Integrated approach to the characterization and conservation of artefacts of the Brazilian colonial period

Several common-use artifacts (coins, faience, cult objects, etc.) coming from two excavations sites near Rio de Janeiro, two sugar farms Historico do Rochedo and Cruzeiro, have been the subject of this investigation, which aimed to integrate physico-chemical characterizations with the identification of degradation mechanisms, and the proposal of innovative conservation methods, such as PECVD deposition of SiO₂-like films for protection of metallic artifacts. For the microchemical, micromorphological and microstructural analysis, optical microscopy-OM, X-ray diffraction XRD, X-ray fluorescence-XRF, and scanning electron microscopy equipped with electron microprobe-SEM+EDS have been employed.A cleaning step followed by a consolidation step has been carried out on glassy artefacts, while on metallic artefacts the mechanical cleaning has been followed by a stabilization treatment when necessary.For long-term protection the deposition by PECVD of SiO₂-like films has been performed on a series of copper-based alloys in a home made reactor fed with an tetraethoxysilane-oxygen-argon mixture. The coatings show a good barrier effect against the diffusion of water and oxygen from the environment to the metal surface, that increases with increasing the oxygen to monomer ratio in the feeding gas mixture and the input power density. Moreover, the coating adhesion increases if the deposition process is performed after a hydrogen plasma treatment. PACS 68.55.Jk; 68.35.Dv; 68.37.Hk; 68.55.Nq; 81.05.Bx     

多腔耦合微波表面波PECVD法沉积 DLC薄膜研究

报道了利用多腔耦合微波表面波等离子体增强化学气相沉积(PECVD)的方法制备类金刚石(DLC)薄膜。通过发射光谱(OES)测量,对Ar等离子体中的各种放电参数以及全部四个腔室内放电的均匀性作出评估。采用表面轮廓仪测量了薄膜的厚度;薄膜的表面形貌、组成结构通过原子力显微镜(AFM)、激光拉曼光谱和X射线衍射光谱(XPS)进行了表征。在12.5μm厚度的有机薄膜聚酯(PET)表面沉积一定厚度DLC后,通过测量水蒸气透过率(WVTR)对DLC薄膜的阻隔性能进行了研究。结果表明,这种多腔耦合微波表面波等离子体装置,不仅能够实现四个腔室同时相对均匀的放电,也能够实现单个腔室的轴向均匀放电。制备的DLC薄膜结构致密、成分均匀,可以使PET薄膜阻隔性能提高约20倍。     

Microwave plasma deposition of diamond like carbon coatings

The promising applications of the microwave plasmas have been appearing in the fields of chemical processes and semiconductor manufacturing. Applications include surface deposition of all types including diamond/diamond like carbon (DLC) coatings, etching of semiconductors, promotion of organic reactions, etching of polymers to improve bonding of the other materials etc. With a 2.45 GHz. 700 W, microwave induced plasma chemical vapor deposition (CVD) system set up in our laboratory we have deposited diamond like carbon coatings. The microwave plasma generation was effected using a wave guide single mode applicator. We have deposited DLC coatings on the substrates like stainless steel, Cu-Be, Cu and Si. The deposited coatings have been characterized by FTIR, Raman spectroscopy and ellipsometric techniques. The results show that we have achieved depositing ∼95% sp³ bonded carbon in the films. The films are unform with golden yellow color. The films are found to be excellent insulators. The ellipsometric measurements of optical constant on silicon substrates indicate that the films are transparent above 900 nm.     

The influence of the structures and compounds of DLC coatings on the barrier properties of PET bottles

To reduce the oxygen transmission rate through a polyethylene terephthalate (PET) bottle (an organic plastic) diamond-like carbon (DLC) coatings on the inner surface of the PET bottle were deposited by radio frequency plasma-enhanced chemical vapour deposition (RF-PECVD) technology with C₂H₂ as the source of carbon and Ar as the diluted gas. As the barrier layer to humidity and gas permeation, this paper analyses the DLC film structure, composition, morphology and barrier properties by Fourier transform infrared, atomic force microscopy, scanning electron microscopy and oxygen transmission rate in detail. From the spectrum, it is found that the DLC film mainly consists of sp³ bonds. The barrier property of the films is significantly relevant to the sp³ bond concentration in the coating, the film thickness and morphology. Additionally, it is found that DLC film deposited in an inductively coupled plasma enhanced capacitively coupled plasma source shows a compact, homogeneous and crack-free surface, which is beneficial for a good gas barrier property in PET bottles.     

Design and fabrication of ultra broadband infrared antireflection hard coatings on ZnSe in the range from 2 to 16 μm

In conventional infrared multilayer antireflection coatings (MLAR) materials of fluoride and chalcogenide types are used, which are disadvantaged due to their low mechanical strength and poor stability against humidity and environmental impacts. In this paper, we show that high performance ultra broadband and hard infrared multilayer antireflection coatings on ZnSe substrates in the wavelength range from 2 to 16 μm can be designed and fabricated. Diamond-like carbon (DLC) hard coating as a mechanical and environmental protection layer was proposed and deposited onto MLAR surfaces (MLAR + DLC) using a pulsed vacuum arc ion deposition technique. The thickness of the high optical quality DLC can be optimized in the design simulation to achieve a practically best antireflection and surface protection performance. We show that a germanium thin film (15 nm) between the MLAR and DLC surfaces can be used as a transition layer for optical and material match. The average transmission of the fabricated MLAR+DLC surfaces was 93.1% in the wavelength range between 2 and 16 μm. The peak transmission was about 97.6%, close to the simulated values. The durability and stability against mechanical impacts and environmental tests was improved significantly compared with the conventional infrared windows.     

Modulation of residual stress in diamond like carbon films with incorporation of nanocrystalline gold

Residual stress modulation in the diamond-like carbon coatings with incorporation of gold nanoparticles was studied critically. The films were deposited on glass and Si (1 0 0) substrates by using capacitatively coupled plasma chemical vapor deposition. Stresses in the films were determined from the broadening of the optical absorption tail and were found to decrease from 2.3 GPa to 0.48 GPa with increasing gold content (2-7 at.% Au) in the DLC matrix. Gold incorporation also made the films harder than the corresponding DLC coatings. Modulation of stress with nanocrystalline gold content in the DLC matrix was related to the relative amount of sp²/sp³ content in the DLC films.     

The microstructure, mechanical and friction properties of protective diamond like carbon films on magnesium alloy

Protective hard coatings deposited on magnesium alloys are believed to be effective for overcoming their poor wear properties. In this work, diamond-like carbon (DLC) films as hard protective films were deposited on AZ91 magnesium alloy by arc ion plating under negative pulse bias voltages ranging from 0 to −200 V. The microstructure, composition and mechanical properties of the DLC films were analyzed by scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and nanoindentation. The tribological behavior of uncoated and coated AZ91 magnesium alloy was investigated using a ball-on-disk tribotester. The results show that the negative pulse bias voltage used for film deposition has a significant effect on the sp³ carbon content and mechanical properties of the deposited DLC films. A maximum sp³ content of 33.3% was obtained at −100 V, resulting in a high hardness of 28.6 GPa and elastic modulus of 300.0 GPa. The DLC films showed very good adhesion to the AZ91 magnesium alloy with no observable cracks and delamination even during friction testing. Compared with the uncoated AZ91 magnesium alloy, the magnesium alloy coated with DLC films exhibits a low friction coefficient and a narrow, shallow wear track. The wear resistance and surface hardness of AZ91 magnesium alloy can be significantly improved by coating a layer of DLC protective film due to its high hardness and low friction coefficient.     

Improvement in the properties of plasma-sprayed metallic, alloy and ceramic coatings using dry-ice blasting

Dry-ice blasting, as an environmental-friendly method, was introduced into atmospheric plasma spraying for improving properties of metallic, alloy and ceramic coatings. The deposited coatings were then compared with coatings plasma-sprayed using conventional air cooling in terms of microstructure, temperature, oxidation, porosity, residual stress and adhesion. It was found that a denser steel or CoNiCrAlY alloy coating with a lower content of oxide can be achieved with the application of dry-ice blasting during the plasma spraying. In addition, the adhesive strength of Al₂O₃ coating deposited with dry-ice blasting exceeded 60 MPa, which was nearly increased by 30% compared with that of the coating deposited with conventional air cooling. The improvement in properties of plasma-sprayed metallic, alloy and ceramic coatings caused by dry-ice blasting was attributed to the decrease of annulus-ringed disk like splats, the better cooling efficiency of dry-ice pellets and even the mechanical effect of dry-ice impact.     

Study of well adherent DLC film deposited on piezoelectric LiTaO3 substrate

A well adherent diamond-like carbon (DLC) film was deposited on piezoelectric LiTaO₃ substrate using PECVD by inserting SiO₂ interlayer. DLC film was characterized using Raman spectroscopy and AFM. Physical and mechanical properties were measured using XRR, ellipsometry, scratch test and nano-indentation. The DLC film exhibits the characteristics of hydrogenated amorphous carbon and a very smooth surface with a 0.25 nm RMS. Scratch test shows that critical load (L_c) is 18 N, which is good enough for applying DLC film to SAW device. The measured mass density, refractive index, hardness and Young’s modulus of DLC film deposited on LiTaO₃ are comparable to the reported values for hydrogenated amorphous carbon film, irrespective of substrates on which the films were deposited.     

超短脉冲准分子激光淀积类金刚石薄膜的实验研究

利用ＫｒＦ超短脉冲激光器开展了超短脉冲激光淀积金刚石薄膜实验研究,薄膜生长速率０．０２ｎｍ／ｐｕｌｓｅ,厚度０．５－０．６μｍ,显微硬度５５ＧＰａ,光学透过率优于９０％,采用等离子本的时间－空间分辨的发射光谱技术,给出了等离子体的粒子成份以及等离子体的时间－空间的演化图像,以及在不同激光参数条件下等离子体特性的变化,发现超短脉冲激光的等离子体有能量高、持续时间短（高通量）的特点,适合类金刚石薄膜的     

Defect effect on tribological behavior of diamond-like carbon films deposited with hydrogen diluted benzene gas in aqueous environment

This study examined the friction and wear behavior of diamond-like carbon (DLC) films deposited from a radio frequency glow discharge using a hydrogen diluted benzene gas mixture. The DLC films were deposited on Si (1 0 0) and polished stainless steel substrates by radio frequency plasma-assisted chemical vapor deposition (r.f.-PACVD) at hydrogen to benzene ratios, or the hydrogen dilution ratio, ranging from 0 to 2.0. The wear test was carried out in both ambient and aqueous environments using a homemade ball-on-disk type wear rig. The stability of the DLC coating in an aqueous environment was improved by diluting the benzene precursor gas with hydrogen, suggesting that hydrogen dilution during the deposition of DLC films suppressed the initiation of defects in the film and improved the adhesion of the coating to the interface.     

Characterization of doped diamond-like carbon films deposited by hot wire plasma sputtering of graphite

Diamond-like carbon (DLC) films doped with nitrogen and oxygen were deposited on silicon(100) and polytetrafluoroethylene (PTFE) substrates by hot wire plasma sputtering of graphite. The morphology and chemical composition of deposited films has been characterized by scanning electron microscopy, XPS, Auger, FTIR spectroscopy and micro-Raman scattering. Plasmon loss structure accompanying the XPS C 1s peak and electron energy loss spectroscopy (EELS) in reflection mode was used to study the fraction of sp³ bonded C atoms and the density of valence electrons. Raman spectra show two basic C–C bands around 1575 cm^-1 (G line) and 1360 cm^-1 (D line) . Auger depth profiling spectroscopy was used to measure the spatial distributions of C, N and O atoms in the surface layer of DLC films. The fraction of sp³ bonded atoms of about 40% was detected in DLC films by XPS plasmon loss and EELS techniques. Nitrile and iso-nitrile groups observed in FTIR spectra demonstrated the existence of sp bonded carbon in doped DLC films. The typical for DLC films specific density 1.7–1.8 g/cm³ was obtained from EELS and XPS data. PACS 52.77.Dq; 81.65.-b; 82.80.Pv     

Effect of H2 and O2 plasma etching treatment on the surface of diamond-like carbon thin film

In this study, we investigated the surface properties of diamond-like carbon (DLC) films for biomedical applications through plasma etching treatment using oxygen (O₂) and hydrogen (H₂) gas. The synthesis and post-plasma etching treatment of DLC films were carried out by 13.56 MHz RF plasma enhanced chemical vapor deposition (PECVD) system. In order to characterize the surface of DLC films, they were etched to a thickness of approximately 100 nm and were compared with an as-deposited DLC film. We obtained the optimum condition through power variation, at which the etching rate by H₂ and O₂ was 30 and 80 nm/min, respectively. The structural and chemical properties of these thin films after the plasma etching treatment were evaluated by Raman and Fourier transform infrared (FT-IR) spectroscopy. In the case of as-deposited and H₂ plasma etching-treated DLC film, the contact angle was 86.4° and 83.7°, respectively, whereas it was reduced to 35.5° in the etching-treated DLC film in O₂ plasma. The surface roughness of plasma etching-treated DLC with H₂ or O₂ was maintained smooth at 0.1 nm. These results indicated that the surface of the etching-treated DLC film in O₂ plasma was hydrophilic as well as smooth.     

Wettability and antibacterial activity of modified diamond-like carbon films

Diamond-like carbon (DLC) films can be used in a numerous industrial applications, including biomedical coatings with bactericidal properties. It has been demonstrated that DLC surface can be modified with oxygen plasma treatment. The purpose of this paper is to study the wettability and bactericidal activity of oxygen plasma-treated DLC films produced by plasma enhanced chemical vapor deposition technique. The sp³/sp² ratio increased after the treatment due to the increase in the generation of the unstable carbon bonds caused by the energetic ions, especially O-H group. The treated DLC surface becomes superhydrophilic and rougher, although the roughness values are still lower. DLC antibacterial activity did not increased with plasma treatment. Therefore, oxygen plasma treatment can be used to make superhydrophilic DLC but not to increase its bactericidal properties.     

Nanoindentation measurements on modified diamond-like carbon thin films

In the present study, we explored the effect of metallic interlayers (Cu and Ti) and indentation loads (5-20 mN) on the mechanical properties of plasma produced diamond-like carbon (DLC) thin films. Also a comparison has been made for mechanical properties of these films with pure DLC and nitrogen incorporated DLC films. Introduction of N in DLC led to a drastic decrease in residual stress (S) from 1.8 to 0.7 GPa, but with expenses of hardness (H) and other mechanical properties. In contrast, addition of Cu and Ti interlayers between substrate Si and DLC, results in significant decrease in S with little enhancement of hardness and other mechanical properties. Among various DLC films, maximum hardness 30.8 GPa is observed in Ti-DLC film. Besides hardness and elastic modulus, various other mechanical parameters have also been estimated using load versus displacement curves.     

Deposition of thick and adherent Teflon-like coating on industrial scale stainless steel shell using pulsed dc and RF PECVD

A unique combination of pulsed dc and radio frequency (RF) discharge deposition was used to deposit thick (∼5 μm) and adherent (2-4 MPa) Teflon-like coatings on a stainless steel (SS) shell of 2 m diameter size, through plasma enhanced chemical vapor deposition (PECVD). The details of deposition on such a big industrial scale component are reported for the first time. In this method, highly adherent thin interface layers were grown on SS shell that was electrically grounded, using pulsed dc discharge, followed by RF discharge deposition to build up the required coating thickness. The fluorocarbon precursor molecules, required for the deposition of Teflon-like coating, are generated indigenously by pyrolyzing the Teflon powder. The deposited coating was studied for its chemical bond state, surface roughness (Ra), morphology, thickness, and adhesive strength. These studies were carried out by using XPS, AFM, SEM, etc. The adhesive strength of the coating was measured by pin-pull test as per ASTM D4541 standard test. The coatings deposited with pulsed dc discharge were observed to have higher adhesive strength when compared with those deposited with RF discharge.     

Deposition of SiOx barrier films by O2/TMDSO RF-PECVD

This paper reports that the SiOx barrier films are deposited on polyethylene terephthalate substrate by plasmaenhanced chemical vapour deposition （PECVD） for the application of transparent barrier packaging. The variations of 02/Tetramethyldisiloxane （TMDSO） ratio and input power in radio frequency （RF） plasma are carried out to optimize barrier properties of the SiOx coated film. The properties of the coatings are characterized by Fourier transform infrared, water vapour transmission rate （WVTR）, oxygen transmission rate （OTR）, and atomic force microscopy analysers. It is found that the 02/TMDSO ratio exceeding 2：1 and the input power over 200 W yield SiOx films with low carbon contents which can be good to the barrier （WVTR and OTR） properties of the SiOx coatings. Also, the film properties not only depend on oxygen concentration of the inlet gas mixtures and input power, but also relate to the surface morphology of the coating.     

横向电场下的类金刚石薄膜激光损伤

类金刚石(DLC)薄膜在红外区有很高的透过率,但激光损伤阈值低,严重限制了其应用领域。采用直接在DLC薄膜上沉积Ti电极,基于激光损伤阈值(LIDT)测试平台,用1-on-1零几率损伤法,研究了在不同偏置电场下DLC薄膜损伤阈值及损伤形貌的变化。发现电场强度从0增加到700V/cm,损伤阈值明显增大;进一步增大偏置电场,损伤阈值相对不变。分析认为偏置电场改变了激光辐照DLC薄膜区域的光生载流子漂移速度,减小了DLC薄膜的局部热累积,减缓了薄膜的石墨化进程,提高了DLC薄膜的抗激光损伤阈值。     

Atomic oxygen resistant behaviors of Mo/diamond-like carbon nanocomposite lubricating films

Mo doped diamond-like carbon (Mo/DLC) films were deposited on Si substrates via unbalanced magnetron sputtering of molybdenum combined with plasma chemical vapor deposition of CH₄/Ar. The microstructure of the films, characterized by transmission electron microscopy and selected area electron diffraction, was considered as a nanocomposite with nano-sized MoC particles uniformly embedded in the amorphous carbon matrix. The structure, morphology, surface composition and tribological properties of the Mo/DLC films before and after the atomic oxygen (AO) irradiation were investigated and a comparison made with the DLC films. The Mo/DLC films exhibited more excellent degradation resistant behaviors in AO environment than the DLC films, and the MoC nanoparticles were proved to play a critical role of preventing the incursion of AO and maintaining the intrinsic structure and excellent tribological properties of DLC films.     

脉冲准分子激光淀积薄膜的实验研究

 利用两种脉宽(30ns，500fs)的KrF准分子激光展开了淀积类金刚石薄膜的实验研究，并且成功地制备了大面积不含氢成分的HF-DLC薄膜，运用时空分辨的等离子体发射光谱诊断系统和离子探针系统研究了等离子体特性对薄膜性能的影响。尝试了利用准分子激光制备非晶硅薄膜，研究了实验参数对非晶硅薄膜制备的影响，并分析了制备具有良好电学和光学性能的非晶硅薄膜的条件。