Multilayer DLC coatings via alternating bias during magnetron sputtering

To combat the high residual stress problem in monolayer diamond-like carbon coatings, this paper fabricated multilayer diamond-like carbon coatings with alternate soft and hard layers via alternating bias during magnetron sputtering. The surface, cross sectional morphology, bonding structures and mechanical properties are investigated. The atomic force microscopy images indicate low bias results in rougher surface with large graphite clusters and voids suggesting low coating density. The multilayered coatings demonstrate relatively smooth surface stemming from higher bias. The cross sectional images from field emission scanning electron microscopy indicate coating thickness decreases as substrate bias increases and confirm that higher bias results in denser coating. Delamination is observed in monolayer coatings due to high residual stress. The trend of sp³/sp² fraction estimated by X-ray photoelectron spectroscopy is consistent with that of I_D/I_G ratios from Raman spectra, indicating the change of bonding structure with change of substrate bias. Hardness of multilayer diamond-like carbon coating is comparable to the coatings deposited at low constant bias but the adhesion strength and toughness are significantly improved. Alternately biased sputtering deposition provides an alternative when combination of hardness, toughness and adhesion strength is needed in an all diamond-like carbon coating.     

Tribological performance of DLC coatings deposited by ion beam deposition under dry friction and oil lubricated conditions

Understanding the reaction between lubricant additives and diamond-like carbon coatings is imperative for the improvement of the friction and wear properties of mechanical parts with diamond-like carbon coatings. Diamond-like carbon coatings were deposited with ion beam deposition and the influence of lubricant additives on the friction coefficients and wear rates of diamond-like carbon coatings under the lubricated conditions was studied. It was revealed that the wear rates of diamond-like carbon coatings under unlubricated conditions are 1.5 × 10⁻¹⁴ m³/(Nm) while they are decreased to 3 × 10⁻¹⁷ m³/(Nm) to 1.7 × 10⁻¹⁶ m³/(Nm) when lubricated by PAO-4 base oil with three additives. The addition of molybdenum dithiocarbamate in PAO-4 base oil decreases the friction coefficients of diamond-like carbon coatings to 0.07, but increases the wear rate of diamond-like carbon coatings. The addition of zinc dialkyl dithiophosphate to PAO-4 can slightly decrease the friction coefficient of diamond-like carbon coatings and improve the wear resistance of diamond-like carbon coatings. The addition of amine sulfuric-phosphate diester in PAO-4 can greatly decrease the wear rate of diamond-like carbon coatings to 3 × 10⁻¹⁷ m³/(Nm) but has a negligible effect on the friction coefficients of diamond-like carbon coatings.     

Characterization of the silicon oxide thin films deposited on polyethylene terephthalate substrates by radio frequency reactive magnetron sputtering

Transparent silicon oxide films were deposited on polyethylene terephthalate substrates by means of reactive magnetron sputtering with a mixture of argon and oxygen gases. The influences of process parameters, including the oxygen flow ratio, work pressure, radio frequency (RF) power density and deposition time, on the film properties, such as: deposition rate, morphology, surface roughness, water vapor/oxygen transmission rate and flexibility, were investigated. The experimental results show that the SiO_x films deposited at RF power density of 4.9 W/cm², work pressure of 0.27 Pa and oxygen flow ratio of 40% have better performance in preventing the permeation of water vapor and oxygen. Cracks are produced in the SiO_x films after the flexion of more than 100 cycles. The minimum transmission rates of water vapor and oxygen were found to be 2.6 g/m² day atm and 15.4 cc/m² day atm, respectively.     

Silicon oxide diffusion barrier coatings on polypropylene

In this study the influence of process conditions for the plasma-enhanced chemical vapor deposition of SiO_x diffusion barrier coatings on polypropylene (PP) is investigated and compared to results obtained on polyethylene terephthalate (PET). It was observed that the thermal load during deposition is much more crucial in the case of PP. If the thermal load is not the limiting factor, the composite parameter (CP) energy input per mass of precursor showed to be valuable to describe plasma conditions at constant oxygen to monomer ratio. Low oxygen transmission rates (OTRs) of 5.1 ± 3.6 and 0.3 ± 0.1 cm³/m²day/atm were achieved on PP and PET foil, respectively, for an optimal CP of 4.1 × 10⁵ J/g. Fourier transform infrared (FTIR) spectroscopy revealed that low carbon and silanol content is necessary for good barrier performance. Low RF power, necessary to reduce thermal load on PP, can be compensated by increasing the oxygen to monomer ratio.For favorable plasma conditions, the dependence of the OTR on the coating thickness follows a similar trend for both substrate materials with a critical thickness of approximately 12 nm. The residual permeation can be correlated to the defect density at each stage of film growth by means of a simple correlation. Further support for permeation through defects is found by the activated rate theory, since the apparent activation energy of oxygen permeation is below typical values of amorphous glasses and remains unchanged due to the deposition of SiO_x on both substrates.     

A comparative study of oxygen transmission rates through polymer films based on fluorescence quenching

Information on oxygen permeability through polymer films is essential for some applications, especially in food packaging where the control of oxygen levels can be critical in avoiding food spoilage. A permeability testing device using fluorescence‐based optical oxygen sensing was developed as a potential new instrument for measuring the oxygen permeability of packaging films. The fluorescence‐based permeability tester was validated against two existing commercial oxygen permeability measuring devices, the Mocon Ox‐Tran 2/20 and PBI‐Dansensor OPT‐5000. Oxygen transmission rates (OTR) of polylactide (PLA) and nanoclay‐reinforced PLA films, as well as polyethylene/poly(ethylene terephthalate) (PE/PET) and polypropylene/poly(ethylene terephthalate) (PP/PET) laminated films were determined at 23°C and 50% relative humidity using each of these instruments. No significant differences were observed between mean OTR values obtained by the fluorescence method and the corresponding values obtained using the OPT‐5000 but significantly lower values were measured when using the Mocon Ox‐Tran 2/20. In general, oxygen permeability data for the tested films were within the range of values found in the literature; however, in terms of further development, the fluorescence‐based technique gave OTR with relatively high standard deviation compared to the commercial methods and equipment modifications to address this issue are considered desirable. Copyright © 2010 John Wiley & Sons, Ltd.     

The permeability of Lost Foam pattern coatings for Al alloy castings

The Lost Foam casting of Al alloys has not yet reached its full potential because of the complexity of the process, and the fact that it is still poorly understood. In this paper, the permeability of typical pattern coatings for the Lost Foam casting of Al was measured, and found to vary from about 0.1 Darcy, (10⁻¹³ m²), for a low permeability coating, to about 1 Darcy (10⁻¹² m²), for a high permeability coating. Permeability was reduced by increasing coating thickness, but examination of the coatings on a hot-stage SEM suggested it would be unaffected by increased temperature. The results were used to infer how the filling of a Lost Foam polystyrene pattern could be influenced by the permeability of the pattern coating.     

Laser cladding nickel-titanium carbide composite coating on a 45 carbon steel: Preparation,microstructure and wear behavior

Almost fully dense nickel-titanium carbide composite coatings with varied titanium carbide content were deposited on 45 carbon steel by laser cladding. High content of titanium carbide particles up to 50 wt.% with bimodal microstructure could be homogeneously distributed in the nickel based matrix. Due to the presence of the harder nickel-titanium carbide composite coating on the 45 carbon steel, the surface hardness and wear properties were significantly improved. The Vickers hardness (HV 3) increased from about 260 HV 3 for the 45 carbon steel to 300 HV 3 – 360 HV 3 for nickel based composite coating containing 30 wt.% titanium carbide and 550 HV 3 – 680 HV 3 for nickel based composite coating containing 50 wt.% titanium carbide composite coating, respectively. The coefficient of friction and volume wear rate was reduced down to 0.41×10⁻⁶ mm³ N⁻¹ m⁻¹ and 9.3×10⁻⁶ mm³ N⁻¹ ⋅ m⁻¹ when a nickel based composite coating containing 50 wt.% titanium carbide was coated on the 45 carbon steel, respectively. The enhanced wear performance of the composite coating was due to presence of harder nickel-titanium carbide composite coating and formation of varied soft and lubricant metal oxides consisting of mainly titanium oxides and minor iron and nickel oxides.     

Effects of argon and oxygen flow rate on water vapor barrier properties of silicon oxide coatings deposited on polyethylene terephthalate by plasma enhanced chemical vapor deposition

Plasma polymer coatings were deposited from hexamethyldisiloxane on polyethylene terephthalate (PET) substrates while varying the operating conditions, such as the Ar and O₂ flow rates, at a fixed radio frequency power of 300 W. The water vapor transmission rate (WVTR) of the untreated PET was 54.56 g/m²/day and was decreased after depositing the silicon oxide (SiO_x) coatings. The minimum WVTR, 0.47 g/m²/day, was observed at Ar and O₂ flow rates of 4 and 20 sccm, respectively, with a coating thickness of 415.44 nm. The intensity of the peaks for the Si-O-Si bending at 800-820 cm^− 1 and Si-O-Si stretching at 1000-1150 cm^− 1 varied depending on the Ar and O₂ flow rates. The contact angle of the SiO_x coated PET increased as the Ar flow rate was increased from 2 to 8 sccm at a fixed O₂ flow rate of 20 sccm. It decreased gradually as the oxygen flow rate increased from 12 to 28 sccm at a fixed Ar carrier gas flow rate. The examination by atomic force microscopy revealed a correlation of the SiO_x morphology and the water vapor barrier performance with the Ar and O₂ flow rates. The roughness of the deposited coatings increased when either the O₂ or Ar flow rate was increased.     

Development of Palladium‐based Oxygen Scavenger: Optimization of Substrate and Palladium Layer Thickness

Oxygen scavenging films based on vacuum deposited palladium layers were developed to remove residual oxygen remaining in food packages after modified atmosphere packaging. Palladium (Pd) was coated on to a range of packaging films and in different thicknesses using magnetron sputtering technology. To improve the substrate surface, an additional silicon oxide (SiO_x) layer was also applied to the films before Pd deposition. To determine the oxygen scavenging activity, the scavenger films were placed into an airtight cell, which was flushed with a gas mixture containing 2 vol.% oxygen and 5 vol.% hydrogen. The results showed that the oxygen scavenging rate was strongly dependent on the coating substrate as well as on the Pd deposition thickness. Packaging films such as polyethylene terephthalate, aluminium oxide‐coated polyethylene terephthalate, oriented polypropylene and polylactic acid were found to be the most suitable substrates for Pd‐based oxygen scavengers. Moreover, it was demonstrated that the intermediate SiO_x layer between the substrate and the Pd layer led to a substantial increase in the oxygen scavenging activity rate (up to 33‐fold) for all applied packaging films. Additionally, it was shown that the optimal Pd layer thickness for the investigated oxygen scavenging films lies between 0.7 and 3.4 nm. The resulting scavenger films have the potential to scavenge residual headspace oxygen of sensitive foods within a matter of minutes leading to shelf life extension and overall quality improvements. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of coating thickness on the deformation behaviour of diamond-like carbon-silicon system

The effect of coating thickness on the deformation behaviour of diamond-like carbon (DLC) coatings on silicon substrates was investigated. Following nanoindentation of a 0.6 µm thick DLC coating, the subsurface microstructures were characterized and the data was compared to prior studies on a similar, but thicker coating. Indentation resulted in localized plastic compression in the coating without any through-thickness cracking. It was shown that the discontinuities in the load-displacement curves appeared at lower loads for the thinner coating. Accordingly, the silicon substrate exhibited cracking, plastic deformation and phase transformation at significantly lower loads than in the case of the thicker coating. Further, the widths, parallel to the interface, over which slip and the phase transformation zone are spread out in the substrate, was found to increase with the thickness of the coating. The mechanism responsible for the first pop-in was found to change from phase transformation in uncoated silicon to dislocation nucleation in the presence of the coating.     

Thickness of diamond-like carbon coatings quantified with Raman spectroscopy

A model is developed for quantifying the thickness of thin coatings and wear scars using Raman spectroscopy. The model, which assumes that both incident and Raman light obey Beer's law, was applied to Raman spectra from a diamond-like carbon (DLC) coating containing Si and O, known as DLN (diamond-like nanocomposite). The coatings ranged in thickness from 10 nm to 2 μm, according to stylus profilometry. Systematic variations in the Raman carbon (G band) and Si (1st order) peak intensities vs. thickness were found. Fits to the model gave an optical mean free path of λ250 nm for DLN. This value is in good agreement with optical absorption coefficient values of other DLC films. Thickness profiles of wear tracks in the coatings determined by the model compared well with depths determined by profilometry.     

Cellulose Nanocrystals from Lignocellulosic Raw Materials,for Oxygen Barrier Coatings on Food Packaging Films

Cellulose nanocrystals (CNCs) are unique, renewable top‐down nano particles from which coatings with improved gas barrier properties and new functionalities can be prepared. In this paper, the potential for obtaining such high performing nanocrystals from low‐cost lignocellulosic by‐products or raw materials is proved by a comparison study on CNCs obtained both from cotton linters and kraft pulp, by means of the ammonium persulfate (APS) process. Morphological and chemical characterization of the nanocrystals obtained, as well as the main functional properties of the poly(ethylene terephthalate) coated films, showed quite similar characteristics and performances of CNCs obtained from pure cellulose raw material (cotton linters) and the nanoparticles produced from a potential discard of paper making processes (kraft pulp). In particular, the gas barrier properties of the coating produced with CNCs obtained from kraft pulp were very promising, providing oxygen and carbon dioxide permeability values hundreds of times lower than those of equal thickness in comparison with common barrier synthetic polymers, over a broad range of temperatures. The results obtained are relevant not only for the outstanding performances achieved, but also because they evoke a possible positive example of industrial symbiosis in the packaging field, merging together the requirements and needs of the paper and plastic industries and addressing the way towards a better management of waste and materials. Copyright © 2017 John Wiley & Sons, Ltd.     

Silicon Migration from High‐barrier Coated Multilayer Polymeric Films to Selected Food Simulants after Microwave Processing Treatments

The use of microwave (MW) technology for in‐package food sterilization and pasteurization has the potential for widespread use in the food industry. Because the use of MW technology requires that food be processed inside its packaging, the interaction between food and its packaging during processing must be studied to ensure package integrity as well as consumer safety. In this study, two commercially available multilayer films developed for retort sterilization were evaluated for their suitability to MW processing. Film A was composed of oriented nylon//coated polyethylene terephthalate//cast polypropylene (CPP); film B consisted of oriented nylon//coated nylon//CPP with overall oxygen transmission rates <0.2 cc/m². day. Silicon (Si) was a major component in the coated polyethylene terephthalate layer and food‐contact CPP layer. This study evaluated the influence of MW processing on Si migration from films into selected food‐simulating liquids (FSLs; water and 3% acetic acid) using inductively coupled plasma‐mass spectroscopy, as compared with conventional thermal processing. This study also assessed migration of Si into FSL in terms of process temperature (70–123 °C) and time (18–34 min). A Fourier transform infrared spectrometer was used to evaluate the stability of the silicon–oxygen (Si–O) bonds in the metal‐oxide coated and food‐contact layer of the packaging film. Overall, there were no significant differences (p > 0.05) between the level of Si migration from films to FSL and the stability of Si–O–Si bonds during MW processing as compared with the conventional thermal processing. However, we found that the final processing temperature and time had a significant (p < 0.05) impact on Si migration into the FSL. Copyright © 2013 John Wiley & Sons, Ltd.     

Study on tribological property of CrCN coating based on magnetron sputtering plating technique

The influence of carbon doping on tribological properties of CrCN coating was studied through preparation of coatings deposited on single crystal silicon and M2 high-speed steel (HSS) substrate using closed-field unbalanced magnetron sputtering ion plating technique. The friction coefficients were measured by pin-on-disc set-up and the wear traces of the coatings were observed by optical microscope. The microstructure and bond states of the coatings were characterized by atomic force microscope (AFM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results show that the friction coefficient of coating decreases from 0.75 to 0.38, the micro-hardness increases from 1930 HV to 2300 HV, and the specific wear ratio of the coatings decreases from 8.351 × 10⁻¹⁵ m³/Nm to 3.859 × 10⁻¹⁵ m³/Nm with the increasing of carbon target current (I_C) from 0 A to 1.5 A. The grain size and the roughness of the coatings both decrease with the increasing of carbon target current, at the same time the coatings transform from crystalline state to amorphous state.     

Evaluation of a bio‐coating as a solution to improve barrier,friction and optical properties of plastic films

The present research dealt with evaluating barrier, friction and optical properties of three different plastic films after deposition of a gelatin‐based bio‐coating. The composite films showed improved barrier properties against oxygen and UV radiation. The oxygen transmission rate decreased in the order of 73% for oriented polypropylene (OPP), 56% for low‐density polyethylene (LDPE) and 40% for polyethylene terephthalate (PET). The increased UV barrier characteristics ranged from 20% for OPP to 12% for both LDPE and PET. Static and kinetic coefficients of friction significantly decreased both in the film‐to‐film and in the film‐to‐metal tests, leading to a desirable value for many applications. However, bio‐coated films showed lower optical performances in terms of transparency and haze. Transparency decreased mainly for LDPE (36%), whereas the haze index increased especially for OPP (85%). Non‐significant differences were observed as far as the water vapour permeability was concerned, except for a slight reduction for PET (from 15.78 to 13.53 cm³/m²/day at 23°C and 90% of relative humidity), suggesting that non‐meaningful effects arose from the addition of a hydrophobic component in the original formulation. Finally, the solubility of the coating in water was around 25% for all the three plastic substrates. The obtained data suggest that the lipid protein coating tested in this study, in spite of its great potential for enhancing some characteristics of plastic packaging films, still exhibits negative aspects which necessitate further improvement. Copyright © 2008 John Wiley & Sons, Ltd.     

Mechanical buckling instability of thin coatings deposited on soft polymer substrates

Deformation of rubber and poly(ethylene terephthalate) coated with a platinum or a gold film was studied. The thickness of the coating film was approximately ten nanometers. The polymer substrates were 10⁴ to 10⁵-fold softer than the coating. Folding of the coating leading to the appearance of a wave-like pattern on an originally smooth surface was observed both in tension and after shrinkage. In tension the wave crests are oriented along the elongation direction. After shrinkage the wave crests are perpendicular to the shrinkage direction. For rubber substrates, the appearance of the wave is explained by a mechanical buckling instability of the coating under compressive force. The length of the surface wave depends on the thickness of the coating layer and the rigidity of the polymer substrate. In addition to folding, regular fragmentation of the coating film on long and comparatively narrow bands is observed. The cracks are perpendicular to the wave crests both in tension and after shrinkage.     

Comparison between poly(methyl methacrylate)-carbon black and polyaniline conductive coatings

This work aims to develop and compare two types of conductive, polymer-based coatings via a dip coating process. The first type of coatings was made by dispersing and incorporating carbon black (CB) nanoparticles in a poly(methyl methacrylate) (PMMA) solution followed by dip coating. The CB content and dipping parameters were varied to explore their effects on the particle dispersion, coating thickness, and conductivity of the coatings. The dispersion of the CB particles in the polymer matrix was examined by scanning electron microscopy (SEM), while the coating thickness and conductivity were measured with a surface profilometer and a four-point probe electrometer, respectively. The good dispersion of carbon nanoparticles in the PMMA matrix was observed in the coatings. The conductivity of the PMMA-CB composite coatings was found to be mainly affected by CB content, particle dispersion as well as coating thickness. On the other hand, polyaniline (PANI) was used to make conductive coatings by dip coating and doping, and the advantages and limitations of the PANI coatings were compared with the PMMA-CB coatings.     

Iron-included carbon nanocapsules coated with biocompatible poly(ethylene glycol) shells

Nanoparticles of iron carbides wrapped in multilayered graphitic sheets (carbon nanocapsules) were synthesized by electric plasma discharge in an ultrasonic cavitation field in liquid ethanol and purified by selective oxidation and magnetic separation. The particles had 100–200 nm in diameter after centrifuging for 10 min at 4000 rpm. Carbon nanocapsules were covered by wispy poly(ethylene glycol) PEG coating about 7–10 nm in thickness. The number of PEG chains coated on carbon nanocapsules could be estimated as 9.15%. The values of saturation magnetization Ms and coercivity Hc of purified carbon nanocapsules without PEG coating were 112 emu g⁻¹ and 75 Oe respectively. Magnetically soft carbon nanocapsules with a poly(ethylene glycol) coating on the surface may possibly be used as biocompatible magnetic nanoparticles in medical applications.     

Formation mechanisms of zinc,molybdenum, sulfur and phosphorus containing reaction layers on a diamond-like carbon (DLC) coating

Diamond-like carbon (DLC) coatings are nowadays successfully applied on industrial components like pistons, piston rings and bearings in lubricated tribological contacts due to friction and wear reducing effects. In contradiction thereto, todays lubricants and additives are designed for tribological steel/steel contacts, whereby the knowledge on tribochemical layer formation on steel surfaces is comprehensive in contrast to the physical-chemical interactions between diamond-like carbon coatings, lubricants and additives. Therefore the formation mechanisms of zinc, molybdenum, sulfur and phosphorus containing reaction layers on a zirconium modified diamond-like carbon coating a-C : H : Zr (ZrC_g) in lubricated tribological contacts were analyzed by means of pin-on-disc (PoD) tribometer by varying the distances from s = 200 m–3,000 m under boundary and mixed friction conditions at T = 90 °C and a contact pressure p = 1,300 MPa regarding the application of diamond-like carbon coatings on gears. The base lubricant poly-alpha-olefin (PAO) was formulated using the anti-wear (AW) and extreme pressure (EP) additive zinc dialkyldithiophosphate (ZnDTP) and the friction modifier (FM) additive molybdenum dialkyldithiophosphate (MoDTP). The chemical composition of the tribochemical reaction layers by means of and Raman spectroscopy and x-ray photoelectron spectroscopy (XPS) as well as for the thickness differ significantly by varying the additivation.     

Experimental investigation of the current-induced breakage of metal-coated polymer films

We have experimentally studied the phenomenon of current-induced breakage of thin (∼20-to 30-nm-thick) metal films deposited onto poly(ethylene terephthalate) (PETP) and poly(propylene) (PP) substrates. Two mechanisms leading to the current-induced breakage of the metal film are established, which are characterized by different average threshold current densities: j _H ∼ 1.5 × 10¹⁰ A/m² and j _L ∼ 0.7 × 10¹⁰ A/m². The possible nature of these mechanisms is discussed.