K. G. Sandeman

A bimetallic iron(iii) catalyst for CO2/epoxide coupling

A novel di-iron(III) catalyst for the copolymerisation of cyclohexene oxide and CO(2) to yield poly(cyclohexene carbonate), under mild conditions, is reported. The catalyst selectivity was completely changed on addition of an ammonium co-catalyst to yield only the cis-isomer of the cyclic carbonate, also under mild conditions. Additionally, the catalyst was active for propylene carbonate and styrene carbonate production at 1 atm pressure.

Magnetocaloric materials: The search for new systems

Abstract The prospect of efficient solid-state refrigeration at room temperature is driving research into magnetic cooling engine design and magnetic phase transition-based refrigerants. I construct what I believe is the first Ashby-style map of magnetic refrigerant properties, comparing popular materials with limits derived from an idealized first-order transition model. This comparison demonstrates the potential for new magnetocaloric material systems to be established through structural control and optimization at the atomic-, nano- and microscales.

Reducing extrinsic hysteresis in first-order La(Fe,Co,Si)13 magnetocaloric systems

Simultaneous magnetization and sample temperature measurements were performed as a function of magnetic field and magnetic field sweep-rates to study the influence of these conditions on the hysteresis of the magnetocaloric transition in La(Fe1−x−yCoxSiy)13 samples. The large magnetocaloric effect in the compounds that show a first-order transition cause a significant departure from isothermal conditions leading to dynamic sweep-rate dependent magnetic hysteresis. Here we show how this deleterious effect can be greatly reduced by changing the sample geometry or by use of materials which show a second-order transition only. The key signatures of nonisothermal conditions in the magnetization data are highlighted.

Negative magnetocaloric effect from highly sensitive metamagnetism in CoMnSi1-xGex

We report a novel negative magnetocaloric effect in CoMnSi_{1-x}Ge_{x} arising from a metamagnetic magnetoelastic transition. The effect is of relevance to magnetic refrigeration over a wide range of temperature, including room temperature. In addition we report a very high shift in the metamagnetic transition temperature with applied magnetic field. This is driven by competition between antiferromagnetic and ferromagnetic order which can be readily tuned by applied pressure and compositional changes.

Ferromagnetic Superconductivity Driven by Changing Fermi Surface Topology

We introduce a simple but powerful zero temperature Stoner model to explain the unusual phase dia-gram of the ferromagnetic superconductor, UGe2. Triplet superconductivity is driven in the ferromagnetic phase by tuning the majority spin Fermi level through one of two peaks in the paramagnetic density of states (DOS). Each peak is associated with a metamagnetic jump in magnetization. The twin-peak DOS may be derived from a tight-binding, quasi-one-dimensional band structure, inspired by previous band-structure calculations.

Solid-state cooling with caloric materials

The drive to replace volatile liquid refrigerants is gaining steam, with potentially disruptive technologies on the horizon.

Giant Magnetoelastic Coupling in a Metallic Helical Metamagnet

Using high resolution neutron diffraction and capacitance dilatometry we show that the thermal evolution of the helimagnetic state in CoMnSi is accompanied by a change in interatomic distances of up to 2%, the largest ever found in a metallic magnet. Our results and the picture of competing exchange and strongly anisotropic thermal expansion that we use to understand them sheds light on a new mechanism for large magnetoelastic effects that does not require large spin-orbit coupling.

Contributions to the entropy change in melt-spun LaFe11.6Si1.4

Here we study the calorimetric and magnetic behaviour of melt-spun LaFe11.6Si1.4, a potential magnetic refrigerant material system that exhibits the rare combination of a large entropy change and low thermal and magnetic field hysteresis. We are able to separate the calorimetric contribution from latent heat and changes in equilibrium heat capacity explicitly by using two separate calorimetric probes. The heat capacity of this sample exhibits significant changes of the order of 500?1000?J?K?1?kg?1 in response to magnetic field that results in large changes in entropy. The different contributions to entropy change from latent heat and heat capacity are shown to evolve as the material is field driven through its itinerant metamagnetic transition. We demonstrate explicitly that in the melt-spun sample studied here, the majority of the total entropy change comes from the equilibrium change of heat capacity.

Designed metamagnetism in CoMnGe1−xPx

We extend our previous theoretical study of Mn-based orthorhombic metamagnets to those that possess large nearest neighbour Mn-Mn separations (d1>3.22A). Based on our calculations, we design and synthesize a series of alloys, CoMnGe_{1-x}P_{x}, to experimentally demonstrate the validity of the model. Unusually, we predict and prepare several metamagnets from two ferromagnetic end-members, thus demonstrating a new example of how to vary crystal structure, within the Pnma symmetry group, to provide highly tunable metamagnetism.

Structurally driven metamagnetism in MnP and related Pnma compounds

We investigate the structural conditions for metamagnetism in MnP and related materials using Density Functional Theory. A magnetic stability plot is constructed taking into account the two shortest Mn-Mn distances. We find that a particular Mn-Mn separation plays the dominant role in determining the change from antiferromagnetic to ferromagnetic order in such systems. We establish a good correlation between our calculations and structural and magnetic data from the literature. Based on our approach it should be possible to find new Mn-containing alloys that possess field-induced metamagnetism and associated magnetocaloric effects.