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At least 145 records · Page 8

Surface chemistry of iron sliding in air and nitrogen lubricated with hexadecane and hexadecane containing dibenzyl-dilsulfide

Wear experiments were conducted on iron sliding in hexadecane and hexadecane plus one weight percent dibenzyl dilsulfide (DBDS) in atmospheres of air and nitrogen at room temperature. The wear scars and the wear debris were analyzed by X-ray photoelectron spectroscopy. The presence of air reduced wear but increased friction, while DBDS reduced friction but had little effect on wear except that the wear increased somewhat when DBDS was used in air. Wear scar analysis indicated that oxygen and sulfur competed chemically for the surface, with the oxide predominating. Low wear was associated with a thick oxide layer and low friction with a thin predominantly sulfide layer. Analysis of the wear debris indicated the presence of a sulfate in the high wear case (hexadecane plus DBDS in air), and showed the presence of an organic sulfide in the low wear case (Hexadecane plus DBDS in nitrogen).

Wheeler, D. R.↗

Application of ESCA to the determination of stoichiometry in sputtered coatings and interface regions

X-ray Photoelectron Spectroscopy (XPS) was used to characterize radiofrequency sputter deposited films of several refractory compounds. Both the bulk film properties such as purity and stoichiometry and the character of the interfacial region between the film and substrate were examined. The materials were CrB2, MoS2, Mo2C, and Mo2B5 deposited on 440C steel. It was found that oxygen from the sputtering target was the primary impurity in all cases. Biasing improves the film purity. The effect of biasing on film stoichiometry is different for each compound. Comparison of the interfacial composition with friction data suggests that adhesion of these films is improved if a region of mixed film and iron oxides can be formed.

Wheeler, D. R.↗

An XPS study of the adherence of refractory carbide, silicide, and boride RF-sputtered wear-resistant coatings

Radio frequency sputtering was used to deposit refractory carbide, silicide, and boride coatings on 440-C steel substrates. Both sputter etched and pre-oxidized substrates were used and the films were deposited with and without a substrate bias. The composition of the coatings was determined as a function of depth by X-ray photoelectron spectroscopy combined with argon ion etching. Friction and wear tests were conducted to evaluate coating adherence. In the interfacial region there was evidence that bias may produce a graded interface for some compounds. Biasing, while generally improving bulk film stoichiometry, can adversely affect adherence by removing interfacial oxide layers. Oxides of all film constituents except carbon and iron were present in all cases but the iron oxide coverage was only complete on the preoxidized substrates. The film and iron oxides were mixed in the MoSi2 and Mo2C films but layered in the Mo2B5 films. In the case of mixed oxides, preoxidation enhanced film adherence. In the layered case it did not.

Brainard, W. A.↗

Use of a nitrogen-argon plasma to improve adherence of sputtered titanium carbide coatings on steel

Friction and wear experiments on 440-C steel surfaces that had been RF-sputtered with titanium carbide when a small percentage of nitrogen was added to the plasma were conducted. X-ray photoelectron spectroscopy and X-ray diffraction were used to analyze the resultant coatings. Results indicate that a small partial pressure of nitrogen (about 0.5%) markedly improves the adherence, friction, and wear properties when compared with coatings applied on sputter-etched oxidized surfaces or in the presence of a small oxygen partial pressure. The improvements are related to the formation of an interface containing a mixture of the nitrides of titanium and iron, which are harder than their corresponding oxides.

Brainard, W. A.↗

Adherence of sputtered titanium carbides

The study searches for interface treatment that would increase the adhesion of TiC coating to nickel- and titanium-base alloys. Rene 41 (19 wt percent Cr, 11 wt percent Mo, 3 wt percent Ti, balance Ni) and Ti-6Al-4V (6 wt percent Al, 4 wt percent V, balance Ti) are considered. Adhesion of the coatings is evaluated in pin-and disk friction tests. The coatings and interface regions are examined by X-ray photoelectron spectroscopy. Results suggest that sputtered refractory compound coatings adhere best when a mixed compound of coating and substrate metals is formed in the interfacial region. The most effective type of refractory compound interface appears to depend on both substrate and coating material. A combination of metallic interlayer deposition and mixed compound interface formation may be more effective for some substrate coating combinations than either alone.

Brainard, W. A.↗

Improved adherence of T1C coatings to steel

Modified process for RF sputtering of titanium carbide coatings onto 440-C steel has resulted in improved adherence. Small partial pressure of nitrogen, approximately 0.5 percent, during first minutes of deposition markedby improved adherence, friction, and wear properties when compared with coatings applied on sputter-etched surfaces, or oxidized surfaces or in presence of small oxygen partial pressure. X-ray photoelectron spectroscopy and X-ray diffraction were used to characterize resultant coatings.

Brainard, W. A.↗

Chemical processes involved in the initiation of hot corrosion of B-1900 and NASA-TRW VIA

Sodium sulfate induced hot corrosion of B-1900 and NASA-TRW VIA at 900 C was studied with special emphasis on the chemical reactions occurring during and immediately after the induction period. Thermogravimetric tests were run for set periods of time after which the samples were washed with water and water soluable metal salts and/or residual sulfates were analyzed chemically. Element distributions within the oxide layer were obtained from electron microprobe X-ray micrographs. A third set of samples were subjected to surface analysis by X-ray photoelectron spectroscopy. Evolution of SO2 was monitored throughout many of the hot corrosion tests. Results are interpreted in terms of acid-base fluxing mechanisms.

Fryburg, G. C.↗

Local atomic and electronic structure of oxide/GaAs and SiO2/Si interfaces using high-resolution XPS

The chemical structures of thin SiO2 films, thin native oxides of GaAs (20-30 A), and the respective oxide-semiconductor interfaces, have been investigated using high-resolution X-ray photoelectron spectroscopy. Depth profiles of these structures have been obtained using argon ion bombardment and wet chemical etching techniques. The chemical destruction induced by the ion profiling method is shown by direct comparison of these methods for identical samples. Fourier transform data-reduction methods based on linear prediction with maximum entropy constraints are used to analyze the discrete structure in oxides and substrates. This discrete structure is interpreted by means of a structure-induced charge-transfer model.

Grunthaner, F. J.↗

Improved adhesion of sputtered refractory carbides to metal substrates

Sputtered coatings of the refractory metal carbides are of great interest for applications where hard wear-resistant materials are desired. The usefulness of sputtered refractory carbides is often limited in practice by spalling or interfacial separation. In this work improvements in the adherence of refractory carbides on iron, nickel and titanium base alloys were obtained by using oxidation, reactive sputtering or sputtered interlayers to alter the coating-substrate interfacial region. X-ray photoelectron spectroscopy and argon ion etching were used to characterize the interfacial regions, and an attempt was made to correlate adherence as measured in wear tests with the chemical nature of the interface.

Wheeler, D. R.↗

XPS study of the chemical structure of the nickel/silicon interface

The chemical nature of the Ni/Si, Ni/Ni2Si, and Si/Ni2Si interfaces is studied using X-ray photoelectron spectroscopy. Two approaches are employed: (1) the Ni/silicide and Si/silicide interfaces are examined by dynamically monitoring the advancing reaction front during in situ growth and (2) as-deposited Ni/Si interfacial properties are analyzed by sequential evaporating monolayer Ni films on Si. These experiments show that the Ni/Ni2Si interface consists of a Ni-rich silicide phase, while the Si/Ni2Si interface has a transitional region that is correspondingly Si-rich silicide.

Grunthaner, P. J.↗

Chemical depth profiles of the GaAs/native oxide interface

The final-state oxidation products and their distribution in thin native oxides (30-40 A) on GaAs have been studied using X-ray photoelectron spectroscopy in conjunction with chemical depth profiling. Extended room-temperature-oxidation conditions have been chosen to allow the native oxide to attain its equilibrium composition and structure. The work emphasizes the use of chemical depth-profiling methods which make it possible to examine the variation in chemical reactivity of the oxide structure. A minimum of two distinct regions of Ga2O3 with differing chemical reactivity is observed. Chemical shift data indicate the presence of As2O3 in the oxide together with an elemental As overlayer at the interface. A change in relative charge transfer between oxygen and both arsenic and gallium-oxide species is observed in the region of the interface.

Grunthaner, P. J.↗

XPS Study of SiO2 and the Si/SiO2 Interface

X-ray photoelectron spectroscopy (XPS) is analytical technique for understanding electronic structure of atoms close to surface in solids, in preference to bulk structure of material. Study found evidence for core-level chemical shifts arising from changes in local structural environment in amorphous SiO2 and at Si/SiO2 interface. Observed XPS spectra may be understood as sequential convolution of several functions, each with well-defined physical interpretation.

Grunthaner, F. J.↗

An investigation of adhesive/adherend and fiber matrix interactions

Research during the report period focused on continued scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) of lap shear samples and flatwise tensile specimens and on the surface characterization of TiO2, Ti 6-4, and Ti powders with particular emphasis on their interaction with primer solutions of both polyphenylquinoxaline and LaRC-13 polyimide. The use of SEM and XPS in the analysis of Ti 6-4 adherend surfaces is described as well as differences in Ti 6-4 surface composition after different chemical pretreatments. Analysis of fractured surfaces is used to established the failure mode. The surface acidity of Ti 6-4 coupons can be established by reflectance visible spectroscopy using indicator dyes.

Beck, B.↗

Photoexcitation and ionization in carbon dioxide - Theoretical studies in the separated-channel static-exchange approximation

Vertical-electronic static-exchange photoexcitation and ionization cross sections are reported which provide a first approximation to the complete dipole spectrum of CO2. Separated-channel static-exchange calculations of vertical-electronic transition energies and oscillator strengths, and Stieltjes-Chebyshev moment methods were used in the development. Detailed comparisons were made of the static-exchange excitation and ionization spectra with photoabsorption, electron-impact excitation, and quantum-defect estimates of discrete transition energies and intensities, and with partial-channel photoionization cross sections obtained from fluorescence measurements and from tunable-source and (e, 2e) photoelectron spectroscopy. Results show that the separate-channel static-exchange approximation is generally satisfactory in CO2.

Padial, N.↗

XPS studies of structure-induced radiation effects at the Si/SiO2 interface

The interfacial structures of radiation hard and soft oxides grown by dry and wet processes on silicon substrates have been examined by high-resolution X-ray photoelectron spectroscopy. It is found that the primary difference in the local atomic structure at the Si/SiO2 interface is the significantly higher concentration of strained 120 deg SiO2 bonds and SiO interfacial species in soft samples. Results of in situ radiation damage experiments using low energy electrons (0-20 eV) are reported which correlate with the presence of a strained layer of SiO2 (20 A) at the interface. The results are interpreted in terms of a structural model for hole and electron trap generation by ionizing radiation.

Grunthaner, F. J.↗

X-ray photoemission studies of superficially oxidized cesium antimonide photoemitters

Superficially oxidized cesium antimonide photoemitting surfaces prepared in ultrahigh vacuum were studied by X-ray photoelectron spectroscopy. Oxidation of Cs3Sb to produce a surface with enhanced photosensitivity converts part of the antimony to elemental antimony and part of the cesium to cesium suboxide. The latter is identified on the basis of an O1 s peak at 531.3 eV, characteristic of Cs11O3. The production of Cs2O is not ruled out in this process since its signature at 527.5 eV is masked by an antimony shake-up peak at 527 eV.

Bates, C. W., Jr.↗

Water vapor resistance of plasma-polymerized coatings on potassium bromide windows

Plasma-polymerized tetrafluoroethylene (PPTFE) coated potassium bromide IR window are shown to possess better resistance to moisture than either ethylene or chlorotrifluoroethylene. The PPTFE-coated windows tolerated an upper limit relative humidity of about 80% at 297 K, without visible damage to either window or coating, over a period of 24 hours. Elemental analysis of the bulk, and photoelectron spectroscopy of the coating surface, showed that PPTFE coatings deposited downstream of the internal plasma reactor electrodes contained less atmospheric oxygen than coatings deposited between the electrodes; perhaps accounting for the improved moisture resistance.

Wydeven, T.↗

Metal-semiconductor interfacial reactions - Ni/Si system

X-ray photoelectron spectroscopy and channeling measurements with MeV He-4(+) ions have been used to probe the structure of the interface in the Ni/Si system. It is found that reactions occur where Ni is deposited on Si at 10 to the -10th torr: Si atoms are displaced from lattice sites, the Ni atoms are in an Si-rich environment, and the Ni/Si interface is graded in composition. Composition gradients are present at both interfaces in the Si/Ni2/Si/Ni system. For the Ni-Si system, cooling the substrate to 100 K slows down the reaction rate. The temperature dependence of the interfacial reactivity indicates the kinetic nature of metal-semiconductor interfaces.

Cheung, N. W.↗