载银自抛光 / 低表面能环保涂层的制备及其耐微生物附着性能研究

目的制备一种新型绿色环保的耐海洋微生物附着涂层。方法通过聚硅氧烷(有机硅)改性丙烯酸树脂,合成以硅氧烷为侧链,丙烯酸树脂为主链的有机硅改性丙烯酸树脂。利用聚多巴胺的粘附性和还原性,制备二氧化硅/聚多巴胺/纳米银(Si O2/PD/Ag)纳米复合材料。以制备的有机硅改性丙烯酸树脂为成膜物,以载银纳米颗粒为杀菌剂,制备耐微生物附着环保涂层。通过傅里叶红外光谱仪(FTIR)和接触角检测仪(CA)分别对有机硅改性丙烯酸树脂的Si—O基团和接触角作表征,通过透射电子显微镜(TEM)表征Si O2/PD/Ag的制备过程,通过水解率和细菌附着等实验评价涂层的防污性能。结果Si—O—Si和Si—O—C的接入使得丙烯酸树脂改性后的接触角从72°提高到96°。Si O2/PD/Ag是一种特殊"核-壳-卫星"结构的载银纳米颗粒,纳米银均匀分散在Si O2的表面。涂层的水解性能良好,水解率为1.03μm/d,杀菌剂分散均匀。结论该涂层通过自抛光和低表面能双重物理抑菌作用和纳米银的杀菌作用,能有效抑制海洋微生物在试样表面的附着。     

Mechanical properties of SiOx gas barrier coatings on polyester films

This paper reports the impressive mechanical properties of 1 μm thick carbon-containing SiO_x gas barrier coatings, characterised using the uniaxial fragmentation test. Such coatings have been found to act as excellent barriers to water vapour permeation partly because they can be made so thick without stress induced cracking. The impressive mechanical properties are thought to be due in part to the high amount of carbon they contain, which gives them a more organic character, as well as the fact that they are deposited as a succession of thinner layers. The adhesion of the coatings to the polyester film is good in all cases, reflecting a high density of covalent bonding at the interface. Improvement of the mechanical properties of a SiO_x/PET composite can be achieved by altering the substrate. By replacing the PET with a heat-stabilised (HS) PET film, a HS film with an acrylate layer or PEN, it is found that the coating displays improved mechanical properties and adhesive strength (as well as barrier). This is thought to be due to the superior surface thermal and mechanical properties of these substrates. Deposition temperatures are at least 80 °C, which causes molecular motion at the surface of a plain PET film and creates defects in the SiO_x coating as it grows, making it more brittle and permeable to gas flow.     

CrAlYCN/CrCN nanoscale multilayer PVD coatings deposited by the combined High Power Impulse Magnetron Sputtering/Unbalanced Magnetron Sputtering (HIPIMS/UBM) technology

CrAlYCN/CrCN coating combining high hardness (H_p = 36 GPa) and low friction coefficient (µ = 0.42 against Al₂O₃) has been developed for machining of Si containing Al-alloys. The coating was deposited by the combined High Power Impulse Magnetron Sputtering/Unbalanced Magnetron sputtering, (HIPIMS/UBM) technology. Macroparticle free Cr⁺ ion flux was generated by HIPIMS discharge to sputter clean the substrates prior to the coating deposition. The use of HIPIMS for surface pre treatment resulted in excellent adhesion, scratch test adhesion critical load value of Lc = 55 N on HSS and Lc = 68 N due to the local epitaxial growth and extremely smooth coating surface, Ra = 0.012 μm due to the elimination of growth defects.The coating crystallised in fcc structure with a preferred {220} orientation. XTEM analysis revealed a nanoscale multilayer structure of the coating with carbon segregated at the column boundaries but also vertically to form a lateral phase at the interfaces between the individual nanolayers.Addition of C to CrAlYN/CrN increased the chemical inertness between cutting tool and workpiece material without deteriorating the oxidation resistance of the coating. Thermo gravimetric analysis showed that the temperature for the onset of rapid oxidation was as high as 940 °C.In dry milling of AlSi9Cu1 alloy, CrAlYCN/CrCN coated 8 mm diameter cemented carbide end mills outperformed non coated end mills by factor of 2.5 with effective hindered built up edge formation mechanism.     

Preparation of silver nanostructure from silver(I) coordination polymer and fabrication of nano silver(I) bromide by reverse micelles technique

A new one-dimensional silver(I) coordination polymer, [Ag(μ-bpfb)(NO₃)]_n (1); bpfb = N,N′-bis(4-pyridylformamide)-1,4-benzene, has been synthesized and characterized by IR, ¹H NMR and ¹³C NMR spectroscopy. The single crystal X-ray data show that the silver(I) 1D coordination polymer grows into a three-dimensional network by hydrogen bonding and π–π stacking interactions. Compound 1 with nanorod morphology was also prepared by sonochemical method. The cetyltrimethylammonium bromide (CTAB) as a cationic surfactant was used in reverse micelles technique to obtain spongy silver(I) bromide nanoparticles from compound 1. Also, different silver nanoparticles have been prepared via direct calcination at 673 K and thermal decomposition in oleic acid from compound 1. The nanostructures of [Ag(μ-bpfb)(NO₃)]_n (1), silver and silver(I) bromide were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive X-ray (EDAX) analysis. Thermal stability of compound 1 in both bulk and nano-sized form was studied by thermal gravimetric (TG) and differential thermal (DT) analyses.     

Adaptive VN/Ag nanocomposite coatings with lubricious behavior from 25 to 1000 °C

A two-phase nanocomposite coating that consists of inclusions of silver in a vanadium nitride matrix (VN/Ag) was investigated as a potential adaptive coating with a reduced friction coefficient from 25 to 1000 °C. This nanocomposite structure was selected based on the premise that silver and silver vanadate phases would form on the surface of these coatings, reducing their friction coefficient in the (i) room to mid-range and (ii) mid-range to high temperatures, respectively. Silver and vanadium were expected to react with oxygen at high temperatures and create a lubricious silver vanadate film on the coating. The VN/Ag coatings were deposited using unbalanced magnetron sputtering and their elemental composition was evaluated using X-ray photoelectron spectroscopy. The tribological properties of the materials against Si₃N₄ balls were investigated at different temperatures. The lowest friction coefficients recorded for samples with identical compositions were 0.35, 0.30, 0.10 and 0.20 at 25, 350, 700 and 1000 °C, respectively. Post-wear testing Raman spectroscopy and X-ray diffraction (XRD) measurements revealed the formation of silver vanadate compounds on the surface of these coatings. In addition, real time Raman spectroscopy and high temperature XRD revealed that silver vanadate, vanadium oxide and elemental silver formed on the surface of these coatings upon heating to 1000 °C. Upon cooling, silver and vanadium oxide were found to combine at about 400 °C, leading predominantly to the formation of silver vanadate phases on the surface of these materials.     

Effect of high substrate bias and hydrogen and nitrogen incorporation on spectroscopic ellipsometric and atomic force microscopic studies of tetrahedral amorphous carbon films

The influence of substrate bias and hydrogen/nitrogen incorporation on the optical properties [studied by spectroscopic ellipsometry (SE)] and surface morphology [studied by atomic force microscopy] of tetrahedral amorphous carbon (ta-C) films, deposited by S bend filtered cathodic vacuum arc (FCVA) process, is reported. SE spectra of the imaginary part of the dielectric constant are used to estimate carbon bonding ratios. In ta-C films, optical constants increase with substrate bias and hydrogen/nitrogen incorporation. The optical band gap (E_g) and sp³ content increase up to −200 V substrate bias and then decrease. E_g increases with hydrogen incorporation but is unchanged by nitrogen incorporation.     

Aggregation in thin-film silver: Induced by chlorine and inhibited by alloying with two dopants

The Ag aggregation mechanism triggered by chlorine (Cl) is discussed. The frontier orbital theory by K. Fukui is applied in order to determine the growing point in the silver (Ag) cluster. Ag in the thin-film silver would grow to Ag_nCl and stack, triggered by Cl from the outside according to the mechanism described. This would lead to an aggregate with a high Ag density. It is suggested that this would be the generating mechanism of the silver-gray aggregate consisting mostly of Ag, which is generated by exposing it to Cl.Two tactics in order to prevent restrain aggregation induced by Cl according to the mechanism are proposed. Tactic 1 is a restraining of structure change to a plane in the process of Ag₆Cl + Ag → Ag₇Cl. Tactic 2 is the trapping of Cl before it generates a bond to Ag.The ability of the two combined dopants with the abilities of tactics 1 and 2, such as in an Ag alloy including palladium and copper (APC), and including neodymium and gold (ANA) is expected to be very high. The aggregation resistance of an Ag alloy including two dopants is evaluated by a salt water immersion test. The APC and ANA demonstrated a very high resistance to Cl, because of the combination of the dopants working with tactic 1 (Pd, Au) and tactic 2 (Cu, Nd).The multilayer sputter coating with an ANA layer demonstrated a very interesting profile where the light transmittance and the electrical sheet resistance are almost the same as the multilayer sputter coating with a pure Ag. The multilayer sputter coating with AIS also demonstrates a very interesting profile, where the light transmittance is higher than the multilayer sputter coating with a pure Ag.     

Ti2AlC coatings deposited by High Velocity Oxy-Fuel spraying

High Velocity Oxy-Fuel has been utilized to spray coatings from Ti₂AlC (MAXTHAL 211^®) powders. X-ray diffraction showed that the coatings consist predominantly of Ti₂AlC with inclusions of the phases Ti₃AlC₂, TiC, and Al-Ti alloys. The fraction of Ti₂AlC in coatings sprayed with a powder size of 38 μm was found to increase with decreasing power of the spraying flame as controlled by the total gas flow of H₂ and O₂. A more coarse powder (56 μm) is less sensitive to the total gas flow and retains higher volume fraction of MAX-phase in the coatings, however, at the expense of increasing porosity. X-ray pole figure measurements showed a preferred crystal orientation in the coatings with the Ti₂AlC (000l) planes aligned to the substrate surface. Bending tests show a good adhesion to stainless steel substrates and indentation yields a hardness of 3-5 GPa for the coatings sprayed with a powder size of 38 μm.     

Composition and structure-property relationship of low friction, wear resistant TiN-MoSx composite coating deposited by pulsed closed-field unbalanced magnetron sputtering

Effect of MoS_x content has been studied in TiN-MoS_x composite coating deposited by closed-field unbalanced magnetron sputtering (CFUBMS) using separate MoS₂ and Ti target in N₂ gas environment. Pulsed dc power was applied for both the targets as well as for substrate biasing. Crystallographic orientation and structure of the coating was analysed by grazing incidence X-ray diffraction (GIXRD) technique. The surface morphology and coating fractograph were studied with field emission scanning electron microscopy (FESEM) whereas the composition of the coating was determined by energy dispersive spectroscopy (EDS) by X-ray. Scratch adhesion test, Vickers microhardness test and pin-on-disc test with cemented carbide (WC-6%Co) ball were carried out to investigate mechanical and tribological properties of the coating. Increase in MoS_x content (from 6.22 wt.% to 30.43 wt.%) was found to be associated with decrease in grain size (from 63 nm to 24 nm). Maximum hardness of 32 GPa was obtained for TiN- MoS_x composite coating. Film substrate adhesion was also observed to depend on MoS_x content of the composite coating. Significant improvement in tribological properties was observed. With optimal MoS_x content, it was possible to achieve low friction (µ = 0.02-0.04) and wear resistant (wear coefficient = 5.5 × 10^− 16 m³/Nm) composite solid lubricant coating.     

Tensile testing of free-standing Cu,Ag and Al thin films and Ag/Cu multilayers

Free standing polycrystalline thin films with a strong 〈111〉 texture were tested in uniaxial tension. Studied were electron-beam deposited Ag, Cu and Al films, and Ag/Cu multilayers consisting of alternating Ag and Cu layers of equal thickness, between 1.5 nm and 1.5 μm (bilayer repeat length, λ, between 3 nm and 3 μm). The films had a total thickness of about 3 μm. A thin polymeric two-dimensional diffraction grid was deposited on the film surface by microlithographic techniques. Strains were measured in situ from the relative displacements of two laser spots diffracted from the grid. The average values of the Young’s moduli, determined from hundreds of measurements, are 63 GPa for Ag, 102 GPa for Cu, 57 GPa for Al and 87.5 GPa for Ag/Cu multilayers. In all cases, these values are about 20% lower than those calculated from the literature data and, for the Ag/Cu multilayers, are independent of λ. No “supermodulus” effect was observed. The 20% reduction in modulus is most likely the result of incomplete cohesion (“microcracking”) of the grain boundaries. The ductility of the Ag/Cu multilayers decreases when λ is reduced. For λ<80 nm, the films are brittle at room temperature: they break without macroscopic plastic flow. For λ>80 nm, the yield stress increases with decreasing λ according to a Hall–Petch-type relation. No softening with decreasing grain size was observed even at the lowest values of λ.     

Adhesion characteristics of copper thin film deposited on PET substrate by electron cyclotron resonance-metal organic chemical vapor deposition

The adhesion characteristics of Cu/C:H films on the pretreated PET (polyethylene terephthalate) substrate prepared by ECR-MOCVD with a periodic DC bias system were investigated in the aspect of surface energy, surface morphology, roughness, and adhesion force. For a chromo-sulfuric acid pretreatment, the surface roughness of PET substrate was increased up to a maximum value at 60 min of acid-soaking time, followed by a gradual decrease for longer acid-soaking times. The changes of surface energy by various pretreatment methods (such as Ar-ion implantation, O₂ plasma, chromo-sulfuric acid, and sandblasting) barely affected on the adhesion force because the pretreated PET was changed into hydrophobic surface through ECR-plasma polymerization of hfac (1,1,1,5,5,5-hexafluoro-2,4-pentandione) ligand of copper precursor. The acid pretreatment followed by ECR-deposition was confirmed as an effective method for the good adhesion of copper thin film on PET substrate at room temperature. The adhesion force of deposited metallic films primarily depended on the surface roughness of the pretreated substrate, and there was no strong correlation between the surface energy of the pretreated PET and the adhesion force of deposited Cu/C:H films.     

The influence of SDS and CTAB surfactants on the surface morphology and surface topography of electroless Ni–P deposits

The effect of surfactants sodium dodecyl sulphate (SDS) and cetyltrimethyl ammonium bromide (CTAB) on the surface roughness, surface morphology and surface topography of electroless nickel (EN)–phosphorus surface protective coating obtained from an alkaline bath is presented in this paper. In this study the influence of surfactant concentrations on the surface roughness of coated samples were investigated. It was observed that the surface roughness, surface morphology and surface topography of Ni–P coating were clearly influenced by the addition of surfactants SDS and CTAB. EN deposits with addition of surfactant SDS and CTAB at a concentration of 0.6 g/l produce a smooth surface and the average roughness (R_a) value is 1.715 μm for SDS and 1.607 μm for CTAB which is less than the R_a value of EN deposit without surfactant addition (1.885 μm). The mean average roughness (R_a) value with addition of surfactant is 1.796 μm.EN deposit with addition of surfactants consists of a significant fraction of particles of nickel. In the presence of SDS, fine nickel particles have dispersed uniformly on the substrate surface resulting in smoother surface finish of the deposited layers. In the presence of CTAB, at lower concentrations (upto 0.6 g/l) coalescence of nickel particles have been deposited on the substrate surface and at the higher concentration (above 0.6 g/l) uniformly improved surface finish of the deposited layer is resulted. The complete experimental details, results obtained and their analysis are presented in this paper.     

The effect of the microstructure and the surface topography on the electrical properties of thin Ag films deposited by high power pulsed magnetron sputtering

In this work thin silver (Ag) films are grown employing high power pulsed magnetron sputtering (HPPMS) for various pulse on/off time configurations, as well as by dc magnetron sputtering (dcMS), for reference. It is shown that the increase of the pulse off-time from 450 μs to 3450 μs, while the pulse on-time is kept constant at 50 μs, results in an increase of the peak target current (I_Tp) from 3 A to 22 A. The increase of I_Tp is accompanied by an increase of the ion flux towards the growing film. This is particularly pronounced for I_Tp > 11 A. The microstructure, the surface topography and the electrical properties of Ag films grown at I_Tp = 11 A, I_Tp = 22 A and by dcMS are investigated, as a function of the film thickness d. It is shown that for d > 20 nm the electrical resistivity of films sputtered at I_Tp = 22 A is similar to that of films grown by dcMS. Slightly higher values are measured for films grown at I_Tp = 11 A. It is found that in this thickness range the film conductivity is strongly affected by the vertical grain size and the scattering of the charged carriers at the film interfaces. For d < 15 nm the resistivity of films deposited at I_Tp = 22 A is substantially lower as compared to that of films grown by dcMS. Films deposited at I_Tp = 11 A exhibit also in this case a higher conductivity. In this thickness regime the electronic transport and, thus the conductivity are profoundly determined by the surface topography and the film density.     

Effects of tetrahedral amorphous carbon film deposited on dental cobalt–chromium alloys on bacterial adhesion

The dental cobalt–chromium alloys are an important biomaterial used in making artificial dentures. Bacterial adhesion to cobalt–chromium alloys usually results in severe complications such as periodontal infection, secondary caries, and denture stomatitis, which have severe adverse impacts on human health. Therefore, an effective method is needed to reduce the bacterial adhesion to dental cobalt–chromium alloys. The aim of this study was to investigate the effects of ta-C films deposited on a dental cobalt–chromium alloy on the adhesion of Streptococcus mutans (ATCC175), Actinomyces viscosus (ATCC19246) and Candida albicans (ATCC76615). A filtered cathodic vacuum arc (FCVA) technique was used to coat the cobalt–chromium alloy with a ta-C film. Atomic force microscopy (AFM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to analyze the surface characteristics of the coating. Surface roughness was detected. Surface free energy and its components were calculated by measuring the contact angle. The results showed that the maximum sp³ fraction was achieved at 200 V substrate bias voltage. Compared with uncoated specimens, the ta-C film coated specimens had a lower surface roughness, a higher surface energy and a higher hydrophilicity. Most importantly, the adhesion of the three tested bacterial strains to the ta-C film coated cobalt–chromium alloy was significantly decreased. These results showed that ta-C film surface treatment could significantly reduce the bacterial adhesion to dental cobalt–chromium alloys, suggesting the potential of ta-C film surface treatment in artificial denture applications.     

Elastic properties of Ni and Ni + Mo coatings electrodeposited on stainless steel substrate

Adhesion coefficient and Young's modulus of Ni and Ni + Mo coatings electrochemically deposited on stainless steel were examined by applying vibrating reed technique. It was shown that adhesion coefficient of the Ni coating slightly decreases (about 8%) with increasing layer thickness (5-40 μm). Young's modulus E_f of these coatings at room temperature was found to be about 130 GPa. The relative adhesion coefficient of the Ni layer decreases with increasing temperature (300-600 K) in relation to the thinnest examined layer (5 μm). Young's modulus of the Ni + Mo coatings decreases with increasing Mo content; for 9 wt.% of Mo E_f = 40 GPa and for 32 wt.% of Mo E_f = 23 GPa.     

In situ imaging of dealloying during nanoporous gold formation by transmission X-ray microscopy

The dealloying process is directly imaged, for the first time, by using transmission X-ray microscopy for the case of an Ag–30 at.% Au wire dealloyed under free corrosion in nitric acid. The propagation of a sharp dealloying front separating the alloy from nanoporous Au was observed by two-dimensional real-time in situ imaging at 30 nm resolution and measured in detail in three dimensions by an ex situ nanotomography technique at fixed time intervals. The rate of the dealloying front propagation is independent of the dealloying time up to a 3 μm depth, indicating that the dealloying process to this depth is dominated by interfacial effects (i.e. gold surface diffusion and/or silver dissolution) rather than long-range transport effects (i.e. diffusion of acid and corrosion product in and out of the porous layer). The constant dealloying rate corresponds to a constant silver flux and a constant current density, even though the potential might be fluctuating under free corrosion conditions and the interfacial area is shrinking as a function of time. Free corrosion in this system generates a high current density, implying it is driven by a chemical potential difference that is much higher than the critical potential.     

Mechanical properties of thermal barrier coatings after isothermal oxidation.: Depth sensing indentation analysis

Thermal barrier coatings (TBC) are extensively used to protect metallic components in applications where the operating conditions include aggressive environment at high temperatures. Isothermal oxidation degrades the performance of these coatings, so this work analyses the mechanical properties (Young's modulus, E, and hardness, H) of TBC and its evolution after thermal exposure in air. ZrO₂(Y₂O₃) top coat and NiCrAlY bond coating were air plasma sprayed onto an Inconel 600 Ni base alloy. The TBC were isothermally oxidized in air at 950 °C and 1050 °C for 72, 144 and 336 h. Depth sensing indentation tests were carried out on the ceramic coating to evaluate E and H in the as-sprayed materials and after isothermal oxidation. An approach based on multiple tests at different loads was used to determine size independent apparent E an H. These mechanical properties, measured perpendicular to the surface, clearly decreased after isothermal oxidation as a consequence of microcracking within the ceramic coating.     

Microstructures and cyclic oxidation behaviour of Pt-free and low-Pt NiAl coatings on the Ni-base superalloy Rene-80

Aluminizing of bare and 3 μm-Pt-electroplated specimens has been utilised to prepare NiAl and low platinum (Ni,Pt)Al coatings. Cyclic oxidation of the coatings was investigated by exposing samples to 1 h cyclic oxidation at 1100 °C. The modified coating exhibited an external layer of NiAl-25 vol.% PtAl₂ above a three-zone structure. This structure endured over the whole testing time, while the NiAl coating failed after 77 cycles. The (Ni,Pt)Al coating did not reduce the scale growth rate, but it improved scale adhesion. In addition, Pt limited the outward diffusion of Ti from substrate and hence prohibited formation of undesirable TiO₂.     

Adhesion Behavior of <Emphasis Type="Italic">Escherichia coli</Emphasis> on Plasma-Sprayed Zn and Ag Co-incorporated Calcium Silicate Coatings with Varying Surface Roughness

Our previous work demonstrated the good biocompatibility and bactericidal activity of a plasma-sprayed Zn and Ag co-incorporated calcium silicate ceramic coating (Ag-Ca₂ZnSi₂O₇), namely Ag-HT. In this work, we evaluated the influence of the surface roughness of Ag-HT coatings for Escherichia coli adhesion behavior, considering that surface topography is an important factor that regulates bacterial responses to biomaterials. Surface characteristics of as-sprayed and satin-finished Ag-HT coatings were investigated by scanning electron microscopy and measured using a surface roughness tester. Bacterial adhesion experiments showed that the number of viable E. coli cells on the as-sprayed or satin-finished coating surfaces was substantially lower than on the Ti-6Al-4V control surface, which can be explained by the antimicrobial effect of Ag and/or Zn. Moreover, the density of E. coli on the as-sprayed Ag-HT coating was considerably lower than on the satin-finished derivative. We attribute this difference to the fact that the as-sprayed coating surface was relatively smooth at a scale comparable to the size of an individual bacterium, while the satin-finished surface was slightly rough at this length scale and thus favored bacterial adhesion.     

Antibacterial TaN-Ag coatings on titanium dental implants

Titanium-based materials have been used for dental implants due to their excellent biological compatibility, superior mechanical strength and high corrosion resistance. The osseointegration of titanium dental implants is related to their composition and surface treatment. A better anti-bacterial performance of the abutment seated in the prosthetic crown is beneficial for the osseointegration and for avoiding the infection after implantation surgery. In this study, TaN-Ag coatings with different Ag contents were deposited on a bio-grade pure Ti dental implant material. A twin-gun magnetron sputtering system was used for the deposition of TaN-Ag coatings. The Ag content in the deposited coatings was controlled by the magnetron power ratio of Ag/(Ta + Ag) targets. To verify the susceptibility of implant surface to bacterial adhesion, Staphylococcus aureus, one of the major pathogen frequently found in the implant-associated infections, was chosen for in vitro anti-bacterial analyses. In addition, the biocompatibility of human gingival fibroblast (HGF) cells on coatings was also evaluated. A composite structure of crystalline TaN and Ag nanoparticles was identified. The TaN-Ag coating with the highest Ag content of 21.4 at.% possessed the lowest bacterial retention and viability of S. aureus. From the MTT assay test, the mean optical density values for the TaN and TaN-Ag coated samples after 72 h of HGF adhesion were greater than the value obtained from the uncoated Ti. The results suggested that the TaN-Ag coatings improve antibacterial performance with compatible biological response.