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Aging Behavior of ADN Solid Rocket Propellants and Their Glass-Rubber Transition Characteristics

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Chemical Rocket Propulsion

Part of the book series: Springer Aerospace Technology ((SAT))

Abstract

Solid rocket propellants (SRPs) using ammonium dinitramide (ADN) as oxidizer are of interest because they belong to the classes of “green propellants” and signature-reduced propellants. The present study investigated several ADN-based rocket propellant formulations containing different prepolymers (glycidyl azide polymer (GAP); Desmophen® D2200), curing agents (bis-propargyl succinate (BPS); Desmodur® N3400), and filler types (aluminum (Al); octogen (HMX)). Ammonium perchlorate (AP)-based formulations have also been manufactured to make comparisons. SRP formulations have been investigated using dynamic mechanical analyses (DMA), mass loss, and tensile strength measurements. The accelerated aging program was between 60 and 85 °C with aging times adjusted to a thermal equivalent load of 15 years at 25 °C. The dynamic mechanical behavior of the ADN formulations differs from the hydroxyl-terminated polybutadiene (HTPB)-based materials: results show only one obvious peak in the loss factor curve instead of two. Fuel fillers, oxidizers, and curing agents have influences on the glass-rubber transition temperature (Tg) and the peak broadness. The loss factor peak of the GAP formulations is broader than the one of the Desmophen® formulations. Lowering of Tg by using AP instead of ADN was found. DMA investigations revealed distinct changes in the shape of the loss factor curves. Their detailed analyses with exponentially modified Gaussian (EMG) functions showed that the loss factor curves have two parts with different molecular mobilities during the transition of the material from energy-elastic (glassy) to the entropy-elastic (rubbery) state. Aging acts strongly on the part with restricted mobility.

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Abbreviations

ADN:

Ammonium dinitramide

Al:

Aluminum

AN:

Ammonium nitrate

AP:

Ammonium perchlorate, sometimes also named APC

BLC:

Baseline correction

BPS:

Bis-propargyl succinate, a non-isocyanate curing agent, applicable with GAP; curing based on the Huisgen reaction between the ethine groups of BPS and organic azides of GAP

CRP:

Composite rocket propellant

D2200:

Polyester polyol type, Desmophen® D2200, inert binder

DMA:

Dynamic mechanical analysis

DSC:

Differential scanning calorimeter

Ea :

Activation energy, [kJ·mol−1]

EMG:

Exponential modified Gauss function

G′:

Storage shear modulus, determined by torsion DMA, [Pa]

G″:

Loss shear modulus, determined by torsion DMA, [Pa]

GAP:

Glycidyl azide polymer, energetic binder, polyether type

GvH:

Generalized van’t Hoff rule

HCl:

Hydrogen chloride

HDI:

Hexane diisocyanate, curing agent

HEC:

High explosive charge

HMX:

Octogen, energetic filler

HNF:

Hydrazinium nitroformate

HTPB:

Hydroxyl terminated polybutadiene, inert binder, butadiene based

HX-880:

Bonding agent, N,N-bis (2-hydroxyethyl) glycol amide, referred as BHEGA, delivered from MACH I company (HX-880 may act also as a cross-linker)

ICT:

Fraunhofer Institute of Chemical Technology

IPDI:

Isophorone diisocyanate, curing agent to produce PUR elastomers

Is :

Gravimetric or mass specific impulse, [s], [Ns kg−1]

JANNAF:

Joint Army, Navy, NASA, Air Force Interagency Propulsion Committee

ML:

Mass loss

N100:

Polyisocyanate curing agent, HDI-based, Desmodur® N100, to produce PUR elastomers

N3400:

Polyisocyanate curing agent, HDI-based, Desmodur® N3400, to produce PUR elastomers

nAl:

Nanometer sized Al powder

NCO:

Isocyanate group, also a functional group in PUR formation

OH:

Hydroxyl group, also a functional group in isocyanate curing

PUR:

Polyurethane

Req:

Equivalent ratio between two reactive sites, here mostly between OH groups and NCO groups to form polyurethane elastomers taking into account the molecular conditions of the substances carrying these functional groups, [−]

RP:

Rocket propellant

SEM:

Scanning electron microscopy

SRP:

Solid rocket propellant

tan δ:

Loss factor, tanδ = G′′/G′ = E′′/E′, [−]

TEL:

Thermal equivalent load

Tg,DMA,f :

Glass-to-rubber transition temperature determined by DMA, [°C]; full information includes also the used excitation frequency f, Tg,DMA, xxHz

Tg,DSC,h :

Glass-to-rubber transition temperature determined by DSC, [°C]; full information includes also the used heat rate h, Tg,DSC, xx°C/min

TMETN:

Trimethylolethyltrinitrate, liquid energetic filler, in part acting as plasticizer

μAl:

Micrometer sized Al powder

–C≡C:

Ethine group, also a functional group in azide curing

–N=N=N:

Azide group, also a functional group in BPS curing (1,3 dipolar cycloaddition)

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Acknowledgments

This work was carried out as part of the PhD thesis of Sara Cerri done at Politecnico di Milano, Energy Department (Italy), and Fraunhofer ICT (Germany) [40]. Authors would like to thank both institutions. Moreover, authors would also like to thank our colleague Dr. Klaus Menke for the careful manufacturing of the solid propellant formulations and for providing information about the ingredients.

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Authors and Affiliations

  1. Fraunhofer-Institut für Chemische Technologie (ICT), Energetic Materials, 76318, Pfinztal, Germany

    Manfred A. Bohn

  2. SC Consulting, 28060, Cureggio, NO, Italy

    Sara Cerri

Authors
  1. Manfred A. Bohn
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  2. Sara Cerri
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Corresponding author

Correspondence to Manfred A. Bohn .

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Editors and Affiliations

  1. Space Propulsion Laboratory (SPLab) Department of Aerospace Science and Technology, Politecnico di Milano, Milan, Italy

    Luigi T. De Luca

  2. Institute of Space and Astronautical Science (ISAS), Japan Aerospace Exploration Agency (JAXA), Sagamihara, Japan

    Toru Shimada

  3. Department of Chemical Engineering, Mendeleev University of Chemical Technology, Moscow, Russia

    Valery P. Sinditskii

  4. The Inner Arch, Poissy, France

    Max Calabro

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Bohn, M.A., Cerri, S. (2017). Aging Behavior of ADN Solid Rocket Propellants and Their Glass-Rubber Transition Characteristics. In: De Luca, L., Shimada, T., Sinditskii, V., Calabro, M. (eds) Chemical Rocket Propulsion. Springer Aerospace Technology. Springer, Cham. https://doi.org/10.1007/978-3-319-27748-6_32

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  • DOI: https://doi.org/10.1007/978-3-319-27748-6_32

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