Hydrogenated Amorphous Carbon Research Articles

Superlubricity of Silicon-Based Ceramics Sliding against Hydrogenated Amorphous Carbon in Ultrahigh Vacuum: Mechanisms of Transfer Film Formation.

Tribological interfaces between silicon-based ceramics, such as Si3N4 or SiC, are characterized by high friction and wear in unlubricated conditions. A solution to this problem is to use them in combination with a hydrogenated amorphous carbon (a-C:H) countersurface from which a passivating carbon film is transferred onto the ceramic surface. However, the mechanisms underlying a stable film transfer process and the conditions that favor it remain elusive. Here, we present friction experiments in ultrahigh vacuum in which friction coefficients lower than 0.01 are achieved by sliding Si3N4 against a-C:H with 36 at. % hydrogen but not against a-C:H with 20 at. % hydrogen. Chemical surface analyses confirm that the superlubric interface forms via the transfer of a hydrocarbon nanofilm onto the Si3N4 surface. Quantum-mechanical simulations reveal that a stable passivating a-C:H film can only be transferred if, after initial cold welding of the tribological interface, the plastic shear deformation is localized within the a-C:H coating. This occurs if the yield shear stress for plastic flow of a-C:H is lower than that of the ceramic and of the shear strength of the a-C:H-ceramic interface, i.e., if the a-C:H hydrogen content ranges between ∼30 and ∼50 at. %. While the importance of a relatively high hydrogen content to achieve an efficient passivation of a-C:H surfaces in a vacuum is well-documented, this work reveals how the hydrogen content is also crucial for obtaining a stable a-C:H transfer film. These results can be extended to glass, SiC, and steel, supporting the generality of the proposed mechanism.

An ultraviolet spectral study of fullerene-rich planetary nebulae

ABSTRACT Several planetary nebulae (PNe) have been found to contain both polycyclic aromatic hydrocarbon (PAH-like) species and fullerenes (C60) distinguished by their mid-infrared emission. Previous laboratory and astronomical studies suggest that the formation of both species could be related to the decomposition, by photochemical processing, of hydrogenated amorphous carbon (HAC) grains. Then, HACs and, seemingly, big-fullerene related species (e.g. carbon onions) have been suggested as potential carriers of the ultraviolet (UV) bump at 2175 Å and the far-UV rise common to interstellar extinction curves. Our goal is to investigate the UV bump with the possible presence of an HAC extinction component in the International Ultraviolet Explorer (IUE) spectra of C-rich PNe; both with detected and non-detected fullerenes. The considered sample includes three C60-PNe (Tc 1, IC 418, and IC 2501) and the non-C60-PN Hen 2-5. Independently of the presence of C60 in their circumstellar envelopes, we found that the UV bump in all sample PNe is well explained by interstellar extinction, suggesting that species different from those of the foreground interstellar medium, e.g. large fullerene-related species like carbon onions, are not the carrier. Interestingly, we found that PNe Tc 1 and Hen 2-5 show an absorption in the FUV rise. Their IUE continuum spectra may be very well reproduced by including the extinction curve of HAC-like very small grains. The possible presence of both species, HAC-like grains and fullerenes (C60), in Tc 1 could support the HAC photochemical processing scenario for the formation of fullerenes in the complex circumstellar envelopes of PNe.

(Invited) Plasma-Enhanced Deposition Mechanism of Hydrogenated Amorphous Carbon Analyzed By Combining Reactive Species Measurement and Machine Learning

Hydrogenated amorphous carbon (a-C:H) thin films synthesized by plasma-enhanced chemical vapor deposition (PECVD)are widely used in various fields of science and technology. For example, they are essential as etching hard masks for the production of 3D-NAND flash memory, because of their high selectivity to Si-based materials and chemical stability. With the demand for higher aspect ratio etching, there is a strong need to improve etching resistance and reduce residual stress of a-C:H masks. They are also widely used in the field of tribology as an important coating for improving friction resistance and slidability. Analyzing the plasma process in which synergistic effects among reactive species and higher-order reactions contribute is generally difficult. Therefore, similar to other process technologies, machine learning-based condition optimization approaches have been actively investigated in recent years. However, machine learning models are generally black boxes, and it is difficult to understand their mechanism of action. Also, the versatility of the learning model is low between different devices. On the other hand, reactive species measurement is effective for understanding the reaction mechanism of the plasma process, but the synergy of multiple reactive species is still extremely complicated. In this study, the contribution of radical species to the etching resistance of a-C:H thin films were quantitatively analyzed using machine learning.The deposition of a-C:H by PECVD using H2/C3H6/CH4 plasma and etching with O2 plasma were alternately repeated at 120 conditions. The radicals generated during the film deposition were measured by a quadrupole mass spectrometer (QMS), and film thickness change during the etching was measured by spectroscopic ellipsometry (SE). A random forest model was learned to predict the etching rate from the mass spectra, and the contribution of each radical to the etching rate was quantitatively evaluated by SHapley additive exPlanation (SHAP).The distribution of SHAP values for the 10 most influential radicals is shown in Figure 1. The positive and negative SHAP values represent the correlation between QMS intensity and SHAP value. The radicals with high hydrogen ratios such as CH~CH4, C2H5, C4H9, C5H9, and C5H11 contributed to the increase of etching rate, while the radicals with low hydrogen ratios such as C3H3 and C5H5 contributed to the decrease of etching rate. The deposition of radicals with low hydrogen ratios and multiple bonds, and the effect of hydrogen extraction in the film are considered to have increased the density of a-C:H and reduced the etching rate. It was found that the control of C/H ratio of radicals as film precursors is important to improve etching resistance. Comparisons with different data set range or other contribution degrees such as LIME enable us to understand the mechanism of action of local active species. By using the contribution analysis methods, it is possible to quantitatively analyze the synergistic effect of reactive species in the process plasma. Figure 1

Experimental Phase Function and Degree of Linear Polarization of Light Scattered by Hydrogenated Amorphous Carbon Circumstellar Dust Analogs

Astronomical observations of the polarized intensity of scattered visible light have revealed the presence of dust envelopes around different types of evolved stars. These observations have helped determine the diameter and width of dust shells around stars with unprecedented accuracy. Simple geometric particle models are used in order to retrieve dust properties from these observations. In this work, we have synthesized and characterized a particulate sample of hydrogenated amorphous carbon (HAC), which is considered to be a realistic carbonaceous interstellar dust analog based on infrared absorption spectroscopy, and we have measured its phase function and degree of linear polarization curves at 514 nm using the CODULAB apparatus at IAA-CSIC. The experimental light-scattering data has been examined in order to explore possible improvements in the interpretation of astronomical observations of circumstellar dust from the point of view of the retrieval of dust properties, including size and porosity. Our results suggest that circumstellar dust observations of linearly polarized scattered light, which are commonly attributed to a population of spherical grains with a radius of ∼0.1 μm, are consistent with larger porous aggregates composed of nanometer-sized grains. In addition, an internal 50wt% mixture of HAC and ultrafine forsterite powder has been generated to study the effect of the mixing of these two components on the light-scattering behavior of dust in cometary environments and protoplanetary disks. In this case, the HAC component, which is not very absorbent, has a very small effect, and the mixture scatters light similarly to the forsterite sample.

Internal and External Alignment of Carbonaceous Grains within the Radiative Torque Paradigm

We study the internal and external alignment of carbonaceous grains in the interstellar medium (ISM) within the Radiative Torque (RAT) paradigm. For internal alignment (IA), we find that hydrogenated amorphous carbon (HAC) grains having nuclear paramagnetism due to hydrogen protons have efficient nuclear relaxation, whereas both HAC and graphite grains can have efficient inelastic relaxation at both low-J and high-J attractors. For external alignment, HAC and pure graphite grains can align with the radiation direction (k-RAT) at low-J attractors but cannot have stable alignment at high-J attractors due to the suppression of radiative precession. However, HAC grains can align with the magnetic field (B-RAT) at high-J attractors due to fast Larmor precession compared to gas collisions. For HAC grains drifting through the ISM, they can align along the induced electric field (E-RAT) at low-J attractors due to the fast electric precession and only small HAC grains can align at high-J attractors. Nuclear paramagnetic relaxation is inefficient for HAC due to the suppression of nuclear susceptibility. We then study the alignment of carbon dust in the envelope of a C-rich Asymptotic Giant Branch star (IRC+10216) and find that grains aligned at low-J attractors may occur via k-RAT with the wrong IA in the inner region but via B-RAT in the outer region. However, grains aligned at high-J attractors have the right IA alignment via k-RAT due to efficient inelastic relaxation. The polarization pattern observed toward IRC+10216 by SOFIA/HAWC+ can be reproduced when only grains at low-J attractors are present due to the removal of grains at high-J attractors by the RAT disruption.

Hydrophilic Surface Modification of Amorphous Hydrogenated Carbon Nanocomposite Films via Atmospheric Oxygen Plasma Treatment

Herein we investigated hydrophilic surface modification of SiOx containing amorphous hydrogenated carbon nanocomposite films (DLC:SiOx) via the use of atmospheric oxygen plasma treatment. The modified films exhibited effective hydrophilic properties with complete surface wetting. More detailed water droplet contact angle (CA) measurements revealed that oxygen plasma treated DLC:SiOx films maintained good wetting properties with CA of up to 28 ± 1° after 20 days of aging in ambient air at room temperature. This treatment process also increased surface root mean square roughness from 0.27 nm to 1.26 nm. Analysis of the surface chemical states suggested that the hydrophilic behavior of DLC:SiOx treated with oxygen plasma is attributed to surface enrichment with C-O-C, SiO2, and Si-Si chemical bonds as well as significant removal of hydrophobic Si-CHx functional groups. The latter functional groups are prone to restoration and are mainly responsible for the increase in CA with aging. Possible applications of the modified DLC:SiOx nanocomposite films could include biocompatible coatings for biomedical applications, antifogging coatings for optical components, and protective coatings to prevent against corrosion and wear.

Impact of HAC evolution on the formation of small hydrocarbons in the Orion Bar and the Horsehead PDRs

ABSTRACT We study evolution of hydrogenated amorphous carbon (HAC) grains under harsh UV radiation in photodissociation regions (PDRs) near young massive stars. Our aim is to evaluate the impact of the HAC grains on formation of observed small hydrocarbons: C2H, C2H2, C3H+, C3H, C3H2, C4H, in PDRs. We developed a microscopic model of the HAC grains based on available experimental results. The model includes processes of photo and thermo-desorption, accretion of hydrogen and carbon atoms and subsequent formation of carbonaceous mantle on dust surface. H2, CH4, C2H2, C2H4, C2H6, C3H4, C3H6, C3H8 are considered as the main fragments of the HAC photodestruction. We simulated evolution of the HAC grains under the physical conditions of two PDRs, the Orion Bar and the Horsehead nebula. We estimated the production rates of the HAC’ fragments in gas phase chemical reactions and compared them with the production rates of fragments due to the HAC destruction. The latter rates may dominate under some conditions, namely, at AV = 0.1 in both PDRs. We coupled our model with the gas-grain chemical model MONACO and calculated abundances of observed small hydrocarbons. We conclude that the contribution of the HAC destruction fragments to chemistry is not enough to match the observed abundances, although it increases the abundances by several orders of magnitude in the Orion Bar at AV = 0.1. Additionally, we found that the process of carbonaceous mantle formation on dust surface can be an inhibitor for the formation of observed small hydrocarbons in PDRs.

Interstellar hydrocarbons: degradation chemistry in diffuse clouds

ABSTRACT Observations of diffuse clouds showed that they contain a number of simple hydrocarbons [e.g. CH, C2H, (l- and c-)C3H2, and C4H] in abundances that may be difficult to understand on the basis of conventional gas-phase chemical models. Recent experimental results revealed that the photodecomposition mechanisms of hydrogenated amorphous carbon (HAC) and solid hexane release a range of hydrocarbons into the gas, containing up to six C-atoms for the case of HAC decomposition. These findings motivated us to introduce a new potential input to interstellar chemistry: the ‘top-down’ or degradation scheme, as opposed to the conventional ‘build-up’ or synthesis scheme. In this work, we demonstrate the feasibility of the top-down approach in diffuse clouds using gas–grain chemical models. In order to examine this scheme, we derived an expression to account for the formation of hydrocarbons when HACs are photodecomposed after their injection from grain mantles. Then, we calculated the actual formation rate of these species by knowing their injected fraction (from experimental work) and the average rate of mantle carbon injection into the interstellar medium (from observations). Our preliminary results are promising and reveal that the degradation scheme can be considered as an efficient mechanism for the formation of some simple hydrocarbons in diffuse clouds. However, an actual proof of the efficiency of this process and its rate constants would require comprehensive experimental determination.

Probing the Tribochemical Impact on Wear Rate Dynamics of Hydrogenated Amorphous Carbon via Raman-Based Profilometry.

Solid-liquid lubricating systems have received significant attention as a promising way for energy saving and emission control. For deeply understanding their tribological behaviors, it is necessary to study interaction mechanisms between solid and liquid lubricants from the tribochemical viewpoint, as tribofilms formed by tribochemical products on contact surfaces critically affect the whole tribological process. Continually or periodically monitoring tribofilm formation and evolution can contribute significantly to clarifying its dominating role in tribological behavior under boundary lubrication. However, detecting tribofilms in situ remains a big challenge for conventional surface analytical approaches, mainly due to their limitations in accessing tribofilms or low signal intensities of thin tribofilms. In this study, highly sensitive Raman-based profilometry with in situ potential has been developed for detecting molybdenum dialkyldithiocarbamate (MoDTC)-derived tribofilms and exploring their effect on a-C:H wear over time. The optical properties of tribochemical products formed on the coating surface in different wear stages could result in extra attenuation of Raman signal intensities in the form of measurement deviations in wear depth. By monitoring the deviations, key information of tribofilm compositions was obtained and a two-stage wear progression mechanism was proposed for the first time to clarify the detrimental effect of MoDTC-derived tribofilms on a-C:H wear by combining detailed structure and composition analyses.

The Growth Behavior of Amorphous Hydrogenated Carbon a-C:H Layers on Industrial Polycarbonates—A Weak Interlayer and a Distinct Dehydrogenation Zone

Polycarbonate (PC) is a material that is used in many areas: automotive, aerospace engineering and data storage industries. Its hardness is of particular importance, but some applications are affected by its low wettability or scratch susceptibility. This can be changed either by blending with other polymers, or by surface modifications, such as the application of an amorphous hydrogenated carbon layer (a-C:H). In this study, individual a-C:H layers of different thicknesses (10–2000 nm) were deposited on PC by RF PECVD. Both the layer morphology with AFM and SEM and the bonding states of the carbon on the surface with synchrotron-assisted XPS and NEXAFS were studied. The aim was to investigate the coatability of PC and the stability of the a-C:H. Special attention was paid to the interlayer region from 0 to 100 nm, since this is responsible for the layer to base material bonding, and to the zone of dehydrogenation (from about 1000 nm), since this changes the surface composition considerably. For PC, the interlayer was relatively small with a thickness of only 20 nm. Additionally, a correlation was found between the evolving grain structure and the development of the C‒H peak according to NEXAFS C K-edge measurements.

Plasma Supported Deposition of Amorphous Hydrogenated Carbon (a-C:H) on Polyamide 6: Determining Interlayer Completion and Dehydrogenation Effects during Layer Growth

Polyamide 6 (PA6) is a commonly used material in many different sectors of modern industry. Herein, PA6 samples were coated with amorphous carbon layers (a-C:H) with increasing thickness up to 2 µm using radio frequency plasma enhanced chemical vapor deposition for surface adjustment. The morphology of the carbon coatings was inspected by ex situ atomic force microscopy and scanning electron microscopy. Surface wettability was checked by contact angle measurements. The chemical composition was analyzed using the surface sensitive synchrotron X-ray-based techniques near-edge X-ray absorption fine structure and X-ray photoelectron spectroscopy, supported by diffuse reflectance infrared Fourier transform spectroscopy. Particular attention was paid to the coating interval from 0 to 100 nm, to specify the interlayer thickness between the PA6 polymer and a-C:H coating, and the region between 1000 and 2000 nm, where dehydrogenation of the a-C:H layer occurs. The interlayer is decisive for the linkage of the deposited carbon layer on the polymer: the more pronounced it is, the better the adhesion. The thickness of the interlayer could be narrowed down to 40 nm in all used methods, and the dehydrogenation process takes place at a layer thickness of 1500 nm.

Electrical Conduction Properties of Hydrogenated Amorphous Carbon Films with Different Structures.

Hydrogenated amorphous carbon (a-C:H) films have optical and electrical properties that vary widely depending on deposition conditions; however, the electrical conduction mechanism, which is dependent on the film structure, has not yet been fully revealed. To understand the relationship between the film structure and electrical conduction mechanism, three types of a-C:H films were prepared and their film structures and electrical properties were evaluated. The sp2/(sp2 + sp3) ratios were measured by a near-edge X-ray absorption fine structure technique. From the conductivity–temperature relationship, variable-range hopping (VRH) conduction was shown to be the dominant conduction mechanism at low temperatures, and the electrical conduction mechanism changed at a transition temperature from VRH conduction to thermally activated band conduction. On the basis of structural analyses, a model of the microstructure of a-C:H that consists of sp2 and sp3-bonded carbon clusters, hydrogen atoms and dangling bonds was built. Furthermore, it is explained how several electrical conduction parameters are affected by the carrier transportation path among the clusters.

Thermal Conductivity Enhancement in Ion-Irradiated Hydrogenated Amorphous Carbon Films.

Amorphous solids are traditionally assumed to set the lower bound to the vibrational thermal conductivity of a material due to the high degree of structural disorder. Here, were demonstrate the ability to increase the thermal conductivity of amorphous solids through ion irradiation, in turn, altering the bonding network configuration. We report on the thermal conductivity of hydrogenated amorphous carbon implanted with C+ ions spanning fluences of 3 × 1014-8.6 × 1014 cm-2 and energies of 10-20 keV. Time-domain thermoreflectance measurements of the films' thermal conductivities reveal significant enhancement, up to a factor of 3, depending upon the preirradiation composition. Films with higher initial hydrogen content provide the greatest increase, which is complemented by an increased stiffening and densification from the irradiation process. This enhancement in vibrational transport is unique when contrasted to crystalline materials, for which ion implantation is known to produce structural degradation and significantly reduced thermal conductivities.

How Hydrogen and Oxygen Vapor Affect the Tribochemistry of Silicon- and Oxygen-Containing Hydrogenated Amorphous Carbon under Low-Friction Conditions: A Study Combining X-ray Absorption Spectromicroscopy and Data Science Methods.

The incorporation of silicon and oxygen into hydrogenated amorphous carbon (a-C:H) is an effective approach to decrease the dependence of the tribological properties of a-C:H on the environment. Here, we evaluate the effect of hydrogen and oxygen partial pressures in vacuum on the tribological response of steel pins sliding against films consisting of silicon- and oxygen-containing a-C:H (a-C:H:Si:O). Experiments are conducted in the low-friction/low-wear regime, where sufficient gas pressure prevents steel from adhering to the a-C:H:Si:O, with the velocity accommodation mode being interfacial sliding between the tribotrack formed in the a-C:H:Si:O film and the carbonaceous tribofilm that is formed on the countersurface. The experiments indicated a decrease (increase) in friction and wear with the hydrogen (oxygen) pressure (hydrogen pressures between 50 and 2000 mbar; oxygen pressures between 10 and 1000 mbar). Characterization by X-ray photoelectron and absorption spectroscopies indicated the occurrence of tribologically induced rehybridization of carbon-carbon bonds from sp3 to sp2. This mechanically induced structural transformation coincided with the dissociative surface reaction between hydrogen (oxygen) gas molecules and sp2 carbon-carbon bonds that are highly strained, which results in the formation of carbon-hydrogen groups (carbonyl or ether groups together with silicon atoms having higher oxidation states). On the basis of variations of the fraction of these surface functional groups with gas pressure, a phenomenological model is proposed for the gas pressure dependence of friction for steel when sliding on a-C:H:Si:O films: while the decrease in friction with hydrogen pressure is induced by an increase in the percentage of carbon-hydrogen groups, the increase in friction with oxygen pressure is caused by a progressive increase in the relative fraction of silicon atoms having higher oxidation states and an increase in surface oxygen concentration.

Effect of Water Adsorption on the Frictional Properties of Hydrogenated Amorphous Carbon Films in Various Relative Humidities.

The tribological properties of hydrogenated amorphous carbon (a-C:H) films in ambient air were investigated from the microstructural point of view. a-C:H films with various microstructures (polymer-like, diamond-like, and graphite-like structures) were prepared, and the thickness of water adsorption layers on the films was measured. The adsorption behavior of water molecules on a-C:H films could be expressed with the Brunauer-Emmett-Teller (BET) isotherm, while the thicknesses of icelike and liquidlike water layers adsorbed on the films could be determined using the BET parameters C and nma. The polymer-like films exhibited the thickest icelike and liquidlike water adsorption layers, which decreased as the film structure changed to a diamond-like or a graphite-like structure. A strong relationship was observed between the thickness of water adsorption layers and the surface oxidation of the a-C:H films. The friction coefficient of the films in ambient air can be well explained by the surface oxidation and the thickness of water adsorption layers. Polymer-like films showed high friction coefficients due to the formation of a thick water layer on the films originated from the high surface oxidation of the film surface, whereas the graphite-like film exhibited a low friction coefficient due to low oxidation and a thin water adsorption layer. Furthermore, friction tests between the a-C:H films with different microstructures under ambient air were performed to determine the lowest friction pair in various relative humidities (RHs).

Hydrogenated Amorphous Carbon Films from Palmyra Sugar

A simple, highly reproducible, and environmentally friendly method is a considered approach in generating renewable energy materials. Here, hydrogenated amorphous carbon (a-C) films have been successfully prepared from palmyra liquid sugar, employing spin-coating and spraying methods. Compared with the former method, the latter shows a significance in producing a better homogeneity in particle size and film thickness. The obtained films have a thickness of approximately 1000 to 100 nm and contain an sp2 hexagonal structure (~70%) and sp3 tetrahedral configuration (~30%) of carbons. The introduction of boron (B) and nitrogen (N) as dopants has created the local structural modification of bonding, inducing a slight change of electrical conductivity, electronic energy bandgap, and optical transparency near-infrared region. The obtained a-C film features a “green” semiconducting material.

Hydrogenated Amorphous Carbon Film Deposited by Plasma on Recycled Polypropylene as a Functional Barrier to Hazardous Migrants

Hydrogenated Amorphous Carbon Film Deposited by Plasma on Recycled Polypropylene as a Functional Barrier to Hazardous Migrants

Effect of Cellulose Nanocrystals on the Coating of Chitosan Nanocomposite Film Using Plasma-Mediated Deposition of Amorphous Hydrogenated Carbon (a–C:H) Layers

The substitution of petroleum-based polymers with naturally derived biopolymers may be a good alternative for the conservation of natural fossil resources and the alleviation of pollution and waste disposal problems. However, in order to be used in a wide range of applications, some biopolymers’ properties should be enhanced. In this study, biocompatible, non-toxic, and biodegradable chitosan (CS) film and CS reinforced with 10 wt% of cellulose nanocrystals (CN–CS) were coated with amorphous hydrogenated carbon layers (a–C:H) of different thickness. To investigate the effect of the nano-reinforcement on the a–C:H layer applied, mild radio frequency plasma enhanced chemical vapor deposition (RF-PECVD) was used to coat the CS and its CN–CS bio-nanocomposite film. Both the surface characteristics and the chemical composition were analyzed. The surface morphology and wettability were examined by ex-situ atomic force microscopy (AFM) and contact angle measurements (CA), respectively. Hereby, the relationship between sp2/sp3 ratios on a macroscopic scale was also evaluated. For the investigation of the chemical composition, the surface sensitive synchrotron X-ray radiation techniques near edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS) as well as diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) were used.

Nanoscale Run-In of Silicon Oxide-Doped Hydrogenated Amorphous Carbon: Dependence of Interfacial Shear Strength on Sliding Length and Humidity

We conducted atomic force microscopy (AFM) experiments by sliding hard tetrahedral amorphous carbon (ta-C)-coated and diamond AFM probes against silicon oxide-doped hydrogenated amorphous carbon (a-C:H:Si:O) films. We reproducibly observe a substantial reduction in friction with repeated sliding. This behavior qualitatively resembles the run-in effects generally seen in macroscale frictional sliding on diamond-like carbons (DLCs), including this a-C:H:Si:O film in particular. As the applied normal load is increased with repetitive sliding, the friction reduces in tandem. The lateral stiffness of the nanoscale contact is measured as a function of applied normal load, thus the real contact area and the interfacial shear strength are inferred throughout the sliding experiments. These measurements show that the friction reduction is caused by a reduction in the interfacial shear strength of the contact. We propose that this arises from sliding-induced structural modification of the a-C:H:Si:O film. The calculated shear strengths are more than an order of magnitude higher than estimates from macroscale friction experiments. Additionally, humidity-controlled experiments show no significant humidity dependence of the friction despite a very strong dependence at macroscale. Reasons for these contradictions with macroscale experiments are discussed.

Refinement of Sustainable Polybutylene Adipate Terephthalate (PBAT) with Amorphous Hydrogenated Carbon Films (a-C:H) Revealing Film Instabilities Influenced by a Thickness-Dependent Change of sp2/sp3 Ratio

The increasing use of polymers is related to a growing disposal problem. Switching to biodegradable polymers such as polybutylene adipate terephthalate (PBAT) is a feasible possibility, but after industrial production of commercially available material PBAT is not suitable for every application. Therefore, surface refinements with amorphous hydrogenated carbon films (a-C:H) produced by plasma-assisted chemical vapor deposition (PE-CVD) changing the top layer characteristics are used. Here, 50 µm-thick PBAT films are coated with a-C:H layers up to 500 nm in 50 nm steps. The top surface sp2/sp3 bonding ratios are analyzed by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) both synchrotron-based. In addition, measurements using diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) were performed for detailed chemical composition. Surface topography was analyzed by scanning electron microscopy (SEM) and the surface wettability by contact angle measurements. With increasing a-C:H layer thickness not only does the topography change but also the sp2 to sp3 ratio, which in combination indicates internal stress-induced phenomena. The results obtained provide a more detailed understanding of the mostly inorganic a-C:H coatings on the biodegradable organic polymer PBAT via in situ growth and stepwise height-dependent analysis.