The mechanisms of dissolution and passivation of bulk polycrystalline icosahedral Al63Cu25Fe12 during electrolytic corrosion in 0.1 N NaOH and 1 N H2SO4 were studied in detail. In 1 N H2SO4 selective dissolution of Al and Fe occurs at the open circuit potential, which leads to a porous layer of recrystallized fcc Cu; after anodic polarization dissolution of the alloy is followed by redeposition of Cu and formation of Cu2O. In 0.1 N NaOH selective dissolution of Al was observed and a nanocrystalline layer consisting of Cu2O and FeOOH forms at the open circuit potential as well as during anodic polarization up to -150 mVSHE. At higher potentials Cu-ions dissolve into the electrolyte, which allows building up an Al-hydroxide layer. Presumably due to the loss of Al during polarization phase transforma-tions of the quasicrystals (e.g. continuous transformation or precipitation) were observed by transmission electron microscopy.

In order to clarify the influence of the quasicrystalline structure on the corrosion, open circuit potentials and current densities of the quasicrystalline and three ternary crystalline phases with different Al-content, but approximately constant ratio Cu:Fe of 2:1 were compared. Lower current densities, but a less noble open circuit potential for the quasicrystals than expected from the trend over the Al-content indicate a small influence of the quasicrystalline structure.

The influence of grain orientation on the friction and wear behavior of single-phase quasicrystalline alloys is investigated. Pin-on-disc wear tests and friction coefficient measurements have been performed on bulk samples of icosahedral phase AlPdMn and decagonal phase AlNiCo alloys. Wear behavior has been evaluated by optical microscopy, scanning electron microscopy (SEM) and electron back-scattered diffraction (EBSD). Coefficient of friction values of the decagonal AlNiCo alloy are found to be widely scattered (between 0.03 and 0.55) compared to the far more consistent values of the icosahedral alloys. This is explained by considering the significant variation in wear behavior that is observed between different – sometimes adjacent – oriented grains in the decagonal specimens.

Electronic properties (conductivity and density of states) of quasicrystals present strong similarities with disordered semiconductor based systems on both sides of the Mott-Anderson metal-insulator (MI) transition. We revisit the conductivity of the i-AlCuFe and i-AlPdMn phases, which has temperature and magnetic field dependence characteristic of the metallic side of the transition. The i-AlPdRe ribbon samples can be on either side of the transition depending on their conductivity value. In all these i-phases, the density of states at the Fermi level EF is low. Its energy dependence close to EF is similar to disordered systems close to the MI transition where it is ascribed to effects of interactions between electrons and disorder.

Thin film coatings of Al-based quasicrystals were deposited by magnetron sputtering. Sputtering targets of Al65Cu23Fe12 and Al65Cu23Fe12+5v/o Fe-Al were prepared with plasma arc spraying by forming thick (∼5mm) coatings onto Cu substrates. By incorporating a controlled fraction of porosity and micro-cracks within the plasma sprayed target, cracking or delamination of the target during magnetron sputtering could be avoided. Compositions of the as-deposited PVD films were close to the sputtering target composition when the bias voltage was kept around –40V; higher bias voltages (e.g., -100 to -200V) lead to coatings that were deficient in Al. As-deposited coatings prepared with the lower bias voltage could be subsequently annealed at 700°C for two hours to yield a nearly single-phase icosahedral structure. After annealing, composite coatings indicate the presence of an Fe-Al phase along with the icosahedral phase.

Metallic-covalent bonding conversion in icosahedral clusters of Al and B by small changes of the structure was demonstrated by molecular orbital calculations. According to the electron density distribution obtained using the maximum entropy method and the Rietveld method, the bonding conversion phenomenon occurs even in cluster solids such as some Al- and B-based icosahedral approximant phases (Al12Re, α-AlMnSi, α-rhombohedral boron). The multiple-shell atomic structure, the electrical and optical conductivity are compared for metal doped β-rhombohedral boron and AlLiCu or AlPdRe icosahedral quasicrystal. Photoemission and electron energy loss spectroscopy investigations for V doped β-rhombohedral have been discussed. Conclusions are the following two. It is difficult to distinguish a Hume-Rothery, i.e. structure-induced, pseudogap, and a covalent bonding, i.e. hybridization, pseudogap for materials with a highly symmetric Brillouin zone and a strong potential for valence electrons. Because hybridization is necessary not only for covalent bonds but also for metallic ones, it is better to use the covalent bonding pseudogap than the hybridization pseudogap.

In order to gain an insight into the role of the local atomic environment in the electronic transport of the icosahedral quasicrystal, the electrical resistivity of α-AlReSi, which is the (1/1,1/1,1/1) approximant of the icosahedral phase, has been investigated. Very high resistivity and its pronounced negative temperature dependence have been observed, indicating that the electronic states of the 1/1 cubic approximant are quite similar to those of icosahedral phases. In order to further elucidate which structural entity is responsible for such anomalous transport, a comparison of the electrical resistivity between (1/1,1/1,1/1) and (1/0,1/0,1/0) approximants has been made. The typical transport behavior of icosahedral phases which is also seen in 1/1 and higher-order approximants was not observed in any of the studied 1/0 cubic approximants. The result can be regarded as an implication that the intercluster distance between the TM clusters plays a significant role in the confinement of electronic states.

An experimental comparison has been made between the properties of the surfaces of an Al70Pd21Mn9 quasicrystal and its Al48Pd42Mn10 approximant. The Al70Pd21Mn9 sample was a single grain icosahedral quasicrystal cut to expose its five-fold symmetric (000001) surface. The approximant was polycrystalline β-phase Al48Pd42Mn10, which has a CsCl-type cubic structure. Surfaces of both were prepared under ultra-high vacuum (UHV) conditions and then used for comparative measurements of their frictional properties and oxidation rates. Both materials are oxidized by reaction with O2 to form a thin film of aluminum oxide that ultimately passivates their surfaces. The interesting difference between the two is that the rate of oxidation of the approximant is significantly higher than that of the quasicrystal in spite of the fact that the bulk Al concentration of the approximant is lower than that of the quasicrystal. Friction measurements were made under UHV conditions between pairs of quasicrystals and pairs of approximants whose surfaces were either clean or oxidized to varying degrees. The friction between pairs of the approximant surfaces is significantly higher than that measured between the quasicrystal surfaces under all conditions of surface oxidation.

The interpretation of plastic deformation experiments on quasicrystals is a challenging task due to the occurrence of changes of the structure during deformation. In this paper, we present a quantitative model for quasicrystal plasticity on the basis of a constitutive-equations Ansatz, which takes these effects into account. A single-internal-variable model of the kind commonly used for describing crystal plasticity, is adapted for the description of the dislocation density evolution in a quasicrystal. In addition, we introduce a structural parameter that accounts for the evolution of order in the course of plastic deformation. The numerical solution of the resulting set of evolution equations yields the flow stress and the dislocation density as a function of strain, which can be directly compared to corresponding experimental curves obtained on icosahedral Al-Pd-Mn. An excellent agreement between experiment and the calculated curves obtained using our model is found.

A Rietveld refinement confirmed by ab initio calculations [1] has shown that the structure of the related W-phase [2] 1/1 approximant consists of Bergman clusters connected by “glue” sites. To investigate if the quasicrystal structure contains the same cluster we construct two constrained icosahedral glass models using the Bergman or Mackay cluster, respectively. A comparison with neutron diffraction data yields better agreement if the Bergman cluster is used, suggesting that this is a frequently occurring element in the quasicrystalline structure. Since absorbed hydrogen is known to locate preferentially in tetrahedral interstitial sites in many metals, the tetrahedral sites in the constrained glass were filled with hydrogen. The calculated powder neutron diffraction spectra are similar to the experimental data. It was not possible, however, to differentiate between possible tetrahedral sites where the hydrogen atoms sit. Hydrogen site energies from ab initio calculations indicate preferences that are consistent with fillings of non-Ni bearing tetrahedral sites.

The effect of pure electronic excitations (by ∼ 835 MeV Kr irradiation) on a stable icosahedral quasicrystal is compared with the effect of electronic excitations combined with the nuclear collisions (by 100 MeV Ni irradiation) occurring in a similar quasicrystal. The critical stopping power was kept at 1300 eV/Å for both the experiments. Under the pure electronic excitations, the R(φ)/R(0) [ratio of resistance at fluence φ and the resistance on the same piece with zero fluence) of quasicrystal goes through oscillatory changes, until at ∼ 1 × 1012 ions/cm2where this ratio drops considerably. The ex-situ XRD on the irradiated sample does show the evidence of degradation of the structure. In contrast, the Ni- irradiated sample shows an increase in resistivity after a critical fluence of 2.5 × 1013 ions/cm2, which remains constant for higher fluences. Corresponding defect annihilation effects are observed in the XRD of Ni- irradiated samples.

Growth experiments have been carried out to characterize the occurrence and development of porosity in Bridgman and flux grown Al-Pd-Mn icosahedral quasicrystals. The porosity level has been observed to fluctuate between values of 0.0 and 3.75 percent along the length of Bridgman single crystals implying that the development of porosity is affected by the local growth conditions. Experiments were conducted to evaluate the influence of the rate of solidification on the occurrence of porosity. Alloys were solidified with different growth rates, 1mm/hr and >10 mm/hr, using the Bridgman configuration and at different cooling rates, ranging from 0.29°C/hr to 10°C/hr, using the flux growth method. Porosity levels were analyzed via optical image analysis. These experiments indicate that porosity percentages are greatly influenced by cooling rates and crystal size.

The paper reviews results from in situ straining experiments on Al-Pd-Mn single quasicrystals in a high-voltage electron microscope. Slip planes were determined from the orientation and width of slip traces. Dislocations are generated by a specific cross slip mechanism. On some slip traces, dislocations move at two distinctly different velocities. A stress exponent was determined on a single dislocation by observing its displacement under decreasing load. The in situexperiments reveal the behaviour of individual dislocations in a temperature range where the deformation of bulk specimens is strongly affected by recovery.

In this paper, two independent factors, electronic structure at the Fermi energy and electron scattering, both of which determine the electrical resistivity, are clearly separated by using a plot of ρ4K versus RRR (RRR = ρ4K/ρ300K) for icosahedral quasicrystals and their approximants. Each contribution of the electronic structure and the electron scattering on the electrical resistivity was systematically revealed, and the origin for the high resistivities observed in the quasicrystals and approximants is well understood by taking each effect into account. We found that the quasicrystals and approximants are classified into three groups in terms of the electron scattering mechanism, which dominates the temperature dependence of the resistivity. The temperature dependence of the electrical resistivity in the first group is well understood in terms of the Boltzmann transport mechanism, and those in the second and the third groups are in terms of the weak localization and the Anderson localization, respectively.

The formation of the icosahedral phase, BCC (Body centred cubic) phase and nanocrystals are seen in the as-cast alloy with nominal composition of Mg4Zn94Y2. FCC (face centred cubic) phase and modulated structures are formed in the alloys with higher Y content (10% and 25% Y respectively). These phases are analysed keeping in view their relation to the quasicrystals of the Mg-Zn-Y system.

Spark plasma sintering method was applied to Al-Cu-Fe and Al-Si-Cu-Fe gas-atomized powders to prepare almost pore-free cylindrical specimens with icosahedral and 1/1 cubic approximant phases, respectively. This investigation has revealed that a high density could be obtained despite the short period and low temperature imposed during spark plasma sintering. In comparison to hot press technique, these conditions are favorable since they limit the formation of secondary phases and avoid exaggerated grain growth. The Vickers microhardness and fracture toughness of these two alloy systems were found to be larger than those obtained from cast and hot pressed samples, which could be attributed to a strong bonding between powder particles and the small-grained microstructure of the bulk SPS quasicrystalline specimens.

A model proposed for the atomic structure of the new hexagonal Al-Fe(V)-Si phase which was found in rapidly solidified Al-Fe(V)-Si alloys is discussed in terms of relation this phase to approximants. The structure of this new phase was described as hexagonal packing of double Mackay icosahedral units similar to those of which the cubic α-(AlFeSi) approximant phase is built up. On the basis of this model the experimental high resolution electron microscopic (HREM) images of the hexagonal phase were successfully interpreted. Like the á phase this structure is characterized by the local icosahedral ordering and can be regarded as an approximant.

The icosahedral canonical tiling of the three-dimensional space by six golden tetahedra T*(2F) [1] is decorated for physical applications by the Bergman polytopes [2]. The model can be also formulated as the “primitive) tiling TP [3] decorated by alternating Bergman symmetry axis of and icosahedron, there appear the plans on three mutual distances following the rule of a decorated Fibonacci sequence. All these three distances among the terraces (mutually scaled by a factor τ) have been recently observed by shen et al. [5]. In particular they have measured also the shortest distance of 2.52Å that breaks the Fibonnaci-sequence of terrace like surfaces measured previously by schaub et al. [6]. We predict the frequencies for the appearance of the terraces of different heights in the model under the condition that the model of Boudard et al. [7.8], we decorate the atomic positions by Al, Pd and Mn. We present images of the predicted possible terrace-like surfaces on three possible distances in the fully decorated model by the atomic species.

It is shown how the history of the growth of an icosahedral Zn-Mg-Y single grain can be determined by measuring the yttrium distribution. The growth mechanism and the stabilization of the icosahedral Zn-Mg-Y, RE (RE = rare earth: Ho, Er, Dy, Gd, Tb) quasicrystals are discussed with respect to structural investigations on related crystalline phases. We also show results of optical and ultrasonic investigations on icosahedral Zn-Mg-Y single crystals. They fit well to the discussed growth and stabilization mechanism.

Analysis of the phase relationships of Al-Cu-Fe-Cr based sputtered films, before and after various annealing treatments, was carried out via grazing incidence x-ray scattering (GIXS) at SSRL on beamline 7-2. The “as-deposited” films were composed primarily of nanoscale grains whose structure were mainly quasicrystalline (QC) and its approximants, plus a nano-crystalline phase was also observed in one sample. None of these precursor films exhibited any degree of amorphous character. GIXS studies, in the symmetric and asymmetric modes, revealed that grain growth due to the post-deposition heat treatments caused a decagonal QC phase to evolve and dominate the crystalline phases, which composed the film. These ≍10 µm thick films were created by sputter deposition with a DC magnetron source via an Al-Cu-Fe-Cr powder pressed target, giving a nominal sample composition of Al75Cu4Fe8Cr10O3. Two types of annealing treatments were performed using an Argon atmosphere. Anneal of a precursor film for 4 hours at 500°C showed a large fraction of decagonal and approximant phases, while anneal of a precursor film for 2 hours at 400°C and 2 hours at 550°C showed a large fraction of the crystalline phase.

Quasicrystalline coatings with various aluminum based systems were deposited onto 304 stainless steel substrates using two thermal spraying techniques; plasma spraying and high velocity oxy-fuel spraying. The friction and wear performances of the coatings were evaluated using two different testing devices, varying testing conditions and counterpart materials. Values of the friction coefficient were found to be strongly dependent on the testing devices and the counterpart materials, with values ranging from 0.15 to 0.4. In testing conditions corresponding to high sliding velocity, this study showed that the contact problem was posed over a third body system due to the formation of an intermediate layer. Values of the coefficient of friction were found to be approximately the same for all coating layers regardless of the thermal spraying techniques used, however, larger differences were obtained in the wear performance. The tribological properties were also evaluated at high temperature. It is noted that quasicrystal coating layers exhibit better friction and wear performances at 450oC than at room temperature. In comparison to potential coating candidate such as Cr2O3 for piston rings in automotive engines, tribological property of quasicrystalline coating layers seems to be promising one, however, wear performance need to be improved.