Na2SO4- and NaCl-Induced hot corrosion of six nickel-base superalloys

The short-time hot-corrosion behavior of six industrial nickel-base superalloys was investigated with static deposits of Na₂SO₄ or NaCl or both in still air. The oxidation kinetics and scale morphologies were measured with traditional laboratory techniques-thermobalance, metallography, electron microprobe, and x-ray analyses. Susceptibility to hot corrosion was found to be correlated to the type of scale produced during simple oxidation. Alloys forming an A1₂O₃ scale were found to be susceptible to Na₂SO₄ deposits, independent of their chromium content. The quantity of Na₂SO₄ deposit dictated the nature of the attack and, under certain conditions, the refractory element alloy additions appeared to play an essential role. Alloys containing Cr₂O₃ or TiO₂ in the simple oxidation scale proved to be sensitive to NaCl attack. Again, the severity of the attack within the susceptible alloy group was not related to the chromium or titanium content. Although less intensive than the Na₂SO₄ -induced hot corrosion, NaCl contaminations provoked extensive spalling. All of the hotcorrosion types encountered in this study were interpreted in the light of existing theories.Supported by the Délégation Générale à la Recherche Scientifique et Technique.     

Microstructure and properties of Nb-Mo-Zr based refractory alloys

Microstructure and mechanical properties of five Nb alloys containing 8 to 17 at.% Mo, 8 or 35 at.% Zr, up to 7 at.% Ti, up to 2 at.% Al and up to 2 at.% Cr are reported. These alloys have been developed to replace heavy, expensive and difficult to process commercial Nb alloys, such as C-3009, for use at temperatures up to 1600 °C. The density of the alloys is in the range from 7.6 to 8.6 g/cm³. The alloys have a BCC matrix phase, and they also contain small amounts of secondary phases, which are rich in Zr and have BCC, FCC, hexagonal or monoclinic crystal structures depending on the concentration of other alloying elements, including oxygen and nitrogen. In the temperature range from 25 °C to 1600 °C, the alloys with a smaller amount of Zr are ductile and have higher specific strength than C-3009. The alloy containing 35 at.% Zr is stronger, but less ductile, than other alloys at temperatures up to 600 °C; however, it loses the strength rapidly at higher temperatures and becomes softer than other alloys at T > 1000 °C. The possible strengthening mechanisms responsible for the observed temperature dependence of the yield stress of the alloys are also discussed.     

Galvanically coupled process for the conversion of Ag2O to AgI

The conversion of Ag₂O, grown-on Ag substrates, to AgI has in been investigated, using open-circuit potential, linear polarization, and potentiostatic control measurements. Three distinct reaction stages were clearly identified from the time-dependent behaviour of the open-circuit potential, E_OC, and the corrosion currents measured by linear polarization. In the early stages, when the silver surface was covered with a coherent Ag₂O film with low porosity, E_OC∼(E^e)_Ag2O/Ag and only chemical conversion of Ag₂O to AgI was observed. As Ag₂O was consumed and the area of Ag exposed to I⁻ solution increased, galvanic coupling of Ag₂O reduction to Ag and the oxidation of the Ag substrate to AgI also occurred. Once all the Ag₂O has been reduced, AgI formation stopped and E_OC fell to (E^e)_AgI/Ag. Chemical conversion was shown to produce fine particulate AgI whereas that formed anodically via galvanic coupling was in the form of large crystals. Since few larger crystals were observed, conversion via galvanic coupling appeared to be a minor process.     

A 19F.N.M.R. study of graphite fluorosulfates

Graphite fluorosulfates, C_nSO₃F, with n = 7 for stage-one materials, are ideally suited for ¹⁹F n.m.r. studies due to the unambiguous identity of the intercalate and its axially symmetric nature. The intensity of the signal shows a clear dependence on the orientation of the c axis with respect to the oscillating radio-frequency field H₁. The chemical shift value, however, is affected by the orientation of the c axis with respect to H₀. The powder spectrum of the stage-one material C₇SO₃F extends from 10 to 100 ppm at low temperatures, while motional narrowing at room temperature contributes to a sharp signal at the lower field end of the powder spectrum, corresponding to an axially symmetric chemical shift tensor. Angular dependence studies on C₇SO₃F samples made from HOPG indicate that the majority of the intercalated SO₃F⁻ ions are oriented with their molecular C₃ symmetry axes parallel to the c axis of graphite, or normal to H₀. Multi-staged samples made from HOPG demonstrate the stage dependence of the chemical shift of intercalated SO₃F⁻ ions. The chemical shift of the stage-one material is observed in the region of 10 – 12 ppm, while higher-staged materials show resonances at less shielded regions.     

Modeling of stress ratio effect on Al alloy SAE AMS 7475-T7351: Influence of loading direction

The main goal of this work was to evaluate the effectiveness of Walker’s equation in collapsing the fatigue crack propagation data of a SAE AMS 7475-T7351 aluminum alloy loaded either longitudinally (L-T) or transversely (T-L) to the rolling direction. T-L orientation testpieces presented lower ductility and fracture toughness values than L-T orientation. As a consequence, during the fatigue crack propagation tests, T-L testpieces exhibited a stronger influence of monotonic modes of fracture, resulting in higher Paris exponent values,m. Walker’s model was able to collapse fatigue crack propagation data of L-T test pieces at different applied stress ratios,R. However, for the T-L orientation, due to theR ratio dependency onm andC, simply averaging ofm values for the calculations of Walker’s exponent proved to be inefficient. A simple analytical procedure was proposed by the authors to modify Walker’s model to take into account such effect. For T-L test pieces, when Walker’s model is modified by considering both Paris’s exponent as well the coefficient as a function of theR ratio, the fatigue crack growth data collapses within a narrow band, thus allowing predictions to be made satisfactorily. The collapsed band is even narrower if the empirical relationm=a+blogC is used instead of simple polynomial equations due to a better correlation coefficient.     

Effects of Li content on microstructure and mechanical properties of as-cast Mg−xLi−3Al−2Zn−0.5Y alloys

The effects of Li content on the microstructure and mechanical properties of the as-cast Mg?xLi?3Al?2Zn? 0.5Y (LAZx32-0.5Y) alloys were investigated by XRD, SEM, TEM, hardness tester and universal testing machine. The results show that the matrix of the alloy transforms from α-Mg to α-Mg+β-Li and then to β-Li when the Li content increases from 4% to 14% (mass fraction). All LAZx32-0.5Y alloys contain AlLi and Al₂Y, while MgLi₂Al appears only in the alloy containing the β-Li matrix. As the Li content increases, the content of AlLi and MgLi₂Al gradually increases, while the content of Al₂Y does not change much. As the Li content increases from 4% to 10%, the ultimate tensile strength and hardness of the as-cast LAZx32-0.5Y alloys gradually decrease while the elongation gradually increases. The corresponding fracture mechanism changes from cleavage fracture to quasi-cleavage fracture and then to microporous aggregation fracture. This is mainly attributed to the decrease of α-Mg and the increase of β-Li in the alloy. When the Li content continues to increase to 10% and 14%, the yield strength, ultimate tensile strength and hardness of the as-cast LAZx32-0.5Y alloys gradually increase, while the elongation decreases sharply, which is mainly attributed to the nano-scale MgLi₂Al uniformly distributed in the β-Li matrix.     

Microstructural Analysis and Photocatalytic Activity of Plasma-Sprayed Titania-Hydroxyapatite Coatings

Hydroxyapatite (HAp Ca₁₀(PO₄)₆(OH)₂) is known to be a biomaterial and an adsorbent for chromatography. In this study, HAp was agglomerated with anatase TiO₂ to manufacture thermal-spray powders to improve the adsorption activity of TiO₂, and then to improve its photocatalytic activity. The microstructures, compositions and photocatalytic activity of plasma-sprayed TiO₂, TiO₂-10%HAp, TiO₂-30%HAp, and HAp coatings were investigated. Due to the low thermal conductivity of HAp compound, not all HAp particles fully melted even under the arc current of 800 A. The addition of HAp inhibited the phase transformation of anatase TiO₂ to rutile. Under the arc current of 600 A, the anatase content in the TiO₂, TiO₂-10%HAp and TiO₂-30%HAp coatings was 11, 20 and 42%, respectively. With the increasing of the spraying distance from 70 to 110 mm, the anatase content in the TiO₂-30%HAp coatings decreased from 34 to 17% under arc current of 700 A. Furthermore, a slight decomposition of HAp to α-Ca₃(PO₄)₂ was found in the TiO₂-30%HAp coatings, it did not decompose to CaO and P₂O₅ according to the XRD and EDAX analysis. The addition of the secondary gas of helium had no significant influence on the melting state of the TiO₂-HAp feedstock powders. Moreover, the HAp in the TiO₂-10%HAp and TiO₂-30%HAp coatings had adsorption characteristic to acetaldehyde. The photocatalytic activity of TiO₂-10%HAp coating was highest among TiO₂, TiO₂-10%HAp, and TiO₂-30%HAp coatings sprayed under the arc current of 600 A for the optimum adsorption property and anatase content. This article is an invited paper selected from presentations at the 2007 International Thermal Spray Conference and has been expanded from the original presentation. It is simultaneously published in Global Coating Solutions, Proceedings of the 2007 International Thermal Spray Conference, Beijing, China, May 14-16, 2007, Basil R. Marple, Margaret M. Hyland, Yuk-Chiu Lau, Chang-Jiu Li, Rogerio S. Lima, and Ghislain Montavon, Ed., ASM International, Materials Park, OH, 2007.     

Multifunctional and Low-Density Inorganic Nanocomposites

We summarize our recent studies on the use of low-density nanoporous silica structures prepared through templating of a self-assembling disordered liquid-crystalline L ₃ phase, as a matrix for use in numerous applications, including sensing, optical data storage, drug release, and structural. The silica matrix exhibits low density (0.5 g cm⁻³ to 0.8 g cm⁻³ for monoliths, 0.6 g cm⁻³ to 0.99 g cm⁻³ for fibers) coupled with high surface areas (up 1400 m² g⁻¹) and void volumes (65% or higher). High-surface-area coatings are used to increase the sensitivity of mass-detecting quartz crystal microbalances to over 4000 times that of uncoated crystals. Monoliths, films, and fibers are produced using the templated silica gel. Once dried and converted to silica, the nanostructured material exhibits high fracture strength (up to 35 MPa in fibers) and Young’s modulus (30 GPa to 40 GPa in fibers). These values are, respectively, two orders of magnitude and twice those of nanostructured silicas having comparable densities.     

Thermal and transport properties of as-grown Ni-rich TiNi shape memory alloys

Electrical resistivity, Seebeck coefficient, specific heat and thermal conductivity measurements on the Ti_50−xNi_50+x (x = 0.0–1.6 at.%) shape memory alloys are performed to investigate their thermal and transport properties. In this study, anomalous features are observed in both cooling and heating cycles in all measured physical properties of the slightly Ni-rich TiNi alloys (x ≤ 1.0), corresponds to the transformation between the B19′ martensite and B2 austenite phases. Besides, the transition temperature is found to decrease gradually with increasing Ni content, and the driving force for the transition is also found to diminish slowly with the addition of excess Ni, as revealed by specific heat measurements. While the signature of martensitic transformation vanishes for the Ni-rich TiNi alloys with x ≥ 1.3, the characteristics of strain glass transition start to appear. The Seebeck coefficients of these TiNi alloys were found to be positive, suggesting the hole-type carriers dominate the thermoelectric transport. From the high-temperature Seebeck coefficients, the estimated value of Fermi energy ranges from ∼1.5 eV (Ti_48.4Ni_51.6) to ∼2.1 eV (Ti₅₀Ni₅₀), indicating the metallic nature of these alloys. In addition, the thermal conductivity of the slightly Ni-rich TiNi alloys with x ≤ 1.0 shows a distinct anomalous feature at the B19′ → B2 transition, likely due to the variation in lattice thermal conductivity.     

Co-Sn单相合金深过冷凝固时Co3Sn2 相生长形貌的演变机制

开展了(Co₆₀Sn₄₀)_100-xNb_x (x=0,0.4,0.6,0.8,at%)单相合金的深过冷凝固实验,研究了Co₃Sn₂相生长形貌的演变机制。结果表明,在小过冷度下,Co₃Sn₂相在x=0,0.4以海藻状的模式进行生长,随着添加的Nb含量增加至0.6at%,其生长形貌转变为树枝晶,并在x=0.8进一步转变为分形海藻晶,这主要是由于界面能各向异性和动力学各向异性的变化。随着过冷度的增加,(Co₆₀Sn₄₀)_99.4Nb_0.6合金中Co₃Sn₂相生长形貌在过冷度大于28 K时从树枝晶转变为分形海藻,当过冷度高于143 K时转变为密集海藻。少量的Nb添加在小过冷度和中间过冷度时能提高Co₃Sn₂相的生长速度,但是在大过冷度下会显著降低生长速度。Co₃Sn₂相生长速度随过冷度变化规律的转变对应其生长形貌从分形海藻向密集海藻的转变。     

CO2对H2S／CO2环境中P110钢应力腐蚀的影响研究

采用恒载荷拉伸法、腐蚀电化学测试和断口分析技术等,研究了P110钢在不同H2S／CO2含量的NACE-A溶液中的硫化物应力腐蚀（SSCC）行为．结果表明,在加载初期,P110钢的自腐蚀电位Ecorr）急剧下降,至极小值后缓慢升高,达到稳定值后直至断裂,试样断口呈脆性解理状．当通入CO2量达到17％时,P110钢的自腐蚀...     

Supersonic Nozzle Flow Simulations for Particle Coating Applications: Effects of Shockwaves,Nozzle Geometry,Ambient Pressure,and Substrate Location upon Flow Characteristics

Characteristics of supersonic flow are examined with specific regard to nano-particle thin-film coating. Effects of shockwaves, nozzle geometry, chamber pressure, and substrate location were studied computationally. Shockwaves are minimized to reduce fluctuations in flow properties at the discontinuities across diamond shock structures. Nozzle geometry was adjusted to ensure optimal expansion (i.e., P _exit = P _ambient), where shock formation was significantly reduced and flow kinetic energy maximized. When the ambient pressure was reduced from 1 to 0.01316 bar, the nozzle’s diverging angle must be increased to yield the optimum condition of minimized adversed effects. Beyond some critical distance, substrate location did not seem to be a sensitive parameter on flow characteristics when P _amb = 0.01316 bar; however, overly close proximity to the nozzle exit caused flow disturbances inside the nozzle, thereby adversely affecting coating gas flow.     

Al2O3-nanodiamond composite coatings with high durability and hydrophobicity prepared by aerosol deposition

We attempted the room-temperature fabrication of Al₂O₃-based nanodiamond (ND) composite coating films on glass substrates by an aerosol deposition (AD) process to improve the anti-scratch and anti-smudge properties of the films. Submicron Al₂O₃ powder capable of fabricating transparent hard coating films was used as a base material for the starting powders, and ND treated by 1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFOTES) was added to the Al₂O₃ to increase the hydrophobicity and anti-wear properties. The ND powder treated by PFOTES was mixed with the Al₂O₃ powder by ball milling to ratios of 0.01 wt.%, 0.03 wt.%, and 0.05 wt.% ND. The water contact angle (CA) of the Al₂O₃-ND composite coating films was increased as the ND ratio increased, and the maximum water CA among all the films was 110°. In contrast to the water CA, the Al₂O₃-ND composite coating films showed low transmittance values of below 50% at a wavelength of 550 nm due to the strong agglomeration of ND. To prevent the agglomeration of ND, the starting powders were mixed by attrition milling. As a result, Al₂O₃-ND composite coating films were produced that showed high transmittance values of close to 80%, even though the starting powder included 1.0 wt.% ND. In addition, the Al₂O₃-ND composite coating films had a high water CA of 109° and superior anti-wear properties compared to those of glass substrates.     

Carburisation of ferritic Fe–Cr alloys by low carbon activity gases

Model Fe–Cr alloys were exposed to Ar–CO₂–H₂O gas mixtures at 650 and 800 °C. At equilibrium, these atmospheres are oxidising to the alloys, but decarburising (a_C ≈ 10⁻¹⁵ to 10⁻¹³). In addition to developing external oxide scales, however, the alloys also carburised. Carbon supersaturation at the scale/alloy interface relative to the gas reflects local equilibrium: a low oxygen potential corresponds to a high p_CO/p_CO2 ratio, and hence to a high carbon activity. Interfacial carbon activities calculated on the basis of scale–alloy equilibrium are shown to be in good agreement with measured carburisation rates and precipitate volume fractions, providing support for the validity of the thermodynamic model.     

Application of Bu2Sn(acac)2 for the deposition of nanocrystallite SnO2 films: Nucleation, growth and physical properties

High-quality uniform SnO₂ thin films were successfully prepared by pulsed-spray evaporation chemical vapor deposition (PSE-CVD) method, using a cost-efficient precursor of ⁿBu₂Sn(acac)₂. The volatility and stability of ⁿBu₂Sn(acac)₂ were studied through thermogravimetric-differential thermal (TG-DTA) analysis and mass spectrometry, indicating the good adaptability for the CVD process. Deposition of SnO₂ films was made in the range of 250-450 °C to investigate the effect of substrate temperature on their structural and physical properties. The film growth activation energy changes from 66.5 kJ/mol in the range of 250-330 °C to 0 kJ/mol at 330-450 °C, suggesting the change of the rate-limiting step from surface kinetics to diffusion control. All films possess the rutile-type tetragonal structure, while a change of preferred orientation from (1 1 0) to (1 0 1) plane is observed upon the increase of the deposition temperature. The different variation of the nucleation and growth rates with the deposition temperature is proposed to explain the observed unusual change of crystallite size. A significant deterioration of the electrical conductivity was observed upon the increase of the deposition temperature, which was tentatively attributed to the non-specific decomposition of the precursor at high temperature leading to carbon contamination. Optical measurements show transparencies above 80% in the visible spectral range for all films, while band gap energy increases from 4.02 eV to 4.08 eV when the deposition temperature was raised from 250 °C to 450 °C.     

Quantenchemische Modellrechnungen Zum Wirkungsmechanismus Von Sparbeizinhibitoren

EHT calculations of the interaction between an iron atom and XH_n or XH_n+1⁺ (X = N, P, As and O, S, Se), respectively, show the stability of these aggregates to enhance with increasing atomic number within a group of elements of the Periodic Table. This is found to be due to an increase in charge transfer to the metal accompanied by completion of its 3d orbitals, but not to be due to the strengthening of the X—Fe covalent bond. Aggregation of the cations considerably diminishes the stability of their X—H bonds. The results are used to classify the inhibitive action on the acid corrosion of iron experimentally established for species of the general structures XR_n and XR_n+1⁺ (R normally being an alkyl group) and to understand their order of efficiency.     

Effects of surface-modified photoelectrode on the power conversion efficiency of dye-sensitized solar cells

The effects of Na₂SO₄ as a surface modification material on the performance of dye-sensitized solar cells (DSSCs) were studied. The surfaces of TiO₂ films were firstly modified with aqueous Na₂SO₄ solution by a dip coating process, and then the resulting electrode was applied to the photoelectrode of a DSSC. The DSSC with the Na₂SO₄-modified photoelectrode had a power conversion efficiency of 9.01% compared with that (7.97%) of the reference cell, which corresponds to an increase of about 13.0% in the efficiency due to an enhancement in short-circuit current (J _sc ) and open-circuit voltage (V _oc ). A series of measurements such as UV-visible absorption, electrochemical impedance, incident photon to current conversion (IPCE) efficiency and dark current revealed that incorporation of Na₂SO₄ onto the TiO₂ film led to an increase of dye adsorption and a longer lifetime of electrons injected from dyes to the TiO₂ electrodes, resulting in the improvement in both J _sc and V _oc , compared to those of a reference device without surface modification.     

High-rate deposition of amorphous and nanocomposite Ti-Si-C multifunctional coatings

Amorphous (a) and nanocomposite Ti-Si-C coatings were deposited at rates up to 16 μm/h by direct current magnetron sputtering from a Ti₃SiC₂ compound target, using an industrial pilot-plant system, onto high-speed steel, Si, and SiO₂ substrates as well as Ni-plated Cu cylinders, kept at a temperature of 200 or 270 °C. Electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction analyses showed that TiC/a-C/a-SiC nanocomposites were formed consisting of textured TiC nanocrystallites (nc) embedded in a matrix of a-C and a-SiC. Elastic recoil detection analysis showed that coatings deposited at a target-to-substrate distance of 2 cm and an Ar pressure of 10 mTorr have a composition close to that of the Ti₃SiC₂ compound target, as explained by ballistic transport of the species. Increased target-to-substrate distance from 2 cm to 8 cm resulted in a higher carbon-to-titanium ratio in the coatings than for the Ti₃SiC₂ compound target, due to different gas-phase scattering properties between the sputtered species. The coating microstructure could be modified from nanocrystalline to predominantly amorphous by changing the pressure and target-to-substrate conditions to 4 mTorr and 2 cm, respectively. A decreased pressure from 10 mTorr to 4 or 2 mTorr at a target-to-substrate distance of 2 cm decreased the deposition rate up to a factor of ~ 7 as explained by resputtering and an increase in the plasma sheath thickness. The coatings exhibited electrical resistivity in the range 160-800 μΩ cm, contact resistance down to 0.8 mΩ at a contact force of 40 N, and nanoindentation hardness in the range of 6-38 GPa.     

Degradation in Thermal Properties and Morphology of Polyetheretherketone-Alumina Composites Exposed to Gamma Radiation

Sheets of polyetheretherketone (PEEK) and PEEK-alumina composites with micron-sized alumina powder with 5, 10, 15, 20, and 25% by weight were fabricated, irradiated with gamma rays up to 10 MGy and the degradation in their thermal properties and morphology were evaluated. The radicals generated during irradiation get stabilized by chain scission and crosslinking. Chain scission is predominant on the surface and crosslinking is predominant in the bulk of the samples. Owing to radiation damage, the glass transition temperature, T _g increased for pure PEEK from 136 to 140.5?°C, whereas the shift in T _g for the composites decreased with increase in alumina content and for PEEK-25% alumina, the change in T _g was insignificant, as alumina acts as an excitation energy sink and reduces the crosslinking density, which in turn decreased the shift in T _g towards higher temperature. Similarly, the melting temperature, T _m and enthalpy of melting, ??H _m of PEEK and PEEK-alumina composites decreased on account of radiation owing to the restriction of chain mobility and disordering of structures caused by crosslinks. The decrease in T _m and ??H _m was more pronounced in pure PEEK and the extent of decrease in T _m and ??H _m was less for composites. SEM images revealed the formation of micro-cracks and micro-pores in PEEK due to radiation. The SEM image of irradiated PEEK-alumina (25%) composite showed negligible micro-cracks and micro-pores, because of the reinforcing effect of high alumina content in the PEEK matrix which helps in reducing the degradation in the properties of the polymer. Though alumina reduces the degradation of the polymer matrix during irradiation, an optimum level of ceramic fillers only have to be loaded to the polymer to avoid the reduction in toughness.     

Differential thermal analysis (DTA) on the reaction mechanism in Fe–Ti–B4C system

Differential thermal analysis (DTA) was undertaken to determine the reaction mechanism in the Fe–Ti–B₄C system under argon. When the mixtures were heated to about 786 °C, Fe₂B and C appeared as a result of Fe reacting with B₄C. As the temperature continued to increase, FeTi formed by an interdiffusion between Fe and Ti. When the mixtures were heated to 1089 °C, FeTi reacted with Ti, leading to the formation of a Fe–Ti melt, into which the displaced C and B from B₄C dissolve, forming a Fe–Ti–C–B melt. Finally, when the concentration of C and B attained a certain value, Ti reacted with C and B, yielding TiC and TiB₂ in the melt, and simultaneously considerable heat released.