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International Journal of Materials Research

International Journal of Materials Research

Volume 103 Issue 4

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Contents

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Contents

June 11, 2013 Page range: 399-399
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Editorial

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Mullite 2011

Hartmut Schneider June 11, 2013 Page range: 401-401
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Original Contributions

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Mullite and mullite-type crystal structures

Reinhard X. Fischer, Andrea Gaede-Köhler, Johannes Birkenstock, Hartmut Schneider June 11, 2013 Page range: 402-407
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Abstract

Synthetic mullites (Al 4+2 x Si 2 –2 x O 10 – x ) belong to one of the most important groups of ceramic materials. Their crystal structure consists of chains of edge-sharing AlO 6 octahedra interconnected by tetrahedral double chains of T O 4 ( T = Al, Si) tetrahedra. The occurrence of oxygen vacancies is associated with the formation of triclusters of T O 4 groups. The distribution of oxygen vacancies and the distribution of Al and Si on the tetrahedral sites are partially ordered yielding an incommensurately modulated crystal structure with satellite reflections in diffraction patterns. The number of symmetrically independent distribution patterns of oxygen vacancies is given for a 2 × 2 × 2 and a 3 × 3 × 2 superstructure model. Many other compounds have chain structures similar to mullite. These compounds are assigned to subgroups, all derived from a hypothetical tetragonal aristotype structure.
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Faradaic current in different mullite materials: single crystal, ceramic and cermets

Gustavo Mata-Osoro, Jose S. Moya, Miguel Morales, L. Antonio Díaz, Hartmut Schneider, Carlos Pecharromán June 11, 2013 Page range: 408-411
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Abstract

Faradaic current measurements have been carried out on three different types of mullite: 2:1 mullite single crystals ( E ⊥ c ), 3:2 ceramics and 11% mullite/Mo composites. Measurements were carried out on very thin samples (60 μm) at high voltages (500 to 1000 V). Under these conditions, measurable currents were recorded even at room temperature. Results indicate notable differences between these three samples, which suggest that, although they share the same name and similar crystalline structure, binding energies and defect distributions seem to be very different. Finally, it has been seen that the excellent behaviour against dielectric breakdown of ceramic mullite does not hold for single crystals or mullite based cermets.
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Metakaolin–nanosilver as biocide mullite precursor

Belén Cabal, Jesús Sanz, Luis A. Díaz, Ramón Torrecillas, José S. Moya June 11, 2013 Page range: 412-415
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Abstract

Incorporation of silver nanoparticles enhances the biocide functionality of Ag supported kaolinite/metakaolite materials. In this regard, structural evolution of supports in the presence of silver nanoparticles is investigated. For this purpose, 27 Al and 29 Si magic-angle-spinning nuclear magnetic resonance spectroscopy was applied to investigate the bonding between silver nanoparticles and kaolinite/metakaolin materials. The incorporation of silver nanoparticles, following a chemical or thermal reduction, does not change the structure of kaolin, whereas in the case of metakaolin, a preferential interaction with tetrahedral sheets was observed and some stabilization of hexacoordinated aluminium is favoured.
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Sintering of mullite–β-eucryptite ceramics with very low thermal expansion

Olga García-Moreno, Adolfo Fernández, Ramón Torrecillas June 11, 2013 Page range: 416-421
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Abstract

Sintering of composite ceramic materials with an appropriate proportion of mullite and β-eucryptite to obtain a very low thermal expansion material has been tested by conventional and spark plasma sintering methods. The adjustment of the thermal expansion coefficient of the composites was performed by means of dilatometries and modifying the mullite–β-eucryptite proportions in the starting materials. Control of the reactivity between both phases at high temperature is the key to controlling not only the sinterability of the composites in the solid state, but also to controlling the final expansion properties of the material. X-ray diffraction with Rietveld refinement and field emission scanning microscopy have been used to characterize the sintered materials, together with some mechanical characterization.
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Crystal chemistry and properties of mullite-type Bi2M4O9: An overview

Hartmut Schneider, Reinhard X. Fischer, Thorsten M. Gesing, Jürgen Schreuer, Manfred Mühlberg June 11, 2013 Page range: 422-429
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Abstract

Bi 2 M 4 O 9 ( M = Al 3+ , Ga 3+ , Fe 3+ ) belongs to the family of mullite-type crystal structures. The phases are orthorhombic with the space group Pbam. The backbones of the isostructural phases are edge-connected, mullite-type octahedral chains. The octahedral chains are linked by dimers of M 2 O 7 tetrahedral groups and by BiO polyhedra. The Bi 3+ cations in Bi 2 M 4 O 9 contain stereo-chemically active 6s 2 lone electron pairs (LEPs) which are essential for the stabilization of the structure. Although the octahedral chains of the closely related Bi 2 Mn 4 O 10 are similar to those of Bi 2 M 4 O 9 , Bi 2 Mn 4 O 10 contains dimers of edge-connected, five-fold coordinated pyramids instead of four-fold coordinated tetrahedra. Also the 6s 2 LEPs of Bi 3+ in Bi 2 Mn 4 O 10 are not stereo-chemically active. Complete and continuous solid solutions exist for Bi 2 (Al 1 – x Fe x ) 4 O 9 and Bi 2 (Ga 1 – x Fe x ) 4 O 9 ( x = 0–1). Things are more complex in the case of the Bi 2 (Fe 1 – x Mn x ) 4 O 9+ y mixed crystals, where a miscibility gap occurs between x = 0.25–0.75. In the Fe-rich mixed crystals most Mn atoms enter the octahedra as Mn 4+ , with part of the tetrahedral dimers being replaced by fivefold coordinated polyhedra, whereas in the Mn-rich compound Fe 3+ favorably replaces Mn 3+ in the pyramids. The crystal structure of Bi 2 M 4 O 9 directly controls its mechanical properties. The stiffnesses of phases are highest parallel to the strongly bonded octahedral chains running parallel to the crystallographic c -axis. Perpendicular to the octahedral chains little anisotropy is observed. The temperature-induced expansion perpendicular to the octahedral chains is probably superimposed by contractions. As a result the c -axis expansion appears as relatively high and does not display its lowest value parallel to c , as could be inferred. Maximally 6% of Bi 3+ is substituted by Sr 2+ in Bi 2 Al 4 O 9 corresponding to a composition of (Bi 0.94 Sr 0.06 ) 2 Al 4 O 8.94 . Sr 2+ for Bi 3+ substitution is probably associated with formation of vacancies of oxygen atoms bridging the tetrahedral dimers. Hopping of oxygen atoms towards the vacancies should strongly enhance the oxygen conductivity. Actually the conductivity is rather low ( σ = 7 · 10 − 2 S m − 1 at 1073 K, 800°C). An explanation could be the low thermal stability of Sr-doped Bi 2 Al 4 O 9 , especially in coexistence with liquid Bi 2 O 3 . Therefore, Bi 2 Al 4 O 9 single crystals and polycrystalline ceramics both with significant amounts of M 2+ doping ( M = Ca 2+ , Sr 2+ ) have not been produced yet. Thus the question whether or not M 2+ -doped Bi 2 M 4 O 9 is an oxygen conducting material is still open.
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Temperature-dependent 57Fe Mössbauer spectroscopy and local structure of mullite-type Bi2(FexAl1–x)4O9 (0.1≤x≤1) solid solutions

Sven-Ulf Weber, Thorsten Gesing, Jens Röder, F. Jochen Litterst, Reinhard X. Fischer, Klaus-Dieter Becker June 11, 2013 Page range: 430-437
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Abstract

Oxides of the chemical composition Bi 2 (Fe x Al 1 – x ) 4 O 9 (0.1≤ x ≤1) possessing a mullite-type structure have been investigated using 57 Fe Mössbauer spectroscopy in the temperature range between room temperature and 1073K. The spectra have been fitted with two quadrupole doublets for Fe 3 + ions in octahedral and tetrahedral oxygen coordination. The distribution of iron on the two inequivalent structural sites has been determined from the relative areas of the subspectra. The site occupancy is found to be random within experimental error: it does not exhibit any preference of iron for the octahedral or tetrahedral sites, either as a function of temperature or with a dependence on the composition of the solid solutions.
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Thermal expansion and elastic properties of mullite-type Bi2Ga4O9 and Bi2Fe4O9 single crystals

Thomas F. Krenzel, Jürgen Schreuer, Thorsten M. Gesing, Manfred Burianek, Manfred Mühlberg, Hartmut Schneider June 11, 2013 Page range: 438-448
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Abstract

Resonant ultrasound spectroscopy was used to characterize the elastic properties of single crystal orthorhombic Bi 2 Ga 4 O 9 and Bi 2 Fe 4 O 9 between room temperature and about 1200 K. Additionally, the coefficients of thermal expansion were studied in the range 100 K to 1280 K using high-resolution dilatometry and X-ray powder diffraction. The elastic constants at 295 K are in GPa c 11 = 143.4(1), c 22 = 161.9(1), c 33 = 224.5(1), c 44 = 68.4(1), c 55 = 49.3(1), c 66 = 76.6(1), c 12 = 74.2(1), c 13 = 62.2(1), c 23 = 70.5(1) for Bi 2 Ga 4 O 9 , and c 11 = 106.7(1), c 22 = 141.2(1), c 33 = 183.7(2), c 44 = 53.7(1), c 55 = 41.9(1), c 66 = 63.8(1), c 12 = 63.5(1), c 13 = 59.8(1), c 23 = 63.4(2) for Bi 2 Fe 4 O 9 . In both mullite-type compounds the strong bond chains built up by edge-sharing coordination octahedra extending parallel to [001] dominate the anisotropy of their elastic and thermoelastic properties. Smaller variations of elastic anisotropy within the (001) plane can be attributed to the specific type of cross-linking of the octahedral chains. The temperature evolution of the c ij shows no hint on any structural instability or glass-like transition that might be related to the suspected ion conductivity at high temperatures. However, in both crystal species characteristic anelastic relaxation phenomena occur in the ultrasonic frequency regime close to room temperature. The smallest thermal expansion is observed in the plane perpendicular to the stiffest octahedral chains. A model is discussed to explain the apparent discrepancy in terms of cross-correlations within the three-dimensional framework of edge- and corner-linked coordination polyhedra.
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Single crystal growth and characterization of mullite-type Bi2Mn4O10

Manfred Burianek, Thomas F. Krenzel, Martin Schmittner, Jürgen Schreuer, Reinhard X. Fischer, Manfred Mühlberg, Gwilherm Nénert, Hartmut Schneider, Thorsten M. Gesing June 11, 2013 Page range: 449-455
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Abstract

A part of the pseudo-binary join Bi 2 O 3 –Bi 2 Mn 4 O 10 of the ternary system Bi 2 O 3 –MnO–MnO 2 was examined using thermo-analytical methods. Because Bi 2 Mn 4 O 10 melts incongruently single crystals of up to 20mm in diameter were grown by the top seeded solution growth method in the temperature range from about 1223K to 1173K. Single crystal neutron diffraction confirmed the principles of the crystal structure of Bi 2 Mn 4 O 10 but revealed much smaller distortions of the cation coordination polyhedra. In contrast to the anisotropy observed in other mullite-type Bi containing compounds, the linear thermal expansion of Bi 2 Mn 4 O 10 , as studied by means of dilatometry and X-ray powder diffraction techniques, is characterized by α 11 > α 33 > α 22 at room temperature. The relatively large expansion along the a -axis can be attributed to the two oxygen atoms bridging two corner shared MnO 5 tetrahedral pyramids which alternate with the structural void between two adjacent Bi 3 + cations.
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Synthesis and electrical conductivity of mullite-type Bi2Al4O9 and (Bi,Ca)2Al4O9 ceramics

Wen-Cheng James Wei, S. Y. Chuang, Y. C. Hu, Hartmut Schneider June 11, 2013 Page range: 456-463
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Abstract

Mullite-type Bi 2 Al 4 O 9 is a potential material for electrolytes in solid oxide fuel cells. Colloidal dispersed homogeneous mixtures of commercial, submicron Bi 2 O 3 , Al 2 O 3 and CaCO 3 powders were used to fabricate mullite-type Bi 2 Al 4 O 9 and (Bi,Ca) 2 Al 4 O 9 by means of reaction sintering in the solid state or in liquid-phase assisted processes. The products were characterized using X-ray diffraction, scanning and transmission electron microscopy, and the sintering density was compared to two conventional sintering runs. This showed that the formation of the mullite-type Bi 2 Al 4 O 9 proceeds via dissolution of Al 2 O 3 in Bi 2 O 3 at the temperatures > 750°C. Details on the formation mechanisms of mullite phase, electrical conductivity versus the residual γ-Bi 24 Al 2 O 39 phase, and effects of Ca-dopant are reported.
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New pressure induced phase transitions in mullite-type Bi2(Fe4–xMnx)O10–δ complex oxides

Patricia E. Kalita, Andrew L. Cornelius, Kristina E. Lipinska, Michael W. Lufaso, Zachary R. Kann, Stanislav Sinogeikin, Oliver A. Hemmers, Hartmut Schneider June 11, 2013 Page range: 464-468
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Abstract

Single phased mullite-type Bi 2 Fe 4 – x Mn x O 10 – δ mixed crystals (0.25 ≤ x ≤ 3.125) and the end-member Bi 2 Fe 4 O 9 , synthesized from the oxides by reaction sintering up to 825°C, were studied at high-pressures in order to probe their high-pressure behavior and any possible structural phase transitions. In-situ synchrotron radiation-based powder X-ray diffraction was carried out in a diamond anvil cell, under quasi-hydrostatic conditions, up to a pressure of about 20 GPa at room temperature for each sample. A pressure-induced phase transition was found in all samples. The transition appeared spread over a pressure range and was not completed at the top investigated pressure. This is the first report of a pressure-induced phase transition in Bi 2 Fe 4 – x Mn x O 10 – δ mixed crystals.
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Morphological characterization of the Al–Ag–Cu ternary eutectic

Amber Genau, Lorenz Ratke June 11, 2013 Page range: 469-475
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Abstract

Ternary eutectic microstructures have a level of complexity far exceeding that of binary eutectics. As there is currently no detailed description of ternary eutectic structures in the literature, we have undertaken a systematic investigation of the structures formed by directional solidification of the ternary eutectic Al–Ag–Cu. Using a constant temperature gradient of 3 K mm −1 and solidification velocities between 0.2 and 5 μm s −1 , we are able to observe different forms of the eutectic structure with varying degrees of alignment. We describe these structures both qualitatively and quantitatively, using measures including the volume fraction and composition of all phases, the distribution of interphase separations, and the number of nearest neighbor phases. The effects of solid-state transformations on the microstructure are also discussed.
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Bainite: Fragmentation of crystallographically homogeneous domains

Junhak Pak, Dong Woo Suh, Harshad K. D. H. Bhadeshia June 11, 2013 Page range: 476-482
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Abstract

It becomes possible in appropriate circumstances for similarly oriented plates of bainite or martensite to merge and form coarse crystallographically homogeneous domains whose presence leads to a deterioration in mechanical properties. A method is presented here for breaking up such domains, by introducing very small scale chemical composition variations in the austenite prior to its transformation.
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Influence of grain size on the dynamic recrystallization behavior of AISI 304 stainless steel during hot deformation

Javad Rasti, Abbas Najafizadeh, Mahmood Meratian June 11, 2013 Page range: 483-489
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Abstract

The effects of two initial grain sizes of 15 and 40μm on the dynamic recrystallization behavior of a type 304 stainless steel have been investigated at temperatures of 950–1100°C and strain rates of 0.005–0.5s −1 using hot compression testing. Microstructural investigations showed that the dimensionless parameter of Z / A can be used to express in which conditions dynamic recrystallization progressed via a necklace structure. Electron backscattered diffraction maps exhibited some evidence that confirmed the dynamic recrystallization mechanism changed from discontinuous to continuous with a decrease in the initial grain size. Results showed that the coarse grained material produced finer and more homogeneous metadynamic recrystallized grains, possibly due to the uniform substructure observed in the grains interior.
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Li–Cr substituted nickel–zinc–copper ferrite powders: structural and magnetic properties

Ailin Xia, Shunkai Liu, Chuangui Jin, Dexin Du, Jinlian Hu June 11, 2013 Page range: 490-493
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Abstract

Li–Cr substituted NiZnCu ferrite powder specimens with the nominal composition Ni 0. 25 –2 x Li x Cr x Cu 0.15 Zn 0.6 Fe 2 O 4 ( x =0.00, 0.01, 0.02, 0.03, 0.04) were prepared primarily via chemical coprecipitation. X-ray diffractometry, scanning electron microscopy and vibrating sample magnetometry were used to study their structural or magnetic properties. It is found that all the specimens exhibit a single phase after annealing. The variation tendency of saturation magnetization with x exhibts a strange variation tendency and can be attributed to the different site occupation of Li + ions. It is also found that suitable Li–Cr substitutions help decrease the annealing temperature.
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A model to calculate the viscosity of silicate melts

Eli Brosh, Arthur D. Pelton, Sergei A. Decterov June 11, 2013 Page range: 494-501
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Abstract

Our recently developed model for the viscosity of silicate melts is extended to describe and predict the viscosities of oxide melts containing boron. The model requires three adjustable parameters to reproduce the viscosity of B 2 O 3 –SiO 2 melts and two parameters for each B 2 O 3 – M O x melt, where M O x is a basic oxide other than an alkali oxide. All available experimental data have been collected for binary melts formed by B 2 O 3 with SiO 2 , Al 2 O 3 , CaO, MgO, ZnO, PbO to calibrate the model. The viscosities of the B 2 O 3 -containing ternary and higher-order subsystems of the B 2 O 3 –CaO–MgO–PbO–ZnO–SiO 2 system and of the B 2 O 3 –CaO–MgO–PbO–ZnO–Al 2 O 3 system are then predicted by the model without any additional adjustable parameters. Experimental data were found for only five such subsystems: B 2 O 3 –PbO–SiO 2 , B 2 O 3 –CaO–SiO 2 , B 2 O 3 –PbO–ZnO, B 2 O 3 –PbO–Al 2 O 3 and B 2 O 3 –CaO–Al 2 O 3 . Predictions of the model are compared to these experimental data.
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Lattice dynamics analysis of the thermal properties of liquid iron

Zenghui Wang, Mingjiu Ni June 11, 2013 Page range: 502-505
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Abstract

In this paper, the embedded atom method potential and Johnson potential are applied to calculate the thermal properties of liquid iron with an emphasis on a wide rage of temperatures and pressures. The results show that the liquid iron self-diffusion coefficient increases with increasing temperature and decreases with increasing pressure. The calculated self-diffusion coefficient is in good agreement with Protopapas' hard-sphere model at atmospheric pressure. According to the simulation results, we can get the Arrhenius equation between diffusion coefficient, temperature and activation energy. Increasing pressure enlarges the liquid iron activation energy and reduces the movement of atoms in liquid iron. Liquid iron thermal conductivity is computed using non-equilibrium molecular dynamics simulation and the simulation results are consistent with Pottlacher's experimental results with acceptable uncertainty in the 1535–2700 K temperature range.
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Evaluation of the mechanical properties of natural asphalt-modified hot mixture

Baha Vural Kök, Mehmet Yílmaz, Paki Turgut, Necati Kuloğlu June 11, 2013 Page range: 506-512
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The objective of this study is to evaluate the usage of natural asphalt in hot mix asphalt by means of determining the Marshall stability, stiffness modulus, indirect tensile strength, and dynamic creep tests. Natural asphalt, which consists of 17% asphalt fraction and 83% mineral fraction, was obtained from Syrian. The optimum bitumen content was determined to be 1% lower for natural asphalt-modified mixtures compared to control mixtures. The stiffness modulus values of the natural asphalt-modified mixtures were higher than those of the control mixtures. The moisture susceptibility of natural asphalt-modified mixtures and control mixtures were evaluated during different freeze–thaw cycles. The natural asphalt-modified mixtures were not as susceptible as control mixtures to moisture damage. Adding natural asphalt to mixtures remarkably decreased susceptibility to permanent deformation. The results presented here demonstrate the positive effects of using natural asphalt.
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Prediction of the transverse Young's modulus of unidirectional triangle-section carbon fiber reinforced plastics

Rongguo Wang, Xin Liu, Wenbo Liu, Xiaodong He, Fan Yang June 11, 2013 Page range: 513-517
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Abstract

In order to research the mechanical behavior of unidirectional triangle-section carbon fiber reinforced plastics (TCFRP), the composite was manufactured using the filament winding process, with a fiber volume fraction of 49.40%, and the transverse Young's modulus of TCFRP was tested. The distribution of triangle-section carbon fibers (TCFs) in the cross-section of TCFRP was investigated by observing and analyzing a lot of micrographs of the composite. By utilizing ANSYS software package and the Halpin–Tsai analytical method, the transverse Young's modulus of six groups models of unidirectional TCFRP with different fiber volume fractions (50.00%; 48.27%; 46.63%; 45.07%; 43.58% and 42.17%) were investigated, and the shape factors in the Halpin–Tsai equations were obtained. Based on the fitting curve, the relationship between the shape factors and fiber volume fractions was expressed as an equation, which could be used to predict the transverse Young's modulus of TCFRP with arbitrary TCFs content. For the TCFRP whose the fiber volume fraction was 49.40%, the prediction of transverse Young's modulus of TCFRP was compared with experimental data and the result shows good agreement.

People

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Prof. Dr. Bernd Stritzker – 65th birthday

Hans-Jörg Fecht June 11, 2013 Page range: 518-518
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Professor Dr.-Ing. Rainer Schmid-Fetzer – 65 Years

Hans J. Seifert June 11, 2013 Page range: 519-520
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DGM News

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DGM News

June 11, 2013 Page range: 521-526
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About this journal

The International Journal of Materials Research (IJMR) publishes original high quality experimental and theoretical papers and reviews on basic and applied research in the field of materials science and engineering, with focus on synthesis, processing, constitution, and properties of all classes of materials. Particular emphasis is placed on microstructural design, phase relations, computational thermodynamics, and kinetics at the nano to macro scale. Contributions may also focus on progress in advanced characterization techniques.
All articles are subject to thorough, independent peer review.
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