Nanotube Grafted Carbon Fibre for Hierarchical Composites

David Anthony MSci (Hons)
Project Supervisors: Milo Shaffer & Alexander Bismarck
Funding: EPRSC

The aim of the project is to produce a hierarchical composite structure containing carbon fibres which have been grafted with carbon nanotubes to act as a reinforcement in polymer (thermoplastic) or epoxy (thermoset) matrix. The addition of the carbon nanotubes to the surface of the carbon fibre using current methods damages the surface of the carbon fibre but improves other characteristics of the new material.

The addition of the carbon nanotubes is desirable due to the unique properties inherent to their structure. Carbon nanotubes have extraordinarily high tensile strength, high thermal conductivity, can be electrically conducting and have a good aspect ratio. Carbon nanotubes which are deposited on the carbon fibre also increase the contact surface for interaction to the matrix.

Carbon nanotubes grafted to carbon fibre are sometimes called hairy fibres due to their appearance.

Image left: Scanning electron micrographs of carbon fibres (a) before and (b) after carbon nanotube growth. Courtesy of Hui Qian [1]

Aims of the project include;

Optimise grafting to minimise damage to the original fibre properties, the catalyst will be deposited electrochemically in a bath containing metal salts, prior to CVD growth. The diameters of the grafted CNT are dependent on the time left for deposition of the chosen catalyst on the carbon fibre.

To design, build, and commission a rig for continuous CNT grafting onto CF. Ideally integrate a resin impregnated step for composite line / pre-impregnated (prepreg) production. Ensuring that the composite is coated in a resin, it can be considered safe for handling.

Use a number of mechanical tests and analytical techniques to identify the fundamental properties of the composite and the single fibres produced.

Identify the failure mode (fractography) and relate to the defects of the composite, be it the interface between the components or the individual component limit being reached. Testing and following ASTM standards to assist production application.

A diagram of the proposed set up;

Reference:

[1]          Hui Qian, Hierarchical Composites With Carbon nanotube Grafted Fibres, 2007.

Nano structured Catalysts for CO₂ Reduction to CH₃OH

Dr. Neil Brown AMRSC

The key aspects of the project are to form stable Cu/ZnO catalytic species from molecular pre-cursors to act as hydrogenation catalysts for carbon dioxide and to develop molecular organometallic analogues of the catalyst surface to study the mechanism

Publications

Synthesis, redox chemistry and electronic structure of the butadiynyl and hexatriynyl complexes [Mo{(C≡C)x-(C≡CR)}(L2)(η7-C7H7)]n+ (x = 1, 2; n = 0 or 1; R = SiMe3 or H; L = 2,2-bipyridine or Ph2PCH2CH2PPh2).  N.J. Brown, E.C. Fitzgerald, H.N. Lancashire, D. Collison, R. Edge, M. Helliwell, P.J. Low, M.W. Whiteley, Organometallics, 2012, 31, 157.

The synthesis, molecular and electronic structure of cyanovinylidene complexes.  E.M. Long, N.J. Brown, W.Y. Man, M.A. Fox, D.S. Yufit, J.A.K. Howard, P.J. Low, Inorg. Chim. Acta., 2012, 380, 358.
Orbital symmetry control of electronic coupling in a symmetrical, all-carbon-bridged “mixed valence” compound: synthesis, spectroscopy, and electronic structure of [{Mo(dppe)(η-C₇H₇)}₂(μ-C₄)]n⁺ (n = 0, 1, or 2).  E.C. Fitzgerald, N.J. Brown, R. Edge, M. Helliwell, H.N. Roberts, F. Tuna, A. Beeby, D. Collison, P.J. Low, and M.W. Whiteley. Organometallics, 2012, 31, 157.

Synthesis, Spectroscopy and Electronic Structure of [{Fe(dppe)Cp*}(μ-C≡CC₆H₄C≡C){Mo(dppe)(η-C₇H₇)}]ⁿ⁺ (n = 0, 1 or 2): A 1,4-Diethynylbenzene Bridged Heterobimetallic Featuring two Different Electron-rich Metal End Caps.  E.C. Fitzgerald, A. Ladjarafi,N.J. Brown, D. Collison, K. Costuas, R. Edge, J-F. Halet, F. Justaud, P.J. Low, H. Meghezzi, T. Roisnel, M.W. Whiteley, C. Lapinte, Organometallics, 2011, 30, 4180.

Synthesis, Redox Chemistry, and Electronic Structure of the Alkynyl Cyclopentadienyl Molybdenum Complexes [Mo(CºCR)(CO)(L2)Cp0]ⁿ⁺ (n = 0 or 1; R = Ph or C₆H₄-4-Me, L₂ = Ph₂PCH₂CH₂PPh₂ or 2PMe₃, Cp’ = Cp or Cp*).  H.N. Roberts (nee Lancashire), N.J. Brown, R. Edge, R. Lewin, D. Collison, P.J. Low, M.W. Whiteley, Organometallics, 2011, 30, 3763.

Spectroscopic and Computational Studies of the Ligand Redox Non-Innocence in Mono- and Bi-nuclear Ruthenium Vinyl Complexes. W.Y. Man, J-L. Xia, N.J. Brown, J.D. Farmer, D.S. Yufit, J.A.K. Howard, S Hua Liu, P.J. Low, Organometallics, 2011, 30, 1852.

Synthesis, spectroscopy and electronic structure of [{Mo(dppe)(η⁷-C₇H₇)}₂(μ-C≡C(C₂B₁₀H₁₀)C≡C)]ⁿ⁺ (n = 0, 1 or 2):  A true organometallic mixed valence complex.  N.J. Brown, H.N. Lancashire, M.A. Fox, R. Edge, D. Collison, D.S. Yufit, J.A.K. Howard, M.W. Whiteley, P.J. Low, Organometallics, 2011, 30, 884. (Organometallics Front cover 24^th February 2011)

Synthesis, spectroscopy and electronic structure of vinylidene and alkynyl complexes in the cycloheptatrienyl tungsten series [W(C=CHR)(dppe)(h-C7H7)]⁺ and [W(CºCR)(dppe)(h-C7H7)]ⁿ⁺ (n = 0 or 1).  H.N. Lancashire, N.J. Brown, L. Carthy, D. Collison, E.C. Fitzgerald, R. Edge, M. Helliwell, M. Holden, P.J. Low, J.J.W. McDouall, M.W. Whiteley.  Dalton Trans. 2011, 40, 1267.

Electronic interaction between and through covalently-bonded polymetallic complexes.  P.J. Low, N.J. Brown.  J. Cluster Sci., 2010, 21, 235.

Spectroscopic properties and electronic structure of the cycloheptatrienyl molybdenum alkynyl complexes [Mo(CºCR)(Ph₂PCH₂CH₂PPh₂)(h-C₇H₇)]ⁿ⁺ (n = 0 or 1; R = Bu^t, Fc, CO₂Me, or C₆H₄-4-X, X = NH₂, OMe, Me, H, CHO, CO₂Me).  N.J. Brown, D. Collison, R. Edge, E.C. Fitzgerald, M. Helliwell, J.A.K. Howard, H.N. Lancashire, P.J. Low, J.J.W. McDouall, J. Raftery, C.A. Smith, D.S. Yufit, M.W. Whiteley.  Organometallics, 2010, 29, 1261. 

Metal Stabilised diynyl radical: structure and reactivity of Mo(CºCCºCSiMe₃)L₂(h-C₇H₇)]^.+ (L₂ = 2,2’-bipyridine or dppe).  N.J. Brown, D. Collison, R. Edge, E.C. Fitzgerald, P.J. Low, M. Helliwell, Y.T. Ta, M.W. Whiteley.  Chem. Commun., 2010, 46, 2253.

The synthesis and structures of mono- and di-bromovinylidenes.  N.J. Brown, M.A. Fox, M.E. Smith, D.S. Yufit, J.A.K. Howard, P.J. Low.  J. Organomet. Chem., 2009, 694, 4042.

The preparation and characterization of ruthenium cyanovinylidene complexes.  N.J. Brown, P.K. Eckert, M.A. Fox, D.S. Yufit, J.A.K. Howard and P.J. Low.  Dalton Trans., 2008, 433. 

Synthesis, surface characteristics and directed assembly of anisotropic carbon and TiO2 nanomaterials

Robert Menzel PhD, MRes, DC
Project Supervisors: Milo Shaffer & Alexander Bismarck
Funding: EPRSC & DSTL
Partner: Surface Measurement Systems Ltd

• Synthesis of one- and two-dimensional TiO2 nanocrystals
• Carbon nanotube and TiO2 nanoparticle surface chemistry
• Inverse gas chromatography for the thermodynamic surface characterisation of nanomaterials
• Directed assembly of anisotropic nanostructures

Nanostructured materials can exhibit distinctively different intrinsic properties compared to their macroscopically structured counterparts, including unique strength, remarkable electrical conductivity or significantly enhanced reactivity. The exploitation of these exceptional properties in concrete, practical applications, such as structural composites, heterocatalytic systems, sensors or photovoltaic devices, requires full control over the morphology and surface characteristics of the nanostructures. My work addresses these issues, focusing on two of the most promising inorganic nanomaterials, carbon nanotubes and nanostructured TiO2.

Different strategies, including non-hydrolytic sol-gel reactions and hydrothermal conversions, are explored to synthesise anisotropic TiO2 and titanate nanostructures, including nanotubes, nanorods and nanoplatelets, and to control the crystallographic structure and surface chemistry of the nanomaterials produced. The impact of morphology and predominant crystal facet is studied in terms of selective adsorption of organic ligands, self-assembly and photocatalytic activity of the nanostructures.

Further, a versatile, thermochemical furnace treatment was developed that allows the introduction of a wide variety of functional species onto the surface of carbon nanotubes (CNTs) whilst maintaining the excellent properties of the untreated materials. The reaction is extremely versatile and can be applied entirely in the gas-phase, greatly simplifying work-up and improving scalability. Thermochemical functionalisation is a straightforward method to introduce specific binding sites and to control the surface energy of CNTs, an essential prerequisite for the fabrication of hybrid materials, such as metal-decorated CNTs and CNT/polymer composites.

For the assessment of the altered surface properties, we have focused on the versatile and sensitive technique of inverse gas chromatography (IGC). The application of IGC to nanomaterials has required significant development, but provides a new means to probe these exceptional materials and extract important thermodynamic surface parameters, including surface energies, electron accepting and donating capabilities and adsorption capacities. Other analytical techniques utilised to study the surface of the nanomaterials produced, are TGA-IR-MS, XPS and contact angle measurements.

Publications

Impact of Hydrothermal Processing Conditions on High Aspect Ratio Titanate Nanostructures. Menzel, R.; Peiro, A.; Durrant, J.; Shaffer, M.S.P. Chemistry of Materials 18, 6059-6068 (2006).

Inverse gas chromatography of as-received and modified carbon nanotubes. Menzel, R.; Lee, A.; Bismarck, A.; Shaffer, M.S.P. Langmuir 25, 8340-8 (2009).

A versatile, solvent-free methodology for the functionalisation of carbon nanotubes. Menzel, R.; Tran M.Q.; Menner, A.; Kay, C.; Bismarck, A.; Shaffer, M.S.P. Chemical Science 1, 603 (2010).

Presentations

Menzel, R., Tran, M., Menner, A., Bismarck, A. and Shaffer, M.S.P. "Surface Modification and characterization of carbon nanotubes: the key to improved composite performance" MC8: Advancing Materials by Chemical Design", London, UK, 02.-05.2007.

Oral Presentation. SMS User Group Meeting; Windsor, UK; 16 October 2006; "Surface Characterisation of Carbon Nanotubes by Inverse gas Chromatography and Temperature Programmed Desorption"

Oral presentation. NanoteC'07; Brighton, UK; 1 September 2007; "Surface Modification and Characterization of Carbon Nanotubes: The key to enhanced composite performance"

Poster Presentation. Summer School on Nanotubes; Cargese, France; 3-15 July 2006; "Surface Modification and Characterization of CNTs: The key to hierarchical reinforced nanocomposites"

Shu Chen PhD. MSc. BSc.

Shu Chen’s research interests are fabrication, functionalization and characterization of hybrid nanomaterials and their physical and biomedical applications.

Bio

Shu Chen graduated with a BSc in ‘Pharmaceutical Science’ from Shenyang Pharmaceutical University, China (2004). He obtained an MSc in ‘Drug Delivery & Targeting’ at The School of Pharmacy, University of London (2005). His MSc research project was the study of polymeric nanoparticles as gene drug carriers. Shu obtained his PhD in Chemistry and Physics in the University of St Andrews in 2011 under the supervision of Dr. Pascal André (Hybrid nano-Colloids Lab, Physics) and Prof. David Cole-Hamilton (Chemistry). His doctoral work was on the design of new chemical syntheses of iron platinum (FePt) alloy magnetic nanoparticles along with toxicity studies and an investigation into their applications as multifunctional biomedical imaging probes. During his PhD, he also contributed to develop collaborations with the University of Glasgow, Queen's University Belfast and the Institute of Medical Science and Technology (Dundee).

Shu Chen joined the groups of Dr. Alexandra Porter (Materials), Prof. Mary Ryan (Materials) and Prof. Milo Shaffer (Chemistry) in March 2011 as a Post-Doctoral research associate. He is working on the investigation of the pulmonary toxicology of silver and carbon materials which is part of the RESAC (Respiratory Effects of Silver and Carbon Nanomaterials) Center grant funded (in part) by National Institute of Environmental Health Sciences (NIEHS) (Grant #  1 U19ES019536-01). This project involves an interactional collaboration with Materials, Chemistry and the Royal Brompton Heart and Lung Institute of Imperials College London, University of Southern California and UMDNJ School of Public Health, USA. His work is focusing on synthesis, functionalization and characterization of carbon nanotubes and silver nanomaterials and using advanced electron microscopy techniques to visualize the cellular and molecular-level events e.g. nanomaterials entry, distribution, biological activity and fate in the lung which depend on the physiochemical properties of nanometerials.

Publications

 A Water-Soluble Temperature nanoProbe based on a Multimodal Magnetic-Luminescent nanoColloid,
S. Chen, C. Hoskins, L. Wang, M.P. MacDonald, P. André
Chem.  Commun., 49, 19, 2501 (2012)

Colloidal Syntheses of FePt nanoParticles (Review)
S. Chen, P. André
International Journal of nanoTechnology 9, 1-2, 39 (2012)

Influence of Ionic Liquid on the Crystalline Structure of nanoColloids
S. Chen, M. J. Muldoon, Kris Anderson, P. André
CrystEngComm, 13, 10, 3330 (2011)

Inhomogeneous Composition of Alloyed Iron-Platinum Magnetic Nanoparticles Synthesized at Low Temperature
S. Chen, D. MacLaren, R.T. Baker, J. Chapman, D.J. Cole-Hamilton, S. Lee, P. André
J. Mater. Chem., 21, 3646 (2011)

Engineered Biocompatible Nanoparticles for in-vivo Imaging Applications
S. Chen, L. Wang, S. Duce, S. Brown, S. Lee, A. Melzer, A. Cuschieri, P. André
J. Am. Chem. Soc., 132, 42, 15022 (2010)

Patents

“Direct Synthesis of fct-FePt nanoParticles in Ionic Liquids”
P. André, S. Chen, M. J. Muldoon, K. Anderson (Aug. 2009, Ref. P16260GB)

Oral Presentations

Engineered Biocompatible FePt nanoParticles for in-vivo Imaging Applications
S. Chen, L. Wang, S. Duce, S. Brown, S. Lee, A. Melzer, A. Cuschieri, P. André ; E-MRS 2011 Spring (Bio-nanomaterials for imaging, sensing and actuating Symposium) ; Nice, France (May 9-13, 2011)

Inhomogeneous Composition of Alloyed Iron-Platinum Magnetic Nanoparticles Synthesized at Low Temperature
S. Chen, D. A. MacLaren, R. T. Baker, J. N. Chapman, S. Lee, D. J. Cole-Hamilton, P. André ; E-MRS 2011 Spring (Size-Dependent Properties of nanoMaterials Symposium); Nice, France (May 9-13, 2011)

Effects of Coated Magnetic nanoColloids on Hybrid OLEDs
S. Gambino, S. Chen, I.D.W. Samuel, P. André ; SPIE Symposium on SPIE Photonic Devices (Organic Light Emitting Materials and Devices XIV) ; San Diego, CA-USA (August 1-5, 2010) - INVITED

Enhanced MRI Contrast Agent Properties in Biocompatible Magnetic nanoParticles
S. Chen, L. Wang, S. Duce, S. Lee, A. Melzer, Sir A. Cuschieri, P. André ; ICSM 2010, Kyoto, Japan, July 4-9, 2010

FePt Magnetic nanoParticles Syntheses, Cell Toxicity Studies and as MRI Contrast Agent
S. Chen, L. Wang, S. Brown, D. Cole-Hamilton, S. Lee, A. Melzer, Sir A. Cuschieri, P. André ; ACS 238th, Division of Colloid & Surface Chemistry (Nanoparticle-Biological Cell Interactions) ; Washington DC, USA, August 16-20, 2009
Synthesis of Iron Platinum Magnetic nanoParticles in Amphiphilic Systems: Strategies to Overcome Co-reduction Limits and Inhomogeneous Chemical Composition

S. Chen, D. MacLaren, R. Baker, J. Chapman, D. Cole-Hamilton, S. Lee, P. André ; ACS 238th, Division of Colloid & Surface Chemistry (Patchy Particles and Surfaces of Engineered Heterogeneity: From Synthesis to Dynamic Function); Washington DC, USA, August 16-20, 2009

Nanoparticles Engineering for Medical Technologies
P. André, S. Chen; JRI in Medical Technologies-Northern Research Partnership workshop on Nanotechnology in Medicine ; Aberdeen (Scotland) Nov. 20, 2008

Size effects in nanoscale dielectric materials

Supervisors: Professor David W McComb (Department of Materials) and Professor Milo SP Shaffer (Department of Chemistry)
Sponsor: EPSRC (Project Studentship)

The electronic properties of materials change substantially when size and shape are reduced to the nanometre scale. In this project we focus on the size dependence of the dielectric function in TiO2 nanostructured materials. The aim is to measure the dielectric function of novel semiconducting nanoscale systems using electron energy-loss spectroscopy (EELS) in the scanning transmission electron microscope (STEM), which provides sub-nanometre spatial resolution. Using the STEM-EELS approach allows to combine atomic resolution imaging with EEL spectroscopy and thus to probe the dielectric function locally while stepping a sub-nanometre probe across the sample. Currently, we are studying nanoplatelets and nanorods of TiO2 anatase and investigating the size dependence by varying the number of overlapping platelets, as well as the diameter and length of the rods. The results are then compared with the bulk case and density-functional theory (DFT) simulations. In this project we also attempt to characterize the atomic structure of the materials through exit wavefunction reconstruction (EWR) using focal series of aberration corrected high resolution TEM images. The aim is to give an insight into the novel intrinsic properties of the nanostructures and besides, discuss the advantages of aberration corrected TEM for very thin structures.

Research Interests

Jodie Melbourne MEng.
2nd year PhD
Nanometrology of the Carbon Nanotube- Lung Interface
As the global requirement and production of carbon nanotubes increase so does the risk of exposure to the people that work with them, presenting a potential health risk. The project aims to improve our understanding of the interaction between inhaled CNTs and the lung-air interface, focusing on the lung lining fluid and lung epithelial cells.

Synthesis and Characterisation of Organozinc Carboxylate Complexes

Organozinc Carboxylates remain a relatively unstudied class of compounds, yet can be useful as molecular building blocks for MOF’s and as models for catalysis. My work has focused on the synthesis of a range of new organozinc carboxylates, and centred around the study of CO2 insertion into diorganozinc compounds, both as a characterisation and kinetic study. Also a series of NNO-phenolate zinc complexes have been synthesised, as a route to mononuclear zinc hydrides. The insertion of CO2 into this series has also been studied, as a method of modelling the catalysis of methanol synthesis by the Cu/ZnO/Al2O3 ternary catalyst.

Research Interests

The aim of this project is to develop nanoparticle catalysts from organometallic precursors for the reduction of carbon dioxide to liquid fuels. Organometallic complexes are also being synthesised to model key intermediates in this reaction. 

Research interests

Mustafa K. Bayazit PhD, MSc (Hons),  BSc (Hons),  MRSC

His research focuses mainly on the chemistry of carbon nanotubes and fullerenes, and development of applications for these materials.
Other research interests include synthetic organic and polymer chemistry.
Project Supervisors: Milo Shaffer & Joachim Steinke

Composite Structural Power Materials

Sherry Hui Qian MSc BEng

This research project is to develop multifunctional structural composite supercapacitors, which could significantly reduce the weight and volume in traditional energy storage devices and simultaneously serve as the load-carrying structural body. The structural supercapacitor is consisted of modified polymeric electrolyte and two conductive carbon fabric electrodes, which are separated by a piece of electrically insulating glass fabric or polymer membrane.

Publications:

Qian, H.; Bismarck, A.; Greenhalgh, E. S.; Kalinka, G.; Shaffer, M. S. P., Hierarchical composites reinforced with carbon nanotube grafted fibers: The potential assessed at the single fiber level. Chem. Mater. 2008, 20, (5), 1862-1869.

Presentations at Conferences & Meetings:

Qian, H., Bismarck, A., Greenhalgh, E., Kalinka, G. and Shaffer, M.S.P. "Hierarchical composites reinforced with carbon nanotube grafted fibres" Carbon Nanotube (CNT)-Polymer Composites International Conference, Cambridge, UK, 10-12.09.2007.
Qian, H., Bismarck, A., Greenhalgh, E. and Shaffer, M.S.P. "Hierarchical composites reinforced with carbon nanotube grafted fibres" 13th European Conference on Composite Materials, Stockholm, Sweden, 2-5.06.2008.

Poster Presentation:

Qian, H., Bismarck, A., Greenhalgh, E., Kalinka, G. and Shaffer, M.S.P. "Hierarchical composites reinforced with carbon nanotube grafted fibres" MC8: Advancing Materials by Chemical Design", London, UK, 02.-05.2007.
Qian, H., Bismarck, A., Greenhalgh, E. and Shaffer, M.S.P. "Hierarchical composites reinforced with carbon nanotube grafted fibres" NT08: Ninth International Conference on the Science and Application of Nanotubes, Montpellier, France, June 29-July 4, 2008.

Separation of Single-Walled Carbon Nanotubes

Stephen Hodge MChem (Hons)
Project Supervisors: Milo Shaffer
Funding: Corrigan Scholarship

Semiconducing Single-Walled Carbon Nanotubes (SWNTs) are used in the fabrication of Field-Effect Transistor (FET) devices, electroluminescent and photovoltaic materials. Metallic SWNTs on the other hand can be used to develop nano-circuitry, transparent conductive coatings, and polymeric nanocomposites [1].

A heterogeneous mixture of these electronic types in such applications would not be useful. SWNTs are produced using various techniques, unfortunately giving distributions of semiconducting and metallic tubes in the ratio of approximately 2:1. To make full use of their outstanding properties, post-production enrichment or complete separation of these types would be a major breakthrough.

The aim of the project is to separate SWNTs by their electronic properties, which can then be used in developing controlled assemblies for future technologies based on nanomaterials.

References:
[1] L. Dai, Carbon Nanotechnology: Recent Developments in Chemistry, Physics, Materials Science and Device Applications, pp. 256, 2006, Elsevier.

Fundamental science research underpinning the development of new polymer composite

Graphenes have recently attracted attention as superior nanofiller candidates for making new polymer composites, owing to their extremely high mechanical, electrical, and thermal properties. Covalent functionalization of graphene with polymers is an attractive route to improved graphene/polymer composites. We have the studies on the synthesis of polymer grafted graphenes by new promising routes, and we focus on controlling the key parameters that control the reaction.

Takuya Morishita - Visiting Researcher