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Microarc oxidation (MAO) is a popular surface treatment process to generate oxide coatings with excellent mechanical properties on valve metals. As a plasma discharge technique, the discharge mechanism in MAO is different from that in the bipolar plate. Due to the alternating arcs and multiple electrolytes in MAO, it is difficult to control and optimize the coating properties. Based on the arcing mechanism and ion motion, the boundary conditions of no-arc discharge, alternating arc discharge, and continuous arc discharge are derived, and the relationship between the discharge current and breakdown current and sustained arc current is investigated. For the same electrolyte, the boundary conditions are determined by equivalent concentration and conductivity. The results show that in the stable alternating arc discharge regime, the higher the concentration and smaller the conductivity, the more intense is the discharge. According to the boundary conditions, MAO experiments are designed using phosphate electrolytes to improve the hardness of oxide coatings. By selecting electrolyte characteristics close to the continuous arc discharge boundary in the stable alternating arc discharge regime, the arc discharge is most intense and brightest and the largest energy is transferred to the Al2O3 coating. Consequently, the crystallinity and mechanical properties are improved significantly.

In physical vapor deposition (PVD), the energy and incident angle of ions can be adjusted easily by applying an electromagnetic field so that coatings with different structures and properties can be produced. In this work, several high-ionization coating techniques are employed to deposit TiAlN coatings to compare the effectiveness of each technique and resulting coating properties. The continuous high-power magnetron sputtering (C-HPMS) technique shows advantages in the deposition rate and coating performance. In addition, a deposition rate of 400 nm/min is achieved by C-HPMS, whereas those of high power impulse magnetron sputtering (HiPIMS) and arc ion plating (AIP) are 85 nm/min and 225 nm/min, respectively. The coating also shows a particle-free and dense morphology with a smaller surface roughness of 22.4 nm. Owing to efficient ionization, the TiAlN coating deposited by C-HPMS has a high hardness of 33.2 GPa which is comparable to those prepared by AIP and HiPIMS but with small residual stress. The results provide valuable information on how to choose the proper techniques and parameters to produce coatings with the desirable adhesion strength, tribological properties, as well as corrosion resistance.

Micro-arc oxidation (MAO) is a popular coating technology for aluminum alloys, but the wear resistance and friction properties are limited by the intrinsic properties of the alumina coatings with high friction coefficients. In this work, CePO4 is identified as a quasi-2D material by the first principle calculation. As a self-lubricating phase, it is firstly formed in situ during the oxidation process and the lubrication mechanism is investigated. Nano-grains of cerium phosphate are formed and imbedded uniformly in the alumina coatings. With increasing Ce contents, the friction coefficients diminish to 0.1–0.15 during the 5-h test without obvious fluctuation. The results reveal the new concept of using self-lubricating additives in MAO oxide on Al alloys to improve the durability and mechanical properties.

Aluminum alloys are widely used in the aerospace and transportation industries, but the corrosion resistance is insufficient in long-term service especially in the high salinity environment. A ceramic coating composed of ZnO nanoparticles is demonstrated to significantly improve the corrosion resistance of the Al alloys. Owing to the similar chemical activity of Zn and Al, ZnO particles fuse into Al2O3 in the micro-arc during plasma electrolytic oxidation (PEO) rendering the coating compactness. The formation mechanism of the PEO coating is investigated and discussed. The corrosion current of the ZnO modified PEO coating is 4 orders of magnitude less than that of the LY12 substrate. Immersion tests performed in 3.5 wt% sodium chloride show that incorporation of ZnO prevents destruction and dissolution of the PEO coating in the high salinity environment.

Developing acid-resistant magnesium alloys is challenging because of the high chemical reactivity of magnesium in acidic media. In this work, a bio-inspired strategy by taking advantage of the super-hydrophobic effects on lotus leaves is described. The self-layered coating consisting of an inner compact layer and outer Mg-Al layered double hydroxide (LDH) microsheet-based layer prepared hydrothermally exhibits enhanced corrosion resistance in saline solutions but cannot resist corrosion in sulfuric acid. After depositing a fluorocarbon polymer film on the microsheets using a polytetrafluoroethylene (PTFE) target by magnetron sputtering, a super-hydrophobic surface is created on the magnesium alloy. Compared to the surface modified hydrothermally, the super-hydrophobic surface provides better corrosion protection in H2SO4 due to trapped air pockets in the microsheet array. The dual process offers a promising means to mitigate corrosion of magnesium alloys in acidic media.

Titanium nitride films deposited by conventional magnetron sputtering are prone to contamination, especially residual gas species, and the composition and properties can be affected. In this work, an anode layer ion source (ALIS) is used in magnetron sputtering to deposit TiN films and the effects of the average energy Ei and ion flux density Ji on the chemical composition of the deposited films are determined. By coupling and varying the magnetron discharge current It, the ALIS can be used to control Ei to as low as 80 eV and Ji as high as 3.5 × 1016 ions cm−2 s−1. To discern the roles of Ei and Ji, the films are deposited under three different conditions of magnetron discharge It. A reduction of 95% in the oxygen concentration and an increase of 30% in the nitrogen concentration are observed by increasing Ji. X-ray photoelectron spectroscopy reveals decreased peak broadening, shifts to higher binding energies, and increase initial slope of the Ti 2p peak with larger Ji. The N 1s peak shows decreased broadening while the O 1s peak indicates less oxide-related compounds. Raman scattering reveals reduced intensity ratios of the Ti to N vibration phonon peaks (ITi/IN) indicating enhanced nitrogen-related optical phonon peaks and that the film resistivity decreases as the oxygen concentration decreases. Our experiments disclose compositional changes especially reduced oxygen incorporation with ALIS assistance during magnetron sputtering. The hybrid technique which can be scaled up readily to meet industrial demand enables control of the film composition without resorting to other parameters like high temperature, biasing, and ultrahigh vacuum that may adversely affect other film properties and add manufacturing costs.

Nb-doped TiO2 (NTO) films have potential to replace indium tin oxide (ITO) as transparent conducting material. However, costly substrates with a specific orientation such as sapphire must be used to avoid formation of the rutile phase and to obtain transparent and conductive NTO films. Furthermore, scaling up is difficult thus hampering commercialization. Herein, in order to control the crystal orientation of TiO2, two-step preparation is described. An amorphous NTO film is first prepared on the economical soda-lime glass substrate by low-energy magnetron sputtering and the sample is annealed in Ar with 5 at% H2 at 400 °C to crystallize the amorphous structure into anatase (101) and anatase (004). The morphology, structure, and optoelectrical properties of the NTO films and relationship with film thickness are studied. The resistivity decreases to 8.1 × 10−4 Ω·cm for a thickness of 320 nm and the average transmittance in the visible region increases monotonically to 73% as the thickness is reduced from 400 nm to 280 nm. The good conductivity and transmittance suggest potential application to smart windows and solar cells.

An anode layer ion source (ALIS) is used in magnetron sputtering to deposit TiN films. The effects of the ion source discharge current (Is) on the microstructure, mechanical, and electrochemical properties, and adhesion characteristics of the deposited films are studied. By coupling with magnetron sputtering discharge (It) and varying the ALIS discharge current, the ion energy (Ei) and ion flux density (Ji) can be increased to 180 eV and 3.5 × 1016 ions·cm−2·s−1, respectively. The preferred orientation of the films changes from (200) to mixed (111) & (200) and finally to (111) with increasing Is. The microstructure changes from a columnar to dense one and the residual stress in all the films is compressive. The stress increases initially and then decreases slightly with the (111) orientation and the hardness and fracture toughness depend on the residual stress with the hardness increasing from 14.5 GPa to 27.0 GPa and fracture toughness increasing to 70%. As shown by the Rockwell C adhesion test, the films deposited by varying the ion source discharge current show improved adhesion. Electrochemical studies reveal reduced corrosion current density and increased impedance by an order of magnitude. The results reveal for the first time significant changes in the mechanical and electrochemical properties of films deposited by magnetron sputtering with ALIS assistance. This hybrid technique has the advantages that the film structure and mechanical and electrochemical properties can be readily adjusted.

The high ion energy produced by the substrate bias is essential to the enhancement of the sp3 content in diamond-like carbon (DLC) coatings and adhesion with the substrate. However, excessive ion energy can turn into heat conversely converting sp3 into sp2 undermining the mechanical properties. In this work, pulsed kV bias is applied to increase the carbonous ion energy to increase the sp3 content in DLC coatings and improve the adhesion with the substrate simultaneously while avoiding adverse temperature increase. The high ionized carbonous ions flux is formed by an anode-layer ion source with C2H2 gas and Cr/CrCx/CrC interlayers are introduced between the DLC coating and high-speed steel (HSS) substrate to release the internal stress by high-power impulse magnetron sputtering (HiPIMS). The DLC coatings not only have a large sp3 content, high hardness of 18.5 GPa, a low friction coefficient of 0.12, superior anti-corrosion behaviors,and wear rate of 0.87 × 10−15 m3/N m for 4 h, but also exhibits outstanding adhesion (Lc = 76 N) with the HSS substrate in spite of a DLC coating thickness of 13 μm.

Owing to the small natural abundance of indium, high-purity anatase Nb-TiO2 (NTO) is proposed as an alternative of indium tin oxide but materials fabrication is quite difficult. Herein, a simple and scalable seed-mediated method is designed to produce high-purity anatase NTO. Owing to the smaller nucleation free energy of anatase than rutile when the grain size is smaller than 14 nm, nanoscale anatase seeds nucleate preferentially by precise energy control. The mechanism of the seed-mediated NTO is studied by TEM. The conductivity depends on the purity of anatase and high transparency with the optimal antireflection layers is demonstrated by simulation.

The sucker rod pump, an important machine in oil exploration and extraction, normally works in a heavy oil and sand environment in which severe abrasion and erosion occur, especially on oil-well tubings. To improve the service life, DLC coatings with different thicknesses are fabricated on the oil-well tubings and the mechanical, tribological, and anti-corrosion properties are investigated. The results show that the thickness can be compromised with adhesion due to the low stress induced by alternate implantation and deposition at the pulsed high-voltage bias. Compared to severe abrasion of the carbonitriding AISI 1045 oil-well tubing, the thick DLC coatings have good anti-abrasion properties in the heavy oil and sand environment. Moreover, excellent erosion resistance is observed from the DLC-coated samples as exemplified by the small corrosion current density and high corrosion potential. The tests conducted in both simulated and practical working conditions reveal that the service life of the oil-well tubing is significantly improved.

The discharge and deposition characteristics of high-power impulse magnetron sputtering using various target materials with different sputtering yields (Cu, Cr, Ti, and C) were analyzed by a plasma global model. The experimental discharge voltages and currents of various target materials were used as the input parameters of the model. The analysis reveals that the ionization fraction of the sputtered species decreases as increasing the sputtering yield, due to the electron temperature was reduced through the cooling effect of sputtered species. However, as the sputtering yield increases, the plasma density under a given discharge power density is increased and the self-sputtering runaway can be fully developed, resulting in a higher fraction of ion density in the form of metal ions in the ion deposition flux. For some high-sputtering yield materials, such as Cu and Cr, this fraction can be up to 95%.

Etching of the cathodes in magnetron sputtering determines the plasma discharge properties and deposition efficiency. In high-power and high-ionization discharges, etching becomes more complicated, resulting in inaccurate results if the conventional models are still used. This work aims at establishing an accurate dynamic model for high-power and high-ionization discharges by combining the cellular automata (CA) method and particle-in-cell/Monte Carlo collision (PIC/MCC) method, in which all the interactions pertaining to the etching morphology, plasma density, electric field, and magnetic field are considered. In high-power discharges such as continuous high-power magnetron sputtering (C-HPMS), strong self-sputtering and intense gas rarefaction stemming from the high temperature in the vicinity of the target influence the etching behavior. Compared to the experimental results, the morphology simulated by the dynamic etching model shows an error of only 0.8% in C-HPMS, which is much less than that obtained by the traditional test-electron Monte Carlo (MC) method (10.1%) and static PIC/MCC method (4.0%). The dynamic etching model provides more accurate results to aid the development and industrial application of HPMS.

Background Odorant-binding proteins (OBPs) and chemosensory proteins (CSPs) are two families of small water-soluble proteins involved in odor detection and subsequent signal transmission. Determination of their binding mechanisms and specificity towards different odorants is important for developing OBPs/CSPs as targets in pest control management. Results We re-annotated genes encoding putative OBPs and CSPs in the Asian citrus psyllid (Diaphorina citri) draft genome using various bioinformatic tools. Genes encoding nine OBPs (seven Classic and two Plus-C) and 12 CSPs were identified, consistent with our previous transcriptomic results. Tissue-specific and developmental expression analyses suggested that genes encoding six OBPs and four CSPs were predominantly expressed in antennae, and displayed various expression patterns in different development stages, suggesting potential involvement in olfactory perception. Competitive fluorescence binding assays with 13 candidate ligands, including known host plant volatiles, sex pheromone components and repellents, showed that DcitOBP3 could bind to various odorants, whereas DcitOBP6, 8 and 9 bound specifically to host plant terpenoids. DcitCSP1 and 12 could also bind to certain terpenoids with high binding specificity. Conclusion OBP- and CSP-encoding genes were systematically identified by annotating the draft D. citri genome and those potentially involved in odorant detection and signal transmission were identified by analyzing their tissue-expression profiles and odorant-binding affinities, particularly to the peripheral molecular perception of host plant terpenoids. The identified genes may provide potential targets for efficient pest control. © 2020 Society of Chemical Industry.

Coherent grain boundaries (CGBs) has been revealed to improve the hardness and toughness simultaneously, but the density are not enough to increase their mechanical properties. Herein, hetero-interfaces are formed by introducing ion bombardment during magnetron sputtering to increase the amount of CGBs in the CrN coatings. By optimizing the sub-layer thickness, the quantity and width of CGBs from the (111) to (200) orientations increase significantly and consequently, the hardness and toughness of the CrN coating increase to 33.4 GPa and 14.98 MPa m1/2, respectively. At last, the effect of the different CGBs to the coating strengthen is discussed.

Better orthopedic implants improve the life quality of patients and elderly people. Compared to Ti and Mg alloys commonly found in bone implants, Al alloys have merits such as high specific strength, excellent casting capability, and low cost, but unfortunately, the poor wear resistance, corrosion resistance, and insufficient biocompatibility have hampered wider application to bone replacements. In this study, well structure designed and excellent adhered Al2O3 coating is fabricated by micro-arc oxidation (MAO) on Al alloys to improve the wear resistance and corrosion resistance and inhibit release of potentially harmful Al ions from the Al alloy substrate. Ca, Fe, and Zn are respectively doped into the Al2O3 coating to enhance the biological properties. In particular, the Al2O3 coating doped with Zn delivers outstanding osteogenic performance and the antibacterial rates against E. coli and S. aureus are 99.5 ± 0.56% and 98.77 ± 0.52%, respectively. The improved mechanical and biological properties reveals that the Al2O3 coated Al alloys prepared by MAO coatings have large potential in orthopedic applications.

The Asian citrus psyllid, Diaphorina citri Kuwayama (Hemiptera: Liviidae), can cause direct damage to citrus trees and is the main vector for the devastating disease, citrus greening disease or huanglongbing. Most molecular studies on this important insect pest use real-time reverse-transcription quantitative polymerase chain reaction (RT-qPCR) to quantify gene expression, including analyzing molecular basis for insecticide resistance in field populations. One critical factor to cause inaccuracy in RT-qPCR results is the lack of appropriate internal reference genes for optimal data normalization. In this study, the expression levels of 10 selected reference genes were evaluated in different tissue samples of psyllid adults and in the insects treated with different temperatures and insecticides. Data were analyzed using different computational algorithms, including Delta Ct, BestKeeper, NormFinder, geNorm, and RefFinder. According to our results, at least two reference genes should be used for the normalization of RT-qPCR data in this insect. The best choices of reference genes for different samples are as follows: ACT1 and Ferritin for different tissue samples, RPS20 and Ferritin for samples treated with different temperatures, TBP and EF1α for samples treated with imidacloprid, and Ferritin and TBP for samples treated with beta-cypermethrin. The reference genes identified in this study should be useful for future studies to analyze the expression patterns of target genes, especially for genes linked with temperature adaptability and insecticide resistance in this insect species in the future.

Magnesium and magnesium alloys are widely used in the electronics, automobile and aerospace industry but the poor corrosion resistance has hindered some applications. In this work, a transparent fluorocarbon polymeric thin film is deposited on magnesium by magnetron sputtering and the corrosion resistance is evaluated. Potentiodynamic polarization and electrochemical impedance spectroscopy in combination with immersion experiments in 3.5 wt% NaCl reveal markedly improved corrosion resistance. The corrosion mechanism is discussed from the perspective of random defects in the fluorocarbon film.

Hydrogenated diamond like carbon (a-C:H) coatings typically have low friction but high residual stress. The hardness which depends on the sp3 proportion increases not only the coating lifetime, but also the residual stress which can lead to easy film delamination especially for thick coatings. In this work, several thick a-C:H coatings (>10 μm) with different stress and hardness are prepared using stress engineering to mitigate stress accumulation while the hardness is retained. A low compressive residual stress of 0.42–0.84 GPa is achieved from the 8 μm thick a-C:H coating in addition to a high critical load of 63–74 N and hardness of over 26 GPa. The other desirable tribological and anticorrosion properties include a small friction coefficient of 0.13, low wear rate of 1.01 × 10−15 m3/N·m, high corrosion potential of - 479.6 mV, as well as small corrosion current density of 1.77 μA/cm2.

Synthesis of zinc oxide (ZnO) nanostructures is reported by electrochemical deposition from an aqueous electrolyte in presence of graphene oxide (GO) with varying oxidation degree. The properties of hybrids were investigated by scanning electron microscopy, X-ray diffraction, Raman, Fourier-Transform Infrared and X-ray photoelectron spectroscopy techniques and photocatalytic measurements. The results indicated the electrodeposition of ZnO in presence of GO with increased oxygen content led to marked differences in the morphology while Raman measurements indicated an increased defect level both in the ZnO and the electrochemically reduced GO (ErGO) within the hybrids. The decrease in C/O atomic ratio of GO (from 0.79 to 0.71) employed for the electrodeposition of ZnO resulted in an increase in photocatalytic efficiency for methylene blue degradation under UV irradiation from 4-folds to 10-folds with respect to non-hybridized ZnO. The observed synergetic effect of cathodic deposition potential and oxygen content in GO towards improving the photocatalytic activity of immobilized ZnO is expected to contribute to further development of more effective deposition approaches for the preparation of high performance hybrid nanostructures.

Diamond-like carbon (DLC) coatings have attracted much attention due to their excellent hardness, low friction, and superior corrosion resistance. Unfortunately, the poor adhesion caused by internal stress limits the typical thickness to below 3–5 μm. This paper presents a novel interlayer design and interface engineering and the induced excellent adhesion of thick diamond-like carbon (DLC) coatings on a high speed steel substrate. The interlayer has fundamentally a graded Cr/CrCx/CrC/DLC structure, but various treatments to the hetero-interfaces have been conducted including sequential energetic ion bombardments with Cr at the substrate/Cr interface using high-power impulse magnetron sputtering (HiPIMS) and with C at the CrC/DLC interface using an anode layer ion source. It has been observed that the critical load has been improved from 18 N for a single Cr interlayer to 77 N for a Cr/CrCx/CrC interlayer for thick DLC coatings of 13 μm. Using the same design, a very high critical load of 73 N has been achieved on the ultra-thick DLC coating of 50 μm. This interlayer design has allowed the deposition of a DLC coating that is not only thick but also hard with excellent tribological properties. The DLC coatings have a high hardness of >18 GPa, a low friction coefficient of 0.12 and a low wear rate of (1.7 ± 0.2) × 10−15 m3/N·m. This paper discusses the effect of the ion bombardment of the interlayer on the coating adhesion and the strengthening mechanisms.

By combining the advantages of the thermo-mechanical properties of TiAlN and self-lubricating properties of diamond-like carbon (DLC), a multi-layered TiAlN/DLC coating is fabricated by filtered cathodic vacuum arc and magnetron sputtering. According to the different morphology and mismatch between the physical and chemical properties of TiAlN and DLC, multiple methods are used to study the growth mechanism of crystalline TiAlN and amorphous DLC in the combined system. The morphology evolution depending on the bias is studied and the brittle interface is assessed by scratch experiments. The results show that an interlamination failure occurs at the top of first DLC layer due to the cluster morphology obtained by small bias, however, the failure moves to the interface above the substrate when the clusters are refined by increasing bias. By adopting the stepwise decreased bias, the 4.5 μm thick TiAlN/DLC multi-layer coating is fabricated and does not exhibit interfacial failure at any interface between TiAlN and DLC in the scratch experiments up to a load of 100 N. Excellent adhesion (Lc = 63 N) is also achieved from coatings deposited on high-speed steel with optimized Cr/CrCx/CrC interlayers prepared by high-power impulse magnetron sputtering.

Target poisoning is prevalent in reactive magnetron sputtering and causes deleterious effects, especially in deposition using metal targets. Both the deposition rate and the stoichiometry ratio of the coatings will be compromised because of the quicker coverage of the poisoning materials on the target relative to removal by sputtering. Continuous high-power magnetron sputtering (C-HPMS) possesses merits such as more rapid sputtering than high-power impulse magnetron sputtering and better target poisoning resistance. In this work, the discharge and plasma characteristics of C-HPMS for an Al metal target in reactive O2/Ar atmospheres are investigated by modeling and alumina deposition. At a constant oxygen partial pressure, larger discharge power increases target etching significantly compared to surface combination with O2, leading to reduced surface poisoning. Besides, a higher temperature is produced near the target to produce more intense rarefaction effects and decrease the risk of target poisoning. In Al discharge, the stable deposition window in the O2/Ar ratio under 120 W/cm2 is 5 times of that under 20 W/cm2. Moreover, a large deposition rate of 112 nm/min is achieved at the poisoning-saturated point and a target/substrate distance can be increased to larger than 40 cm, thus providing more flexibility in the design of deposition parameters and hardware requirement. Our results show that high discharge intensity improves plasma density and ionization rates of reactive particles boding well for the deposition of under-stoichiometric and higher-quality amorphous Al2O3 films. The reactive C-HPMS technique has large potential in the commercial production of functional coatings and thin films.

The corrosion resistance of aluminum and its alloys requires improvement in some applications. In this work, a 20 μm thick compact alumina coating doping Fe and P is obtained on the substrate of LY12 Al alloy by combining micro-arc oxidation (MAO) and phosphating to improve the corrosion resistance. The reaction mechanism is investigated and proposed. The coating shows a relatively small surface roughness (Ra = 0.5 μm) and a high Vickers hardness (1200 HV). The corrosion resistance is evaluated by the salt spraying test and Tafel polarization and a lifetime of up to 1800 h and a passivation potential of above 10 V are observed.

Lead-free solder is widely used in the industry, especially in wave soldering. However, the stainless steel holders used in wave soldering are prone to corrosion by the lead-free solder due to increased reactive wetting. Besides, owing to the high affinity between the holders and solder, they are often used to take solder out of the container. To improve tin repellence and the mechanical properties of the stainless steel holders, Ti/TiC and Ti/TiC/DLC coatings are deposited by filtered cathodic vacuum arc (FCVA) and plasma immersion ion implantation and deposition (PIII&D). The morphology, structure, composition, microhardness, wear resistance, electrochemical properties, and wetting characteristics are investigated systematically. The DLC coating, which has an amorphous structure and I D /I G ratio of about 0.55, further enhances the frictional properties, corrosion resistance, and hydrophobic characteristics of the Ti/TiC structure. The surface-modified holders show excellent tin repellence in wave soldering.

Lead-free solder is increasingly used in the wave soldering but corrosion of the stainless steel holders frequently occurs and produces deleterious effects. To enhance the service life, a Ti/TiC coating is deposited by filtered cathodic vacuum arc (FCVA) on the stainless steel holders. The morphology, structure, composition, microhardness, wear resistance, electron chemical corrosion, and wetting properties against solder are investigated. The results show that not only good frictional properties and corrosion resistance are achieved by the Ti/TiC coatings, but also good tin repelling and hydrophobic characteristics are observed. The Ti/TiC coating provides excellent protection against corrosion of lead-free solder in wave soldering.

Owing to the increasing use of magnesium alloys in the automotive, aerospace, electronics, and biomedical industry, more Mg-based wastes are being produced. Herein, a new process to electrochemically degrade Mg alloy wastes suitable for sewage treatment is described. Mg alloys are immersed in a sodium chloride solution and a small voltage is applied to accelerate degradation. The solid degradation products are composed of mainly nanostructured magnesium hydroxide and can be used to remove methyl orange from the simulated sewage effectively via adsorption/aggregation. This study provides insights into how to turn Mg wastes into useful forms to lessen the environmental impact. Keywords: Magnesium alloy, Polarization, Degradation, Corrosion, Surfaces, Sewage treatment