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Tetrahedral amorphous carbon (ta-C) is studied as a tribological coating for the valve train’s exhaust camshaft of a combustion engine. The coated camshafts were installed in a non-fired engine, tested in a computerized component test bench under practice-relevant conditions and analyzed for their frictional behavior. A notable reduction of the valve train’s drive torque on the test bench is demonstrated. Namely, on a roller cam system with ta-C coated camshaft the reduction is about 15% in average within the entire engine-map. The ta-C coatings were extensively characterized under laboratory conditions before and after the investigations on the test bench. Mechanistic understanding of the tribological behavior of ta-C coatings under dry or starving lubricated conditions was achieved by atomistic simulations of the tribological contact. Industrial utilization of these results would lead to a significant increase of the energy efficiency of combustion engines.

Carbon: nickel (C:Ni) nanocomposite templates (NCTs) were used as catalyst precursors for diameter-controlled growth of single-walled carbon nanotubes (SWCNTs) by chemical vapor deposition (CVD). Two NCT types of 2 nm thickness were prepared by ion beam co-sputtering without (type I) or with assisting Ar+ ion irradiation (type II). NCT type I comprised Ni-rich nanoparticles (NPs) with defined diameter in an amorphous carbon matrix, while NCT type II was a homogenous C:Ni film. Based on the Raman spectra of more than 600 individual SWCNTs, the diameter distribution obtained from both types of NCT was determined. SWCNTs with a selective, monomodal diameter distribution are obtained from NCT type I. About 50% of the SWCNTs have a diameter of (1.36 ± 0.10) nm. In contrast to NCT type I, SWCNTs with a non-selective, relatively homogeneous diameter distribution are obtained from NCT type II. From both catalyst templates predominantly separated as-grown SWCNTs are obtained. They are free of solvents or surfactants, exhibit a low degree of bundling and contain negligible amounts of MWCNTs. The study demonstrates the advantage of predefined catalysts for diameter-controlled SWCNT synthesis in comparison to in situ formed catalysts.

Carbon:nickel nanocomposite templates were used for CVD growth of separated, individual single-walled carbon nanotubes (SWCNTs) free of solvents or surfactants. The as-grown carbon nanotubes were characterized by laser-energy dependent Raman spectroscopy and atomic force microscopy. Raman spectra showing a single radial breathing mode (RBM) line were analyzed with respect to correlations of RBM, G+ line and D line frequencies for SWCNT diameters covering the range of 0.8 nm to 1.6 nm. Opposite line shifts were found for RBM and G+ lines of the individual SWCNTs. However, the line shifts of the G+ line are smaller than the standard deviation of the G+ position for SWCNTs with almost the same RBM frequency, i.e. 1 1/cm compared to ± 1 1/cm for the whole diameter range. The D line often shows a complex shape including up to three components, which makes the identification of correlations with RBM frequencies possible only in selected cases.

Wear in self-mated tetrahedral amorphous carbon (ta-C) films is studied by molecular dynamics and nearedge X-ray absorption fine structure spectroscopy. Both theory and experiment demonstrate the formation of a soft amorphous carbon (a-C) layer with increased sp2 content, which grows faster than an a-C tribolayer found on selfmated diamond sliding under similar conditions. The faster sp3 --> sp2 transition in ta-C is explained by easy breaking of prestressed bonds in a finite, nanoscale ta-C region, whereas diamond amorphization occurs at an atomically sharp interface. A detailed analysis of the underlying rehybridization mechanism reveals that the sp3 --> sp2 transition is triggered by plasticity in the adjacent a-C. Rehybridization therefore occurs in a region that has not yet experienced plastic yield. The resulting soft a-C tribolayer is interpreted as a precursor to the experimentally observed wear.

The automotive industry is an essential branch for the industrial site Saxony. Within the past 20 years high-tech production centers have been built by the leading German car producers Volkswagen, BMW, and Porsche in Zwickau, Dresden, Chemnitz and Leipzig. According to estimations about 10 % of the jobs in Saxony subjected to social insurance are settled in the car related industry. This industrial sector on the one hand faces strong competitors from Asia and the USA, and on the other hand is challenged by the CO2 emission goals of the European Union for the next decade. These complex circumstances have to be dealt with innovative concepts in general and new approaches in research and development (R & D) in particular. The subproject ECEMP D1 is developing new, nanostructured, wear-resistant tribological coatings for the automotive engineering. These coatings provide a significant reduction of the friction in wear loaded car components and enable the more efficient use of fuel and materials.

Metal: matrix templates deposited by physical vapor deposition (PVD) were used to grow separated, individual single-walled carbon nanotubes (SWCNTs). The templates are thin films of 2 nm thickness, where the metal is either segregated as nanoparticles (NPs) or diluted in the matrix. The upper limit of the NP diameter was confined by the film thickness. The function of the matrix is to prevent the metal particle from coalescence during nanotube growth by chemical vapor deposition. SEM, TEM, AFM, and Raman mapping were used for template and carbon nanotube characterization. SWCNTs with a narrow, monomodal diameter distribution are obtained from templates with NPs of 2 nm diameter. About 50 % of the SWCNTs detected by Raman mapping have a diameter between 1.3 nm and 1.5 nm. Smaller SWCNT diameters down to 0.8 nm are obtained from templates where the metal is diluted in the matrix. For these templates a bimodal SWCNT diameter distribution was observed. The two maxima of the CNT diameter distribution were found at about 0.8 nm to 1.0 nm and at about 1.2 nm to 1.4 nm, respectively. The CNTs are in their majority separated each from other.

Single walled carbon nanotubes (SWCNT) grown from C:Ni nanocomposite thin film templates are studied by Raman mapping, scanning, and transmission electron microscopy. The templates consist of few nm thick films of Ni nanoparticles embedded in a protective matrix of amorphous carbon. They are prepared by ion beam sputtering, which allows a precise control of the particle size, shape, and arrangement in a sub nanometer length scale. SWCNT growth is performed by low pressure chemical vapour deposition in C2H2/ H2 at temperatures of about 735°C. The electron micrographs show that a large part of the nanoparticles preserves its initial geometry. The effect of the different particle morphologies on the mean SWCNT diameter and diameter distribution is demonstrated and discussed in the framework of current growth models.

The mechanical and tribological properties of nanostructured carbon:nickel films on silicon substrates are investigated using a multi-scale experimental and theoretical approach. The C:Ni nanostructures comprising either tilted columns or three-dimensionally self-organized nanopatterns are grown by ion-beam assisted deposition (IBAD). Complex layer architectures were obtained by sequential deposition by rotating the substrate in relation to the assisting ion beam after each deposition step. Atomic composition of the films was determined by ion beam analysis. The phase structure of carbon was analyzed by Raman spectroscopy, that of nickel by X-ray diffraction. The microstructure of the films was determined by high resolution transmission electron microscopy. The films show good adhesion as probed by scratch tests. The film hardness is on the order of 20 GPa, and the elastic modulus is at about 200 GPa. Friction coefficients on the order of 0.1 are found for oscillating wear conditions under ambient conditions. Atomistic computer simulations were applied to assist the experimental findings. Dry and liquid contacts are considered. The simulation shows a complex behaviour for the carbon-carbon interaction, e.g. resulting in the formation of a tribo-layer.

Precise control of single walled carbon nanotube (SWCNT) diameter, chirality, alignment, and intertube arrangement are still remaining challenges in the catalytic chemical vapour deposition (CCVD) synthesis. In this context it has still to be clarified whether a predefined size and shape of the nanoparticles can be stabilized by a suitable matrix material while preserving the catalytic activity of the metal. For this study Ni nanoparticles were encapsulated in an amorphous carbon matrix by physical vapour deposition. As prepared Ni catalysts were used for CNT fabrication by laser assisted CVD applying either no external carbon source or C2H4 gas, and by low pressure CVD applying C2H2 or CH4 as carbon source. The broad range of CNT synthesis conditions indicates the robustness of the embedded Ni particles as a catalyst for carbon nanotube formation. SEM and laser wavelength dependent Raman spectroscopy were used for CNT characterisation. The nickel-SWCNT-interaction was modelled by density functional calculations with the projector augmented plane wave method, utilizing the generalized gradient approximation for the exchange-correlation functional.

Tetrahedral amorphous carbon (ta-C) coatings have attracted high scientific attention in recent years due to their outstanding low friction coefficients in lubricated environments and their superior resistance to abrasive as well as adhesive wear. Consequently, they are highly suitable as protective coatings in automotive components such as combustion engines to reduce wear and friction. Nevertheless, ta-C abrade under extreme conditions and an atomistic understanding of the wear processes in ta-C is crucial for optimizing its wear resistance. The present study employs atomic-scale simulations to investigate the basic principles of wear between hydrogen- free tetrahedral-amorphous carbon (ta-C) films, which are modeled state-of-the-art by an improved version of the well-known Brenner bond-order potential. During tribological contact, these mainly sp3 hybridized films tend to form an amorphous carbon (a-C) tribomaterial mainly consisting of carbon atoms in sp2 configuration. Furthermore, the observed tribolayer grows faster than the a-C between diamond surfaces under similar conditions, which can be explained by easy breaking of weak bonds in a finite ta-C region triggered by plasticity in the adjacent a-C while the diamond/a-C transition occurs at an atomically sharp interface. The difference in the a-C tribofilm formation between ta-C and diamond is in agreement with near-edge x-ray absorption fine structure spectroscopy (NEXAFS) studies published recently.

Nanocoatings have the potential to improve the surface properties of various materials. They are of extreme importance for surfaces in sliding contact such as highly stressed automotive engine parts. Here, nanocoatings have to be optimized with respect to low friction properties and a high wear resistance to enhance the energetic and environmental efficiency. The present study employs atomic-scale simulations to investigate the basic principles of wear and friction between hydrogen-free tetrahedral-amorphous carbon (ta-C) films. The ta-C films are modeled state-of-the-art by an improved version of the well-known Brenner bond-order potential, which had been successfully applied to elucidate the wear processes during diamond polishing. We start our work by the preparation of the ta-C film structure, which is then characterized with respect to local and global film properties in comparison to experiments. After validating our ta-C nanocoatings with the help of experimental data, we perform computational sliding experiments to investigate mechanisms of friction and wear between interacting ta-C surfaces. During tribological contact, these diamond-like films (mainly sp3 hybridized) tend to form a soft-amorphous or graphite-like tribomaterial mainly consisting of carbon atoms in sp2 configuration. The sp3 to sp2 transition originates from atom-by-atom extraction events occurring at the sp3/sp2 interface. We discuss the underlying mechanisms by focusing on associated triboreactions and tribological properties such as shear forces.

Nanocoatings have the potential to improve the surface properties of various materials. They are of extreme importance for surfaces in sliding contact such as highly stressed automotive engine parts. Here, nanocoatings have to be optimized with respect to low friction properties and a high wear resistance to enhance the energetic and environmental efficiency. The present study employs atomic-scale simulations to investigate the basic principles of wear and friction between hydrogen-free tetrahedral-amorphous carbon (ta-C) films. The ta-C films are modeled state-of-the-art by an improved version of the well-known Brenner bond-order potential [1,2], which had been successfully applied to elucidate the wear processes during diamond polishing[3]. Our work starts with the preparation of ta-C film structures with different atomic densities, which are then characterized with respect to local and global film properties in comparison to experimental data. With these prepared nanocoatings, we perform computational sliding experiments to investigate mechanisms of friction and wear between interacting ta-C surfaces. Dry and lubricated sliding is considered. Especially for dry sliding and during tribological contact, these diamond-like films (mainly sp3 hybridized) tend to form a soft-amorphous or graphite-like tribomaterial mainly consisting of carbon atoms in sp2 configuration. We discuss underlying mechanisms of the dynamic triboreactions and investigate tribological properties such as shear forces at the sliding interface.

Optimierte, leichte, aber widerstandsfähige Werkstoffe eröffnen dem Fahrzeugbau die Möglichkeit, Energieeffizienz- und Klimaschutzziele mit einer Verbesserung der funktionalen Fähigkeiten des Fahrzeugs zu verbinden. Ziel des Projekts ist die Herstellung und Optimierung der dafür erforderlichen neuartigen, nanoskalig strukturierten, harten und selbstschmierenden Schichten für verschleißbelastete Motorenteile. Konventionelle dünne Funktionsschichten auf Kohlenstoffbasis werden in der Regel durch Niederdruck-Beschichtungsverfahren hergestellt. In den letzten Jahren sind neue Ansätze zur Weiterentwicklung dieser Materialklasse entstanden, die besonders auf nanoskalig strukturierte Systeme fokussieren, und die in Teilprojekt D1 ‘NanoCarbCoat’ für den automobilen Leichtbau erschlossen werden sollen. Dazu verbindet das betont interdisziplinär ausgerichtete Teilprojekt die Expertise von Partnern aus Natur- und Ingenieurwissenschaften zur Abscheidung und physikalischen Charakterisierung kohlenstoffbasierter Schichten, zur Modellierung der tribologischen Vorgänge an Schichten im Kontakt miteinander und mit einem Schmierstoff und zum Test der Beschichtung unter realistischen Bedingungen im Verbrennungsmotor.

Thermodynamic equilibration of complex systems like spin glasses or (degenerate) anisotropic spin crystals by numerical methods can be challenging due to the presence of multiple minima on the potential energy surface. This problem becomes pronounced especially at low temperature, where the system remains mainly in few states. We employ the anisotropic Heisenberg model in two dimensions to simulate and analyze the domain formation and the domain structure of multiferroic oxides. In particular, we discuss various techniques to improve the low-temperature equilibration behavior by means of a trigonal antiferromagnet with single-ion anisotropy. Furthermore, we present a localized sampling method for the Metropolis algorithm, which increases the acceptance ratio significantly.

Nanocoatings have the potential to improve the surface properties of various materials. They are of extreme importance for surfaces in sliding lubricated contact such as highly stressed automotive engine parts. Here, nanocoatings have to be optimized with respect to low friction properties and a high wear resistance to enhance the energetic and environmental efficiency. An additional variation of the tribological characteristics arises due to the presence of the fuel as the lubricant. The present study employs atomic-scale simulations in order to assist the manufacturing and optimization of functional nanocoatings. Our investigations focus on two basic functional film species - tetrahedral amorphous carbon (ta-C) and transition metal enriched carbon (TM:C) coatings. These films are modeled and studied with the help of bond-order potentials such as the reactive empirical bond-order (REBO) potential [1] for carbon-carbon interaction and the Shibuta potential [2] for TM-carbon interaction. Our simulations also incorporate an adaptive cutoff scheme, which is able to enhance the REBO potential characteristics [3]. Since the tribological properties of lubricated engine parts depend not only on the properties of the nanocoatings but also on the lubricant, the hydrocarbon dodecan is selected as a representative of the fuel in the automotive engines. Preliminary results on the ta-C film morphology and its tribological properties such as friction coefficients with and without lubrication are presented. [1] D. W. Brenner et al., J. Phys.: Condens. Matter 14 (2002) 783 [2] Y. Shibuta et al., Chem. Phys. Lett. 472 (2009) 200 [3] L. Pastewka et al., Phys. Rev. B 78 (2008) 161402

Nanocoatings have the potential to improve the surface characteristics of various materials. They are of extreme importance for surfaces in sliding contact such as highly stressed engine parts. Here, nanocoatings have to be optimized with respect to low friction properties and a high wear resistance to enhance the energetic and environmental efficiency. Our research activity focuses on self-lubricating and hard cabon-based nanocoatings (C:TM and taC films) investigated by atomic-scale simulations. We will present morphological as well as tribological properties of the studied systems. Support by the European Union and the Freistaat Sachsen via SAB project 13857/2379 within the ECEMP initiative is gratefully acknowledged.

The electronic transport of electrons and holes through stacks of functionalized quaterthiophene molecules as part of a novel organic ferroic field-effect transistor is investigated. The novel application of a ferroelectric instead of a dielectric substrate provides a bit-wise switching of the ferroelectric domains and enables the opportunity of employing the polarization field of these domains as a gate field in an organic semiconducting device. An already established phenomenological model called multilayer organic light-emitting diodes (MOLED) [1] is extended to transverse fields and numerical results are discussed. Model-specific parameters are determined with the help of experimental and theoretical methods. [1] Houili et al., Comp. Phys. Comm. 156, 103-122 (2003)

Organic semiconductors, which might be suitable for logical as well as optical applications, have attracted a lot of scientific effort in recent years. This includes the understanding of the underlying transport mechanisms, the improvement of the transport characteristics and possible fields of application. The electronic transport through stacks of functionalized quaterthiophene molecules as part of a novel organic device is presented and investigated by means of a phenomenological approach called multilayer organic light-emitting diode (MOLED) [1]. Numerical results including the tuning of carrier injection and optical activity will be discussed. [1] Houili et al., Comp. Phys. Comm. 156, 103-122 (2003)

Hexagonal manganites are oxides, in which structural, electronic, and magnetic degrees of freedom are coupled in a complex manner. Therefore, such materials have the potential for novel, nanoscale sensing and switching applications. Manganites are composed of dense-packed hexagonal manganese oxide layers with strong in-plane and weak interlayer coupling, thus the possible spin configurations may be studied with the help of a two-dimensional model Hamiltonian. Special focus is directed to the efficient sampling of the configuration space at low temperatures and concepts for improved importance sampling will be discussed.

Thermodynamic equilibration of complex systems like spin glasses or (degenerate) anisotropic spin crystals by numerical methods can be challenging due to the presence of multiple minima on the potential energy surface. This problem becomes pronounced especially at low temperature, where the system remains mainly in few states. We employ the anisotropic Heisenberg model in two dimensions to simulate and analyze the domain formation and the domain structure of multiferroic oxides. In particular, we discuss various techniques to improve the low-temperature equilibration behavior by means of a trigonal antiferromagnet with single-ion anisotropy. Furthermore, we present a localized sampling method for the Metropolis algorithm, which increases the acceptance ratio significantly.

The transport and fluctuation properties of organic molecules ordered parallel between two Au contact leads are investigated by the method of surface Green function. From first-principles simulation the relevant hopping parameters are extracted and used to calculate nonlinear transport coefficients with respect to an external bias voltage. A staggering of conductance is found in dependence on the number of molecules squeezed in-between the contacts. The thermal properties show an anomalous behavior whenever the voltage reaches the values of the molecular energy levels active for transport. The thermoelectric figure of merit shows a resonance allowing to reach values even larger than one.

Hexagonal manganites are oxides, in which structural, electronic, and magnetic degrees of freedom are coupled in a complex manner. Therefore, such materials have the potential for novel, nanoscale sensing and switching applications. Manganites are composed of dense-packed hexagonal manganese oxide layers with strong in-plane and weak interlayer coupling, thus the possible spin configurations may be studied with the help of a two-dimensional model Hamiltonian. For this purpose a two-dimensionally periodic trigonal spin system is qualitatively studied with the help of an extended multiparameter Heisenberg model. The temperature dependence of the magnetisation is investigated with the help of a Metropolis-Monte-Carlo algorithm as a function of the anisotropy term and of an external magnetic field. Thermodynamic quantities such as the total energy, the heat capacity and the magnetization are determined by statistical evaluation.

The preferred adsorption sites and the propensity for a self-organised growth of the molybdenum sulfide cluster Mo6S8 on the Au(111) surface are investigated by density-functional band-structure calculations with pseudopotentials and a plane wave basis set. The quasi-cubic cluster preferentially adsorbs via a face and remains structurally intact. It experiences a strong, mostly non-ionic attraction to the surface at several quasi-isoenergetic adsorption positions. A scan of the potential energy surface exhibits only small barriers between adjacent strong adsorption sites. Hence, the cluster may move in a potential well with degenerate local energy minima at room temperature. The analysis of the electronic structure reveals a negligible electron transfer and S-Au hybridised states, which indicate that the luster-surface interaction is dominated by S-Au bonds, with minor contributions from the Mo atom in the surface vicinity. All results indicate that Mo6S8 clusters on the Au(111) surface can undergo a template-mediated self-assembly to an ordered inorganic monolayer, which is still redox active and may be employed as surface-active agent in the integration of noble metal and ionic or biological components within nano-devices. Therefore, a classical potential model was developed on the basis of the DFT data, which allows to study larger cluster assemblies on the Au(111).