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Green Propellants
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Physical Chemistry.
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

To enable future environmentally friendly access to space by means of solid rocket propulsion a viable replacement to the hazardous ammonium perchlorate oxidizer is needed. Ammonium dinitramide (ADN) is one of few such compounds currently known. Unfortunately compatibility issues with many polymer binder systems and unexplained solid-state behavior have thus far hampered the development of ADN-based propellants.

Chapters one, two and three offer a general introduction to the thesis, and into relevant aspects of quantum chemistry and polymer chemistry.

Chapter four of this thesis presents extensive quantum chemical and spectroscopic studies that explain much of ADN’s anomalous reactivity, solid-state behavior and thermal stability. Polarization of surface dinitramide anions has been identified as the main reason for the decreased stability of solid ADN, and theoretical models have been developed to explain and predict the solid-state stability of general dinitramide salts. Experimental decomposition characteristics for ADN, such as activation energy and decomposition products, have been explained for different physical conditions. The reactivity of ADN towards many chemical groups is explained by ammonium-mediated conjugate addition reactions. It is predicted that ADN can be stabilized by changing the surface chemistry with additives, for example by using hydrogen bond donors, and by trapping radical intermediates using suitable amine-functionalities.

Chapter five presents several conceptual green energetic materials (GEMs), including different pentazolate derivatives, which have been subjected to thorough theoretical studies. One of these, trinitramide (TNA), has been synthesized and characterized by vibrational and nuclear magnetic resonance spectroscopy.

Finally, chapter six covers the synthesis of several polymeric materials based on polyoxetanes, which have been tested for compatibility with ADN. Successful formation of polymer matrices based on the ADN-compatible polyglycidyl azide polymer (GAP) has been demonstrated using a novel type of macromolecular curing agent. In light of these results further work towards ADN-propellants is strongly encouraged.

Place, publisher, year, edition, pages
Stockholm: KTH , 2010. , 77 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2010:43
Keyword [en]
Quantum chemistry, reaction kinetics, ammonium dinitramide, high energy density materials, rocket propellants, chemical spectroscopy, polymer synthesis
National Category
Theoretical Chemistry Physical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-25835ISBN: 978-91-7415-758-1 (print)OAI: oai:DiVA.org:kth-25835DiVA: diva2:360054
Public defence
2010-11-23, F1, Lindstedtsvägen 22, KTH, Stockholm, 09:30 (English)
Opponent
Supervisors
Note
QC 20101103Available from: 2010-11-03 Created: 2010-11-02 Last updated: 2011-03-21Bibliographically approved
List of papers
1. Dinitraminic acid (HDN) isomerization and self-decomposition revisited
Open this publication in new window or tab >>Dinitraminic acid (HDN) isomerization and self-decomposition revisited
2008 (English)In: Chemical Physics, ISSN 0301-0104, E-ISSN 1873-4421, Vol. 348, no 1-3, 53-60 p.Article in journal (Refereed) Published
Abstract [en]

Density functional theory (DFT) and the ab initio based CBS-QB3 method have been used to study possible decomposition pathways of dinitraminic acid HN(NO2)(2) (HDN) in gas-phase. The proton transfer isomer of HDN, O2NNN(O)OH, and its conformers can be formed and converted into each other through intra- and intermolecular proton transfer. The latter has been shown to proceed substantially faster via double proton transfer. The main mechanism for HDN decomposition is found to be initiated by a dissociation reaction, splitting of nitrogen dioxide from either HDN or the HDN isomer. This reaction has an activation enthalpy of 36.5 kcal/mol at the CBS-QB3 level, which is in good agreement with experimental estimates of the decomposition barrier.

Keyword
Ammonium dinitramide (ADN), Decomposition pathways, Double proton transfer, Solid rocket propellant, Quantum chemistry, DFT
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-17603 (URN)10.1016/j.chemphys.2008.02.044 (DOI)000256737200007 ()2-s2.0-43849097420 (Scopus ID)
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved
2. Novel 1,3-dipolar cycloadditions of dinitraminic acid: Implications for the chemical stability of ammonium dinitramide
Open this publication in new window or tab >>Novel 1,3-dipolar cycloadditions of dinitraminic acid: Implications for the chemical stability of ammonium dinitramide
2008 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 112, no 11, 2456-2463 p.Article in journal (Refereed) Published
Abstract [en]

Density functional theory at the B3LYP/6-31+G(d,p) level and ab initio calculations at the CBS-QB3 level have been used to analyze 1,3 dipolar cycloaddition reactions of dinitraminic acid (HDN) and its proton transfer isomer (HO(O)NNNO2). It is shown that the nitro group of HDN and the -N-N = O functionality of the isomer react readily with carbon-carbon double bonds. Cycloadditions of HDN are compared with the corresponding reactions with azides and nitrile oxides as 1,3 dipoles. It is shown that the reactivities of HDN and its proton transfer isomer decrease with increasing electron withdrawing power of the substituents adjacent to the carbon-carbon double bond. In contrast, for azides and nitrile oxides, the highest reactivity is obtained with dipolarophiles with strongly electron withdrawing substituents. The observed reactivity trends allow for the design of unsaturated compounds that are highly reactive toward azides and chemically inert toward dinitramides. This may be of relevance for the development of binder materials for ammonium dinitramide based propellants.

Identifiers
urn:nbn:se:kth:diva-17373 (URN)10.1021/jp710559g (DOI)000253946100035 ()2-s2.0-46849106047 (Scopus ID)
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved
3. The anomalous solid state decomposition of ammonium dinitramide: a matter of surface polarization
Open this publication in new window or tab >>The anomalous solid state decomposition of ammonium dinitramide: a matter of surface polarization
2009 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, no 20, 2896-2898 p.Article in journal (Refereed) Published
Abstract [en]

Polarized dinitramide anions on the surface of solid ammonium dinitramide (ADN) have a decomposition barrier that is reduced by 16 kcal mol(-1) and explain the anomalous solid state decomposition of ADN.

Identifiers
urn:nbn:se:kth:diva-18419 (URN)10.1039/b900915a (DOI)000266003700025 ()2-s2.0-67449102222 (Scopus ID)
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved
4. On the Anomalous Decomposition and Reactivity of Ammonium and Potassium Dinitramide
Open this publication in new window or tab >>On the Anomalous Decomposition and Reactivity of Ammonium and Potassium Dinitramide
2010 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 114, no 8, 2845-2854 p.Article in journal (Refereed) Published
Abstract [en]

Mechanistic pathways for the thermal decomposition of the solid-state energetic oxidizers ammonium dinitramide (ADN) and potassium dinitramide (KDN) have been deciphered by carefully considering previously performed experimental studies and using state of the art quantum chemical modeling of molecular clusters. Decomposition is governed by surface chemical processes, involving polarized (twisted) dinitramide anions of reduced stability. Under atmospheric and low-pressure conditions, the rate-determining step for the decomposition of these dinitramide salts is the dissociation into NO, and NNO2- radicals. The activation barriers for these steps are estimated to be 30 and 36 kcal/mol for ADN and KDN, respectively. The known stabilizing effect of water is explained by its hydrogen bonding ability, which counteracts polarization of surface dinitramides. The reactivity of ADN toward Various chemical environments is likely explained through metastable decomposition radical intermediates. Donation of hydrogen bonds, antioxidant character, and basicity are properties believed to correlate with a compound's ability to act as a stabilizer for dinitramide salts.

Keyword
FLEXIBLE ENERGETIC SALTS, SET MODEL CHEMISTRY, THERMAL-DECOMPOSITION, PART 2, STABILITY, MECHANISM, NITROGEN, ACID, EXPLOSIVES, BEHAVIOR
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-19244 (URN)10.1021/jp911277r (DOI)000274842200015 ()2-s2.0-77649314496 (Scopus ID)
Funder
Swedish Research Council
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved
5. The Molecular Surface Structure of Ammonium and Potassium Dinitramide: A Vibrational Sum Frequency Spectroscopy and Quantum Chemical Study
Open this publication in new window or tab >>The Molecular Surface Structure of Ammonium and Potassium Dinitramide: A Vibrational Sum Frequency Spectroscopy and Quantum Chemical Study
2011 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 115, no 21, 10588-10596 p.Article in journal (Refereed) Published
Abstract [en]

Vibrational sum frequency spectroscopy (VSFS) and quantum chemical modeling have been employed to investigate the molecular surface structure of ammonium and potassium dinitramide (ADN and KDN) crystals. Identification of key vibrational modes was made possible by performing density functional theory calculations of molecular clusters. The surface of KDN was found to be partly covered with a thin layer of the decomposition product KNO3, which due to its low thickness was not detectable by infrared and Raman spectroscopy. In contrast, ADN exhibited an extremely inhomogeneous surface, on which polarized dinitramide anions were present, possibly together with a thin layer of NH4NO3. The intertwined use of theoretical and experimental tools proved indispensable in the analysis of these complex surfaces. The experimental verification of polarized and destabilized dinitramide anions stresses the importance of designing surface-active polymer support, stabilizers, and/or coating agents, in order to enable environmentally friendly ADN-based solid-rocket propulsion.

Keyword
THERMAL-DECOMPOSITION, PHASE-TRANSITIONS, ENERGETIC MATERIALS, GENERATION, ADN, INTERFACE, MECHANISM, SALTS, EXPLOSIVES, PARTICLES
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-25888 (URN)10.1021/jp110050f (DOI)000290914700037 ()2-s2.0-79957854287 (Scopus ID)
Funder
Swedish Research CouncilEU, FP7, Seventh Framework Programme, FP7-PEOPLE-ERG-2008
Note
QC 20101103 Uppdaterad från submitted till published (20110627)Available from: 2010-11-03 Created: 2010-11-03 Last updated: 2017-12-12Bibliographically approved
6. Kinetic Stability and Propellant Performance of Green Energetic Materials
Open this publication in new window or tab >>Kinetic Stability and Propellant Performance of Green Energetic Materials
2010 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 16, 6590-6600 p.Article in journal (Refereed) Published
Abstract [en]

A thorough theoretical investigation of four promising green energetic materials is presented. The kinetic stability of the dinitramide, trinitrogen dioxide, pentazole, and oxopentazole anions has been evaluated in the gas phase and in solution by using high-level ab initio and DFT calculations. Theoretical UV spectra, solid-state heats of formation, density, as well as propellant performance for the corresponding ammonium salts are reported. All calculated properties for dinitramide are in excellent agreement with experimental data. The stability of the trinitrogen dioxide anion is deemed sufficient to enable synthesis at low temperature, with a barrier for decomposition of approximately 27.5 kcal mol(-1) in solution. Oxopentazolate is expected to be approximately 1200 times more stable than pentazolate in solution, with a barrier exceeding 30 kcal mol(-1), which should enable handling at room temperature. All compounds are predicted to provide high specific impulses when combined with aluminum fuel and a polymeric binder, and rival or surpass the performance of a corresponding ammonium perchlorate based propellant. The investigated substances are also excellent monopropellant candidates. Further study and attempted synthesis of these materials is merited.

Place, publisher, year, edition, pages
Weinheim: Wiley-VCH Verlag GmbH & Co. KGaA, 2010
Keyword
density functional calculations, energetic materials, green chemistry, kinetics, propellants
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-25830 (URN)10.1002/chem.201000413 (DOI)000279445400022 ()2-s2.0-77953163809 (Scopus ID)
Note
QC 20101103Available from: 2010-11-01 Created: 2010-11-01 Last updated: 2017-12-12Bibliographically approved
7. Envisioning New High Energy Density Materials: Stability, Detection and Performance
Open this publication in new window or tab >>Envisioning New High Energy Density Materials: Stability, Detection and Performance
2010 (English)In: 41st International  Annual Conference of  ICT (Energetic Materials) : , 2010, 9/1-9/11 p.Conference paper, Published paper (Other academic)
Abstract [en]

There is great need for new environmentally friendly energetic materials. One promising oxidizer currently under investigation for numerous applications is ammonium dinitramide (ADN, NH4N(NO2)2). After deciphering the thermal decomposition behavior of this salt theoretically, we have sought to find other all-nitrogen-oxygen compounds with similar advantageous properties. By considering electronic and structural characteristics related to the dinitramide, we have investigated a number of promising energetic anions using high-level density functional theory and ab initio methods.   Theoretical kinetic stabilities, UV-spectra, solid-state heats of formation, densities, as well as propellant performances of the corresponding ammonium salts with aluminum fuel are reported. The potential for significant performance gains is seen by comparison to standard ammonium perchlorate (AP) and ADN-formulations. Reasonable stabilities and straightforward detection at room temperature should encourage attempted synthesis of several of the investigated materials.

Identifiers
urn:nbn:se:kth:diva-25831 (URN)
Note
QC 20101103Available from: 2010-11-01 Created: 2010-11-01 Last updated: 2010-11-03Bibliographically approved
8. Experimental Detection of Trinitramide, N(NO2)(3)
Open this publication in new window or tab >>Experimental Detection of Trinitramide, N(NO2)(3)
2011 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 50, no 5, 1145-1148 p.Article in journal (Refereed) Published
Abstract [en]

Propeller propellant: The largest nitrogen oxide to date, trinitramide (TNA), has been prepared following extensive quantum chemical studies in which its kinetic stability and several physical properties were estimated. TNA was detected using IR and NMR spectroscopy. The compound is highly energetic and shows promise for cryogenic propulsion and as a reagent in high-energy-density material research.

Keyword
energetic materials, nitrogen oxides, propellants, quantum chemistry, trinitramide
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-31650 (URN)10.1002/anie.201007047 (DOI)000287160300028 ()2-s2.0-79251572073 (Scopus ID)
Funder
Swedish Research Council
Note
QC 20110321Available from: 2011-03-21 Created: 2011-03-21 Last updated: 2017-12-11Bibliographically approved
9. Tri-Block Copolymers of Polyethylene Glycol and Hyperbranched Poly-3-ethyl-3-(hydroxymethyl)oxetane Through Cationic Ring Opening Polymerization
Open this publication in new window or tab >>Tri-Block Copolymers of Polyethylene Glycol and Hyperbranched Poly-3-ethyl-3-(hydroxymethyl)oxetane Through Cationic Ring Opening Polymerization
2009 (English)In: Journal of Polymer Science Part A: Polymer Chemistry, ISSN 0887-624X, E-ISSN 1099-0518, Vol. 47, no 22, 6191-6200 p.Article in journal (Refereed) Published
Abstract [en]

Tri-block copolymers of linear poly(ethylene glycol) (PEG) and hyperbranched poly-3-ethyl-3-(hydroxymethyl)oxetane (poly-TMPO) are reported. The novel dumb-bell shaped polyethers were synthesized in bulk with cationic ring-opening polymerization utilizing BF3OEt2 as initiator, via drop-wise addition of the oxetane monomer. The thermal properties of the materials were successfully tuned by varying the amount of poly-TMPO attached to the PEG-chains, ranging from a melting point of 54 degrees C and a degree of crystallinity of 76% for pure PEG, to a melting point of 35 degrees C and a degree of crystallinity of 12% for the polyether copolymer having an average of 14 TMPO units per PEG chain. The materials are of relatively low polydispersity, with M-n/M-w ranging from 1.2 to 1.4. The materials have been evaluated for usage with the energetic oxidizer ammonium dinitramide.

Keyword
ADN, ammonium dinitramide, cationic polymerization, oxetane, polymerization, polyether, thermal properties, TMPO, multihydroxyl branched polyethers, aliphatic polyethers, polymers, 3-ethyl-3-(hydroxymethyl)oxetane, dendrimers, analog
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-18951 (URN)10.1002/pola.23662 (DOI)000271670000025 ()2-s2.0-70350230133 (Scopus ID)
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved
10. Design of an Ammonium Dinitramide Compatible Polymer Matrix
Open this publication in new window or tab >>Design of an Ammonium Dinitramide Compatible Polymer Matrix
(English)Manuscript (preprint) (Other academic)
Identifiers
urn:nbn:se:kth:diva-25891 (URN)
Note
QC 20101103Available from: 2010-11-03 Created: 2010-11-03 Last updated: 2010-11-03Bibliographically approved

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