Transmission electron microscopy study of diamond nucleation and growth on smooth silicon surfaces coated with a thin amorphous carbon film

Amorphous carbon (a-C) films with high contents of tetrahedral carbon bonding (sp³) were synthesized on smooth Si(100) surfaces by cathodic arc deposition. Before diamond growth, the a-C films were pretreated with a low-temperature methane-rich hydrogen plasma in a microwave plasma-enhanced chemical vapor deposition system. The evolution of the morphology and microstructure of the a-C films during the pretreatment and subsequent diamond nucleation and initial growth stages was investigated by high-resolution transmission electron microscopy (TEM). Carbon-rich clusters with a density of ∼10¹⁰ cm⁻² were found on pretreated a-C film surfaces. The clusters comprised an a-C phase rich in sp³ carbon bonds with a high density of randomly oriented nanocrystallites and exhibited a high etching resistance to hydrogen plasma. Selected area diffraction patterns and associated dark-field TEM images of the residual clusters revealed diamond fingerprints in the nanocrystallites, which played the role of diamond nucleation sites. The presence of non-diamond fingerprints indicated the formation of Si–C-rich species at C/Si interfaces. The predominantly spherulitic growth of the clusters without apparent changes in density yielded numerous high surface free energy diamond nucleation sites. The rapid evolution of crystallographic facets in the clusters observed under diamond growth conditions suggested that the enhancement of diamond nucleation and growth resulted from the existing nanocrystallites and the crystallization of the a-C phase caused by the stabilization of sp³ carbon bonds by atomic hydrogen. The significant increase of the diamond nucleation density and growth is interpreted in terms of a simple three-step process which is in accord with the experimental observations.     

Thermostability,oxidation, and high-temperature tribological properties of nano-multilayered AlCrSiN/VN coatings

In this study, monolithic AlCrSiN, VN, and nano-multilayered AlCrSiN/VN coatings were deposited using a hybrid deposition system combining arc ion plating and pulsed direct current magnetron sputtering. The microstructure, thermostability, mechanical, oxidation and tribological properties of the coatings were comparably investigated. The multilayered AlCrSiN/VN coating exhibited a face-centered cubic (fcc) structure with (200) preferred orientation and showed the highest hardness (30.7 ± 0.5 GPa) among these three coatings due to the multilayer interface enhancement mechanism and higher compressive stress. The AlCrSiN sublayers effectively prevented the V element from rapid outward diffusion to the surface of AlCrSiN/VN coating at elevated temperatures, which improved the oxidation resistance of the coating. Decomposition of V (Cr)–N bonds occurred at annealing temperatures from 800 °C to 1000 °C and V₂N phase appeared at 1100 °C. The AlCrSiN/VN coating showed excellent tribological performance at high temperatures by combining the merits of VN layers for low friction coefficient and AlCrSiN layers for superior oxidation resistance. Compared to VN and AlCrSiN coatings, AlCrSiN/VN coating showed the lowest wear rate of 2.6×10^-15 m³/N·m at 600 °C and lowest friction coefficient of 0.26 at 800 °C with a relativity low wear rate of 39.4×10^-15 m³/N·m.     

Raman spectroscopy measurements of DC-magnetron sputtered carbon nitride (a-C:N) thin films for magnetic hard disk coatings

As a protective coating for hard disks in magnetic storage applications, amorphous carbon nitride (a-C:N) thin films have proved superior to DLC (diamond-like carbon) a-C:H films in terms of durability, wear-resistance and adhesion properties. In this study, we present Raman spectroscopy investigations of a-C:N films which were produced by DC-magnetron sputtering systems. The layers were deposited with a variable nitrogen content, thickness and substrate temperature. Raman measurements were carried out with two different excitation lasers at wavelengths of 488 and 532 nm. The spectra show that besides the typical carbon D- and G-bands, two other characteristic bands are present at approximately 690 and 1090 cm⁻¹. The meaning and identification of these bands is not clear in the literature. In order to obtain more information, the films were also characterized by various analytical techniques, e.g. time-of-flight secondary ion mass spectrometry (ToF-SIMS), Auger electron spectroscopy (AES), ellipsometry, and n+k optical measurements. The Raman G-band position shows a systematic shift with the varying nitrogen content of the films. A comparison of layer thickness and the total area of D-, G- and 1090 cm⁻¹ bands also shows a significant correlation. The results offer Raman spectroscopy as a possible monitoring tool for carbon nitride coatings in the production of magnetic hard disk drives.     

Characterization of thick and soft DLC coatings deposited on plasma nitrided austenitic stainless steel

Thick and soft a-C:H:Si coatings containing more than 45% hydrogen (thickness: 25–27 μm, hardness: 6 GPa, Young's Modulus 38 GPa and low ratio of sp³ bonds) were deposited by PACVD with a DC pulsed discharge on nitrided (duplex sample) and non-nitrided austenitic stainless steel (coated sample). After deposition, the chemical, microstructural and tribological properties were studied. Finally, the adhesion and the atmospheric corrosion resistance of a-C:H:Si coatings were also investigated.In pin-on-disk tests, the friction coefficient using an alumina pin of 6 mm in diameter as counterpart, under 0.59 GPa Hertzian pressure was 0.05 for the coated samples and 0.076 for the duplex samples. These values were more than one order of magnitude smaller than the friction coefficient of the nitrided sample without coating, which was around 0.65. In the coated samples, the wear loss could not be measured. In ball-on-disk tests under dry sliding conditions, the coatings were tested under different Hertzian pressures (1.29, 1.44 and 1.57 GPa) using a steel ball with a diameter of 1.5 mm as counterpart. Using a normal load of 9 N, the a-C:H:Si coating of the coated samples was broken and detached thus leading to a coefficient of friction of around 0.429. However, in contrast to that, the friction coefficient of the duplex samples remained stable and reached as maximum a value of 0.208.In abrasive tests, mass loss was undetectable in both duplex and coated samples. Furthermore it could be seen that the a-C:H:Si film showed only some smaller grooves and no severe damage or deformation. On the contrary, severe damage was observed in the only nitrided sample. With respect to adhesion, the critical load to break the coating was higher in the duplex sample (27 N) than in the only coated sample (16.3 N). By chemical analysis using the salt spray fog test, the duplex sample remained clean, but the coated sample failed and presented film delamination as well as general corrosion.     

Mechanical stability,corrosion performance and bioresponse of amorphous diamond-like carbon for medical stents and guidewires

Diamond-ike carbon (DLC) coatings have been investigated with respect to biocompatibility, mechanical stability under biofluid exposure, corrosion resistance and the impact of the fabrication or operation of catheter guidewires and stents upon coating integrity. High mechanical tensile and compressive forces, during guidewire winding or stent expansion, pose severe limitations on the use of DLC-coated stainless steel. Doping with silicon and the use of an a-Si:H interlayer can help minimise the risk of adhesion failure or film cracking. The incorporation of Si increased the hydrogen content and the estimated sp³ fraction but reduced the film hardness. Silicon-doped a-C:H coatings exhibit significantly improved corrosion barrier properties, with over two orders of magnitude increase in the charge transfer resistance. Immersion in biofluid, however, reduced the interfacial adhesion strength by up to 75%. Human microvascular endothelial cell attachment was enhanced while platelet attachment was reduced on Si-doped compared to undoped a-C:H. The macrophage response to non-hydrogenated tetragonal (t-aC) carbon show that these coatings stimulate less inflammatory activity than uncoated materials and produce comparable responses to already existing polyurethane coatings.     

Comparative study on the tribological properties of poly(arylene ether nitrile)/polytetrafluoroethylene composites: The influence of filler size and testing conditions

In this work, the influence of polytetrafluoroethylene (PTFE) filler size and testing conditions (i.e., air, water, and lubricating oil) on the tribological properties of poly(arylene ether nitrile) (PEN) was systematically investigated. The results showed that the addition of PTFE was beneficial to improve the tribological properties of PEN-based composites which was related to the easier formation of transfer film on the surface of friction pair. Samples which were tested in water demonstrated a relatively higher friction coefficient (μ) and wear loss when compared with those tested in dry air and lubricating oil scenarios, which was attributed to the fact that friction induced heat and wear debris could be timely removed by water. In addition, the infiltration of water further reduced the interaction between PTFE filler and PEN, which aggravated the wear loss of sample blocks. When tested in lubricating oil, pure PEN showed the lowest wear loss when compared with that of PEN/PTFE composites. At a given content (20 wt%) of PTFE fillers, PEN/PTFE_1.5μm exhibited the lowest μ in lubricating oil whereas PEN/PTFE_5μm demonstrated the lowest specific wear loss in air condition (1.18 × 10⁻⁶ mm³/N·m). This work provided some useful information for the design and application of PTFE-containing polymer composites that can be targeted in different lubrication scenarios in industrial fields.     

Tribological study of hydrogenated amorphous carbon films with tailored microstructure and composition produced by bias-enhanced plasma chemical vapour deposition

We investigated the mechanical and tribological properties of hydrogenated amorphous carbon (a-C:H) films on silicon substrates by nanoindentation, ball-on-disc tribotesting and scratch testing. The a-C:H films were deposited from an argon/methane gas mixture by bias-enhanced electron cyclotron resonance chemical vapour deposition (ECR-CVD). We found that substrate biasing directly influences the hardness, friction and wear resistance of the a-C:H films. An abrupt change in these properties is observed at a substrate bias of about ?100 V, which is attributed to the bias-controlled transition from polymer- to fullerenelike carbon coatings. Friction coefficients in the range of 0.28–0.39 and wear rates of about 7 × 10^?5 mm³/Nm are derived for the polymeric films when tested against WC–Co balls at atmospheric test conditions. On the other hand, the fullerenelike hydrogenated carbon films produced at ion energies > 100 eV display a nanohardness of about 17 GPa, a strong reduction in the friction coefficient (～ 0.10) and a severe increase in the wear resistance (～ 1 × 10^?7 mm³/Nm). For these films, relative humidity has a detrimental effect on friction but no correlation with the wear rate was found.     

What makes a dangling bond a binding site for thermal CH3 radicals? — A combined molecular dynamics and potential energy analysis study on amorphous hydrocarbon films

Identification of dangling bonds on amorphous films is not as straight forward as in the case of crystalline materials. The task is further complicated in the case of amorphous hydrocarbon (a-C:H) films by the existence of a wide variety of atomic arrangements. We present a technique based on potential energy analysis of a-C:H films to identify dangling bonds and physisorption sites. However, molecular dynamics simulations of the sticking of thermal CH₃ on a-C:H surfaces show that not all dangling bonds are binding sites for a CH₃ radical. Furthermore, the total sticking coefficient of the surface is not solely linked to the number of dangling bonds and can even decrease for the same number of dangling bonds because the carbon atoms that possess a binding site, active carbon atoms, show drastically different reactivity towards CH₃. The reactivity of active carbon atoms is decided by (a) their type, which is decided by the bonding partners, (b) their distance from the local surface and (c) the local environment. The reactivity of the active carbon atoms can be largely increased by energetic ion bombardment due to hydrogen depletion and local rearrangement.     

Hardness of nanocomposite a-C:Si films deposited by magnetron sputtering

Hydrogen-free a-C:Si films with Si concentration from 3 to 70 at.% were prepared by magnetron co-sputtering of pure graphite and silicon at room temperature. Mechanical properties (hardness, intrinsic stress), film composition (EPMA and XPS) and film structure (electron diffraction, Raman spectra) were investigated in dependence on Si concentration, substrate bias and deposition temperature. The film hardness was maximal for ∼ 45 at.% of Si and deposition temperatures 600 and 800 °C. Reflection electron diffraction indicated an amorphous structure of all the films. Raman spectra showed that the films in the range of 35–70 at.% of Si always contain three bands corresponding to the Si, SiC and C clusters. Photoelectron spectra showed dependency of Si–C bond formation on preparation conditions. In the films close to the stoichiometric SiC composition, the surface and sub-surface carbon atoms exhibited dominantly sp³ bonds. Thus, the maximal hardness was observed in nanocomposite a-C:Si films with a small excess of carbon atoms.     

Mechanical and tribological properties of SiC whisker-reinforced SiC composites via oscillatory pressure sintering

SiC whisker (SiCw)-reinforced SiC composites were prepared by an oscillatory pressure sintering (OPS) process, and the effects of SiCw content on the microstructure and mechanical and tribological properties of such composites were investigated. The addition of SiCw could promote the formation of long columnar α-SiC, and the aspect ratio of α-SiC grains first increased and then decreased with the increase of SiCw content. When the SiCw content was 5.42 wt%, the relative density of the SiC–SiCw composite reached up to 99.45%. The SiC–5.42 wt% SiCw composite possessed the highest Vickers hardness, fracture toughness, and flexural strength of 30.68 GPa, 6.66 MPa·m^1/2, and 733 MPa, respectively. In addition, the SiC–5.42 wt% SiCw composite exhibited the excellent wear resistance when rubbed with GCr15 steel balls, with a friction coefficient of .76 and a wear rate of 4.12 × 10⁻⁷ mm³·N⁻¹·m⁻¹. This could be ascribed to the improved mechanical properties of SiC–SiCw composites, which enhanced the ability to resist peeling and micro-cutting, thereby enhancing the tribological properties of the composites.     

Enhanced tribological properties of Y/MoS2 composite coatings prepared by chemical vapor deposition

Chemical vapor deposition (CVD) is an efficient approach to prepare coatings on complex cutting tools. However, MoS₂ with self-lubrication ability and excellent tribological properties fabricated by CVD have been rarely reported in literature. The aim of this study was to deposit pure MoS₂ coatings and yttrium (Y) doped MoS₂ (Y/MoS₂) composite coatings on cemented carbide blades coated with titanium nitride by CVD. The structural and mechanical properties of the coatings were examined by scanning electron microscopy (SEM) and nanoindentation, respectively. The results demonstrated that the microstructure of Y/MoS₂ composite coatings was denser than that of the pure MoS₂ coating. The hardness and the adhesional properties were significantly enhanced for the Y/MoS₂ composite coatings. The tribological performance of the as-deposited coatings were investigated under atmospheric environment. Y/MoS₂ compostite coatings demonstrated an enhanced tribological performance with a stable and low coefficient of friction (COF) over the entire sliding time. In contrast, the COF of pure MoS₂ coating dramatically increased to value above 0.3 after a sliding time of only 30 min. Additionally, the Y/MoS₂ composite coatings showed a decreased wear rate (8.36 ± 0.29 × 10⁻⁷ mm³/Nm) compared to the pure MoS₂ coatings (3.41 ± 0.48 × 10⁻⁵ mm³/Nm) thus reflecting an improvement by two order of magnitude.     

Effect of multi-walled carbon nanotubes as reinforced fibres on tribological behaviour of Ni–P electroless coatings

After multi-walled carbon nanotubes (MWNTs) were modified and dispersed uniformly in electrolyte, the MWNTs composite coatings were prepared by electroless deposition. Hardness tests were carried out using a Vickers Hardness indenter. The friction and wear behavior of the Ni–P–MWNTs composite coatings in carbon-steel rings were investigated by using a ring-on-plate wear tester at pure liquid paraffin. Moreover, the friction and wear behavior of nine kinds of wear combinations, which were composed of plates and rings of different composite coatings, were studied. The experimental results indicated that addition of MWNTs would result in an increase in microhardness and an improvement of tribological properties of the Ni–P composite coating significantly. The Ni–P–MWNTs composite coatings revealed lower wear rate and friction coefficient compared with Si–C composite coatings. Moreover, the wear combination, which composed of the Ni–P–MWNTs composite coatings, showed a more excellent ability of friction-reduction and wear resistance than other combinations, and their friction coefficient and wear rate were 0.1087 and 1.49 × 10^− 6 kg/m, respectively.     

Repair of spline shaft by laser-cladding coarse TiC reinforced Ni-based coating: Process,microstructure and properties

To repair the surface defects of spline shaft and improve wear resistance, the coarse TiC reinforced Ni-based composite coatings were fabricated on the spline shaft surface by laser cladding with six types of precursors containing Ni45, coarse TiC, and fine TiN powder. The effects of ceramic content and fine TiN addition on the formability, microstructure, and mechanical properties of the coatings were studied comprehensively. In TiC reinforced Ni-based coatings 1–3 without fine TiN addition, the porosity decreased from 20.415 % to 0.571 % with the increase of TiC concentration. The coatings mainly consist of CrB, Cr7C3, Cr23C6, coarse TiC, and γ-Ni. With the addition of fine TiN, the length of the ceramic phases in coatings 1#–3# decreased slightly, while volume fraction and porosity increased. Moreover, the ring-shaped Ti (C, N) phases were also detected at the edges of both undissolved TiC and TiN particles, which improved the bonding force between ceramics and matrix. Besides, these ceramics inhibited the generation of columnar crystals and eliminated the heat-affected zone. The performance test results show that the coating 3# with 30 wt% TiC and 6 wt% TiN exhibits the best wear resistance despite slightly decreased hardness, and its friction coefficient of 0.409 and wear rate of 42.44 × 10⁻⁶ mm³ N⁻¹·m⁻¹ are, respectively, 0.667 and 0.307 times those of the substrate. Based on the additive/subtractive hybrid manufacturing technology, the optimized coatings were ground to obtain the finishing surface, which indicates that the coarse TiC reinforced coating can be employed in repairing the damaged parts.     

Mechanical and tribological assessment of composite AlCrN or a-C:Ag-based thin films for implant application

The present study focuses on the comparison of cathodic arc deposited AlCrN (ternary coating) and Ag alloyed a-C (amorphous carbon base coating) on chrome nitride (CrN) medical grade 316 LVM stainless steel. The work comprises of morphological, structural, nanomechanical and tribological evaluation in physiological simulated body fluid (SBF) lubrication following conditions pertaining to simulated hip joint. According to the findings, H/E, H³/E² and E_coating/E_substrate significantly effect the nanomechanical and tribological properties of the coatings. While a-C:Ag/CrN exhibited better L_y value compared to AlCrN/CrN due to better surface quality, the later has shown higher L_c2 value during nanoscratch test attributed to lower H³/E² and higher plastic work done. Inspite of lower friction coefficient, a-C:Ag/CrN observed higher wear rate during simulated tribotest attributed to low hardness, separate graphitic structure due to Ag doping and sudden increase of friction coefficient ascribed to severe abrasive delamination of a-C:Ag top layer. The wear mechanism observed under SEM microscopy indicate severe adhesion of Ti6Al4V counterbody on AlCrN/CrN coated surface. The size of wear debris obtained with AlCrN/CrN-Ti6Al4V tribopair was larger in size compared to a-C:Ag/CrN-Ti6Al4V tribopair. Nevertheless, despite inferior surface quality and lower L_y value and larger wear debris size, AlCrN/CrN coating performed better in nanoscratch (at L_c2 value) and demonstrated lower wear in simulated tribotest in physiological SBF condition.     

Amorphous carbon: how much of free hydrogen?

A method of stepped isochronous heating was used for investigation of the state and amount of free and bonded hydrogen in amorphous carbon (a-C:H) films. Hydrogen and other gas effusion processes were studied on unprotected and Pd layer protected a-C:H film which allow the separation of hydrogen from C_nH_m components. The amount of hydrogen released by the breaking of weak CH bonds was determined to be 10 at.%, and that released by the breaking of strong CH bonds was 12 at.%. The amount of free hydrogen in the material was estimated at 12–14 at.%.     

Thermal stability in oxidative and protective environments of a-C:H cap layer on a functional gradient coating

Three types of hydrogenated amorphous carbon (a-C:H) coatings were synthesized on stainless steel substrates by a Plasma Assisted CVD process, containing hydrogen contents in the range from 25 to 29 at.%. The effect of annealing up to 600 °C in two different environments on both the structure and the mechanical properties of the coatings were investigated by means of Differential Scanning Calorimetry/Thermogravimetry (DCS/TG), Raman Spectroscopy and Depth Sensing Indentation. The results indicate that the structural modifications occurred in the coatings in both protective and oxidative atmospheres up to 400 °C were due to a complex atomic rearrangement involving the dehydrogenation reaction. A small weight loss, detected by isothermal TG analysis confirmed the H₂ effusion. This dense effect proceeds without a change of hardness which was maintained in the diamond-like regime. The annealing in non-oxidative ambiance at temperatures above 500 °C causes both gaseous products effusion and sp³ to sp² transformation. Raman parameters and hardness values were, under these conditions, similar to those known for a typical graphite-like regime. While the onset temperature of the graphitization process was found to be almost independent of the H content range investigated, the situation was completely different in relation to the oxidation reaction. The highest oxidation resistance was found for coatings with the lowest H content.     

Influence of the silicon and oxygen content on the properties of non-hydrogenated amorphous carbon coatings

This work reports the development of non-hydrogenated magnetron-sputtered silicon and silicon-oxygen containing amorphous carbon coatings with increasing silicon and oxygen contents respectively. The Si content of a-C:Si coatings increases linearly with the increase of the power applied to the Si target up to 24 at.%, while to the system a-C:Si:O the O content increases with the increase of the oxygen flow to a maximum of 27 at.%. The hardness of the a-C:Si coatings shows two distinct trends with the increase of the Si content, a decrease of hardness for Si contents lower than 10 at.% and an increment above this value are observed. The coatings of the system a-C:Si:O present a decrease of hardness and Young modulus with the increase of the O content. The tribological performance of the coatings is significantly improved by doping the amorphous carbon coatings with silicon and oxygen with a reduction of the friction from 0.17 for the undoped carbon coating to 0.034 for the coating of the system a-C:Si:O with the highest O content.     

Properties of a-C:H films grown in inert gas ambient with camphoric carbon precursor of pulsed laser deposition

The influence of the ambient argon gas (Ar) pressure on the properties of the hydrogenated amorphous carbon (a-C:H) films deposited by pulsed laser deposition (PLD) using camphoric carbon (CC) target have been studied. The a-C:H films are deposited with varying Ar pressure range from 0.01 to 0.23 Torr. SEM and AFM show that the particle size of films is decreases, while the roughness increases with higher Ar pressure. The FTIR measurement revealed the presence of hydrogen in the a-C:H films. We found the surface morphology, structural and physical properties structure of a-C:H films are influenced by the presence of inert gas and the ratio of sp² trigonal component to sp³ tetrahedral component is strongly dependent on the inert gas pressure. We suggest that these phenomena are due to the effect of the optimum concentration of the Ar atoms in the C lattice. Improvement of the structural properties of the a-C:H films deposited in inert gas environment using CC target reveals different behaviour than reported earlier.     

Fourier transform infrared spectroscopic study of nitrogen-doped ultrananocrystalline diamond/hydrogenated amorphous carbon composite films prepared by pulsed laser deposition

Nitrogen-doped ultrananocrystalline diamond (UNCD)/hydrogenated amorphous carbon (a-C:H) composite films, which possess n-type conduction with enhanced electrical conductivities, were prepared by pulsed laser deposition and they were structurally studied by Fourier transform infrared (FTIR) spectroscopy. The film with a nitrogen content of 7.9 at.% possessed n-type condition with an electrical conductivity of 18 S/cm at 300 K. The FTIR spectra revealed peaks due to nitrogen impurities, C = N, C-N, and CH_n (n = 1, 2, 3) bands. The sp²-CH_n/(sp²-CH_n + sp³-CH_n), estimated from the area-integration of decomposed peaks, were 24.5 and 19.4% for undoped and 7.9 at.% doped films, respectively. The nitrogen-doping not only form the chemical bonds between carbon and nitrogen atoms such as C = N and C-N bonds but also facilitate the formation of both sp² and sp³ bonds, in particular, the sp³-CH_n bond is preferentially formed. From the analysis of the FTIR spectra, it was found that the hydrogen content in the film is increased with an increase in the nitrogen content. The increased hydrogen content might be owing to the enhanced volume of grain boundaries (GBs) between UNCD grains, and those between UNCD grains and an a-C:H matrix, which is caused by a reduction in the UNCD grain size. The CH_n peaks predominantly come from an a-C:H matrix and GBs. Since the nitrogen-doping for a-C:H has been known to be hardly effective, the n-type conduction with the enhanced electrical conductivities might be attributed to the sp²-CH_n formation at the GBs.     

Semiconducting amorphous carbon thin films for transparent conducting electrodes

Semiconducting amorphous carbon thin films were directly grown on SiO₂ substrate by using chemical vapor deposition. Raman spectra and transmission electron microscopy image showed that the a-C films have a short-range ordered amorphous structure. The electrical and optical properties of the a-C thin films were investigated. The films have sheet resistance of 3.7 kΩ/□ and high transmittance of 82%. They exhibit metal-oxide-semiconductor field effect transistor mobility of 10–12 cm² V⁻¹ s⁻¹ at room temperature, which is comparable to previous reported mobility of amorphous carbon. The optical band gap was calculated by Tauc’s relationship and photoluminescence spectra showed that the films are semiconductor with an optical band gap of 1.8 eV. These good physical properties make the a-C films a candidate for the application of transparent conducting electrodes.