High-performance, nano-structured LiMnPO4 synthesized via a polyol method

A novel polyol synthesis was adopted to synthesize nano-structured LiMnPO4. This route yields well-crystallized nanoparticles with platelet morphology that are only similar to 30 nm thick oriented in the b direction. The obtained material presented a good rate behavior and a very long cyclic life both at room temperature (RT) and 50 degrees C. The sample exhibited a specific capacity of 145 mAh g(-1) at C/20, 141 mAh g(-1) at C/10 rate and 113 mAh g(-1) 1C rate. This represents is the highest performance results reported to date for this material. The high rate performance is ascribed to the platelet shape of the LiMnPO4 as it minimizes the paths for Li diffusion. At elevated temperature (50 degrees C) this material demonstrated improved reversible capacity of 159 mAh g(-1) at C/10 and 138 at 1C. The electrode retained 95% of its capacity, over 200 cycles, both at RT and 50 degrees C. This electrochemical stability is ascribed to the structural strength of the P-O bond and the stability of the electrolyte-LiMnPO4 interface. It allows us to conclude that the impact of a possible Jahn-Teller distortion is not critical. These excellent results clarified some ambiguities on LiMnPO4 as cathode materials. and demonstrate its promise for its practical application. (C) 2008 Elsevier B.V. All rights reserved.

The development of material-adapted structural form

Sean Dooley

New structural materials can potentially change the technics and economics of the building and construction industry in a profound way. It is important to identify applications and develop forms that exploit a material's unique properties. The developer of a material can use the knowledge of how materials such as steel and reinforced concrete were first introduced to advance the development and application of new materials today. This project examines why structural forms have evolved as they have and what influences the process of creating form, or form-finding. The purpose of this analysis is to aid the development of structural forms that make the most efficient use of material and take advantage of a material's processing and constructive attributes. Such forms are called material-adapted. This thesis is based on the general history of structural materials used in construction. This research is summarized in six appended case studies that comprise the data of the thesis. The research has extended well beyond these case studies; some of this data is included in the main text. The research showed that the influences on form-finding are: Function; Material Properties; Processing Technologies; Connection Technology; Construction Process; Economics; Socio- Political Factors; Knowledge; and Technological Thought. A Form-Finding Influence Interaction Model summarizes the inter-relationships of these influences. It was first assumed that material-adapted form is determined by material properties alone. Further research showed this untrue. The hypothesis of this thesis is that material properties do not unilaterally determine material-adapted structural form. This statement is true because the nature of a material is a function of its properties and its processing and constructive attributes. A material's processing and constructive attributes are dependent on technology and organizational systems that are not specific to the material. It was further hypothesized that new materials are first used substitutionally in forms and applications of known materials. This concept was found to be misleading and untrue for a number of materials. The knowledge of this thesis was used to examine the current development of fiber reinforced polymer composite materials. It is shown that a material's development can be analyzed not only by the aforementioned influences, but also by characteristics of other material developments. This information is used to suggest how these materials might develop in the future.

EPFL2004

Comportement et modélisation des éléments de structure en béton fibré à ultra-hautes performances avec armatures passives

Dario Redaelli

The present research improves the experimental and theoretical knowledge on the behaviour of structural elements made of ultra high performance fibre reinforced concrete (UHPFRC) with ordinary reinforcement. UHPFRC is a recently developed material with much higher mechanical properties and durability than ordinary concrete. However, it has been used so far in a limited number of structural applications. A better knowledge on the behaviour of UHPFRC in structural members is needed to be able to take advantage of its outstanding properties in structural design. One of the ways in which the structural efficiency of UHPFRC can be studied is to investigate the improvement in structural performance that is gained by using UHPFRC instead of ordinary concrete in common structural members. As an alternative, new structural shapes and structural concepts can be explored, more adapted to the specific material properties. The work presented in this thesis focuses on the first approach by considering the behaviour and modelling of UHPFRC structural members loaded in tension and in bending with axial load, and reinforced with ordinary steel reinforcement. The experimental and theoretical study carried out on tensile members contributes to the understanding of the fundamental mechanisms that control cracking of a tensile member reinforced with both fibres and bars, in service and at ultimate. A numerical model has been developed to solve the differential problem of bond in the presence of strong mechanical non linearity. This model has been used to simulate the main aspects controlling bond in a UHPFRC member. The results obtained with the model help in clarifying the differences between cracking in ordinary concrete and in UHPFRC ties. The model allows identifying the parameters that influence the strength and ductility of the tie and was used to validate simplified assumptions to model the behaviour of UHPFRC ties in service. The behaviour of columns has been studied with a theoretical and experimental approach. The results of two test series on UHPFRC and HPFRC columns are reported in the thesis. An analytical model has been developed to study the behaviour of a confined concrete member in compression. A numerical model has been implemented to simulate the non linear behaviour of ordinary concrete and UHPFRC columns. The models have been used to simulate test results reported in this thesis or taken from the literature. The numerical model has been used to evaluate the effect of variations of the mechanical behaviour of concrete on the structural behaviour of a column, with or without reinforcement. The results of those parametrical studies help understanding the influence of mechanical properties on structural response. This thesis contributes to a better understanding of the behaviour of UHPFRC members with ordinary reinforcement. The comparative approach used in the research makes it possible to show the differences between the structural behaviour of ordinary, high strength and fibre reinforced concrete. Indications are also given on the possible ways in which an effective use of UHPFRC in structural members can be achieved.

EPFL2009

Material and structural performance of fiber-reinforced polymer composites at elevated and high temperatures

As the range of applications for fiber-reinforced polymer (FRP) composite materials in civil engineering constantly increases, there is more and more concern with regard to their performance in critical environments. The fire behavior of composite materials is especially important since complex physical and chemical processes such as the glass transition and decomposition occur when these materials are subjected to elevated and high temperatures, possibly leading to considerable loss of stiffness and strength. This stiffness and strength degradation in composite materials under elevated and high temperatures is the result of changes in polymer molecular structures. When polyester thermosets are subjected to elevated and high temperatures, they undergo three transitions (glass transition, leathery-to-rubbery transition, and rubbery-to-decomposed transition), corresponding to four different states (glassy, leathery, rubbery and decomposed). At a certain temperature, a composite material can therefore be considered as a mixture of materials that are in different states. As the content of each state varies with temperature, the composite material exhibits temperature-dependent properties. Since these changes in state can be described using kinetic theory, the quantity of material in each state can be estimated and the thermophysical and thermomechanical properties of the mixture can thus be determined. These concepts formed a basis for the development of thermophysical and thermomechanical property sub-models for composites at elevated and high temperatures and even for the description of post-fire status. Incorporating these thermophysical property sub-models into a heat transfer governing equation, thermal responses were calculated using a finite difference method. Integrating the thermomechanical property sub-models within structural theory, the mechanical responses were described using a finite element method and the time-to-failure was also predicted by defining a failure criterion. The modeling results for temperature responses, mechanical responses and post-fire behavior were compared with those obtained from structural endurance experiments on full-scale cellular GFRP (glass fiber-reinforced polymer, in this case polyester resin) panels subjected to a four-point bending configuration and fire from one side. The modeling results for time-to-failure were compared with those from the experiments carried out on GFRP tubes under combined compressive and thermal loadings. In each experimental setup, two different thermal boundary conditions were investigated – with and without water cooling through specimen cells – and good agreement was found. The understanding gained and modeling of the behavior of GFRP composites under elevated and high temperatures carried out in this thesis could be applicable for different composite materials, and also benefit investigations regarding both active and passive fire protection techniques in order to improve the fire resistance of structures made of such materials.

EPFL2009

Material and structural performance of fiber-reinforced polymer composites at elevated and high temperatures

EPFL2009

Comportement et modélisation des éléments de structure en béton fibré à ultra-hautes performances avec armatures passives

Dario Redaelli

EPFL2009

The development of material-adapted structural form

Sean Dooley

EPFL2004