer (SEBS) based impact modifier on the mechanical properties of PP filled with 80 wt% of different synthetic graphites was investigated. For that the proportion of SEBS in the PP component was varied systematically. The conductivities were influenced by the type of graphite and the content of impact modifier. The results indicate that the impact strength of the composite containing TIMCAL Timrex® KS300-1250 can be increased by approx. 100 % when replacing 50 wt% of the PP component by SEBS.

2017, Krause, Beate, Carval, J., Pötschke, Petra

Polycarbonate composites containing multiwalled carbon nanotubes (MWCNTs, 0.2-2.0 wt%) were melt mixed in small scale at different conditions of screw speed and mixing time to vary the specific mechanical energy (SME) input between 0.4 and 4.0 kWh/kg. Next to the electrical properties of compression molded plates and the MWCNT macrodispersion also the nanotube length and shape were analyzed. For this, the matrix of the composites with 0.75 wt% MWCNT loading was dissolved and the remaining nanotubes were investigated using TEM. It was found that with increasing SME input the number of remaining CNT agglomerates decreases. The MWCNT length decreased from initially about 1.4 micrometers towards 350 nanometers at a SME of 4 kWh/kg and the mean curling values were also reduced. The electrical percolation threshold increases with SME from about 0.4 wt% to 0.6 wt%.

2017, Krause, Beate, Predtechenskiy, M., Ilin, E., Pötschke, Petra

Polypropylene composites filled with singlewalled carbon nanotubes TUBALL® (SWCNTs) were studied with regard to the effect of ionic liquid (IL) addition in different SWCNT:IL ratios (1:0.5 - 1:6). The incorporation of IL leads to a decrease of the electrical percolation threshold and already at 0.025 wt% SWCNT loading reduced resistivity values can be observed. However, the SWCNT macro dispersion, already relatively good without IL, was not affected by the IL incorporation. In addition, the nucleation effect of the SWCNT in polypropylene is not influenced when simultaneously adding IL, whereas the crystallization enthalpy slightly decreases with its addition.

2017, Luo, J., Krause, Beate, Pötschke, Petra

The thermoelectric (TE) performance of electrically conductive thermoplastic composites prepared by melt mixing was investigated. A cost effective widely used in industry polymer, namely polypropylene (PP), was chosen as the matrix to fabricate the composites. Singlewalled carbon nanotubes (SWCNTs), the amount (2 wt%) of which was selected to be above the electrical percolation threshold (< 0.2 wt%), were used to form an electrical conducting network. Besides as-produced SWCNTs plasma modified tubes were employed to study the influence of the functionalization on the morphology, dispersion and TE properties of the PP composites. In addition, melt processing conditions, e.g. temperature, rotation speed, and time during mixing in a small-scale compounder were varied. Furthermore, an ionic liquid (IL, 1-methyl-3-octylimidazolium tetrafluoroborate) was used as a processing additive during melt mixing, which was confirmed to improve the electrical conductivity of the composites. Simultaneous increase in the Seebeck coefficient up to a value of 64 μV/K was recorded, leading to a much better power factor of 0.26 μW/(m·K2) compared to composites without IL. This melt mixing strategy opens new avenues for solvent-free, large scale fabrication of polymer based TE materials.

2016, Luo, Jinji, Krause, Beate, Pötschke, Petra

Flexible thermoelectric materials are prepared by melt mixing technique, which can be easily scaled up to industrial level. Hybrid filler systems of carbon nanotubes (CNTs) and copper oxide (CuO), which are environmental friendly materials and contain abundant earth elements, are melt mixed into a thermoplastic matrix, namely polypropylene (PP). With the CNT addition, an electrical network could be built up inside the insulating PP for effective charge transport. The effect of CuO addition is determined by the corresponding CNT concentration. At high CNT concentration, largely above the percolation threshold (φc, ca. 0.1 wt%), the change in the TE properties is small. In contrast, at CNT concentration close to φc, the co-addition of CuO could simultaneously increase the electrical conductivity and Seebeck coefficient. With 5 wt% CuO and 0.8 wt% CNTs where a loose percolated network is formed, the Seebeck coefficient was increased from 34.1 µV/K to 45 µV/K while the electrical conductivity was from 1.6 × 10−3 S/cm to 3.8 × 10−3 S/cm, leading to a power factor of 9.6 × 10−4 µW/mK2 (cf. 1.8 × 10−4 µW/mK2 for the composite with only 0.8 wt% CNTs).

2017, Müller, M. T., Krause, Beate, Kretzschmar, B., Jahn, I., Pötschke, Petra

In this study composite materials based on high-density polyethylene (HDPE) with fillers containing nanostructures were prepared using melt mixing. Vapour Grown Carbon Fibers (VGCF), multiwalled carbon nanotubes (MWCNT) of the types Baytubes® C150P and Nanocyl™ NC7000, anthracite powder, microsilica, organoclay and expanded graphite (EG) as well as mixtures of these fillers were used. The amount and mixing ratios of the hybrid filled systems have been varied to determine their effects on the achievable level of thermal conductivity as measured on compression molded plates. The filler dispersion and phase adhesion were studied using scanning electron microscopy. When limiting the maximum filler content to 10 wt%, the highest enhancement in thermal conductivity by 166% was found for VGCF followed by a 1:1 filler combination of VGCF with EG (148%).