Graphene nanochains and nanoislands in the layers of room-temperature fluorinated graphite

Intercalated compound of graphite fluoride with n-heptane has been synthesized at room temperature using a multi-stage process including fluorination by a gaseous BrF₃ and a set of intercalant exchange reactions. It was found that composition of the compound is CF_0.40(C₇H₁₆)_0.04 and the guest molecules interact with the graphite fluoride layers through the van der Waals forces. Since the distance between the filled layers is 1.04 nm and the unfilled layers are separated by ∼0.60 nm, the obtained compound can be considered as a stack of the fluorinated graphenes. These fluorinated graphenes are large in area making it possible to study local destruction of the π conjugated system on the basal plane. It was shown that fluorine atoms form short chains, while non-fluorinated sp² carbon atoms are organized in very narrow ribbons and aromatic areas with a size smaller than 3 nm. These π electron nanochains and nanoislands preserved after the fluorination process are likely responsible for the value of the energy gap of the compound of ∼2.5 eV. Variation in the size and the shape of π electron regions within the fluorinated graphene layers could be a way for tuning the electronic and optical characteristics of the graphene-based materials.     

Microstructure effects on BaTiO3/BaTi0.8Zr0.2O3 composites properties

The dielectric, pyroelectric and ferroelectric properties of bilayered BaTiO₃/BaTi_0.8Zr_0.2O₃ ceramics are described and correlated with their microstructure. Different sintering times are employed to change the microstructure and promote interdiffusion between the layers. The effects of constrained sintering on both compositions are analyzed and their properties are compared to that of single phase BaTiO₃ and BaTi_0.8Zr_0.2O₃ ceramics. The results show that, at sintering times until 2 h, the bilayer properties are predominantly affected by the presence of residual stresses. Only after 4 h sintering, the properties are predominantly affected by interdiffusion between the layers.     

Dilatometric study of anisotropic sintering of alumina/zirconia laminates with controlled fracture behaviour

Al₂O₃ and ZrO₂ monoliths as well as layered Al₂O₃/ZrO₂ composites with a varying layer thickness ratio were prepared by electrophoretic deposition. The sintering shrinkage of these materials in the transversal (perpendicular to the layers, i.e. in the direction of deposition) as well as in the longitudinal (parallel with layers interfaces) direction were monitored using high-temperature dilatometry. The sintering of layered composites exhibited anisotropic behaviour. The detailed study revealed that sintering shrinkage in the longitudinal direction was governed by alumina (material with a higher sintering temperature), whilst in the transversal direction it was accelerated by the directional sintering of zirconia layers. For interpretation of such anisotropic sintering kinetics, the Master Shrinkage Curve model was developed and applied. Crack propagation through laminates with a different alumina/zirconia thickness ratio was described with the help of scanning electron microscopy and confocal laser microscopy.     

Durability and performance of CGO barriers and LSCF cathode deposited by spray-pyrolysis

Ce_0.9Gd_0.1O_1.95 (CGO) protective layers are prepared by two different methods to prevent the reaction between the Zr_0.84Y_0.16O_1.92 (YSZ) electrolyte and the La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF) cathode. In the first method, the CGO layers are deposited by an airbrushing technique from an ink containing CGO particles without and with cobalt as sintering aids. The second strategy consists in preparing both a dense CGO barrier layer and a porous LSCF cathode by spray-pyrolysis deposition, in order to further reduce the fabrication temperature and minimize the reaction between the cell components. The samples prepared by spray-pyrolysis exhibit better performance and durability than those obtained by conventional sintering methods. The results suggest that the interfacial reactivity between YSZ and LSCF as well as the Sr-enrichment at the cathode surface can be avoided by using low-temperature fabrication methods and by operating at temperatures lower than 650?°C.     

Pressureless sintering of ZrO2–ZrSiO4/NiCr functionally graded materials with a shrinkage matching process

Shrinkage matching was applied as the basic concept for the processing of five-layered ZrO₂–ZrSiO₄/NiCr functionally graded materials (FGMs) by pressureless sintering. Shrinkage behavior of the constituent layers of FGM was matched based on the strategy of reducing the mismatches of shrinkage rate between the adjacent layers by a systematic adjustment of the ZrSiO₄ inclusion content and the particle size of ZrO₂ matrix. Before shrinkage matching, sintering defects such as warping towards the ceramic-rich side of FGM and cracking in the 100 vol% ceramic layer were generated, due to the relatively high mismatches of shrinkage rate between the ceramic- and the metal-rich sides and at the interface of 100 and 75 vol% ceramic layers, respectively. After shrinkage matching, FGMs without any sintering defects were obtained, whereas the green bodies warped towards the metal-rich side already before sintering, due to the relatively higher shrinkage of the metal-rich side during isostatic pressing.     

The lamellar preparation of continuous porosity-graded Si3N4 ceramics without obvious interfaces for broadband radome application

Traditional layered broadband radomes are challenging to meet the needs of the high-temperature application, due to thermal mismatch between their layers. In this study, porous Si₃N₄ ceramics with a novel continuous porosity gradient from 54.7% to 82.4% were achieved by lamellar gel-casting, freeze-drying, and subsequent sintering process. The porosity-graded structure in Si₃N₄ ceramics shows no failure or cracks after sintering, benefiting from the low shrinkage after sintering at 1900 °C with the rapid sintering rate. The continuous porosity-graded structure without obvious interfaces was architected by ice crystal growth during solidification and the growth of rodlike β-Si₃N₄ grains across the interfaces during sintering. This approach can be beneficial to designing high wave transmission performance at specific broadband for radome.     

The master sintering curves for BaTi0.975Sn0.025O3/BaTi0.85Sn0.15O3 functionally graded materials

The most important aim in the design and processing of functionally graded materials (FGMs) is to produce devices free from any deformation. Smart choices of different combination of graded layers, as well as the heating rate during sintering, are important for the fabrication of high-quality FGMs. In this study, BaTi_0.975Sn_0.025O₃/BaTi_0.85Sn_0.15O₃ (noted as BTS2.5 and BTS15, respectively) FGM was used as a model system for the construction of master sintering curves (MSCs) and estimation of the effective activation energies of sintering for different BTS graded layers. The MSCs were constructed, for BTS2.5 and BTS15 graded layers in FGMs, using shrinkage data obtained by a heating microscope during sintering at four constant heating rates, 2, 5, 10 and 20 °/min. The effective activation energies were determined using the concept of MSC; values of 359.5 and 340.5 kJ/mol were obtained for graded layers BTS2.5 and BTS15, respectively. A small difference of the effective activation energies of chosen powders made it possible for us to prepare high-quality FGMs, without delamination, distortion or other forms of defects.     

Direct fluorination of the polyimide matrimid® 5218: The formation kinetics and physicochemical properties of the fluorinated layers

Fluorinated polymers have a set of unique properties, including improved chemical stability and thermal stability and good barrier and membrane parameters, which are mainly defined by their surface properties. This article presents systematic data on the direct fluorination of the polyimide Matrimid® 5218, a commercially available polymer suitable for the formation of gas‐separation hollow fibers. Changing the fluorination conditions (i.e., the fluorinated mixture composition, fluorine partial pressure, and treatment duration) allows the rate of formation of the surface‐fluorinated layer over the 0.1–10 μm range to be kept under control. The physicochemical properties of modified layers (i.e., the chemical composition, formation of radicals, refractive index, IR and UV spectra, density, and surface energy) are examined. The thickness of the fluorinated layer (δ_F) depends on the fluorination duration (t): δ_F ～ t^0.5. During fluorination, hydrogen atoms are replaced with fluorine, double bonds are saturated with fluorine, and at least one CN bond in the five‐member ring is disrupted. Fluorination results in a significant increase in the polymer density, transparency in the visible and ultraviolet regions of spectra, and a reduction of the refractive index. A high concentration of long‐living radicals (up to ～5 × 10¹⁹ radicals/cm³ of the fluorinated layer) is generated under fluorination. This can be used for subsequent grafting (e.g., with acrylonitrile). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 6–17, 2004     

Spark Plasma Sintering of Functionally Graded SiO2/Mo Laminated Layer Material

A functionally graded sintered body consisting of laminated SiO₂/Mo layers was fabricated using spark plasma sintering. A high sintered‐body density was achieved using fine powders of SiO₂ (4.0 μm) and Mo (1.3 μm), which ensured no cracks were formed between layers. The highest joining stress (1.2 MPa) was found to occur at the interface between SiO₂ layers with 0 and 8 vol% Mo, with the electrical resistance decreasing rapidly when the Mo content was increased to 13 and 22 vol%. This is attributed to the use of spark plasma sintering, suggesting further work is needed to fully optimize this process.     

Electrical percolation and infrared emissivity of pressureless sintered SiC-MoSi2 composites tailored by sintering temperature

SiC-MoSi₂ composites with low electrical resistivity and high infrared emissivity were fabricated via pressureless sintering. The relationship between microstructure evolution and electrical behaviors along with infrared emission properties of the resulting composites is investigated at various sintering temperatures. The electrical resistivity undergoes two significant drops with increasing sintering temperature. Pore elimination bears responsible for the initial decrease in electrical resistivity. Transmission electron microscopy (TEM) observation manifests that the thinned amorphous layers at SiC/MoSi₂ interface decrease grain boundary resistivity and allow for electrical percolation to occur when sintering temperature further rises. Additionally, increasing sintering temperature leads to a higher infrared emissivity owing to the formation of Mo_4.8Si₃C_0.6 and the decreased boundaries. The lowest electrical resistivity of 7.2 Ω cm and the highest infrared emissivity of 0.721 are recorded for composite sintered at 2000 ℃. Overall, SiC-MoSi₂ composites exhibit a promising prospect as infrared source elements that must endure harsh environments.     

Influence of powder mixing processes and WC contents on microstructure,shrinkage behavior,and mechanical properties of WC-Si3N4 composites

WC-Si₃N₄ composite structural material with excellent mechanical properties is essential for achieving high-strength connections between WC and Si₃N₄. Proper powder mixing process can significantly improve the mechanical properties of sintered samples. This study investigates the effects of two different ball milling methods: (1) mixing WC powder, Si₃N₄ powder, and sintering aid powders and then ball milling for 24 h (BM24); and (2) ball milling WC powder, Si₃N₄ powder, and sintering aid powders separately for 12 h and then ball milling in same jar for 12 h (BM12 + 12), as well as WC content on sintering shrinkage behavior of mixed powders. Furthermore, the bonding between the layers of one-time sintered sample of the WC-Si₃N₄ composite structure was investigated. The results showed that the microstrains of powders prepared by BM24 mixing process were greater than those of the powders prepared by BM12 + 12 mixing process. Shrinkage displacements and shrinkage rates during sintering of BM12 + 12 powders were greater than those of BM24 powders to varying degrees. Moreover, sintering temperature at which shrinkage rate of composite powders reaches its maximum value gradually increases as WC content decreases, while maximum value of shrinkage rate gradually decreases. Additionally, mechanical properties of all BM12 + 12 samples were better than those of BM24 samples. WC-Si₃N₄ composite structure sample sintered with BM12 + 12 powders had a smooth transition between the layers without any defects.     

Camber Evolution and Stress Development of Porous Ceramic Bilayers During Co‐Firing

Camber evolution and stress development during co‐firing of asymmetric bilayer laminates, consisting of porous Ce_0.9Gd_0.1O_1.95 gadolinium‐doped cerium oxide (CGO) and La_0.85Sr_0.15MnO₃ lanthanum strontium manganate (LSM)‐CGO were investigated. Individual layer shrinkage was measured by optical dilatometer, and the uniaxial viscosities were determined as a function of layer density using a vertical sintering approach. The camber evolution in the bilayer laminates was recorded in situ during co‐firing and it was found to correspond well with the one predicted by the theoretical model. The estimated sintering mismatch stress in co‐fired CGO‐LSM/CGO bilayer laminates was significantly lower than general sintering stresses expected for free sintering conditions. As a result, no co‐firing defects were observed in the bilayer laminates, illustrating an acceptable sintering compatibility of the ceramic layers.     

The effect of sintering parameters on spark plasma sintering of B4C

The effects of sintering temperature, heating rate, and holding time on the density and hardness of the spark plasma sintered B₄C were investigated. Experimental results are compared with the predictions from computational thermodynamics. It is explained how the choice of sintering parameters can affect the mechanical properties of the sintered samples. The fundamental mechanisms of how the sintering parameters affect the properties of the sintered B₄C are discussed with the sintering experiments and the predictions from the CALPHAD (Calculation of Phase Diagrams) approach. The effect of the number of graphite foil layers to pack the powder was also investigated. It is proposed that increasing the number of graphite foil layers may increase the driving force for the C-B₂O₃ reaction to proceed. Higher density and hardness is thus achieved with the removal of free carbon and B₂O₃ from the sample.     

Prevention of Cracks in Functionally Graded SiO2‐Mo Materials Fabricated by Uniaxial Compression Casting and Pressureless Sintering

In industrial high‐intensity discharge lamps, cracks and delaminations occasionally develop at the interface between SiO₂ and the Mo foil in the seal. Here, functionally graded SiO₂‐Mo materials for use in these lamps were fabricated by uniaxial compression casting and pressureless sintering. Consequently, vertical cracks developed across the sintered body layers, and interfacial cracks developed between the 100 wt% SiO₂ and 90 wt% SiO₂‐Mo layers. Therefore, the effects of residual stress, difference in the coefficient of thermal expansion (CTE), and difference in the volume shrinkage on these cracks were investigated. Vertical cracks were suppressed when residual stress was relaxed by annealing near the annealing point of silica glass during the cooling step in the sintering process. Interfacial cracks were suppressed when the difference in the CTE of the interface between the 100 wt% SiO₂ and 90 wt% SiO₂‐Mo layers was relaxed by inserting layers of 95 wt% SiO₂‐Mo between them. Furthermore, the suppression effect became stronger when the difference in the volume shrinkage of the layers was relaxed by sintering to join the separately sintered monolayers. Thus, the development of these cracks was influenced by the residual stress, CTE, and volume shrinkage. Therefore, these cracks can be prevented by optimizing these factors.     

Piezo-spectroscopic characterization of alumina-aluminium titanate laminates

A multilayered alumina-aluminium titanate composite was prepared by a colloidal route from aqueous suspensions. The structure of the laminate was symmetric and constituted of two external Al₂O₃ layers (width ≅ 1750 μm), one central Al₂O₃ layer (width ≅ 1200 μm) and two intermediate thin (width ≅ 315–330 μm) Al₂O₃–Al₂TiO₅ layers.Additional monolithic materials with the same compositions as those of the layers were fabricated as reference materials. Young's modulus of the monoliths was determined by three point bending. Dilatometry determinations were performed on green specimens, following the same heating and cooling schedules as those used for sintering the laminate, in order to determine the actual dimensional changes on cooling after sintering. The dimensional changes of the sintered specimens on heating and on cooling were also determined. Microscopic distributions of residual stresses were evaluated by fluorescence piezo-spectroscopy, and they revealed the existence of weak tensile and compressive hydrostatic stresses in the aluminium titanate and alumina layers, respectively. The level and sign of these stresses was in good agreement with those predicted based on analysis of the Young's modulus and the dimensional variations during cooling after sintering of the monoliths with the same compositions as those of the layers. Dimensional variations during cooling after sintering were different from those for sintered materials, which presented hysteresis between heating and cooling. In spite of the presence of compressive residual stresses in the external layers of the laminate, strength values of notched samples of the laminated specimens were lower than those for monoliths of the same composition as the external layers.     

Fabrication and optical characterizations of hot-pressed transparent SrF2/Nd:SrF2/SrF2 composite ceramic

A novel transparent SrF₂/Nd:SrF₂/SrF₂ composite ceramic with sandwich-like laminar configuration was designed and successfully fabricated by the hot-pressed sintering method. The composite ceramic possesses an apparent transition interfacial (about 200 μm in thickness) between SrF₂ and Nd:SrF₂ layers, formed by non-uniform distribution of raw powders and the diffusion of Nd ions during the high temperature sintering. The average grain sizes of SrF₂ and Nd:SrF₂ layers are about 262.1 μm and 28.6 μm, respectively. For a 2-mm thick transparent SrF₂/Nd:SrF₂/SrF₂ composite ceramic hot-pressed at 900 °C for 2 h, the transmittance at 500 nm and 1200 nm are about 49.6 % and 62.3 %, respectively. The microstructure, emission spectra and thermal conductivities of ceramics are also detected and studied.     

Enhancement of the chemical resistance of nitrile rubber by direct fluorination

Nitrile rubber (NBR), poly(acrylonitrile‐co‐butadiene) or NBR packers, are used to seal oil‐well tubing, where they often come into contact with ZnBr₂ brines at high temperatures and pressures. Under these conditions, NBR exhibits accelerated chemical degradation, which results in embrittlement and cracking. Although alternative fluoropolymers exhibit excellent chemical resistance, their strength is less than NBR, and replacement of the usual gasket materials with fluoroelastomers is expensive. We have demonstrated that a fluoropolymer surface on a nitrile elastomer provides the necessary chemical resistance while the elastomer retains strength. This can be achieved by direct fluorination, a rather easy and inexpensive process. Samples of NBR O‐rings were fluorinated by exposure to F₂ and F₂/HF mixtures at various temperatures. Although fluorination by F₂ produced the desired fluoropolymer layer, fluorination by F₂/HF (hydrofluoric acid) mixtures gave a smoother fluorinated layer at lower temperatures and shorter reaction times. Elemental analysis showed that the fluorinated layer eliminated ZnBr₂ diffusion into the NBR polymeric matrix. Surface fluorination also significantly retarded the loss of the mechanical properties of NBR when it was exposed to zinc bromide fluid. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 971–979, 2003     

Carbon nanofibres fluorinated using TbF4 as fluorinating agent. Part I: Structural properties

Fluorination of carbon nanofibres (CNFs) under fluorine gas at 480 °C leads to high fluorine content but also to some partial exfoliation. In order to avoid such phenomenon, an alternative route has been performed at temperatures ranged between 420 and 500 °C using a fluorinating agent, i.e. terbium tetrafluoride. The structural properties of the fluorinated CNFs are discussed taking into account the data of ¹³C solid state NMR, Raman spectroscopy, SEM, TEM and XRD. Whatever the fluorination temperature, a fluorinated phase of (CF)_n structural type, is formed contrary to the direct process using F₂ gas for which a (C₂F)_n-type fluorinated phase appeared for fluorination temperatures lower than 450 °C. The progressive release of fluorine atoms from the thermal decomposition of TbF₄ allows an homogenous distribution of the fluorinated part into the CNFs matrix and the formation of a unique (CF)_n type structure. Moreover, for high fluorination temperatures (480 and 500 °C), the fluorination leads to some nanofibres breaking but in no way to exfoliation.     

Fluorination of carbon blacks: an X-ray photoelectron spectroscopy study: IV. Reactivity of different carbon blacks in CF4 radiofrequency plasma

The effect of CF₄-plasma enhanced fluorination on the surface modification of carbon blacks has been examined using XPS. Three different types of carbon blacks have been studied: a thermal black, a furnace black and a high electrical conducting black. The analysis of the XPS spectra of fluorinated carbon black samples indicates that all fluorine atoms, fixed at the surface and in a subsuperficial zone of the particles, are covalently linked to carbon atoms. The influence of the physicochemical properties and morphology of these three types of carbon blacks on the fluorination reaction has also been investigated. The proportion of different types of fluorinated carbon atoms, i.e. on one hand CF_x surface and border groups of graphitic bulk domains for which the planar configuration of the graphene layers is preserved together with the sp² character of C, i.e. structures of type I, on the other hand polyalicyclic perfluorinated structures in which sp³C form puckered layers similar to those of covalent fluorographites, i.e. structures of type II, and also the F/C ratio of the fluorinated groups are related to the surface morphology and depend on the microstructural organization of particles. When the microstructure ordering and graphitic character of the carbon increase, the size of the ordered graphitic domain also increases. At the same time the density, the size of defects and proportion of protonated sp³C entities bridging the graphene layers decrease. As a consequence, the proportion of carbon atoms, potentially able to form perfluorinated CF₂ and CF₃ groups, decreases. The relative contribution of those groups is appreciably higher in fluorinated compounds which are derived from carbon blacks with a lower structural order.     

Enhanced sintering behavior of LSGM electrolyte and its performance for solid oxide fuel cells deposited by vacuum cold spray

How to obtain dense La_0.8Sr_0.2Ga_0.8Mg_0.2O₃ (LSGM) electrolyte at low sintering temperature (<1300 °C) is a challenge to improve solid oxide fuel cell (SOFC) performance at intermediate operation temperature. In this study, a double-layer design method for vacuum cold spray (VCS) prepared-LSGM electrolyte assisted with two-step sintering at a low temperature was proposed. The sintering behavior of VCS deposited LSGM layers at 1200 °C was investigated. The LSGM layers became denser in most regions except the appearance of some cracks. Subsequently, the effect of a second LSGM layer on the sintered top layer was studied to block cracks. Results showed that the co-sintered layer with a thickness of approximately 5 μm presented a maximum open circuit voltage of ∼0.956 V at 650 °C and a maximum power density of 592 mW/cm² at 750 °C. Result indicates that the sintering assisted VCS is a promising method to prepare the LSGM electrolyte applied in intermediate temperature SOFCs.