ICMCTF2015 Session GP: Symposium G Poster Session

Thursday, April 23, 2015 5:00 PM in Room Grand Hall

Thursday Afternoon

Time Period ThP Sessions | Topic G Sessions | Time Periods | Topics | ICMCTF2015 Schedule

GP-1 Characteristics of SiOC(-H) Films with Line Type Atmospheric Pressure Plasma Enhanced CVD Method
Takanori Mori, Taiki Masuko, Tetsuya Suzuki (Keio University, Japan)

Silica-based films are widely used by polymeric materials for industrial fields due to their properties such as optical transparency, gas barrier property, hardness and low-k. A linear type atmospheric pressure plasma enhanced chemical vapor deposition (AP-PECVD) method using DBD system has been attracted much attention as a method of high-speed synthesis to large area. However, deposition on a tridimensional figuration or thick substrate using a conventional linear type AP-PECVD method is impossible because substrates set in the discharge region whose gap typically is a few millimeters. A remote-type PECVD method which the plasma stream exits the discharge generation region between electrodes enables the deposition to complex configuration substrates.

In this study, we designed and set up a line type AP-PECVD equipment capable of deposition on tridimensional or thick substrate to large area. We synthesized SiOC(-H) films by this equipment under atmospheric pressure and investigate the properties of the SiOC(-H) films for potential application to industrial field. The SiOC(-H) films were prepared using trimethylsilane (TrMS) gas as a raw material because TrMS is a gas phase at room temperature in contrast to other organosilicon compounds. Silicon wafers with a thickness of 0.38 mm were set on a movable plate at a distance of 10 mm under the bottom of electrodes. Process gases, helium as a dilution gas and oxygen as oxidation of TrMS, were introduced between the parallel plate electrodes. The voltage between electrodes was changed from 10 kV to 15 kV. From the OES results, it was found that the plasma was produced outside of electrodes by the penning ionization with nitrogen in air. The hardness of the SiOC(-H) films exhibited about 1.1 GPa with high voltage at 15 kV. The SiOC(-H) films consisted of particles under any experimental conditions and the deposition rate of the films increased with an increase the particle size. From FT-IR spectra, the intensity of hydroxy group and the shape of Si-O-Si bonds were strongly depended on deposition condition. The improvement of hardness of the films should be owing to increase network structure of Si-O-Si bonds which had a densely structure similar to SiOx depending on degradation of raw material and oxidization of the films.
GP-2 Plasma-Nitriding Assisted Micro-Texturing onto Stainless Steel Molds
Tatsuhiko Aizawa (Shibaura Institute of Technology, Japan); Tetsuya Yamaguchi (Sanko-Light Engineering, Co. Ltd., Japan)
Micro-textured surface and interface promotes the joining strength between engineering plastic part and silicone even at the presence of thin adhesive primer layer. Under the minimum quantity lubrication condition, micro-dimples on the sliding interface work as an oil pocket to significantly reduce the friction coefficient even in the mixed lubrication regime. However, formation of these micro-dimple patterns onto the steel and plastic parts by mechanical milling, needs huge amount of lead-time for preparation of CAM data and actual machining process; e.g. it takes 107 s for mechanical machining of micro-dimples with the diameter of 20 mμm onto 70 x 120 mm2 mold-die surface.

In the present paper, the plasma nitriding assisted texturing is proposed as an alternative method to form the millions of micro-dimples on the stainless steel mold-die surface in the order of 104 s. First, the original micro-texture pattern is printed onto the mold-die surface and followed by the low temperature plasma-nitriding. In the latter, significant amount of nitrogen atoms is infiltrated into the unmasked regions of surface; e.g. 5 mass% down to the depth of 16 – 20 mμm after plasma-nitriding for 7.2 ks at 693 K. Since the unmasked regions have hardness more than 1400 Hv, the printed micro-patterns are selectively removed down to 10-15 mμm in depth via the mechanical blasting for 100 s. This surface-treated mold-die is utilized as a mold for injection molding of plastic parts; i.e. the micro-dimple pattern formed on the mold-die by the present method is transferred onto the surface of plastic parts as a micro-bump pattern.

GP-4 Micro-Texturing into CVD-Diamond Coatings via Hollow-Cathode Oxygen Plasma Etching
Ercy-Edo Yunata, Tatsuhiko Aizawa (Shibaura Institute of Technology, Japan)
The CVD diamond films have been utilized not only for protective coating of tools but also for semi-conductive coating with sufficient mechanical properties even at the elevated temperature. In the former, the diamond-coated molds and dies with the designed micro-textures on their surface are expected to be working for duplication of micro-pillars and micro-grids onto the metallic parts and the oxide-glass optical elements. In the latter, bio-MEMS circuits are formed onto the thin and thick diamond coatings for bio-MEMS applications.

In the present paper, the hollow-cathode oxygen plasma etching system is developed to make fast-rate micro-texturing onto the CVD-diamond coatings with the depth of 20 μm on the WC (Co) and silicon substrates. Two types of imprinting procedures are employed to construct the original two-dimensional micro-patterns onto the surface of diamond films: ink-jet printing and mask-less patterning. The former method is used to imprint the micro-dot and micro-line patterns with the characteristic size down to 10 μm onto the diamond film. After the present etching for 7.2 ks, these 2D micro-patterns are transformed into micro-disc and micro-grid textures with the height of 20 μm. Through precise analysis by the Raman spectroscopy, no diamonds area left on the etched bottom surfaces of these micro-textures. The surface profiling measurement proves that the formed edges in these micro-discs and micro-grids have higher steep angles than 87o. The latter method is also used to make finer micro-textures with the spatial resolution down to 1 μm. Micro-pillar patterns with higher aspect ratio than 10.0 are formed by this high-density plasma etching when starting from the 2D micro-dot patterns with the diameter of 1 μm.

GP-5 Aceylene Plasma Polymer Films Treated by Argon Plasma Immersion Ion Implantation
Rogério Pinto Mota, Roberto Yzumi Honda, NilsonCristino Cruz, ElidianoCipriano Rangel (São Paulo State University - UNESP, Brazil); DeborahCristinaRibeiro dos Santos (College of Technology, CEETEPS-Pindamonhangaba-SP-Brazil)
Structural and surface properties of acetylene plasma polymer films were carried out as a function of the time treatment using Plasma Immersion Ion Implantation (PIII). The polymer films were obtained from acetylene-argon mixture using radiofrequency glow discharge and then treted by argon PIII in several times.It was used XPS(X-ray photoelectron spectroscopy) to analyze the composition of the films before and after PIII treatment.With rising exposure time, XPS revealed an increase of oxygen to carbon (O/C) atomic ratio from 0.23 to 2.43. It can be explained by recombination processes between dangling bonds or created radicals in the polymer structure and atmospheric water and oxygen. It was observed that the film structure was predominantly formed C-H and C-C bonds, but there was an increment of the C=O proportion bonds upon argon PIII teatment. The wettability of the polymer films was investigated using contact angle measurements for water. After the argon ion implatation, the contact angle was reduced form 55 to 24 degrees, attributed to incorporation of polar groups in the polymer structure. Upon aging in atmosphere, all samples lost the high wettability, but the hydrophilic character of the films was maintained. It was used atomic force microscopy (AFM) to investigate the roughness of the samples. After argon PIII treatment, the roughness of the polymer films decreased from 8.1 to 5.5 nm, mainly due to ablation processes like sputtering one. The hardness and elastic modulus of the polymer films were investigated by nanoindentation technique. The hardness was enhanced from 0.68 to 5.35 GPa and the elastic modulus increased from 28 to 97 GPa. In general, the results show that argon PIII turned acetylene plasma polymer films smoother and mechanically more resistant. This effect depends on plasma immersion ion implantation treatment time.
GP-6 Thin Films Growth by PIIID Technique from Hexamethyldisilazane/Aargon Mixture
Felipe Vicente de Paula Kodaira, Rogério Pinto Mota, Pedro William Paiva Moreira Jr. (São Paulo State University - UNESP, Brazil)

Thin films growth by plasma techniques are very attractive due to its applicability in many sectors, such as electronics, biologics, optics, mechanics, covering, among others for its properties including high cross-linked structure, homogeneity, insolubility in mild acids and bases, controlled thickness and good adhesion to different substrates.

In this work, plasma polymerized hexamethyldisilazane/Argon films (ppHMDSN/Ar) were deposited in a stainless steel parallel plates reactor. The plasma was fed by a radio-frequency source at 50W and 13.56MHz, and ions were implanted by a -10kV and 10Hz source. The total pressure inside the chamber was 80mTorr, where the monomer HMDSN and the Ar gas were mixed in several different proportions, keeping the total pressure constant in every condition.

The properties of the film observed were its molecular structure, contact angle for water, surface energy, refractive index, thickness and hardness.

The molecular structure was characterized by FTIR spectroscopy where absorptions were observed from 2960 to 2900 cm-1, 2130 cm-1, 1410 cm-1, 1260 cm-1, 1180 cm-1, 1025 cm-1, from 1020 to 1100 cm-1, 940 cm-1, 850 cm-1, 800 cm-1, 680 cm-1, corresponding to stretching CHx, stretching Si-H, CH3 bending in Si-(CH3)x, N-H bending, CH2 wagging in Si-CH2-Si bonds, Si-O stretching in Si-O-Si, Si-N stretching in Si-H-Si, CH3 rocking in Si-(CH3)3, stretching of the Si-C bonds in Si-(CH3)2, wagging Si-H.

The contact angle and surface energy was measured by goniometric technique, the contact angle for water was approximately 98 degrees and the surface energy 30mJ/m2. Showing an hydrophobic behavior.

A UV-Visible technique was used to evaluate its refractive index, presenting values from 1.56 to 1.64.

The thickness of the films showed values from 96 to 210nm using profilometry.

Hardness values from 0.9 to 2.6GPa were obtained using nanoindentation technique.

GP-7 Performance of Carbide Coated Tools with DLC in the Drilling of SAE 323 Aluminum Alloy
William Silva (FCA - Botucatu, UNESP – Univ. Estadual Paulista, Brazil); Jose Carneiro, Leisiane Jesus (Pontificia Universidade Catolica de Minas Gerais, Brazil); Vladimir Airoldi (Instituto Nacional de Pesquisas Espaciais, Brazil)

It is widely known that the performance of a drilling tool increases with the application of coatings. Nowadays, the most widely used coatings for machining aluminum alloys are TiCN and TiN, due to their mechanical properties such as high hardness with low friction. This work presents a study on the performance of cemented carbide coated with diamond-like carbon (DLC) in the drilling of aluminum alloy, since the DLC is a promising material as a coating and has the same mechanical characteristics of the coatings used regularly. Samples of DLC coatings were deposited using PECVD. Initially, the adhesion between film and substrate did not occur. In order to avoid this, it was added intermediate silicon layer. After an extensive investigation of the deposition parameters, drilling coated tools were obtained. The characterization of the tool substrate through the X-ray diffraction showed the standard pattern of the WC-Co. For the coating, the typical spectrum of DLC was checked by Raman spectroscopy. An amount of two hundred pieces of molten on aluminum alloy (SA-323) were chosen for the respective analyzes of roundness, radial deviation, deviation of diameter and roughness. All these geometries were measured as a function of the number of holes produced by each tool, under coated and uncoated condition. Visual inspections by SEM and EDX analysis of worn tool were performed before and after each sequence. Finally, it was found that the DLC coating improves the tool performance, improving the geometry quality. However, the effect of peeling on the coating gradually increased.

GP-9 Formation of Carbon Nanotube by Thermal CVD Method with Addition of Water into Source Gas
Akira Hirai, Yutaro Ueno, Anas Almowarai, Yoshiyuki Show (Tokai University, Japan)

The chemical vapor deposition (CVD) method is one of the reliable methods for growing carbon nanotubes (CNT). This method generally enables growing the vertically aligned CNTs on the substrate, which is a suitable feature as the interconnections in an integrated circuits (IC) and electrodes of electrical double layer capacitors (EDLC) etc. It has been reported that the water addition into the source gas increased the growth speed of CNT. In this study, the effects of the water addition on the CNT growth was investigated.

Vertically aligned CNTs were formed by using thermal CVD method on Si substrate. Fe particles on Si substrate were used as the catalyst of CNT growth. Acetylene and argon gases were used as source gas. The concentration of acetylene gas and the total gas flow rate were kept at 2 % and 1000 sccm, respectively. Water addition into the source gas was carried out by flowing argon gas into the water. The flow rate of argon gas flowing into the water was varied from 0 sccm to 10 sccm in order to control the concentration of water vapor in the source gas. Growth temperature and time was 750 oC and 15 minutes, respectively.

The vertically aligned CNTs with the length of 140 micro meters were formed on the Si substrate without the addition of the water vapor into the source gas. The growth speed of the CNTs was increased with the addition of the water vapor. The CNTs with the length of 520 micro meters were formed at the growth time of 15 minutes, when the argon gas was flowed at 6 sccm into the water for the addition of the water vapor into the source gas. When the argon gas was flowed into the water above 7 sccm, the growth speed was decreased. At the flow rate of 8 sccm, the length of the CNT was lower than that of the CNT deposited without the addition of water.

The above results indicate that the water in the source gas prevents forming amorphous carbon and enhances the catalytic reaction of the Fe particle. Therefore, the growth speed of the CNT was increased by the addition of water. However, the water in the source gas also reacts to the CNT surface and decrease the growth speed of the CNT when the high amount of water is added.
GP-10 Preparation of Ceramic Core with High Strength using Inorganic Precursor and Gel-casting Method
Geun-Ho Cho, Jing Li, Eun-Hee Kim, Yeon-Gil Jung (Changwon National University, Republic of Korea)
Ceramic cores with high fracture strength were prepared with an inorganic precursor binder, which consists of tetraethyl orthosilicate (TEOS) and sodium methoxide (NaOMe), using a gel-casting method for the investment casting of hollow components. The ceramic powders were mixed in an aqueous solvent with or without the inorganic precursor binder, and then the gel-casting process proceeded. In this study, two processes were employed to improve the strength; the inorganic binder was infiltrated onto the ceramic core after the gel-casting (process I) and the gel-casting was performed with the powders coated with the inorganic binder (process II). Both cases did not show any shrinkage and shape deformation. The process II indicated the higher fracture strength of about 10 MPa than process I, after heat treatment at 1000°C for 1h. The Na element from NaOMe was uniformly detected for process II in EDS analysis, while the inorganic binder in process I showed a limited infiltration depth, indicating that the coating sequence has an important influence on the fracture strength in the coating process combined with the gel-casting method. The relationship between thermomechanical properties and process parameters is extensively discussed based on microstructure development.
GP-11 Effect of Electroless Nickel Interlayer on Erosive and Corrosive Behavior of PVD-(Cr, Zr)N Multilayer Coated ADI
Cheng-Hsun Hsu, Chun-Hao Peng, Pi-Ching Pan (Tatung University, Taiwan); Chung-Kwei Lin (Taipei Medical University, Taiwan)
This study utilized electrloess nickel (EN) and cathodic arc deposition (CAD) technologies, with the known advantage of low processing temperature, to treat the austempered ductile iron (ADI) substrates. The feasibility of applying the EN as interlayer for CrN/ZrN multilayer films on ADI, along with the coating properties, such as roughness, hardness, and adhesion were evaluated and analyzed. Moreover, the microstructures of ADI were observed before and after both the surface treatments. In addition, erosion tests and polarization tests were performed to understand the coating effect on the erosive and corrosive behavior of ADI. The results showed that the unique microstructure of ADI did not deteriorate after the EN and CAD treatments. The CrN/ZrN coating was a nano-multilayer type to have the per-layered thickness of about 42 nm, while the EN coating was an amorphous structure mixed with a little of Ni3P crystalline. When the CrN/ZrN coating had a 25μm-EN as interlayer, not only there was an increase in coating hardness and adhesion to raise the erosion resistance, but also the corrosion resistance was remarkably improved.
GP-12 Structural Analysis of the Enhanced Gas Barrier Properties of γ-APS Coating on Polypropylene after Plasma Treatment
Kazuhisa Tsuji (Keio University, Japan); Akira Uedono (University of Tsukuba, Japan); Atsushi Hotta (Keio University, Japan)

Our current study on the successful plasma treated γ-APS coating of polypropylene (PP) has improved the gas barrier property of PP by a factor of 15. The positron annihilation lifetime spectroscopy (PALS) revealed the decrease in the size of the free volume at the surface of the plasma treated γ-APS coating. To understand the mechanism of the improvement in the gas barrier properties of γ-APS/PP, this work focused on the investigation of the relation between the gas barrier enhancement and the structural change of γ-APS/PP caused by the alteration of the plasma power.

The plasma treatment time was fixed to 5 seconds, while the plasma power was shifted from 50 to 200 W. It was found that the oxygen transmission rate (OTR) was considerably reduced from 809.3 cc/m2/day/atm to 262.9 at the power of 200 W. The atomic fractions of the components of Si, O, C, and N at the surface of the γ-APS/PP were analyzed by X-ray photoelectron spectroscopy (XPS), revealing that C-atom fraction was decreased from 37.5% to 13.9% and Si-atom fraction increased from 17.8% to 23.5% after the plasma treatment. It was consequently surmised that the γ-APS surface was converted into SiOx by the plasma treatment, while the C-atom fraction was decreased by the etching effect of the plasma. The C-atom was found to be at the fragment state of C4H10N or C8H14NO after the treatment, which was revealed by the time of flight secondary ion mass spectroscopy (TOF-SIMS). Such fragments were considered to make the free-volume size larger, and thus the decreasing amount of the C-atom fraction was important for the improvement of the gas barrier properties. In fact, the C/Si ratio calculated from the fractions was found to be strongly related to the OTR results, which was also confirmed in other plasma treatments. It was concluded that the effective plasma processing of the γ-APS crosslinkings into SiOx and the significant reduction of the amount of C fragments lessened the size of the free volume at the surface of the plasma-treated γ-APS coating, leading to the improvement in the gas barrier properties of PP.

GP-13 Surface Hardening of a SAE 1045 Steel by Plasma Transferred Arc
Cesar Neitzke, Fred Amorim, Irionson Bassani, Paulo Soares Jr, Ricardo Torres (Pucpr, Brazil)
The aim of this work was to hard a surface of SAE 1045 by plasma transferred arc torch, a processes typically used for metal cutting. It was investigated parameters such as electric current, torch speed and torch distance, using argon gas with a pressure of 6 bar. As dependent variable, the size and the shape of the modified plasma arc layer, adjacent to the surface, was evaluated. It was also characterized the microstructure and the hardness of the SAE 1045 modified by plasma arc. It was found that using the plasma arc power source an optimum process parameters can be achieved, consequently the steel surface was properly hardened. It was found two distinct modified regions, one partially and the other fully martensitic with a maximum surface hardness of 750 HV.
GP-15 Study of Cracks Induced by Laser Shock in Plasma Sprayed Ceramic Coatings with 3D Structuration of the Interface
Hélène Sapardanis, Vincent Guipont, Alain Köster, Jean-Dominique Bartout, François Borit, Vincent Maurel (Ecole des Mines, France)

Plasma sprayed ceramic coatings are used for various industrial applications like thermal insulation, electrical insulation or corrosion protection. The interfacial strength of a ceramic coating is a key issue to achieve reliable coated components. The laser shock technique allows to debond a ceramic coating. The LASAT method (LAser Shock Adhesion Test) enables to measure the adhesion strength of a ceramic coating if the crack is located at the interface. In case of conventional ceramic coatings, it leads to a cracked disk area of a few mm² at the ceramic/metal interface and subsequent coating buckling. In this work, the LASAT method is applied to investigate the influence of various morphologies of the substrate on the resulting damage induced by laser shock at the interface or within the ceramic coating. Several processes were implemented to obtain different surface morphologies on a cobalt base alloy substrate. Random or deterministic surface morphologies were carried out involving either removal methods (grit blasting and electric discharged machining) or additive methods (plasma spraying and laser beam melting). A ceramic coating was then deposited on the different structured substrates by air plasma spraying. The size, location and profile of the laser-induced cracks were assessed with both destructive (scanning electron microscopy) and non-destructive (infrared thermography, 3D profilometry) methods. These crack features and the height of the buckling are discussed paying attention to 2D and 3D analyses of the morphology at the interface. The influence of the shock wave propagation through such structured interfaces is also discussed. From the assessment of the debonding behaviour under laser shock, a comparison of the interfacial strength level for the various interfaces is proposed.

Time Period ThP Sessions | Topic G Sessions | Time Periods | Topics | ICMCTF2015 Schedule