Summer Meeting 2017

Book of Abstracts

Department of Chemical and Environmental Engineering, University of , Nottingham

July 4th-6th 2017

2 Welcome to Nottingham!

The Molten Salts Discussion Group have the pleasure of welcoming you to Nottingham for our annual summer meeting. We hope that you enjoy the meeting and your time in Nottingham.

MSDG Organising Committee

Venue and Registration Information

The meeting is held in the ’s Engineering and Sciences Learning Centre (ESLC), located on the University Park Campus. The ESLC can be found on the University of Nottingham map, number 54. Registration will be on B- floor at the start of the meeting.

Tuesday and Wednesday lectures will be situated in room B07 and Thursday in room A09.

Dinner on Tuesday evening will be held at Mr Man’s Chinese restaurant in Wollaton (NG8 2AD).

The conference trip will be to the Nottingham Industrial Museum, located in the beautiful Wollaton Deer Park, just opposite the University Park campus.

The conference dinner on Wednesday night will be in the Council Rooms. These are located in the Trent building, number 11 on the University map.

Getting to University Park

From Nottingham and Beeston

A number of public transport services run close to or through our campuses.

By bus There are a number of bus services running from Nottingham to University Park Campus. The University of Nottingham provides free hopper bus services that run from the main University Park Campus to Jubilee, Sutton Bonington and King's Meadow campuses, and the Royal Derby Hospital Centre. A number of bus services run from the city centre to University Park, including the Eighteen, Indigo, Red Arrow, Skylink, i4, and 21 services run by Trent Barton, and the 35, 35a, 35b, 36 and N36 (night service), and 53 services run by Nottingham City Transport.

3 By tram If you are coming to University Park Campus from Nottingham Train Station, you can now hop on a tram which is accessible by the walkway leading from the station. Tickets must be purchased before boarding. The Toton line takes you directly to the University and visitors should disembark at the University of Nottingham stop, just outside the Lakeside park.

By taxi There are taxi ranks throughout the city and immediately adjacent to the main railway and bus stations. The journey to the campus takes approximately 15 minutes.

By train The nearest train stations are located in or Beeston. Taxis and buses are available at both stations.

From

From East Midlands Airport you can take the Trent Barton Indigo service directly to the campus or the Skylink bus to Nottingham. Buses leave from outside the Airport Arrivals hall.

You can also walk to the taxi rank on the terminal forecourt and take a direct taxi to the University. The cost of a single/one way journey is approximately £20.

From M1 motorway

Leave the M1 motorway at Junction 25 to join the A52 to Nottingham. Follow the A52 for approximately 4 miles, at the Toby Carvery roundabout turn right onto the A6464, turn left at the next roundabout to enter the University's West Entrance. Paid parking is available at the University’s Visitor’s car park. This is located between buildings 16 and 18 on the University map.

Getting around Nottingham

Nottingham and Nottinghamshire have lots of things on if you are staying for longer. You can find information at the Tourist Centre in the town centre (and at their website: www.experiencenottinghamshire.com), accessible by a short tram ride from the University. A map of the city centre is included in this booklet.

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University Park campus, University of Nottingham

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Other services (A-Z) Admissions Service Careers and Employability Childcare Services Auditorium Coates Road Cripps Health Centre/Chemist/Dentist Estates Office rooms Faith/Prayer George Green Library School Graduate Greenfield Medical Library Library Hallward Auditorium Keighton Language Centre Museum Nottingham New Theatre Hall Recital Control Security Sports Student Service Centres court Students’ Union/Retail/Food of Nottingham International University College of Nottingham Sports and University Social Club Broadgate 1 2 7 7 5 7 29 28 11 16 37 11 16 55 20 40 33 PD 26/44 14/17 46/48 23/46 Park 37/46/48 1 Ancaster Broadgate Pool Abbey House David Ross 29/30/31/36 Swimming Sports Village 15/18/22/25/53 31/35/36/39/41 31/36/38/39/41/42 To Beeston To

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PD A52 24-hour ambulance/fire/police To M1 To Jcn 25 The University of Nottingham The University Architecture and Built Environment Engineering Chemical and Environmental Chemistry Civil Engineering Cultures, Languages and Area Studies Economics Electrical and Electronic Engineering English Studies Geography Health Sciences History Humanities Law Life Sciences Mathematical Sciences Mechanical, Materials and Manufacturing Engineering Medicine MRC Institute of Hearing Research Music Pharmacy and Astronomy Physics and International Relations Politics Psychology Sociology and Social Policy Academic schools and departments (A-Z) (5 miles)

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Engineering and Sciences Learning Centre, B-floor (Tuesday and Wednesday)

Engineering & Science Learning Centre (ESLC) - B Floor Plan

B04 Seminar Room B01 Seminar Room B02 B17

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B06

Seminar Room B07 Meeting Rm B16 Void

Meeting Rm B15 Seminar Room B08

B10 B09 Seminar Rm Seminar Rm B12 Seminar Room B13 B14 B11

Key Designated Badge-Holder Parking Entrance (Female / Male) Stairs ReceptionToilet Access Ramp Accessible Entrance }Accessible Toilet Lift Refectory/Cafe Automatic Doors Evacuation Chair Shower Central Timetabled Room Fire Assembly Point Accessible Lift Emergency Refuge Circulation August 2011 Accessible Shower Estate Office www.nottingham.ac.uk/estate/

Engineering and Sciences Learning Centre, A-floor (Thursday)

Engineering & Science Learning Centre (ESLC) - A Floor Plan

A02 Engineering Student Support Centre A06 DRI A01 A03

Print A04 A03a A07 A08 UP D A05 R

Atrium A17 A16 A09 Seminar Room

A13 P U 1 2 3 A14 4 5 A11 6 7 A10 8 9 A15 Social space A12

A19 (Link to Coates Building)

Key Designated Badge-Holder Parking Entrance (Female / Male) Stairs ReceptionToilet Access Ramp Accessible Entrance }Accessible Toilet Lift Refectory/Cafe Automatic Doors Evacuation Chair Shower Central Timetabled Room Fire Assembly Point Accessible Lift Emergency Refuge Circulation August 2011 Accessible Shower Estate Office www.nottingham.ac.uk/estate/

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Trent Building, Council Chamber (A21) (Conference dinner)

Mr Man’s restaurant and Nottingham Industrial Park (Tuesday Night and Wednesday Afternoon, respectively)

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Nottingham City Centre NOTTINGHAM For more information please visit www.experiencenottinghamshire.com or pick up a free copy of our 2016/17 Visitor Guide.

A60 Mansfield Road to: NET Park & Ride, Goose Fair site, City Hospital (A611), Mansfield, Sherwood Forest (A614)

N This map should be used as a guide only. O 2 R All information correct at Apr 2016. T H

S H E Nottingham Navigator Car parking R W Information Point OVE O GR O D D EA D Taxi Ranks (anytime) ST R W E S Nottingham Tourism N H T R G E U Centre Taxi Ranks (between 6pm - 7am) OV E GR E H O EY ESL T U R ANN N O B Toilets T Tram route and stops I D N O Tram route to: G O Disabled Toilets D W The Forest Park & Ride, O 4 8 Phoenix Park & Ride, 21 M N 6 Changing Places B Hucknall A S N T Toilets S R E F Shopmobility I E E T 47 L D A 6

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79 40 52 A612 to: Colwick, Nottingham A6005 to: 1 23 l Racecourse, Queen’s Medical Centre (QMC), Cana ham Green’s Mill, ting University Hospital NHS Trust, 44 Not Southwell, University of Nottingham, Newark (A46) Showcase Cinema, Castle Marina Retail Park, 42 Beeston, Long Eaton C A 50 49 R

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9 S A453 to: 1 T 0 CROCUS ST A6 6 REET M1 Junction 24 (southbound), D 019 A A60 to: R WATERW East Midlands Airport, Donington Park, S AY STREE , West Bridgford, N T WEST Ashby De-La Zouch (A453), Birmingham (M42), E MEAD Notts County FC, Nottingham Forest FC, E OWS W 45 Riverside Retail Park, Castle Marina Retail Park, U AY Trent Bridge Cricket Ground, Loughborough, Nottingham Trent University Clifton Campus Q MEADOWS WAY National Water Sports Centre, Newark (A46), Leicester (A46), Grantham (A52)

Information points (H4) 17 Public offices, community Centres of learning Train station National Express Travel Centre (K7) 1 /Rescue Rooms (F4, F5) 18 centres and facilities Nottingham Railway Station 4 Central College (K6) 62 NCT Travel Centre (H6) 2 TRCH - Theatre Royal and (L8, M8) BBC East Midlands (K10) 41 New College Nottingham (H9) 63 NET Travel Centre (G7) 3 Royal Concert Hall (G5, G6) 19 Tram stops Citizens Advice Bureau (L7) 42 Nottingham Trent University (D4, E4, E5, F5) 64 Motorpoint Arena (H10, H11) 20 Nottingham Railway Station Council House/ (H8) 4 (M8) (L8, M8) Nottingham Register Office (H7) 43 Places of worship Nottingham Trent University (E4) Nottingham Tourism Centre (H7) 5 Crown and County Courts (K8) 44 Central Methodist Mission (G8) 65 Places of interest and (H6) key attractions Fire Station (N10) 45 Christian Centre (F2) 66 Royal Centre (G5) (L6, M6) 46 67 Main shopping locations Arboretum (C3, D3) 21 HMRC - Inland Revenue Congregational Church (I6) (D6) 68 Car parks Bridlesmith Gate (I7) Bonington Art Gallery (E5) 22 International Community Centre 47 Friends Meeting House (E3) Arndale (K6) 6 Brewhouse Yard Museum (K5) 23 Job Centre (Parliament Street) (G5) 48 Islamic Centre (E9) 69 Intu Broadmarsh (J7, K7) Broadmarsh (K8) Brian Clough statue (H6) 24 Job Centre (Loxley House) (L8, L9) 49 Nottingham Buddhist Centre (I8) 70 Clumber Street (G7, H7) Castle (K7) (J8) 25 Loxley House - Nottingham (L8, L9) 50 St Andrew’s with Castle Gate (URC) (F5) 71 Cobden Chambers (H8) 7 Cowan Street (F9) Galleries of Justice Museum (J9) 26 City Council St Barnabas RC Cathederal (G3) 72 Derby Road (G2, G3) Curzon Street (E9) (I10, I11) 27 Magistrates’ Court (L5, M5) 51 St Mary’s Church (J9) 73 Exchange, The (H7) 8 Huntingdon Street (E8) National Videogame Arcade (GameCity) (H9) 28 (K11) 5253 Flying Horse Walk (H7) 9 NHS Urgent Care Centre St Nicholas’ Church (J6) 74 Lace Market (I8) 53 Hockley (H9, H10) - Nottingham Central Library (H5) St Peter’s (and St James’) Church (I7) 75 Manvers Street (I12) 54 Lister Gate (J7) Museum and Art Gallery (K4) 29 Nottinghamshire Archives (L6) Synagogue (E5) 76 Mount Street (H4) and Castle Gatehouse (J5) 30 55 Intu (E7, F7) 10 Police - Central Station, Byron House (F6) Unitarian Chapel (I10) 77 Nottingham Arena (G10) 56 Victoria Market (F7) 11 (J8) 31 Police - Canning Circus (G1) William Booth Memorial Hall (F9) 78 Nottingham Station (M8) 57 West End Arcade (H5) /Left Lion (H7) 32 Post Office (G6) Sneinton Market Square (G12) Old Market Square (H6) 33 Public Toilets (Greyhound St) (H7) 58 Transport St James Street (I5) Robin Hood statue (J5) 34 The Samaritans of Nottingham (F3) 59 Stoney Street (I9) Entertainment Sky Mirror (H3) 35 Victoria Leisure Centre (E6) 60 Bus stations Talbot Street (F4) Albert Hall (H4) 12 Sneinton Square (G11) 36 YMCA (G11) 61 Broadmarsh (K7) 79 Trinity Square (F7) Broadway Media Centre (G9) 13 Speakers’ Corner (H6) 37 Victoria (E7) 80 Upper Parliament Street (G5) Cornerhouse, The (F6, G6) 14 Trinity Square (F7) 38 Victoria Centre North (D7) Citycard Cycle Hire (mobile phone) (I8) 15 Victoria Clock Tower (E7) 39 Victoria Centre South (F8) (H8) 16 Ye Olde Trip to Jerusalem (PH) (K5) 40 Citycard Cycle Hubs Wollaton Street (G5)

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8 Programme Schedule

Tuesday 4/7 Wednesday 5/7 Thursday 6/7 ESLC B07 ESLC B07 ESLC A09 D. Sri Maha 9:00-9:30 S. Kandhasamy Vishnu 9:30-10:00 H. Wang E. Olson 10:00-10:30 J. Sure O. Al-Juboori

10:30-11:00 Coffee/Tea Coffee/Tea K. Schaffarczyk- 11:00-11:30 G. Haarberg McHale 11:30-12:00 D. Gunasekera G. Doughty 12:00-12:30 Lunch and S. Muzammal Lunch and 12:30-13:00 Registration, B07 B. Hu Conference close 13:00-13:30 ESLC Chairman’s Lunch 13:30-14:00 welcome 14:00-14:30 S. Mucklejohn 14:30-15:00 P. Coxon Tour of 15:00-15:30 A. Kamali Nottingham 15:30-16:00 Coffee/Tea Industrial Museum, 16:00-16:30 G. Chen Wollaton Park 16:30-17:00 A. Doherty 17:00-18:00 Committee 18:00-19:00 Meeting 19:00-19:30 Drinks reception Dinner at Mr Man’s Conference dinner 19:30-21:00 at Council Chamber

9 Programme

Tuesday, 4th July (ESLC B07)

12:00-13:45 Coffee & Registration: ESLC Room B07

12:45-13:45 Lunch

13:50-14:00 Chairman’s welcome by Dr Andrew Doherty

14:00-15:30 Technical Session 1 Chair Andrew Doherty

14:00-14:30 Why we need to understand molten salt thermodynamics and phase equilibria to make widgets Stuart Mucklejohn Ceravision Ltd

14:30-15:00 Energy applications of black silicon by molten salt electrolysis Paul R. Coxon, Hyun-Kung Kim, Derek J. Fray Dept of Materials Science & Metallurgy, University of Cambridge.

15:00-15:30 Molten salt preparation of graphene hybrid nanostructures and their applications A. R. Kamali1 and D. J. Fray2 1 School of Metallurgy, Northeastern University, Shenyang, 110819, China 2 Departments of Materials Science and Metallurgy, University of Cambridge, Cambridge CB3 0FS, UK

15:30-16:00 Tea break

16:00-17:00 Technical Session 2 Chair: Derek Fray

16:00-16:30 Electrochemical Analysis in Ultrahigh Temperature Molten Slags Y. M. Gao1,2, C. H. Yang1,2, C. L. Zhang1,2, Q. W. Qin1,2, and George Z. Chen1,2,3 1 The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, China; 2 Key Laboratory for Ferrous Metallurgy and Resources Utilization of Ministry of Education, Wuhan University of Science and Technology, Wuhan 430081, China; 3 Department of Chemical and Environmental Engineering, and Energy Engineering Research Group, Faculty of Science Engineering, University of Nottingham Ningbo China, Ningbo 315100, China

16:30-17:00 Mechanism and Kinetics of Electrocarboxylations in in Ionic liquid Media Andrew P. Doherty and Eunan Marley School of Chemistry and Chemical Engineering, The Queen’s University of Belfast, Belfast, BT9 AG, UK

18:00 – 20:00 Dinner at Mr Man’s Chinese Restaurant

10 Wednesday, 5th July (ESLC B07)

09:00-10:30 Technical Sessions 3 Chair: Stuart Mucklejohn

09:00-09:30 Direct electrochemical synthesis of Ti-35Nb-7.9Sn alloy from mixed oxide discs in CaCl2 melt D. Sri Maha Vishnu1,2, Jagadeesh Sure1,2, R. Vasant Kumar2 and Carsten Schwandt1,2 1Department of Materials Science and Metallurgy, University of Nizwa, Birkat Al Mouz, 616 Nizwa, Sultanate of Oman 2Department of Materials Science and Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge CB3 0FS, United Kingdom

09:30-10:00 Current Progress on Molten Salt Electrolysis in GLABAT Han Wang, Zhanglong Yu, Sheng Fang, Chunrong Zhao, BingYu, Ning Wang, and Juanyu Yang Department of Material R&D, China Automotive Battery Research Institute Co. Ltd., Beijing, China

10:00-10:30 Synthesis of Ti-5Ta-2Nb Alloy from Solid Oxides by Electro-reduction in Molten Salt and its Corrosion Behaviour in Concentrated Nitric Acid Jagadeesh Sure1,2*, D. Sri Maha Vishnu1,2, R. Vasant Kumar2 and Carsten Schwandt1,2 1Department of Materials Science and Metallurgy, University of Nizwa, Nizwa, Birkat Al Mouz, 616 Nizwa, Sultanate of Oman 2Department of Materials Science and Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge CB3 0FS, United Kingdom

10:30-11:00 Coffee break

11:00-12:30 Technical Session 4 Chair: George Chen

11:00-11:30 Towards understanding microscopic interactions in ionic liquids and their effects on SN2 processes Karin Schaffarczyk McHale, Ron Haines and Jason B. Harper School of Chemistry, The University of New South Wales, Sydney NSW, Australia

11:30-12:00 Three Dimensional Printing of Biomaterial-Laden Ionic Liquids Deshani H. A. T. Gunasekera1, Christopher Tuck1, Anna K. Croft2 and Ricky D. Wildman1 1Centre for Additive Manufacturing (CfAM), Department of Mechanical, Materials & Manufacturing Engineering, University of Nottingham, Nottingham, NG7 2RD, United Kingdom. 2Department of Chemical and Environmental Engineering, University of Nottingham, NG7 2RD, United Kingdom.

11 12:00-12:30 Molecular Interactions of Protein-based materials with Ionic Liquids Shafaq Muzammal1, Christof Jaeger1, Peter Licence2, Anna K. Croft1 1Department of Chemical and Environmental Engineering, University of Nottingham,UK 2School of Chemistry, University of Nottingham, UK

12:30-13:00 The role of C8mimPF6 in miniemulsion stabilized by silica nanoparticles Yiyang Kong, Rongmeihui Zheng and Binjie Hu Department of Chemical and Environmental Engineering, The University of Nottingham Ningbo China, 199 Taikang East Road, Ningbo 315100, China

13:00-14:00 Lunch

14:00-17:00 Tour of the Industrial Museum at

18:00-19:00 Committee Meeting

19:00-19:30 Drinks reception at the University Council Room

19:30-21:00 Banquet at the University Council Room:

After dinner speech: “The Discovery of Black Snow and Other Adventures in the World of Molten Slag” Some Recollections from a Jack of All Trades. Dr Fred Starr PhD, C.Eng, FIMMM, M.IMechE

12 Thursday, 6th July (ESLC A09)

09:00-10:30 Technical Session 5: Chair: George Chen

09:00-09:30 High Seebeck Coefficient Thermocell with Molten Carbonate Electrolyte S. Kandhasamy1, O. S. Burheim2, A. Solheim3, S. Kjelstrup4 and G. M. Haarberg1 1 Department of Materials Science and Engineering, Norwegian University of Science and Technology (NTNU), Trondheim, Norway 2 Department of Electrical Engineering and Renewable Energy, NTNU, Trondheim, Norway 3 SINTEF Materials and Chemistry, SINTEF, Trondheim, Norway

09:30-10:00 Carbon Capture in Molten Salts (CCMS) E. Olsen, H. S. Nygård and M. Hansen Norwegian University of Life Sciences, Drøbakveien 31, N-1432 Ås, Norway

10:00-10:30 Co-reduction of CO2 and steam in molten electrolytes. Ossama Al-Juboori and George Z. Chen Department of Chemical and Environmental Engineering, University of Nottingham, NG7 2RD, United Kingdom.

10:30-11:00 Coffee break

11:00-12:00 Technical Session 6: Chair: Anna Croft

11:00-11:30 A liquid sodium-zinc and molten chloride battery Geir Martin Haarberg1, Junli Xu2, Karen S. Osen3, and Ole S. Kjos3 1Department of Materials Science and Engineering, Norwegian University of Science and Technology (NTNU), NO-7491 Trondheim, Norway 2School of Science, Northeastern University, Shenyang 110004, China 3SINTEF Materials and Chemistry, NO-7465 Trondheim, Norway

11:30-12:00 Solid state production of a seven-component niobium-silicide based alloy G. R. Doughty Metalysis Ltd. Advanced Manufacturing Park, Brinley Way, Catcliffe, Rotherham, S60 5FS

12:00-13:00 Lunch

13:00 Close

13

Summer Meeting 2017

Abstracts

Abstracts presented on the following pages are compiled by the MSDG for distribution amongst attendees of the 2017 MSDG Summer Research Meeting. The abstracts are based on the submitted versions received from the authors, who are responsible for issues related to the scientific and linguistic correctness and copyright. This booklet is also available from the MSDG’s website.

MSDG Summer Meeting 4th-6th July 2017 University of Nottingham

16 MSDG Summer Meeting 4th-6th July 2017 University of Nottingham

Poster Presentations

Poster sessions will be held during the tea/coffee breaks and over lunch.

17 MSDG Summer Meeting 4th-6th July 2017 University of Nottingham

Notes

18 MSDG Summer Meeting 4th-6th July 2017 University of Nottingham

Electrochemical reduction of plutonium oxide Steven Wilcock

AWE plc, Aldermaston, Reading, RG7 4PR, UK Contact E-mail: [email protected]

The conversion of PuO2 to metal is an important step in the processing of plutonium. In the past this would be achieved via a reaction with calcium in molten CaCl2, but the limited solubility of the CaO by-product makes this process inefficient in terms of the salt volume required and, therefore, the waste produced. This work presents the development of an Electrochemical Oxide Reduction (EOR) process designed to produce the same result with a fraction of the waste.

The EOR process breaks down into the following half equations: 2- - Anode (carbon): 2O + C → CO2 + 4e - 2- Cathode: MO2 + 4e → M + 2O

This technique has been demonstrated for other metals such as titanium but working with plutonium requires changes to be made to the method. Most significantly, in order to avoid the radiation dose delivered during additional processing steps, the plutonium process is being designed to operate on oxide powder rather than sintered pellets. This has required the development of new cell designs including a “suspended oxide” system, in which the feed material is distributed throughout the molten salt, and a system in which the oxide is contained in a secondary crucible.

The process has been developed through experiments using simulant materials such as CeO2, Ta2O5 and SnO2, with the aim of maximising the amount of metal produced and minimising contamination of the salt before trials with Pu started. The production of a metallic product has been repeatedly achieved using the techniques described and so the project is moving on to active trials. Whilst much of the process can be proved out in the surrogate studies there is no true replacement for using genuine PuO2 for identifying any issues with material compatibility, product morphology and several other important aspects.

Above: A sample of tin produced during small scale experimentation.

Right: An example set-up of one of the EOR cells under development.

19 MSDG Summer Meeting 4th-6th July 2017 University of Nottingham

Notes

20 MSDG Summer Meeting 4th-6th July 2017 University of Nottingham

Solid State Manufacture of High Entropy Alloys Preliminary Studies

M B D Ellis and G Doughty

Metalysis Ltd, Unit 2, Fairfeild Park, Manvers Way, Wath-upon-Dearne, Rotherham, S63 5DB, UK

Metalysis, for the past ten years, have, through their solid state salt electrolysis process, manufactured tantalum, titanium and titanium alloy powders for a number of high performance applications. This low energy and environmentally friendly process is now being used to manufacture the next generation of High Entropy Alloys (HEAs).

The manufacture of HEAs involves, in most cases, high temperatures which melt and put all the constituent alloying elements into the liquid phase. This can lead to numerous problems and restrict the number of HEAs which can be made, in particular, the alloys where one needs to combine low melting point and low boiling point elements with refractory elements and also where there are significant liquid density differences between the constituents causing melt segregation.

The aim is to present the preliminary work carried out by Metalysis showing how the solid state diffusion process based on molten salt electrolysis lends itself to the manufacture, on an industrial scale, low tonnage quantities of the next generation of HEAs. Metalysis will focus production on the HEAs whose constituent alloying elements have large differences in both their melting points and liquid densities, for example, tungsten, niobium, tantalum, molybdenum, vanadium, titanium and aluminium.

21 MSDG Summer Meeting 4th-6th July 2017 University of Nottingham

22 MSDG Summer Meeting 4th-6th July 2017 University of Nottingham

Oral Presentations

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Why we need to understand molten salt thermodynamics and phase equilibria to make widgets S. A. Mucklejohn Ceravision Limited, Sherbourne Drive, Tilbrook, MK7 8HX, UK Contact E-mail: [email protected]

This paper uses the progress from initial product design through to large scale production to illustrate why it is essential to have an understanding of the thermodynamics and phase equilibria associated with products. Attention must be paid to every detail if a bright idea is to be converted into a successful product that will generate income from sales, satisfy customers and enhance a company's reputation. The design, development and production of high intensity discharge (HID) lamps serves as a generic example. In particular, the route by which metal-to-ceramic seals are made in metal halide discharge lamps with ceramic arctubes will be used to illustrate the most important aspects of converting a laboratory scale operation to a reliable and repeatable manufacturing process.

Ceramic arctubes for high intensity discharge (HID) lamps are fabricated from polycrystalline alumina (PCA) and need seals between the metallic leadwires and the arctube. A schematic diagram of a ceramic arctube for a metal halide lamp is shown in figure 2. The properties required for these seals are very demanding. The seals must be: hermetic; able to cope with many thousands of cycles of thermal expansion and contraction; sufficiently robust to survive vibrations while the lamp is in service; resistant to the dose components within the arctube at high temperatures over the rated life of the lamp. Additionally, the process for making the seals must be robust, cost effective and the cycle time has to be compatible with the required throughput.

Seals for ceramic arctubes are usually formed from a frit ring composed of various metal oxides which form a number of crystalline phases in a glass matrix after processing. The frit ring is accurately located onto the components and the assembly then subjected to a well-defined and precisely controlled heating and cooling cycle. The requirements for the frit rings are specified by weight, composition, size and shape. For metal halide lamps with ceramic arctubes the frit rings are based on the

{Al2O3+Ln2O3+SiO2} system, where Ln = lanthanide element [1]. During the sealing process the frit is subjected to temperatures above the melting temperature of the mixture and then cooled under controlled conditions to allow the appropriate crystal phases to form. Care has to be taken not only to ensure that the required crystal phases are present but also that the size and distribution of the crystals are correct and the composition of the glassy matrix is within pre-defined limits. The sealing process is further constrained by the need to control the penetration of the glass and to ensure that residual stresses are minimised.

Figure 1. 70 W Ceramic metal halide lamp Figure 2. Schematic diagram of an arctube (Image from Philips Lighting) assembly for a low wattage ceramic metal halide lamp References [1] R.K.Datta, Sealing materials for ceramic envelopes. U.S. Patent 4,076,991 (1978).

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Energy applications of black silicon by molten salt electrolysis

Paul R. Coxon, Hyun-Kung Kim, Derek J. Fray

Dept of Materials Science & Metallurgy, University of Cambridge.

Highly texturised silicon surfaces offer new routes within energy generation and storage applications. Several methods to produce black silicon exist yet most depend on complex synthesis procedures, are costly to implement or generate high quantities of waste. The FFC-Cambridge process allows silica surfaces to be simply reduced in molten salt to generate a densely micro-nano-porous layer with applications in solar photovoltaics (PV) by increasing light trapping in photoactive layers, and within anodes of battery devices owing to its very high theoretical capacity. We will present recent work and results on the application of black silicon within a solar PV cell, and its incorporation into a Li-ion half-cell - with a consequential increase in anode performance and stability.

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Molten salt preparation of graphene hybrid nanostructures and their applications A.R.Kamali1* and D.J.Fray2

1 School of Metallurgy, Northeastern University, Shenyang, 110819, China 2 Departments of Materials Science and Metallurgy, University of Cambridge, Cambridge CB3 0FS, UK Contact E-mail: [email protected]

Graphene-based composites are believed to be capable of possessing countless potential applications from biology [1] and structural ceramic composites [2] to energy storage and conversion devices [3]. However, the preparation of graphene and graphene -based composite/ hybrid materials in an efficient and cost-effective way has been a major challenge for widespread usage of graphene [4]. Electrochemical exfoliation of graphite in molten salts has provided opportunities for production of low cost but high quality carbon nanostructures with either sp2 or sp3 hybridised carbon bonds [5], including graphene [6]. An update on progress towards the production of graphene in molten salts [7] and use of molten salt produced graphene in the preparation of structural composites and functional hybrid nanostructures [8] is discussed here.

Graphite can be exfoliated in molten salt to produce encapsulated nanoparticles

References [1] P. T. Yin, S. Shah et al., Chem. Rev.,115, p. 2483−2531(2015). [2] F. del Río, M. G. Boado et al., 37, A. Rama, F. Guitián, J. Eur. Ceram. Soc., 37, p. 3681–693(2017). [3] Q. Shi, Y. Cha et al., Nanoscale, 8, 2016, 8, p. 15414-15447 (2016) [4] A. Zurutuza, C. Marinelli, Nature Nanotechnol., 9, p. 730-734 (2014). [5] A.R.Kamali, D.J. Fray, J.Mat.Sci., 51,p. 569-576 (2016). [6] AR Kamali, DJ Fray, Nanoscale, 7, p.11310-11320 (2015). [7] A.R. Kamali, J. Ind. Eng. Chem.52 (2017) 18–27. [8] A.R. Kamali, D.J. Fray et al., Un-published work.

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Electrochemical Analysis in Ultrahigh Temperature Molten Slags

Y.M. Gaoa,b, C.H. Yanga,b, C.L. Zhanga,b, Q.W. Qina,b, and George Z. Chena,b,c,* a The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, China;

b Key Laboratory for Ferrous Metallurgy and Resources Utilization of Ministry of Education, Wuhan University of Science and Technology, Wuhan 430081, China;

c Department of Chemical and Environmental Engineering, and Energy Engineering Research Group, Faculty of Science Engineering, University of Nottingham Ningbo China, Ningbo 315100, China

Electrodeposition of iron from molten oxide electrolysis (MOE) at ultrahigh temperatures (≥1500 K) using an inert anode promises an alternative route of ironmaking without CO2 emissions. It has drawn increasing attention along with the development of renewable energy technologies in recent years [1-5]. However, only little work has been devoted to understanding of the electrochemistry of iron in molten oxides, probably due to experimental difficulties associated with the operation of ultrahigh- temperature cells, including stabilities of the electrodes and the cell containing the molten oxides [3,6].

This work aims at demonstrating a simple, unique and integrated three-electrode cell constructed from an MgO- Figure 1. CVs of molten slag containing 5 stabilized zirconia (MSZ) tube with a closed end for fundamental wt% FeO at different scan rates (0.06, 0.08, investigation of the electrochemical properties of iron ions in 0.10, 0.12, 0.15, 0.18, 0.20, 0.30, 0.40 V s-1) molten slag at ultrahigh temperatures. The MSZ tube serves as and 1723 K. Inset: the correlation between the container of the melt and an oxide ion conducting membrane cathodic peak current (Ip) and square root of 1/2 to physically separate the working electrode (WE) and the scan rate (v ). RE: MSZ | Pt | O2 (air). counter electrode (CE). It also provides a basal body integrating 2- the CE with a stable “MSZ | Pt | O2 (air)” reference electrode (RE) (in fact an “O |O2” RE). The migration of O2- in the MSZ membrane was found not to be the controlling step in the overall reduction process of electroactive species on the WE. With the aid of the cell, electrochemical behaviour of iron ions was systematically investigated on an iridium (Ir) WE in the mother slag with the base composition of 47 wt% SiO2, 28 wt% CaO, 16 wt% MgO, and 9 wt% Al2O3 at 1723 K by various electrochemical means, including cyclic voltammetry (CV), square wave voltammetry (SWV), chronopotentiometry (CP), and potentiostatic electrolysis (PE). Figure 1 presents CVs of the molten slag containing 5 wt% FeO at 1723 K, showing liquid diffusion controlled electrode reactions, and more details will be discussed in the presentation.

Acknowledgement We thank the NSFC (51174148), the Key Program of Joint Funds of the NSFC and Liaoning Provincial Government (U1508214), and Ningbo Municipal Government (3315 Plan, 2014A35001-1) for funding. References [1] A. Allanore, L. Yin, D.R. Sadoway, Nature, 2013, 497, 353. [2] A. Allanore, Electrochim. Acta , 2013, 110, 587. [3] D.H. Wang, A.J. Gmitter, D.R. Sadoway, J. Electrochem. Soc., 2011, 158 , E51. [4] A. Allanore, J. Electrochem. Soc., 2015, 162, E13. [5] A.H.C. Sirk, D.R. Sadoway, L. Sibille, ECS. Trans., 2010, 28(6), 367. K. Nagata, T. Kawashima, K.S. Goto, ISIJ. Int., 1992, 32, 36.

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Mechanism and Kinetics of Electro-carboxylation in Ionic Liquid Media Andrew P. Doherty and Eunan Marley

School of Chemistry and Chemical Engineering, The Queen’s University of Belfast, Belfast, BT9 AG, UK Contact E-mail: [email protected]

An alternative to the direct electrochemical activation of CO2 is its incorporation into small electro-active molecules through nucleophilic coupling reactions with electro-generated RAs. Such electrocarboxylation reactions involving olefins, aldehydes and ketones are very well known [1] with the carboxylation of aromatic ketones yielding a-hydroxy-acids (AHAs) which are of particular historic interest since this approach has been used commercially to produce intermediates in the synthesis of anti-inflammatory agents such as ibuprofen and naproxen [2].

Over recent years, several reports have appeared detailing the use of CO2 in preparative- scale electrochemical conversions in IL systems [3, 4]. These include the preparative-scale electrocarboxylation of acetophenones [4] to produce the target a-hydroxy-carboxylic acid methylesters at reasonably high yields and efficiencies. ILs provide a safe and convenient medium for such transformations, relative to combustible toxic molecular solvents.

In terms of fundamental electrochemistry, the relatively simple and well understood electrochemistry of aromatic ketones is a powerful probe for investigating the effect of reaction environment on electrochemical reactivity [5]. In this context, we have already shown [6] using comparative voltammetric studies, and Hammett correlations [7], that the electrochemistry of a series of substituted benzophenones (BPs) in aprotic ionic liquids occurs as it does in aprotic organic solvents. Significantly, the solvent parameter (r) of the Hammett relation is the same for [Bmpy][NTf2] IL as for acetonitrile solvent indicating very similar solvent-solute / IL-solute interactions during reversible RA generation. Despite these observations for BP, it is well established that the nature of ILs can strongly influences chemical reactivity including electrochemical activity [8, 9]. The data presented in this talk details the mechanistic and kinetic aspects of the electro-carboxylation of various BPs in [Bmpy][NTf2] media which will be compared to the situation in polar molecular solvent.

Acknowledgments EM thanks the Department of Education Northern Ireland for a PhD Studentship.

References [1] ] D. A. Tyssee, .M. M. Baizer, J. Org. Chem., 39, p. 2819 – 2823 (1974). [2] J. P. Rieu, A. Boucherle, H. Cousse, G. Mouzin, Tetrahedron, 42, p. 4095 – 4131 (1986). [3] M. Feroci, M. Orsini, L. Rossi, G. Sotgiu, A. Inesi, J. Org. Chem., 72, p. 144 – 149 (2007). [4] Q. Feng, K. Huang, S. Liu, J. G. Yu, F. Liu, Electrochim. Acta, 56) p. 5137 – 5141 (2011). [5] P. Zuman, D. Barnes; A. Ryvolova-Kejharova, Disc. Farad. Soc., 45 p. 202 – 226 (1968). [6] S. O'Toole, S. Pentlavalli, A. P. Doherty, J. Phys. Chem. B, 111, p. 9281 – 9287 (2007). [7] L. P. Hammett, J. Am. Chem. Soc., 59, p. 96 – 103 (1937). [8] M. J. Earle, S. P. Katfare, K. R. Seddon, Org. Let., 6, p. 707-710 (2004). [9] C. L. Lagrost, D. Carrié, M. Vaultier, P. Hapiot, J. Phys. Chem. A, 107, p. 745 – 75 (2003).

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Direct electrochemical synthesis of Ti-35Nb-7.9Sn alloy from mixed oxide discs in CaCl2 melt D. Sri Maha Vishnu1,2*, Jagadeesh Sure1,2, R. Vasant Kumar2 and Carsten Schwandt1,2

1Department of Materials Science and Metallurgy, University of Nizwa,Birkat Al Mouz, 616 Nizwa, Sultanate of Oman 2Department of Materials Science and Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge CB3 0FS, United Kingdom *Contact E-mail: [email protected], [email protected]

Titanium-based alloys find extensive application in the field of implant technology due to their excellent biocompatible, corrosion and mechanical properties [1]. Nb and Sn are non-toxic alloying elements and Ti-Nb-Sn-based alloys were reported to have a relatively low modulus of elasticity, close to that of the bone [2]. Attempts were made in the present study to synthesise Ti-35Nb-7.9Sn alloy via the FFC Cambridge process [3] and to gain an insight into the various fundamental issues influencing the electrochemical synthesis of this alloy.

The starting material for the alloy synthesis was TiO2-Nb2O5-SnO2 mixed oxide powder. The material was sintered in air, with sintering at 1100°C giving highly dense, and sintering at 900 or 950°C giving rather porous mixed oxide discs. XRD analysis showed that the sintered material contained TiNb2O7 as the prominent phase in a matrix of rutile TiO2. The discs were then employed as the cathodes in an FFC electrolytic cell, using molten CaCl2 as the electrolyte and graphite rods as the anodes.

Dense mixed oxide discs were electrolysed for periods of 2, 5, 9, 14, 18, 28 and 36 h, aiming to understand the nature of the intermediates formed during the conversion. The surface of the discs was reduced to the intended alloy within 2 h, whereas the bulk showed the presence of TiO2 and TiNb2O7 alone until up to 14 h. Traces of CaTi2O4 along with TiO2 and TiNb2O7 were observed after 14 h, and additional CaTiO3 was seen after 28 h. The presence of Ti3O, Ti6O, Ti2O, TiO0.48 and TiO0.325 after 14 h indicated that the reduction of the Ti oxides proceeded mainly through Ti intermediates despite the concomitant presence of oxides of Nb and Sn. The metal layer thickness progressively increased with increasing electrolysis time.

Porous mixed oxide discs were completely reduced within a period of 18 h. These experiments showed much higher currents and hence faster charge transport than the experiments with the dense discs, indicating the importance of high open porosity and small particle size for effective reduction. Varying the electrolysis temperature showed that 900°C was adequate, while lower temperatures led to sluggish reduction; and varying the polarisation potential showed that only at 3.1 V complete reduction was achieved, while lower applied potentials led to partially unreduced cores inside the discs. The fully reduced alloys were found to have single-phase BCC structure which is an important finding in regard to corrosion-sensitive application.

The effect of composition of the oxide cathode on the alloying process during electro-reduction was studied by electrolysing dense mixed oxide discs, of suitable oxide compositions, to Ti and Ti- 35Nb, in addition to the Ti-35Nb-7.9Sn. It was found that the open porosities of the discs decreased with increasing number of oxide constituents. In spite of that it was also found that the average thickness of the metal or alloy layer around the discs increased for compositions with a larger number of constituents, indicating that multinary materials reduce faster.

References [1] M. Niinomi, Sci. Tech. Adv. Mater., 4, p.445-454 (2003). [2] P.E.L. Moraes, R.J. Contieri, E.S.N. Lopes, A. Robin, R. Caram, Mater. Charact., 96, p.273-281 (2014). [3] G.Z. Chen, D.J. Fray, T.W. Farthing, Nature, 407, p.361-364 (2000)

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Current Progress on Molten Salt Electrolysis in GLABAT

Han Wang*, Zhanglong Yu, Sheng Fang, Chunrong Zhao, BingYu, Ning Wang, and Juanyu Yang*

Department of Material R&D, China Automotive Battery Research Institute Co. Ltd., Beijing, China

* Co-corresponding authors, E-mail address: [email protected], [email protected]

Electrochemical method for the material preparation in molten salts plays an important role in modern metallurgy, for example, the production of Al, Li, Na, K, Mg, Be, rare earth metals, Ti, Zr and Th. Compared with the aqueous electrolyte solutions, molten salts have more satisfactory advantages, such as a wide electrochemical window, a wide range of electrolysis temperature, and good thermal and electric conductivities. Due to these benefits, molten salt electrolysis is widely used as one of important techniques in the fields of materials recovery, power generation, and metals deposition.

China automotive battery research institute Co. Ltd. (GLABAT) as the national automotive battery industry incubator of China, found in 2015, aims to attain revolutionary breakthrough of power batteriesand support the sustainable development of new energy vehicles. Our material R&D department extremely focuses on the research and development of new materials and techniques in order to reach the technical requirements of high specific energy lithium ion power battery. Molten salt electrolysis is one of our developing methods to prepare nano-sized structure materials, such as Si nanowires and SiC nanowires. Here, we would like to present our current progress on the preparation of these materials via molten salt electrolysis.

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Synthesis of Ti-5Ta-2Nb Alloy from Solid Oxides by Electro- reduction in Molten Salt and its Corrosion Behaviour in Concentrated Nitric Acid Jagadeesh Sure1,2*, D. Sri Maha Vishnu1,2, R. Vasant Kumar2 and Carsten Schwandt1,2

1Department of Materials Science and Metallurgy, University of Nizwa, Nizwa, Birkat Al Mouz, 616 Nizwa, Sultanate of Oman 2Department of Materials Science and Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge CB3 0FS, United Kingdom *Contact E-mail: [email protected], [email protected]

Titanium-based alloys are preferred for advanced structural materials1 (chemical and nuclear reprocessing plants under severe oxidizing conditions), as well as for a range of functional and biomedical applications2. From the various titanium-based alloys, nominal composition of Ti-5Ta-2Nb (TTN) was considered for the present study, and the synthesis of the alloy was performed directly from the corresponding metal oxide precursor in a molten salt via the single- 3 step FFC-Cambridge process . In this, TiO2-Ta2O5-Nb2O5 compacted powder mixtures or sintered disks were cathodically polarised against a graphite anode in a calcium chloride electrolyte. Parameters studied were: duration of electrolysis, temperature of electrolysis, applied potential, sintering temperature of the disks (change in open porosity and particle size), and mass of oxide precursor. CaTiO3 intermediate was found in the samples electrolysed for 3 and 6 h which eventually reduced to TTN alloy after 12 h of electrolysis. Ta- and Nb-based intermediates were not detected in the partially reduced products. Increase in electrolysis temperature from 1098 to 1173 K and in applied potential from 2.5 to 3.1 V led to an increase in the rate of reduction of the oxide precursor to TTN alloy. When the cathode size was increased from 1 to 3 g, the time taken for completion of reduction was found to be almost twice that of the former. As the sintering temperature of the oxides increased from 1223 to 1373 K, the porosity of the oxide disks decreased and their reduction became slower.

All electrochemically reduced TTN alloys consisted of the α-phase as confirmed by XRD studies. By heat treatment it is possible to change the phase composition and porosity of the alloy. Heat treatment at 1473 K for 3 h under vacuum changed α-phase into α+β phases and also resulted in low structural porosity. TTN alloys were subjected to corrosion testing in 11.5 4 M (70%) concentrated boiling HNO3, as per ASTM A262-15 Practice C test to assess corrosion resistance. The effect of sintering temperature (1223, 1323 and 1373 K) of the oxide precursor on microhardness and corrosion resistance of the alloy formed was also evaluated. Overall, the alloys were found to have excellent corrosion resistance (0.1 mpy) due to the formation of a protective film composed of TiO2 (porous in nature), resulting from the passivation behaviour of the alloy in HNO3, as confirmed by XRD and SEM/EDX.

This study has demonstrated for the first time the fabrication of advanced structural TTN alloy, for highly corrosive oxidizing environments, by direct electrochemical synthesis from metal oxides.

References [1] B. Raj, U. Kamachi Mudali, Progr. Nucl. Energy, 48, p.283-313 (2006). [2] M. Niinomi, Sci. Tech. Adv. Mater., 4, p.445-454 (2003). [3] C. Schwandt, T. I. Min. Metall. C, 122, p.213-218 (2013). [4] ASTM Standard A262-15, ASTM International, USA, p.1–17 (2015).

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Towards understanding microscopic interactions in ionic liquids and their effects on SN2 processes

Karin Schaffarczyk McHale,a Ron Hainesa and Jason B. Harpera

a School of Chemistry, The University of New South Wales, Sydney NSW, Australia *[email protected]

Ionic liquids, salts with normal melting points below 100 ºC,1 have the potential to alter reaction outcomes relative to molecular solvents.1-2 Previously it has been demonstrated that where pyridine undergoes an SN2 reaction with benzyl halides 2 there is an entropically driven rate enhancement when ionic liquids are used due to favourable cation-nucleophile interactions.3- 5 The effect of varying the constituent ions of ionic liquids on this interaction has been previously investigated, allowing a degree of predictability and therefore progress towards 6 rational selection of an ionic liquid solvent for accelerating SN2 processes. However there is a comparatively limited understanding as to how variation of the chemical nature of reactive species affects SN2 processes in ionic liquids.

Therefore, this work has focused on variation of the electronics of the electrophile 2 to probe the importance of interactions between the transition state and the components of ionic liquid 3 (Scheme 1). The effects of varying the nucleophilic heteroatom down group 15 have also been investigated to determine if there is a trend in the observed ionic liquid effect as you go down a group. The solvent effects have been investigated through studying the dependence of the rate constant on the amount of ionic liquid 3 in the reaction mixture, as well as temperature dependent kinetic studies to gain insight into the interactions between species along the reaction coordinate and the salt 3.

X acetonitrile X PPh3 PPh3 [Bmim][N(SO CF ) ] 3 R 2 3 2 R 1 2 X = Cl, Br, I 4 X = Cl, Br, I Scheme 1: Representative SN2 reactions between a group 15-based nucleophile (triphenylphosphine 4) and benzyl halides 2. R = 3,5-Me-4-MeO, 4-MeO, 4-Me, H, 4-CF3, 4-Br, 4-NO2

References 1. Chiappe, C., D. Pieraccini, J. Phys. Org. Chem. 2005, 18, 275-297. 2. Earle, M. J., S. P. Katdare, K. R. Seddon, Org. Lett. 2004, 6 (5), 707-710. 3. Yau, H. M., A. G. Howe, J. M. Hook, A. K. Croft, J. B. Harper, Org. Bimol. Chem. 2009, 7 (17), 3572-5. 4. Yau, H. M., A. K. Croft, J. B. Harper, Faraday Discuss. 2012, 154, 365-371. 5. Keaveney, S. T., J. B. Harper, RSC Adv. 2013, 3 (36), 15698-15704. 6. Tanner, E. E. L., H. M. Yau, R. R. Hawker, A. K. Croft, J. B. Harper, Org. Bimol. Chem. 2013, 11 (36), 6170-6175.

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Three Dimensional Printing of Biomaterial-Laden Ionic Liquids

Deshani H. A. T. Gunasekera*, Christopher Tuck*, Anna K. Croft† and Ricky D. Wildman*

*Centre for Additive Manufacturing (CfAM), Department of Mechanical, Materials & Manufacturing Engineering, University of Nottingham, Nottingham, NG7 2RD, United Kingdom. † Department of Chemical and Environmental Engineering, University of Nottingham, NG7 2RD, United Kingdom.

Annually, large proportions of waste generated from plants and animals are being discarded and an alternate use of these resources will provide an environmental and economically friendly solution to waste reduction and manufacture of green products. Additive Manufacturing (3D Printing) is a cutting-edge technology that can be used to produce three dimensional objects layer by layer. This manufacturing method eliminates waste and provides economically suitable parts for bespoke applications. Here we show that biomaterials dissolved in ionic liquid can be 3D printed using a jetting system. These 3D printed parts includes but are not limited to applications such as biomedical implants, sensing devices and microfluidic reactors.

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Molecular Interactions of Protein-based materials with Ionic Liquids

Shafaq Muzammala,*, Christof Jaegera, Peter Licenceb, Anna K. Crofta aDepartment of Chemical and Environmental Engineering, University of Nottingham,UK bSchool of Chemistry, University of Nottingham, UK *[email protected]

Ionic liquids (ILs) are solvents consisting purely of ions. The properties of ionic liquids such as low vapor pressure, low flammability and their ability to dissolve polar and nonpolar organic, inorganic and polymeric compounds are a result of a complex interplay of intermolecular interactions between constituent ions, their geometry and charge distribution.

Proteins are polyamides having amino acids (AAs) as building blocks and are essential macromolecules in biological systems. The dissolution and processing of such polymers by standard molecular solvents is hindered by their complex nature and the presence of strong inter and intra-molecular hydrogen bonds. ILs have shown favorable solvation properties for polar substrates, including carbohydrates1 and proteins 2,3 but apart from the beneficial effects found for the use of biocompatible ILs in connection with proteins, remarkably little is known about the molecular basis of the IL–solute interactions.

Here we present our latest results, determined from computational methods showing the microscopic organisation of ionic liquids around amino acid and peptide-based solutes, to help explain the ionic liquid-peptide interactions and to develop a predictive understanding and optimisation of macroscopic processes including solubility and reactivity of proteinaceous materials in ionic liquids.

Figure 1. Organisation of the ionic liquid ions [C2C1Im]+ (blue) and Cl- (red) around the zwitterionic lysine cation in EMIM-Cl IL at 300K , shown as a spatial distribution function.

References. (1) Rosatella, A. A.; Branco, L. C.; Afonso, C. A. M. Green Chemistry 2009, 11, 1406. (2) Idris, A.; Vijayaraghavan, R.; Rana, U. A.; Patti, A. F.; MacFarlane, D. R. Green Chemistry 2014, 16, 2857. (3) Heimer, P.; Tietze, A. A.; Böhm, M.; Giernoth, R.; Kuchenbuch, A.; Stark, A.; Leipold, E.; Heinemann, S. H.; Kandt, C.; Imhof, D. ChemBioChem 2014, 15, 2754.

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The role of C8mimPF6 in miniemulsion stabilized by silica nanoparticles

Yiyang Konga, Rongmeihui Zhenga and Binjie Hua,*

a Department of Chemical and Environmental Engineering, The University of Nottingham Ningbo China, 199 Taikang East Road, Ningbo 315100, China

*Corresponding Author’s Email: [email protected]

Environmental friendly latex coating has become more favorable in replacing solvent-based coating because of its low VOCs emission. However, coalescing agent emission and excessive surfactant residual in the final film, which affect coating performance such as glossy and water resistance in the film formed, etcs have been two major problems. To solve these two problems, we first propose using

C8mimPF6 as potential non-volatile coalescing agents in the miniemulsion and using silica nanoparticles to replace surfactant. The work is divided into two steps, preparation of miniemulsion and further polymerization. Various factors including temperature, pH of water phase, silica nanoparticle concentration, and C8mimPF6 concentration, which might affect droplet size, and its stability before and during the reaction process were investigated. It has been found; temperature, C8mimPF6 concentration and pH of water phase strongly affect droplet size. The presence of C8mimPF6 had significant impact on both initial droplet size and stability of miniemulsion during storage. Adding as little as 1 wt%

C8mimPF6, resulted in a sharp decline in droplet size. The reduction on droplet size tended to be smaller as further increase the concentration of C8mimPF6 to 5 wt%. Above 5 wt%, the droplet size became independent of the change of C8mimPF6 concentration. Measurement of zeta potential, rheological properties for the miniemulsion suggest that variation of surface charge, viscosity as well as the interaction between silica particles and C8mimPF6 could play key roles in stability of miniemulsion. In addition, it also notices that there is a synergetic effect between silica particles and C8mimPF6. The more C8mimPF6 being added, the more stable the miniemulsion will be, which in turn affect the stability of the latex. Measurement of Tg and thermal gravity on latex shows that more C8mimPF6 can enhance thermal stability of latex and reduce Tg which confirm the positive effect of C8mimPF6 in latex products containing silica particles. Such results may be further extended into other applications in the similar system.

Key words: room temperature ionic liquids, miniemulsion, silica nanoparticles

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Dr Fred Starr FIMMM, MIMechE, CEng

Fred Starr is currently most known for his “Recollections”, published in “Materials World”, the house magazine of the Institute of Materials. Here, based on fifty years in the front line of R&D, he takes a sardonic look at what really goes on in the pursuit of truth, and, more importantly, status, while trying to highlight obscure but important bits of materials knowhow. Last year he was awarded a Gold Medal by the Institute for a piece entitled “Lies, Damned Lies, and Nuclear Power”.

Fred did his degree in Metallurgy at Battersea College of Advanced Technology in 1966, whilst working as a student apprentice at Dorman Long, the biggest steelmaking company on Teesside. However, the green fields of the South and of Engineering were more attractive than metallurgy. Almost by accident he got a job as a shift engineer on the world’s most advanced gas making complex, based on steam reforming, at Hitchin. It was like working on a refinery.

From there he joined British Gas - London Research Station, in Fulham, where he did failure investigation on steam reforming plants. But by the middle of the 1970s, there was a perceived need for research into novel gasification processes, based on heavy oil and coal. There were severe high temperature issues, and these became the main interest of Fred’s team.

With the onset of Privatisation, and the belief that supplies of North Sea Gas would last forever, these programmes were shut down. The directive came down, “find new ways of using natural gas as an inexhaustible source of energy”. Fred backed and helped come up with the idea of generating power in the home, using a standard gas boiler incorporating a Stirling Engine. Following a worldwide tour several engines were tested. Fred also got his management interested in the closed cycle gas turbine, and claims to be last person who has actually built such equipment. This was only possible because of a deep, if amateur, interest in jet engine and aircraft design, enabling a “demonstrator” to be built quickly and relatively cheaply.

But R&D began to wind down in British Gas and Fred left in 1996. He had a couple of positions in the power generation sector before moving to the EU’s Institute for Energy in the Netherlands in 2004. There, he did the preliminary design for a plant making hydrogen and generating electricity, while capturing CO2. It was here he came up with the Crappy Coal proposal. He also read for a PhD while he was over there.

The experience in the Netherlands and power plant background has obliged him, in retirement, to keep watch over how renewable energy is impacting on the British and Irish Power Systems. He describes himself as an objective supporter of wind energy, his views having credence with wind’s supporters and denigrators. His other main interest is the industrial history of the 20th Century, and he is an active member of the Newcomen Society for the Study of Engineering History.

Finally, Fred, as part of his after-dinner talk, will be describing some work that he did in his British Gas days, that might be of interest to the Molten Salt Fraternity. This has never been published, but gave him and his colleagues a great deal of fun and excitement, at a time when expense was no object.

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50 MSDG Summer Meeting 4th-6th July 2017 University of Nottingham

High Seebeck Coefficient Thermocell with Molten Carbonate Electrolyte S. Kandhasamy1, O.S. Burheim2, A. Solheim3, S. Kjelstrup4 and G.M. Haarberg1

1 Department of Materials Science and Engineering, Norwegian University of Science and Technology (NTNU), Trondheim, Norway 2 Department of Electrical Engineering and Renewable Energy, NTNU, Trondheim, Norway 3 SINTEF Materials and Chemistry, SINTEF, Trondheim, Norway Contact E-mail: [email protected]

A thermocell with molten carbonate electrolyte mixture with two identical gas (CO2|O2) electrodes shows the possibility to utilize the waste heat as a power source. Molten carbonate thermocells delivers a higher Seebeck coefficient (~ 1 mV/K) than the conventional semiconductor thermoelectric (0.2 mV/K) converters. Also, it has the advantage to harvest industrial waste heat at high temperatures and utilize the available CO2 rich off-gases from metal producing industries.

Dispersion of solid oxide in the molten carbonate electrolyte melt was found to improve the conditions for thermoelectric conversion. It influences the transported entropy of the carbonate ions and the cell Seebeck coefficient. Thus, the change in Seebeck coefficient of the molten carbonate thermocell due to compositional change with various selected solid oxides was studied here. Also the modification in the thermal and physical properties of the electrolyte mixtures was systematically analyzed in detail to understand the contribution of the properties of the dispersed solid oxide on establishing the conditions to enhance thermoelectric conversion in the molten carbonate thermocell. Some results for the obtained Seebeck coefficient are shown in Fig. 1.

Figure 1. Seebeck coefficent of the thermocells at 550 0C with electrolyte mixture consisting of different dispersed solid oxides (55 vol%) in molten eutectic Li2CO3-Na2CO3.

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52 MSDG Summer Meeting 4th-6th July 2017 University of Nottingham

Carbon Capture in Molten Salts (CCMS)

E. Olsen, H.S. Nygård and M. Hansen

Norwegian University of Life Sciences Drøbakveien 31, N-1432 Ås, Norway

Abstract: Carbon capture and sequestration (CCS) has been identified by the IPCC as a key technology to reach the long term goal of keeping human induced atmospheric warming below 2°C. Alternatives to the emission of fossil carbon to the atmosphere exists for many processes such as wind- and solar energy for the generation of electricity. For a number of industrial processes, however, the reductive power and chemical characteristics of carbon cannot be easily replaced. Production of metals such as iron, aluminium and silicon are a few examples. Calcium- or carbonate looping techniques seem particularly suited for extraction of CO2 from industrial flue gases where high temperatures have been utilized. The principle relies on the reversible reaction in Eq. (1) where CaO reacts with CO2 at temperatures around 800°C forming CaCO3. Raising the temperature above 900°C reverses the reaction.

��� + �� ⇌ ���� (1)

Keeping the active substances in molten salts (CaCl2/CaF2) has been shown to be beneficial to the process. CaO has only limited solubility and can be present as solid particles forming a slurry at contents above 5%. Fast reaction controlled kinetics are enabled by the apparent high solubility and rapid dissolution of CaCO3 in the molten matrix. This disables the onset of diffusion control once a monolayer of carbonate has formed on the oxide particles. Performing the process in a molten salt has further been shown to give excellent cyclability, high selectivity and overall high performance. Adding an alkali metal halide (NaF) promotes an ion exchange reaction further enhancing selectivity. Recent research has focused on establishing the fundamentals such as phase equilibria, reaction kinetics and reactivity towards other compounds found in industrial flue gases such as H2O and SO2. In particular, the effect of hydrolysis on the molten salts has been addressed since very limited previous work has been found in the literature. The latest results show that hydrolysis does occur to CaCl2 to a certain extent, according to theory, and that temperature has a strong effect. CaF2, however, hydrolyses only to a very limited extent and only at elevated temperatures.

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54 MSDG Summer Meeting 4th-6th July 2017 University of Nottingham

Co-Reduction of Carbon Dioxide and Steam in Molten Electrolytes Ossama H. Al-Juboori1 and George Z. Chen1,2

1 Department of Chemical and Environmental Engineering, University of Nottingham, Nottingham NG7 2RD, UK 2 Department of Chemical engineering, University of Nottingham Ningbo China, 199 Taikang East Road, Ningbo 315100, P. R. China. Contact E-mail: [email protected]

Using carbon or fossil fuels in power generation has not been considered a serious issue until recent justification of rising atmospheric temperature as a result of increasing CO2 emission. Technologies that can absorb CO2 from the emissions and, more substantially, convert CO2 economically into useful materials, instead of simply storing the gas underground, are urgently needed. The process and chemical engineering aspects of the conversion of CO2 and water to beneficial gases via a molten salt route have not yet been examined properly other than the chemistry of the conversion itself which was well discussed [1,2]. This research investigates the feasibility of producing hydrocarbons by the electrochemical reduction of CO2 and water in molten salts at atmospheric pressure. Various cathodic gases were formed during the electrolysis and the products were analysed using gas chromatography. The effect of molten salt temperature and applied voltage were also examined. As a significant outcome, about 0.1 % of the cathodic gas produced during electrolysis in Li2CO3-Na2CO3-K2CO3 (43.5-31.5-25 mol %) at an applied voltage of 1.5 V and a temperature of 5000C or 4300C was the methane gas. Methane gas was actually the predominant hydrocarbon gas found in all experiments. Some of hydrocarbon species higher o than C5 products can be confirmed also in the first test at 500 C. During electrolysis in molten KOH-NaOH ( 50-50 mol)% at 220 oC and 2V applied votage, methane gas was found to be 0.15% and increased to 0.5 % in the case of 3V. Hydrogen and carbon monoxide gases was found in association with hydrocarbon production during the process in all cases with higher levels of hydrogen gas obviously in the case of molten hydroxide. The effects of molten salt composition and voltage on the electrolysis were also considered and are shown in Table 1. Because the electrolysis was also carried out without the use of any catalyst, the results are promising and encourage further fundamental investigation and technological development.

Table 1 – Effect of molten salt composition and voltage on the electrolysis Operating Average Gas product composition (%) Temperature Test Molten salt voltage current (oC) (V) (A) CO2 H2 CO CH4 >C5 Ar

1 Li2CO3-Na2CO3-K2CO3 500 1.5 0.06 4.2 0.4 0.36 0.03 0.02 95

2 Li2CO3-Na2CO3-K2CO3 430 1.5 0.05 38.3 2.3 0.3 0.1 0.00 59 3 KOH-NaOH 220 2 0.40 0.00 4.4 0.4 0.15 0.00 95 4 KOH-NaOH 220 3 0.95 0.00 2.2 1.43 0.5 0.00 96

References [1] D. Chery, V. Albin, et al. "Thermodynamic and experimental approach of electrochemical reduction of CO2 in molten carbonates." International Journal of Hydrogen Energy 39(23): 12330-12339 (2014). [2] S. H. White and U. M. Twardoch. "The electrochemical behaviour of solutions of molten ternary alkali carbonate mixture equilibrated with carbon dioxide-water mixtures at 460°C." Electrochimica Acta 29(3): 349-359 (1984).

Acknowledgement This work was partially funded by the EPSRC (EP/J000582/1). OHAJ specially thanks his father Hussein Al- Juboori for financial support.

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56 MSDG Summer Meeting 4th-6th July 2017 University of Nottingham

A liquid sodium-zinc and molten chloride battery

Geir Martin Haarberg1, Junli Xu2, Karen S. Osen3, and Ole S. Kjos3

1Department of Materials Science and Engineering, Norwegian University of Science and Technology (NTNU), NO-7491 Trondheim, Norway 2School of Science, Northeastern University, Shenyang 110004, China 3SINTEF Materials and Chemistry, NO-7465 Trondheim, Norway Contact E-mail: [email protected]

An alternative liquid metal battery with molten chloride electrolyte is under development. The o electrodes are liquid sodium and zinc while the electrolyte is molten NaCl-CaCl2 at 560 C. A diaphragm of porous magnesia stabilised zirconia rather than a membrane is used.

The discharge voltage was found to be in the range from 1.4 - 1.8 V and the cycling efficiency was ~90 % at low discharge current densities below 40 mA/cm2. At 100 mA/cm2 the discharge voltage was ~1.1 V and at 200 mA/cm2 it was ~0.8 V. The open circuit cell voltage was ~1.7 - 1.8 V after charging and it could be maintained for 10 h before decreasing to ~1.0 V.

The use of inexpensive and abundant components may give this battery a competitive edge for energy storage systems.

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58 MSDG Summer Meeting 4th-6th July 2017 University of Nottingham

Solid State Production of a Seven Component Niobium Silicide- Based Alloy

G. Doughty1

1 Metalysis Ltd Materials Discovery Centre Brindley Way Catcliffe Rotherham S60 5FS Contact E-mail: [email protected]

The FFC Cambridge Process enables the conversion of mixed metal oxides into alloy powders in a bath of molten salt. As the process takes place at low temperatures, it can produce alloys that may be difficult to produce via conventional melt routes because of the differences in melting point, boiling point and densities of the metal components. Some examples of alloys produced from elements with widely differing melting points and densities will be given followed by a description of the production of a seven component alloy based on Niobium Silicide (nominally Nb-20Si-20Ti-3Cr-6Mo-2Hf-4Sn) with applications at high temperature in oxidising environments. The microstructure consists of niobium silicide plus niobium and titanium solid solutions. Alloys of this type are of interest for replacement of nickel based superalloys1.

References [1] Assessment of a Powder Metallurgical Route for Refractory Metal Silicide Alloys. P. Jehanno, M. Heilmaier, H. Kestler, M. Boning, A. Venskutonis, B. Bewlay, M. Jackson. Met. & Mat. Transactions A, 36A 515- 523, March 2005.

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