T. Dingemans (Theo)

Prof. Dr. T. Dingemans
Antoni van Leeuwenhoek professor
Faculty of Aerospace Engineering
Novel Aerospace Materials
Room 1.34
Kluyverweg 1
2629 HS Delft, The Netherlands
Tel: +31 (0)15 2784520
Fax. +31 (0)15 2784472
Email: t.j.dingemans@tudelft.nl

Associate Editor “High Performance Polymers” 

Biography
After obtaining my chemical engineering degree in Eindhoven, The Netherlands, I moved to the USA to pursue my Ph.D. degree under the direction of Professor Edward T. Samulski at the University of North Carolina at Chapel Hill. My work concentrated on the design and synthesis of novel molecular and polymeric non-linear liquid crystal geometries and I received my Ph.D. degree in 1998. In May 1998 was awarded a National Academy of Sciences NRC research fellowship, which allowed me to work at the National Aeronautic and Space Administration (NASA) in Langley, Virginia. During this period, I developed new liquid crystal thermosetting resin systems in support of NASA's second and third generation Reusable Launch Vehicle (RLV) program. In 2000 I became a permanent staff member at the Advanced Materials and Processing Branch and concentrated my research on developing alternate routes towards high-strength carbon nanostructures for structural applications and we developed novel all-aromatic thermotropic liquid crystalline polyetherimides. In January 2003 I moved back to the Netherlands and joined professor van der Zwaag's Fundamentals of Advanced Materials group and I'm supporting the development of new polymer systems for the aerospace industry. In 2006 the Dutch Science Council (NWO) awarded me a VIDI grant, which allows me to expand our research efforts in the field of high-performance polymers and fibers and composites thereof. In October 2009 I was appointed as the first Dutch Polymer Institute (DPI) Fellow and awarded a 1 million euro grant. This funding will be used to explore novel all-aromatic polymer chemistries for polymer photovoltaic, gas separation membrane and structural applications. 

Research Overview

Our research in the field of aerospace polymers concentrates on the development of new polymeric materials, which will ultimately lead to enabling technologies for the aerospace industry. Our current emphasis is on tailoring and understanding the structure-property relationships of such new polymers. Our research areas include liquid crystal network polymers (LCTs), matrix resins (PEEK-, PEKK-, PES-, PPS-, and epoxy-based) for composites and ballistics applications. Our all-aromatic ester-based nematic network polymers are of interest to the electronic and aerospace industry because these polymers exhibit a unique combination of thermal, physical and mechanical properties, i.e. Tg’s in excess of 200 ^oC, high storage moduli (> 2 GPa above 200 ^oC) and excellent strength and elongation at break (~10% at r.t.). When applied in carbon fiber based composites our polymers perform better than current state-of-the-art high-performance polymers such as PEI or PEEK: 

_{Literature, e.g.: Iqbal, M.; Norder, B.; Mendes, E.; Dingemans, T.J. J. Polm. Sci.: Part A: Polym. Chem., 2009, 47, 1368. Iqbal, M.; Dingemans, T.J., Eur. Polym. J., 2010,46(11), 2174.} 

We are also looking for new routes toward processable all-aromatic polyetherimides (PEIs). We were able to design and synthesize the first thermotropic liquid crystal PEI (all-aromatic, i.e. no aliphatic carbons are present), which can be processed into films and fibers from a stable and accessible nematic melt:

_{Literature: “Poly(ether imide)s from Diamines with Para, Meta, and Ortho-Arylene Substitutions: Synthesis, Characterization and Liquid Crystalline Properties.” Dingemans, T.J.; Mendes, E.; Hinkley, J.J.; Weiser, E.S.; StClair, T.L. Macromolecules, 2008, 41(7) 2474.} 

This LC PEI is currently under investigation as a matrix for O-D (C60), 1-D (SWCNTs) and 2-D (graphene) carbon nanocomposites. This class of polymers is not only of interest for structural and electronic applications.  Backbone modifications of this polymer have resulted in tough, flexible films with excellent gas separation (CO₂/CH₄) performance. We are currently exploring new polyimide chemistries for high-pressure and low-pressure gas separation applications.

_{Literature: “CO2 Sorption and Transport Behavior of ODPA-based Polyetherimide Polymer Films,” Simons, K.; Nijmeijer, K.; Sala, J.G.; van der Werf, H.; Benes, N.E.; Dingemans, T.J.; Wessling, M., Polymer, 2010, 51(17), 3907.}

We have recently started to expand the use of all-aromatic high-performance polymers towards polymer photovoltaic applications. Poly(azomethine)s, as shown below, are easy to perpare and their optoelectronic properties are promising.

_{Most recent publication: “All-aromatic Liquid Crystal Triphenylamine-based Poly(azomethine)s as Hole-transport Materials for Opto-electronic Applications,” Hindson, J.; Ulgut, B.; Friend, R.H.; Greenham, N.C.; Norder, B.; Kotlewski, A.; Dingemans, T.J., J. Mat. Chem. 2010, 20(5), 937.} 

In addition, we are closely collaborating with the Delft Reactor Institute (DRI) on the development of novel Metal Organic Frameworks (MOFs) for hydrogen storage applications. In order to achieve our goals we utilize a wide variety of modeling, synthetic and physical characterization tools:

_{Most recent publication: “Methyl Modified MOF-5: a Water Stable Hydrogen Storage Material,” Yang, J.; Grzech, A.; Mulder, F.M.; Dingemans, T.J., Chem. Comm. 2011, 47(18), 5244.} 

When it comes to the applications of our new materials, the polymer group works closely with the polymer group of professor Picken (TU-Delft, TNW) and other universities, such as Twente University of Technology, Eindhoven University of Technology, The University of North Carolina at Chapel Hill (USA), VanderBilt (USA) and Cambridge (GB). In addition, we believe it is important to collaborate with industry and other institutes. Our group has excellent relations with the Dutch Polymer Institute (DPI) and a variety of industrial partners, and includes NASA, ESA, Stork-Fokker, Airbus, Ten-Cate, Teijin, Corus and DOW.

Courses 

TN2071TU "Polymer science"

AE1202 "Material Science - Introduction to pPolymers"

AE1-701 "Material Science -Introduction to Polymers"
AE4-X02 "Designing Materials with Aerospace Specific Properties"
AE4-X05 "New Developments in Aerospace Polymers"

Publications

2011

“High-performance Composites based on All-aromatic Liquid Crystal Thermosets,” Iqbal, M.; Dingemans, T.J. Comp. Sci. and Technology, 2011, 71(6), 863.

“Methyl Modified MOF-5: a Water Stable Hydrogen Storage Material,” Yang, J.; Grzech, A.; Mulder, F.M.; Dingemans, T.J., Chem. Comm. 2011, 47(18), 5244.

“Thermotropic Liquid Crystalline Polymers as Protective Coatings for Aerospace ,” Guerriero, G.; Alderliesten, R.; Dingemans, T.J.; Benedictus, R., Prog. Org. Coat., 2011, 70(4), 245.

“Sulfonated Liquid Crystalline Polyesters as Resin Matrix for Single Wall Carbon Nanotube and Nanodiamond Composites,” Sordi, D.; de Ruijter, C.; Orlanducci, S.; Picken, S.J.; Sudholter, E.J.R.; Terranova, M.L.; de Smet, L.C.P.M.; Dingemans, T.J., J. Polym. Sci. Part A: Polym. Chem., 2011, 49(5), 1079.

“Elucidation of the Orientational Order and the Phase Diagram of p-quinquephenyl,” Kuiper, S.; Norder, B.; Jager, W.F.; Dingemans, T.J.; van Turnhout, J.; Picken, S.J., J. Phys. Chem. B., 2011, 115(6), 1416.

“Cybotaxis Dominates the Nematic Phase of Bent-core Mesogens: a Small-angle Diffuse X-ray Diffraction Study,” Francescangeli, O.; Vita, F.; Ferrero, C.; Dingemans, T.J.; Samulski, E.T., Soft Matter, 2011, 7(3), 895.

2010

“High Tg Nematic Thermosets: Synthesis, Characterization and Thermo-mechanical Properties,” Iqbal, M.; Dingemans, T.J., Eur. Polym. J., 2010, 46(11), 2174.

“Synthesis, Characterization and Properties of Branched All-aromatic Liquid Crystal Thermosets,” Iqbal, M.; Dingemans, T.J. High Perform. Polym., 2010, 22(8), 891.

“Rhodium-mediated Stereospecific Carbene Polymerization: from Homopolymers to Random and Block Copolymers,” Jellema, E.; Jongerius, A.L.; van Ekenstein, G.A.; Mookhoek, S.D.; Dingemans, T.J.; Reingruber, E.M.; Chojnacka, A.; Schoenmakers, P.J.; Sprenkels, R.; van Eck, E.R.H.; Reek, J.N.H.; de Bruin, B., Macromolecules, 2010, 43(21), 8892.

“All-aromatic Liquid Crystalline Thermosets as High Temperature Adhesives,” Iqbal, M.; Dingemans, T.J., Int. J. Adhesion and Adhesives, 2010, 30(8), 682.

“Development of Flexible LEO-resistant PI Films for Space Applications Using a Self-healing Mechanism by Surface-directed Phase Separation of Block Copolymers,” Fischer, H.R.; Tempelaars, K.; Kerpershoek, A.; Dingemans, T.J.; Iqbal, M.; van Lonkhuyzen, H.; Iwanowsky, B.; Semprimoschnig, C., ACS Appl. Materials&Interfaces, 2010, 2(8), 2218.

“CO2 Sorption and Transport Behavior of ODPA-based Polyetherimide Polymer Films,” Simons, K.; Nijmeijer, K.; Sala, J.G.; van der Werf, H.; Benes, N.E.; Dingemans, T.J.; Wessling, M., Polymer, 2010, 51(17), 3907.

“Hydrogen in the Metal Organic Framework Cr MIL-53,” Mulder, F.M.; Assfour, B.; Huot, J.; Dingemans, T.J.; Wagemaker, M.; Ramirez-Cuesta, A.J., J. Phys. Chem. Part C., 2010, 114(23), 10648.

“Liquid Crystal Thermoset Resins for High Temperature Composites and Adhesives,” Iqbal, M.; Dingemans, T.J., Plastics Rubber and Composites, 2010, 39(3-5), 189.

“The Synthesis and Characterization of Reactive Poly(p-phenylene terephthalamide)s: a Route Towards Compression Stable Aramid Fibres,” Knijnenberg, A.; Bos, J.; Dingemans, T.J., Polymer, 2010, 51(9), 1887.

“All-aromatic Liquid Crystal Triphenylamine-based Poly(azomethine)s as Hole-transport Materials for Opto-electronic Applications,” Hindson, J.; Ulgut, B.; Friend, R.H.; Greenham, N.C.; Norder, B.; Kotlewski, A.; Dingemans, T.J., J. Mat. Chem. 2010, 20(5), 937.

“Liquid Crystalline Matrix Polymers for Armid Ballistic Composites,” de Ruijter, C.; van der Zwaag, S.; Stolze, R.; Dingemans, T.J., Polym. Comp. 2010, 31(4), 612.

2009

“All-aromatic Liquid Crystalline Thermosets with High Glass Transition Temperatures,” Iqbal, M.; Norder, B.; Mendes, E.; Dingemans, T.J., J. Polym. Sci. Part A: Polym. Chem., 2009, 47, 1368.

“Kinetics of Fast and Slow Transitions in a Liquid Crystalline Polyimide,” van Mourik, P.; Norder, B.; Mendes, E.; Dingemans, T.J.; Picken, S.J. High Perform. Polym., 2009, 21, 16.

“Asymmetric Oxadiazole Mesogens as Candidates for Low-temperature Biaxial Nematics,” Zafiropoulos, A.; Lin, W.-B.; Samulski, E.T.; Picken, S.J. Dingemans, T.J. Liquid Crystals, 2009, 36, 649.

“Liquid Crystalline Properties of all Symmetric p-Phenylene and 2,5-Thiophene Pentamers.” Kuiper, S.; Jager, W.F.; Dingemans, T.J.; Picken, S.J. Liquid Crystals, 2009, 36, 389.

2008

“The Performance of Novel Polyetherimides in a Low Earth Orbit Environment”. Stienstra, M.M.; Dingemans, T.J.; van Eesbeek, M.; Rohr, T. High Performance Polymers, 2008, 20, 461.

“A DSC Study on Double Melting and the Kinetics of LCP Transitions in a Polyimide prepared from 1,2,4,5,-benzenetetracarboxylic dianhydride (PMDA) and 1,3-bis[4’-(4’’-aminophenoxy)cumyl]benzene (BACB) van Mourik, P.; Norder, B.; Mendes, E.; Dingemans, T.J.; Picken, S.J. High Performance Polymers, 2008, in press.

“New All-Aromatic Liquid Crystal Architectures,” Zafiropoulos, N.; Dingemans, T.J.; Li, Wen bin; Samulski, E.T.; Choi, E-Joon, Chem. Mater.,2008, 20, 3821.

“Poly(ether imide)s from Diamines with Para, Meta, and Ortho-Arylene Substitutions: Synthesis, Characterization and Liquid Crystalline Properties.” Dingemans, T.J.; Mendes, E.; Hinkley, J.J.; Weiser, E.S.; StClair, T.L. Macromolecules, 2008, 41(7) 2474.

“Hydrogen Adsorption Strength and Sites in the Metal Organic Framework MOF-5”. Mulder, F.M.; Dingemans, T.J.; Kearley, G.J., Chem. Phys., 2008, 351, 72.

“Novel Thermotropic Ester-based Polymers with Broad Nematic Processing Windows,” de Ruijter, C.; Bos, J.; Boerstoel, H.; Dingemans, T.J. J. Polm. Sci.: Part A: Polym. Chem., 2008, 46, 6565.

2006

Comment on “Thermotropic Biaxial Nematic Liquid Crystals.” Madsen, L.A.; Dingemans, T.J.; Nakata, M.; Samulski, E.T. Phys. Rev. Lett. 2006, 96(21), 219804.

“Synthesis and Characterization of a Novel Family of Ester-based, Wholly Aromatic, Liquid Crystalline Thermosets,” Knijnenberg, A.; Weiser, E.S.; StClair, T.L.; Dingemans, T.J. Macromolecules, 2006, 39(20), 6936.

“Uniaxial and Biaxial Nematic Liquid Crystals”. Dingemans, T.J.; Madsen, L.A.; Zafiropoulos, N.A.; Samulski, E.T. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, 2006, 364, 2681.

2005

“Optical Properties of N,N’-bis (3-phenoxy-3-phenoxy-phenoxy)-1,4,5,8-naphthalenetetra- carboxylic diimide by Spectroscopic Ellipsometry,” Yang, D.; Shrestha, R.P.; Dingemans, T.J.; Samulski, E.T.; Irene, E.A. Thin Solid Films, 2005, 500(1-2), 9.

“Hydrogen Adsorption Strength in the Metal Organic Framework MOF-5.”  Mulder, F.M.; Dingemans, T.J.; Kearley, G.J. J. Chem. Phys. 2005, 317, 113.

2004

“Wholly Aromatic Ether-imides. Potential Materials for n-Type Semiconductors,” Dingemans, T.J.; StClair, T.L.; Samulski, E.T., Chem. Mater. 2004, 16, 966.

“Thermotropic Biaxial Nematic Liquid Crystals,” Madsen, L.A.; Dingemans, T.J.; Nakata, M.; Samulski, E.T. Phys. Rev. Lett. 2004, 42(14), 145505.

“The Origin of Heterogeneous Relaxation in a Random Liquid Crystal Thermoset Copolyester,” Kearley, G.J.; Dingemans, T.J.; Kruglova, O.; Stride, J.; Mulder, F.M. Macromolecules, 2004, 37, 9855.

2003

“The Elusive Thermotropic Biaxial Nematic Phase in Rigid Bent-Core Molecules,” Acharya, B.R.; Primak, A.; Kumar, S.; Dingemans, T.J.; Samulski, E.T. Pramana–J. of Physics 2003, 61(2), 231.

“Optical Studies of the Nematic Phase of an Oxazole-Derived Bent-Core Liquid Crystal,” Olivares, J.A.; Stojadinovic, S.; Dingemans, T.J.; Sprunt, S.; Jákli, S. Phys. Rev. E. 2003, 68(4), 041704.

“Ordering of Apolar and Polar solutes in Nematic Solvents,” Dingemans, T.J.; Photinos, D.J.; Terzis, A.; Wutz, C.; Samulski, E.T. J. Chem. Phys. 2003, 118(15), 7046.

2002

“Liquid Crystals Derived from 2-Phenyl-Isoindoles. Synthesis and Characterization,” Jow, K.G.; Dingemans T.J. Liquid Crystals, 2002, 29, 573.

2001

“Javelins, Hockey Sticks and Boomerang-Shaped Liquid Crystals.  Structural Variations on p-Quinquephenyl,” Dingemans, T.J.; Samulski, E.T. J. Phys. Chem. B., 2001, 105, 8845.

2000

“Nonlinear Boomerang-Shaped Liquid Crystals Derived from 2,5-Bis(p-hydroxyphenyl)-1,3,4-oxadiazole,” Dingemans, T.J.; Samulski, E.T. Liquid Crystals, 2000, 27, 131.

“Spectral Tuning of Light Emitting Diodes with Phenyl-Thiophenes,” Dingemans, T.J.; Pedersen, L.G.; Samulski. E.T.; Bacher, A.; Thelakkat, M.; H.-W. Schmidt Synth. Met. 1999, 105, 171.

“Biaxial Smectic Phases in Non-Linear Mesogens: Optical Properties and Phase Behavior of an Oxadiazole Liquid Crystal,” Semmler, K.J.K.; Dingemans, T.J.; Samulski, E.T. Liquid Crystals, 1998, 24, 799.

“Ferroelectric Liquid Crystals Derived from Isoleucine I. Synthesis and Characterization,” Dingemans, T.J.; Poon, C.-D.; Samulski, E.T. Liquid Crystals, 1998, 24, 247.

“Ferroelectric Liquid Crystals Derived from Isoleucine II. Orientational Ordering by Carbon-13 Separated Local Field Spectroscopy,” Chen, A.; Poon, C.-D.; Dingemans, T.J.; Samulski, E.T. Liquid Crystals, 1998, 24, 255.

“Spontaneous Polarization in Tilted Smectics,” Photinos, D.J.; Terzis, A.F.; Samulski, E.T.; Dingemans, T.J.; Chen, A.; Poon, C.-D. Mol. Cryst. Liq. Cryst., 1997, 292, 265.

Book Chapters

• Dingemans, T.J. High-temperature Thermosets. In Comprehensive Polymer Science; Matyjaszewski, K., Moeller, M., Eds; Elsevier, 2011; Chapter 5.30
• Photinos, D.J.; Terzis, A.F.; Samulski, E.T.; Dingemans, T.J.; Chen, A.; Poon, C.-D. Spontaneous Polarization in Tilted Smectics. In Dynamics and Defects in Liquid Crystals; Cladis, P.E., Palffy-Muhoray, P., Eds; Gordon and Breach: Canada, 1998; p 293. 

Patents

1. WO2011035920(A1) “A method of preparing a polyetherimide coating on a metallic substrate.”
2. US Patent 7,964,698. “Wholly aromatic liquid crystalline polyetherimide (LC-PEI) resins.” 2011
3. EP2218807 (A1) “Heat treatment for increasing compressive strength of PPTA filaments.” 2010
4. WO2009143405(A2) “Synthesis of graphene sheets and nanoparticle composites comprising same.”
5. WO2009127532(A1) “Thermotropic copolyester, composite and its use, shaped article, core/sheath-yarn, woven fabric and moulded fabric.”
6. JP2009040804 (A) “Polyamide”
7. WO2007073184 (A1) “Load Sensor”
8. Patent application 2006-039489 (seke-613) Teijin Ltd. “Wholly aromatic polyamides with crosslinkable functionalities.” 2006
9. US Patent 6,939,940. “Liquid crystalline thermosets from oligo-ester, ester-imides, and ester-amides.” 2005
10. US Patent 7,507,784. “Liquid crystalline thermosets from oligo-ester, ester-imides, and ester-amides.” 2009