List of publications

Journal article

Knowles A, Tea-Sung J, Bhowmik A, Jones N, Britton TB, Giuliani F, Stone H, Dye Det al., 2018,

Data on a new beta titanium alloy system reinforced with superlattice intermetallic precipitates

, Data in Brief, Vol: 17, Pages: 863-869, ISSN: 2352-3409

The data presented in this article are related to the research article entitled “a new beta titanium alloy system reinforced with superlattice intermetallic precipitates” (Knowles et al., 2018) [1]. This includes data from the as-cast alloy obtained using scanning electron microscopy (SEM) and x-ray diffraction (XRD) as well as SEM data in the solution heat treated condition. Transmission electron microscopy (TEM) selected area diffraction patterns (SADPs) are included from the alloy in the solution heat treated condition, as well as the aged condition that contained < 100 nm B2 TiFe precipitates [1], the latter of which was found to exhibit double diffraction owing to the precipitate and matrix channels being of a similar width to the foil thickness (Williams and Carter, 2009) [2]. Further details are provided on the macroscopic compression testing of small scale cylinders. Of the micropillar deformation experiment performed in [1], SEM micrographs of focused ion beam (FIB) prepared 2 µm micropillars are presented alongside those obtained at the end of the in-situ SEM deformation as well as videos of the in-situ deformation. Further, a table is included that lists the Schmidt factors of all the possible slip systems given the crystal orientations and loading axis of the deformed micropillars in the solution heat treated and aged conditions.

Journal article

Ferraro C, Meille S, Réthoré J, Ni N, Chevalier J, Saiz Eet al., 2018,

Strong and tough metal/ceramic micro-laminates

, Acta Materialia, Vol: 144, Pages: 202-215, ISSN: 1359-6454

There is a growing interest in the development of composites with complex structures designed to generate enhanced mechanical properties. The challenge is how to implement these structures in practical materials with the required degree of control. Here we show how freeze casting of ceramic preforms combined with metal infiltration can be used to fabricate Al2O3/Al-4wt% Mg micro-laminated composites. By manipulating the solid content of the suspension and the morphology of the ceramic particles (from platelets to round particles) it is possible to access a range of structures with layer thickness varying between 1 and 30 μm and metallic contents between 66 and 86 vol%. The mechanical response of the materials is characterized by combining bending tests with observation of crack propagation in two and three dimensions using different imaging techniques. These composites are able to combine high strength and toughness. They exhibit a rising R-curve behaviour although different structures generate different toughening mechanisms. Composites fabricated with Al2O3 particles exhibit the highest fracture resistance approaching 60 MPa m1/2, while laminates prepared from Al2O3 platelets exhibit higher strengths (above 700 MPa) while retaining fracture resistance up to ∼40 MPa m1/2. The results provide new insights on the effect of structure on the mechanical properties in metal-ceramic composites as well as on the design of appropriate testing procedures.

Journal article

Waheed S, Hao R, Zheng Z, Wheeler J, Michler J, Balint D, Giuliani Fet al., 2018,

Temperature-dependent plastic hysteresis in highly confined polycrystalline Nb films

, Modelling and Simulation in Materials Science and Engineering, Vol: 26, ISSN: 0965-0393

In this study, the effect of temperature on the cyclic deformation behaviour of a confined polycrystalline Nb film is investigated. Micropillars encapsulating a thin niobium interlayer are deformed under cyclic axial compression at different test temperatures. A distinct plastic hysteresis is observed for samples tested at elevated temperatures, whereas negligible plastic hysteresis is observed for samples tested at room temperature. These results are interpreted using planar discrete dislocation plasticity incorporating slip transmission across grain boundaries. The effect of temperature-dependent grain boundary energy and dislocation mobility on dislocation penetration and, consequently, the size of plastic hysteresis is simulated to correlate with the experimental results. It is found that the decrease in grain boundary energy barrier caused by the increase in temperature does not lead to any appreciable change in the cyclic response. However, dislocation mobility significantly affects the size of plastic hysteresis, with high mobilities leading to a larger hysteresis. Therefore, it is postulated that the experimental observations are predominantly caused by an increase in dislocation mobility as the temperature is increased above the critical temperature of body-centred cubic niobium.

Journal article

Rocha VG, Garcia-Tunon E, Botas C, Markoulidis F, Feilden E, D'Elia E, Ni N, Shaffer M, Saiz Eet al., 2017,

Multimaterial 3D Printing of Graphene-Based Electrodes for Electrochemical Energy Storage Using Thermoresponsive Inks

, ACS APPLIED MATERIALS & INTERFACES, Vol: 9, Pages: 37136-37145, ISSN: 1944-8244

The current lifestyles, increasing population, and limited resources result in energy research being at the forefront of worldwide grand challenges, increasing the demand for sustainable and more efficient energy devices. In this context, additive manufacturing brings the possibility of making electrodes and electrical energy storage devices in any desired three-dimensional (3D) shape and dimensions, while preserving the multifunctional properties of the active materials in terms of surface area and conductivity. This paves the way to optimized and more efficient designs for energy devices. Here, we describe how three-dimensional (3D) printing will allow the fabrication of bespoke devices, with complex geometries, tailored to fit specific requirements and applications, by designing water-based thermoresponsive inks to 3D-print different materials in one step, for example, printing the active material precursor (reduced chemically modified graphene (rCMG)) and the current collector (copper) for supercapacitors or anodes for lithium-ion batteries. The formulation of thermoresponsive inks using Pluronic F127 provides an aqueous-based, robust, flexible, and easily upscalable approach. The devices are designed to provide low resistance interface, enhanced electrical properties, mechanical performance, packing of rCMG, and low active material density while facilitating the postprocessing of the multicomponent 3D-printed structures. The electrode materials are selected to match postprocessing conditions. The reduction of the active material (rCMG) and sintering of the current collector (Cu) take place simultaneously. The electrochemical performance of the rCMG-based self-standing binder-free electrode and the two materials coupled rCMG/Cu printed electrode prove the potential of multimaterial printing in energy applications.

Journal article

Feilden E, Ferraro C, Zhang Q, García-Tuñón E, D'Elia E, Giuliani F, Vandeperre L, Saiz Eet al., 2017,

3D printing bioinspired ceramic composites

, Scientific Reports, Vol: 7, ISSN: 2045-2322

Natural structural materials like bone and shell have complex, hierarchical architectures designed to control crack propagation and fracture. In modern composites there is a critical trade-off between strength and toughness. Natural structures provide blueprints to overcome this, however this approach introduces another trade-off between fine structural manipulation and manufacturing complex shapes in practical sizes and times. Here we show that robocasting can be used to build ceramic-based composite parts with a range of geometries, possessing microstructures unattainable by other production technologies. This is achieved by manipulating the rheology of ceramic pastes and the shear forces they experience during printing. To demonstrate the versatility of the approach we have fabricated highly mineralized composites with microscopic Bouligand structures that guide crack propagation and twisting in three dimensions, which we have followed using an original in-situ crack opening technique. In this way we can retain strength while enhancing toughness by using strategies taken from crustacean shells.

Journal article

Ferraro C, Garcia-Tunon E, Barg S, Miranda M, Ni N, Bell R, Saiz Eet al., 2017,

SiC porous structures obtained with innovative shaping technologies

, Journal of the European Ceramic Society, Vol: 38, Pages: 823-835, ISSN: 0955-2219

SiC structures with porosities ranging between 20–60% have been fabricated using two methods emulsification and freeze casting. While emulsification results in foam-like isotropic materials with interconnected pores, freeze casting can be used to fabricate highly anisotropic materials with characteristic layered architectures. The parameters that control the pore size and final porosity have been identified (solid content in the initial suspensions, emulsification times or speed of the freezing front). We have found that liquid state sintering (suing Al2O3 and Y2O3 as additives) at 1800 °C on a powder (SiC/Al2O3) bed provides optimum consolidation for the porous structures. The mechanical strength of the materials depends on their density. Freeze casted materials fabricated with bimodal particle size distributions (a controlled mixture of micro and nanoparticles) exhibit higher compressive strengths that can reach values of up to 280 MPa for materials with densities of 0.47.

Journal article

Garcia-Tunon E, Feilden E, Zheng H, D'Elia E, Leong A, Saiz Eet al., 2017,

Graphene Oxide: An All-in-One Processing Additive for 3D Printing

, ACS Applied Materials and Interfaces, Vol: 9, Pages: 32977-32989, ISSN: 1944-8244

Many 3D printing technologies are based on the development of inks and pastes to build objects through droplet or filament deposition (the latter also known as continuous extrusion, robocasting, or direct ink writing). Controlling and tuning rheological behavior is key for successful manufacturing using these techniques. Different formulations have been proposed, but the search continues for approaches that are clean, flexible, robust and that can be adapted to a wide range of materials. Here, we show how graphene oxide (GO) enables the formulation of water-based pastes to print a wide variety of materials (polymers, ceramics, and steel) using robocasting. This work combines flow and oscillatory rheology to provide further insights into the rheological behavior of suspensions combining GO with other materials. Graphene oxide can be used to manipulate the viscoelastic response, enabling the formulation of pastes with excellent printing behavior that combine shear thinning flow and a fast recovery of their elastic properties. These inks do not contain other additives, only GO and the material of interest. As a proof of concept, we demonstrate the 3D printing of additive-free graphene oxide structures as well as polymers, ceramics, and steel. Due to its amphiphilic nature and 2D structure, graphene oxide plays multiple roles, behaving as a dispersant, viscosifier, and binder. It stabilizes suspensions of different powders, modifies the flow and viscoelasticity of materials with different chemistries, particle sizes and shapes, and binds the particles together, providing green strength for manual handling. This approach enables printing complex 3D ceramic structures using robocasting with similar properties to alternative formulations, thus demonstrating the potential of using 2D colloids in materials manufacturing.

Journal article

Arnold M, Zhao S, Ma S, Giuliani F, Hansen U, Cobb JP, Abel RL, Boughton Oet al., 2017,

Microindentation - a tool for measuring cortical bone stiffness?

, BONE & JOINT RESEARCH, Vol: 6, Pages: 542-549, ISSN: 2046-3758

Journal article

Arnold M, Zhao S, Ma S, Giuliani F, Hansen U, Cobb JP, Abel RL, Boughton ORet al., 2017,

Microindentation: a tool for measuring cortical bone stiffness? A systematic review

, Bone & Joint Research, Vol: 6, Pages: 542-549, ISSN: 2046-3758

Objectives: Microindentation hasthe potential to measuretheelasticity(stiffness)of individualpatients’bone. Bone elasticity plays a crucial role in the press-fit stability of orthopaedic implants.Arming surgeons with accuratebone elasticityinformation may reduce surgical complicationsincluding peri-prosthetic fractures. The question we address with this systematicreview is whether microindentation can accurately measure cortical bone stiffness.Methods: A systematic review of all English language articles using a keyword search was undertaken in Medline, Embase, PubMed, Scopus and Cochrane databases. Studies thatonly used nanoindentation, cancellous boneoranimal tissue were excluded.Results: 1094abstracts were retrieved and 32papers were included in the analysis, 20 of which used reference point indentation and 12of which used traditional depth sensing indentation.There are a number of factors thatmust be taken into account when using microindentation such as tip size, depth and method of analysis.Only two studies validated microindentation againsttraditional mechanical testing techniques. Bothstudies used reference point indentation(RPI) with one showing that RPI parameters correlate well with mechanical testing, butanother suggestedthatthey do not. Conclusion: Microindentation has been used in various studies to assess bone elasticity but only two studies with conflicting results compared microindentation to traditional mechanical testing techniques. Further research,includingmore studies comparingmicroindentationto other mechanical testing methodsare needed,before microindentation can be reliably used to calculate cortical bone stiffness.

Conference paper

Leong AYL, Mahtar MA, Mattevi C, Leong KH, Saiz E, Sum WSet al., 2017,

Graphene filled epoxy coatings for enhanced corrosion protection

, 21st International Conference on Composite Materials (ICCM-21)

© 2017 International Committee on Composite Materials. All rights reserved. The ability of graphene oxide derived fillers to enhance the moisture barrier performance of epoxy coating has been investigated. Films and coatings of virgin and modified graphene oxide (GO) were produced with different dispersion methods. Water vapour transmission rate (WVTR) was evaluated. Reduction in WVTR of GO/epoxy films were less than predicted and in one case, was higher than unfilled epoxy film. However, moisture barrier and corrosion protection performance were improved by reducing the graphene oxide. Films with reduced GO (rGO) have smaller WVTR while corrosion rate of rGO/epoxy coating was also lowered.

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Journal article

Knowles A, Bhowmik A, Purkayastha S, Jones NG, Giuliani F, Clegg WJ, Dye D, Stone HJet al., 2017,

Data on a Laves phase intermetallic matrix composite in situ toughened by ductile precipitates

, Data in Brief, Vol: 14, Pages: 489-493, ISSN: 2352-3409

The data presented in this article are related to the research article entitled “Laves phase intermetallic matrix composite in situ toughened by ductile precipitates” (Knowles et al.) [1]. The composite comprised a Fe2(Mo, Ti) matrix with bcc (Mo, Ti) precipitated laths produced in situ by an aging heat treatment, which was shown to confer a toughening effect (Knowles et al.) [1]. Here, details are given on a focused ion beam (FIB) slice and view experiment performed on the composite so as to determine that the 3D morphology of the bcc (Mo, Ti) precipitates were laths rather than needles. Scanning transmission electron microscopy (S(TEM)) micrographs of the microstructure as well as energy dispersive X-ray spectroscopy (EDX) maps are presented that identify the elemental partitioning between the C14 Laves matrix and the bcc laths, with Mo rejected from the matrix into laths. A TEM selected area diffraction pattern (SADP) and key is provided that was used to validate the orientation relation between the matrix and laths identified in (Knowles et al.) [1] along with details of the transformation matrix determined.

Conference paper

Hauth M, Lawlor V, Cartellieri P, Zechmeister C, Wolff S, Bucher C, Malzbender J, Wei J, Weber A, Tsotridis G, Frandsen HL, Kwok K, Molla TT, Wuillemin Z, Van Herle J, Greco F, Cornu T, Nakajo A, Atkinson A, Vandeperre L, Wang Xet al., 2017,

Production and reliability oriented SOFC cell and stack design

, 15th International Symposium on Solid Oxide Fuel Cells (SOFC), Publisher: Electrochemical Society, Pages: 2231-2249, ISSN: 1938-5862

The paper presents an innovative development methodology for a production and reliability oriented SOFC cell and stack design aiming at improving the stacks robustness, manufacturability, efficiency and cost. Multi-physics models allowed a probabilistic approach to consider statistical variations in production, material and operating parameters for the optimization phase. A methodology for 3D description of spatial distribution of material properties based on a random field models was developed and validated by experiments. Homogenized material models on multiple levels of the SOFC stack were established. The probabilistic models were related to the experimentally obtained properties of base materials to establish a statistical relationship between the material properties and the most relevant load effects. Software algorithms for meta models that allow the detection of relationships between input and output parameters and to perform a sensitivity analysis were developed and implemented. The capabilities of the methodology is illustrated on two practical cases.

Journal article

Sernicola G, Giovannini T, Patel P, Kermode J, Balint D, Britton TB, Giuliani Fet al., 2017,

In situ stable crack growth at the micron scale

, Nature Communications, Vol: 8, ISSN: 2041-1723

Grain boundaries typically dominate fracture toughness, strength, slow crack growth of ceramics. To improve these properties through mechanistically informed grain boundary engineering, precise measurement of the mechanical properties of individual boundaries is essential, although this is rarely achieved due to its complexity. Here we present a new approach to characterise the fracture energy at the lengthscale of individual grain boundaries and demonstrate this capability with measurement of the surface energy of silicon carbide (SiC) single crystals. We perform experiments using an in situscanning electron microscopy based double cantilever beam test, thus enabling viewing and measurement of stable crack growth directly. These experiments correlate well with our density functional theory (DFT) calculations of the surface energy of the same SiC plane. Subsequently, we measure the fracture energy for a bi-crystal of SiC, diffusion bonded with a thin glassy layer. These measurements ultimately promote microstructural engineering of novel and advanced ceramics.

Journal article

Knowles AJ, Jun T-S, Bhowmik A, Jones NG, Giuliani F, Britton TB, Stone HJ, Dye Det al., 2017,

A new beta titanium alloy system reinforced with superlattice intermetallic precipitates

, Scripta Materialia, Vol: 140, Pages: 71-75, ISSN: 1872-8456

Titanium alloys traditionally lack a nm-scale intermetallic precipitate that can be exploited for age-hardening from solid solution. Here such a strengthening concept is developed in the Ti-Fe-Mo system, with it being found that a high temperature β (bcc A2) single-phase field for homogenisation can be obtained, which following ageing (750 °C/80 h) precipitated B2 TiFe <100 nm in size. The orientation relationship was found to be ⟨100⟩A2//⟨100⟩B2, {100}A2//{100}B2, with a misfit of −6.1%. The alloy was found to be very hard (HV0.5 = 6.4 GPa) and strong (σy, 0.2 = 1.9 GPa) with a density of 6.68 g cm−3. TEM observation and micropillar deformation showed that the precipitates resist dislocation cutting.

Journal article

Knowles AJ, Bhowmik, Purkayastha S, Jones NG, Giuliani F, Clegg WJ, Dye D, Stone HJet al., 2017,

Laves phase intermetallic matrix composite in situ toughened by ductile precipitates

, Scripta Materialia, Vol: 140, Pages: 59-62, ISSN: 1872-8456

Laves phase based materials are of interest for elevated temperature applications for their high melting points and strengths but are critically limited by their low fracture toughness. Here, a Laves phase intermetallic matrix composite toughened by ductile precipitates has been studied. This microstructure was produced in situ by heat treating a Fe2(Mo,Ti) based alloy to precipitate ∼ 12% volume fraction of fine ∼ 250 nm bcc, A2 (Mo,Ti), phase, with an orientation relationship of . The precipitated A2 phase increased the indentation fracture toughness from 1.1 to 2.2 MPa m1/2 while maintaining a high hardness of HV0.5 = 8.9 GPa similar to monolithic Laves phases.

Journal article

Ni H, Xu F, Tomsia AP, Saiz E, Jiang L, Cheng Qet al., 2017,

Robust Bioinspired Graphene Film via pi-pi Cross-linking

, ACS APPLIED MATERIALS & INTERFACES, Vol: 9, Pages: 24987-24992, ISSN: 1944-8244

Graphene composite films inspired by nacre are the subject of ongoing research efforts to optimize their properties for applications in flexible energy devices. Noncovalent interactions do not cause interruption of the delocalized conjugated π-electron system, thus preserving graphene’s excellent properties. Herein, we synthesized a conjugated molecule with pyrene groups on both ends of a long linear chain (AP-DSS) from 1-aminopyrene (AP) and disuccinimidyl suberate (DSS). The AP-DSS molecules are used to cross-link adjacent graphene nanosheets via π–π interfacial interactions to improve properties of graphene films. The tensile strength and toughness of resultant graphene films were 4.1 and 6.4 times higher, respectively, than that of pure rGO film. More remarkably, the electrical conductivity showed a simultaneous improvement, which is rare to be achieved in other kinds of covalent or noncovalent functionalization. Such integration demonstrates the advantage of this work to previously reported noncovalent functionalization of graphene.

Journal article

Machado GC, García-Tuñón E, Bell RV, Alini M, Saiz E, Peroglio Met al., 2017,

Calcium phosphate substrates with emulsion-derived roughness: processing, characterisation and interaction with human mesenchymal stem cells

, Journal of the European Ceramic Society, Vol: 38, Pages: 949-961, ISSN: 0955-2219

Calcium phosphates (CaP) have been the subject of several studies that often lack a systematic approach to understanding how their properties affect biological response. CaP particles functionalised with a pH-responsive polymer (BCS) were used to prepare microporous substrates (porosity between 70 and 75% and pore sizes of 5–20 μm) through the aggregation of oil-in-water emulsions by controlling solid loading, emulsification energy, pH, drying and sintering conditions. The combined effect of surface roughness (roughness amplitude, Ra between 0.9–1.7 μm) and chemistry (varying Hydroxyapatite/β-Tricalcium phosphate ratio) on human mesenchymal stem cells was evaluated. HA substrates stimulated higher cell adhesion and proliferation (especially with lower Ra), but cell area increased with β-TCP content. The effect of surface roughness depended of chemistry: HA promoted higher mineralising activity when Ra ∼ 1.5 μm, whereas β-TCP substrates stimulated a more osteogenic profile when Ra ∼ 1.7 μm. A novel templating method to fabricate microporous CaP substrates was developed, opening possibilities for bone substitutes with controlled features.

Journal article

Waheed S, Hao R, Bhowmik A, Balint DS, Giuliani Fet al., 2017,

A unifying scaling for the Bauschinger effect in highly confined thin films: a discrete dislocation plasticity study

, Modelling and Simulation in Materials Science and Engineering, Vol: 25, ISSN: 0965-0393

In this study, sequential sputter deposition, diffusion bonding and focused ion beam milling are used to fabricate sapphire micropillars encapsulating a thin single crystal niobium film. A distinct Bauschinger effect is observed during the cyclic axial compression of the samples. Plain strain discrete dislocation plasticity is used to interpret the experimental results obtained for the encapsulated film-micropillar geometry. The simulations show that the experimental samples correspond to a saturated source density regime, producing the maximum Bauschinger effect for the chosen mean nucleation strength. Next, the source density and mean nucleation strength are shown to have a coupled effect on the size of the Bauschinger effect, understood in terms of the differing number of pile-ups occurring per source in the film. The coupled effect is found to be represented by the density of dislocations annihilated upon unloading: a consistent linear relationship is observed between the size of the Bauschinger effect and the annihilated dislocation density over the entire source density and nucleation strength parameter space investigated. It is found that different film orientations fulfil the same linear relationship, whereas changing the film thickness causes the slope of the linear trend to vary suggesting a length-scale dependence on reverse plasticity. Finally, all results are found to be unified by a power-law relationship quantifying the Bauschinger effect of the form ${{\rm{\Gamma }}}_{{\rm{B}}}\propto {\rm{\Delta }}{\rho }_{{\rm{ann}}}{l}^{n}$ where it is argued that the number of dislocations undergoing reverse glide in the confined film is represented by ${\rm{\Delta }}{\rho }_{{\rm{ann}}}$, the mean free path of dislocations by l and the effect of hardening processes by the exponent n. The net reverse glide is thus represented by ${\rm{\Delta }}{\rho }_{{\rm{ann}}}{l}^{n}$ which can be used as a measure of the Bauschinger effect.

Journal article

Goyos-Ball L, Fernandez E, Diaz R, Fernandez A, Prado C, Torrecillas A, Saiz Gutierrez Eet al., 2017,

Osseous differentiation on freeze casted 10CeTZP-Al2O3 structures

, Journal of the European Ceramic Society, Vol: 37, Pages: 5009-5016, ISSN: 1873-619X

Three-dimensional structures with directionally oriented pore networks were fabricated from a 10 mol% ceria-stabilized zirconia and alumina composite (10CeTZP-Al2O3) via freeze casting. Ceramic suspensions of different concentrations (30, 40 and 50 wt% solids) were frozen at various rates (2, 5 and 10 °C/min) to obtain lamellar structures with aligned tubular pores of different characteristics: porosity (75–84%), pore dimensions (small diameter of the elliptical pores: 10–23 μm; large diameter of the elliptical pores: ∼200 ± 70 μm), lamella thickness (2.7–4 μm) and compression strength (1–12 MPa). In vitro assays confirmed the non-cytotoxic nature of the samples. Furthermore, specific osseous differentiation genes were quantified after incubating osteoblasts on different cross sections of the samples during 7 days in supplemented culture medium; results demonstrated that the freeze casted structures induce up to nine times more osseous gene expression than tissue culture polystyrene (TCPS), an advanced surface used for optimized in vitro cell growth.

Conference paper

Rounthwaite N, McGilvery CM, Jiang J, Williams R, Giuliani F, Britton TBet al., 2017,

A chemical and morphological study of diesel injector nozzle deposits - insights into their formation and growth mechanisms

, SAE 2017 World Congress and Exhibition, Publisher: SAE International, Pages: 106-114, ISSN: 1946-3960

Modern diesel passenger car technology continues to develop rapidly in response to demanding emissions, performance, refinement, cost and fuel efficiency requirements. This has included the implementation of high pressure common rail fuel systems employing high precision injectors with complex injection strategies, higher hydraulic efficiency injector nozzles and in some cases <100µm nozzle hole diameters. With the trend towards lower diameter diesel injector nozzle holes and reduced cleaning through cavitation with higher hydraulic efficiency nozzles, it is increasingly important to focus on understanding the mechanism of diesel injector nozzle deposit formation and growth. In this study such deposits were analysed by cross-sectioning the diesel injector along the length of the nozzle hole enabling in-depth analysis of deposit morphology and composition change from the inlet to the outlet, using state-of-the-art electron microscopy techniques. Deposits produced in the injector nozzles of the industry standard fouling test (CEC F-98-08 DW10B bench engine) were compared with those formed in a vehicle driven on a chassis dynamometer, using a drive cycle more representative of real world vehicle conditions, to explore the effects of differing drive cycles and engine technologies. Fouling in all tests was accelerated with the addition of 1ppm zinc neodecanoate, as specified in the CEC DW10B test. This in-depth characterisation revealed a complex multi-layered system of deposits inside the diesel injector nozzle. Through analysing these layers the mechanisms enabling the initial deposit formation and growth can be postulated.

Journal article

Goyos-Ball L, Garcia-Tunon E, Fernandez-Garcia E, Diaz R, Fernandez A, Prado C, Saiz E, Torrecillas Ret al., 2017,

Mechanical and biological evaluation of 3D printed 10CeTZP-Al2O3 structures

, Journal of the European Ceramic Society, Vol: 37, Pages: 3151-3158, ISSN: 0955-2219

Three-dimensional structures were robocasted from a 10 mol% ceria-stabilized zirconia and alumina composite (10CeTZP-Al2O3). A hydrogel-based printable ink was developed using a unique non-ionic copolymer surfactant. Self-supporting and free-standing structures, including round lattices with interconnected pores (200–600 μm pores; 30–50% porosity), rectangular bars (95% density on average) and cones were successfully printed. The round lattices of 200 μm pores and 30% porosity showed compression strengths similar to those of cortical bone, reaching almost 200 MPa. The maximum flexural strength value attained for the rectangular bars was 575 MPa. In vitro biological studies demonstrated that the samples allow for practically 100% cell viability, confirming their non-cytotoxic nature. Cell differentiation tests were performed using osteoblasts incubated for 7 days in supplemented cell culture medium. Quantification of specific osseous differentiation genes showed that the robocasted structures induced a higher degree of osseous differentiation than tissue culture polystyrene.

Journal article

Olowojoba GB, Kopsidas S, Eslava S, Saiz Gutierrez E, Kinloch AJ, Mattevi C, Garcia Rocha V, Taylor ACet al., 2017,

A facile way to produce epoxy nanocomposites having excellent thermal conductivity with low contents of reduced graphene oxide

, Journal of Materials Science, Vol: 52, Pages: 7323-7344, ISSN: 1573-4803

A well-dispersed phase of exfoliated graphene oxide (GO) nanosheets was initially prepared in water. This was concentrated by centrifugation and was mixed with a liquid epoxy resin. The remaining water was removed by evaporation, leaving a GO dispersion in epoxy resin. A stoichiometric amount of an anhydride curing agent was added to this epoxy-resin mixture containing the GO nanosheets, which was then cured at 90 °C for 1 hour followed by 160 °C for 2 hours. A second thermal treatment step of 200 °C for 30 minutes was then undertaken to reduce further the GO in-situ in the epoxy nanocomposite. An examination of the morphology of such nanocomposites containing reduced graphene oxide (rGO) revealed that a very good dispersion of rGO was achieved throughout the epoxy polymer. Various thermal and mechanical properties of the epoxy nanocomposites were measured and the most noteworthy finding was a remarkable increase in the thermal conductivity when relatively very low contents of rGO were present. For example, a value of 0.25 W/mK was measured at 30 °C for the nanocomposite with merely 0.06 weight percentage (wt%) of rGO present, which represents an increase of ~40% compared with that of the unmodified epoxy polymer. This value represents one of the largest increases in the thermal conductivity per wt% of added rGO yet reported. These observations have been attributed to the excellent dispersion of rGO achieved in these nanocomposites made via this facile production method. The present results show that it is now possible to tune the properties of an epoxy polymer with a simple and viable method of GO addition.

Journal article

Saiz Gutierrez E, Picot O, Ferraro C, Garcia Rocha V, Ni N, D'Elia E, Meille S, Chevalier J, Saunders T, Peijs T, Reece MJet al., 2017,

Using graphene networks to build bioinspired self-monitoring ceramics

, Nature Communications, Vol: 8, ISSN: 2041-1723

The properties of graphene open new opportunities for the fabrication of composites exhibiting unique structural and functional capabilities. However, to achieve this goal we should build materials with carefully designed architectures. Here, we describe the fabrication of ceramic-graphene composites by combining graphene foams with pre-ceramic polymers and spark plasma sintering. The result is a material containing an interconnected, microscopic network of very thin (20–30 nm), electrically conductive, carbon interfaces. This network generates electrical conductivities up to two orders of magnitude higher than those of other ceramics with similar graphene or carbon nanotube contents and can be used to monitor ‘in situ’ structural integrity. In addition, it directs crack propagation, promoting stable crack growth and increasing the fracture resistance by an order of magnitude. These results demonstrate that the rational integration of nanomaterials could be a fruitful path towards building composites combining unique mechanical and functional performances.

Conference paper

Boughton OR, Zhao S, Arnold M, Ma S, Cobb JP, Giuliani F, Hansen U, Abel RLet al., 2017,

Measuring bone stiffness using microindentation

, British Orthopaedic Research Society (BORS) 2016 Conference, Publisher: British Editorial Society of Bone and Joint Surgery, Pages: 31-31, ISSN: 2049-4416

Journal article

Feilden E, Giovannini T, Ni N, Ferraro C, Saiz E, Vandeperre L, Giuliani Fet al., 2017,

Micromechanical strength of individual Al2O3 platelets

, Scripta Materialia, Vol: 131, Pages: 55-58, ISSN: 1359-6462

Optimising the properties of platelet reinforced composites requires the strength of the reinforcing phase to be known, however strength measurements at such small scales are difficult and therefore data is sparse. In this work the flexural strength and Weibull modulus of microscopic, alumina platelets has been measured as 5.3 ± 1.3 GPa and 3.7 respectively, using an in-situ micro 3-point bend test. A general approach to correct for the effect of variation in sample size on the Weibull modulus is presented, and the internal structure of the platelets is revealed by TEM.

Journal article

Glymond D, Vick M, Giuliani F, Vandeperre LJMet al., 2017,

High Temperature Fracture Toughness of Mullite with Monoclinic Zirconia

, Journal of the American Ceramic Society, Vol: 100, Pages: 1570-1577, ISSN: 1551-2916

Reactive sintering of zircon and alumina and zirconia additions to mullite are well establishedmethods for improving the poor fracture toughness of mullite. While it is clear that transformationtoughening is responsible for the improved toughness by addition of partially stabilised zirconia, it isnot clear why adding unstabilised zirconia increases the toughness although microcracking and crackdeflection have been suggested. Therefore the fracture toughness of a mullite composite with 20vol% unstabilised zirconia and a monolithic mullite were investigated at ambient conditions and attemperatures up to 1225 oC. It was found that monoclinic zirconia increases the toughness atambient conditions from the monolithic mullite value of 1.9 MPa m1/2 to 3.9 MPa m1/2. Thetoughness of the composite with zirconia remains relatively constant from ambient to 600 °C butthen decreases rapidly. The mechanism for the toughness enhancement as well as the reason for itsvariation with temperature are explained using changes in residual stress state as deduced using thesphere in shell model from the measured thermal expansion behaviour.

Journal article

Feilden E, Giovannini T, Ni N, Ferraro C, Saiz E, Vandeperre L, Giuliani Fet al.,

Micromechanical strength of Al2O3 platelets

, Scripta Materialia, ISSN: 1359-6462

Optimising the properties of platelet reinforced composites requires the strength of the reinforcing phase to be known, however strength measurements at such small scales are difficult and therefore data is sparse. In this work the flexural strength and Weibull modulus of microscopic, alumina platelets has been measured as 5.3±1.3 GPa and 3.7 respectively, using an in-situ micro 3-point bend test. A general approach to correct for the effect of variation in sample size on the Weibull modulus is presented, and the internal structure of the platelets is revealed by TEM.

Journal article

Feilden E, Ferraro C, Giuliani F, Vandeperre L, Saiz Eet al., 2016,

Progress in novel and unexpected areas

, MATERIALS TODAY, Vol: 19, Pages: 544-545, ISSN: 1369-7021

Journal article

Zhang T, Liang X, Li C, Lorin M, Li Y, Vandeperre LJM, Cheeseman CRet al., 2016,

Control of drying shrinkage in magnesium silicate hydrate (M-S-H) gel mortars

, Cement and Concrete Research, Vol: 88, Pages: 36-42, ISSN: 0008-8846

Magnesium silicate hydrate (M-S-H) gel can be formed by the reaction of MgO with amorphous silica in the presence of sodium hexametaphosphate (Na-HMP). Typical pastes contain 40% MgO and 60% SF and have a w/c ratio of 0.5, but these exhibit shrinkage cracking on drying. The shrinkage characteristics of M-S-H mortar samples containing different additions of sand have been studied using dilatometry. The drying shrinkage was found to decrease with increasing sand addition and to increase with increased water content. Mortars with 60 wt.% sand addition and a w/c ratio of 0.5 had a drying shrinkage of 0.16% and did not show shrinkage cracking. A simple geometrical model based on particle packing is presented that explains the observed changes in drying shrinkage. Based on the geometrical model, the shrinkage of M-S-H mortar system can be reduced to zero when the volume fraction of sand in the mortar is about 0.77.

Journal article

Feilden E, Garcia Tunon Blanca E, Giuliani F, Saiz Gutierrez E, Vandeperre LJMet al., 2016,

Robocasting of structural ceramic parts with hydrogel inks

, Journal of the European Ceramic Society, Vol: 36, Pages: 2525-2533, ISSN: 0955-2219

Robocasting is a 3D printing technique that may be able to achieve the much-coveted goal of reliable, complex ceramic parts with low porosity and high strength. In this work a robust hydrogel formulation was optimised for use as the extrusion paste for robocasting. The paste’s rheological properties were characterised and the printing process was optimised with the aim of attaining dense monolithic ceramic parts. The pastes exhibit a characteristic shear thinning behaviour with yield stresses that can reach values above 1 kPa and depend mostly on their solid content and the particle size distribution. It is possible to formulate printable Al2O3 and SiC inks with solid contents as high as 40 vol% that reached densities up to 95th% for SiC and 97th% for Al2O3 with flexural strengths of 300 MPa and 230 MPa respectively after sintering. The sources of strength limiting defects are identified and related to the printing process.

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Graphene filled epoxy coatings for enhanced corrosion protection

Measuring bone stiffness using microindentation

Micromechanical strength of Al2O3 platelets