Full Paper

DOI: 10.1002/prep.201600058

Understanding the Compatibility of the Energetic Binder

PolyNIMMO with Energetic Plasticizers: Experimental and
DFT Studies
Sujit Kumar Shee,*[a] Priya Nitin Shah,[a] Javaid Athar,[a] Abhijit Dey,[a] R. R. Soman,[a] Arun Kanti Sikder,[a]
Suman Pawar,[a] and Shaibal Banerjee*[b]

Abstract: The development of energetic binders with suita- NIMMO with the plasticizers. The glass transition tempera-
ble energetic plasticizers is required to enhance the me- tures of the blends were determined by low temperature
chanical properties and to reduce the glass transition tem- DSC and showed desirable lowering of glass transition tem-
perature of propellant and explosive formulations. The perature with single peak. The rheological evaluation re-
compatibility of the energetic binder poly(3-nitratomethyl- vealed that the viscosity of the binder is considerably
3-methyloxetane) (polyNIMMO) with five different energetic lowered by means of flow behavior upon addition of 20 %
plasticizers viz. bis(2,2-dinitro propyl)acetal (BDNPA), dini- (w/w) plasticizer. The addition of BuNENA and DEGDN has
tro-diaza-alkanes (DNDA-57), 1,2,4-butanetriol trinitrate maximum effect on the lowering of viscosity of polyNIM-
(BTTN), N-N-butyl-N‘(2-nitroxy-ethyl) nitramine (BuNENA) MO. The predicted relative trend of interaction energies be-
and diethyleneglycoldinitrate (DEGDN) was studied by dif- tween plasticizer and binder is well correlated with the cor-
ferential scanning calorimetry (DSC), rheology, and DFT responding trend of viscosity of binder/plasticizer blends.
methods. The results obtained for the pure binder were These experimental studies verified by theoretical methods
compared with the results obtained for the binder/plasticiz- are valuable to design practical blends of new plasticizers
er blend in regard of the decomposition temperature and and binders.
the format of the peak indicated the compatibility of poly-
Keywords: Thermochemistry · Glass transition temperature · Rheology · Plasticizing effect · Computational study

Introduction

High energy materials are rarely used in their pure form; become an important polymer worth investigating [7, 8].
rather they are used in combination with the inert, as well The uncured material is a high viscosity liquid with
as other energetic materials, for civilian and military appli- a yellow, transparent color and slight odor and is also ex-
cations of explosives and propellants. Since polymeric pected to reduce propellant vulnerability against accidental
binder is one of the major ingredients of propellant and ex- but violent stimulation [9]. The energetic binder poly(3-ni-
plosive formulations, it is very important to choose suitable tratomethyl-3-methyloxetane) (1) is a versatile energetic
binder. Although the workhorse binder, hydroxyl-terminat- pre-polymer consisting of a nitrated ester group where X
ed polybutadiene (HTPB), has excellent elastomeric proper-
ties, it contains little energy and requires high solid loading
[a] S. K. Shee, P. N. Shah, J. Athar, A. Dey, R. R. Soman, A. K. Sikder,
to have a better performance [1, 2]. Energy can be added S. Pawar
to the explosive or propellant system through the use of Energetic Materials Research Division
energetic binder which enables lower solid loading with High Energy Materials Research Laboratory (Defence Research &
improved performance [3, 4]. Unsatisfactory mechanical Development Organisation
properties at low temperatures rules out the use of an en- Pune, 411 021, India
*e-mail: sujitvision2020@gmail.com
ergetic binder GAP (glycidyl azide polymer) in spite of its
high energy content [5]. The aim of insensitive and ener- [b] S. Banerjee
getic binder is to use it as an ingredient to bind with other Defence Institute of Advanced Technology (Defence Research &
Development Organisation)
explosive ingredients and to decrease the likelihood of su- Girinagar, Pune, 411 025, India
perfluous and unanticipated detonation from external stim- *e-mail: shaibal.b2001@gmail.com
uli such as shock, weapon fragments, and heat [6]. Supporting information for this article is available on the WWW
PolyNIMMO has emerged as a promising energetic under http://dx.doi.org/10.1002/prep.201600058 or from the
binder for insensitive munitions and therefore, it has author.

DOI: 10.1002/prep.201600058  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim &1&
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Full Paper S. K. Shee, P. N. Shah, J. Athar, A. Dey, R. R. Soman, A. K. Sikder, S. Pawar, S. Banerjee

and Y are either continuations of the polymeric chain or ent purposes, such as for coatings, films, milling, and
terminating groups. Several synthetic processes for poly- mixing, to obtain a desirable degree of flexibility over
NIMMO and its corresponding monomer have been report- a broad range of operational temperatures. Compatibility
ed in the literature [10, 11]. The scale-up process of poly- testing of ingredients of explosives and propellant compo-
NIMMO has been carried out successfully and the technolo- sitions is done to ensure safety during storage and reliabili-
gy has been transferred for commercial production [8, 12]. ty in services, by determining whether their properties ad-
The results reported by Waring et al. show that polyNIMMO versely are affected by any of the materials used near or in
is very stable for gamma radiation up to doses of 250 kGy contact with them [19]. Nitrate ester plasticized polyether
[13]. The approach of formulating high energy LOVA pro- (NEPE) propellants and other double-based propellants can
pellants, based on the energetic binder polyNIMMO in improve their mechanical properties at low temperature,
amalgamation with various fillers and plasticizers, has been which makes them safer to use due to the incorporation of
examined by Leach et al. by employing low response to nitrate ester plasticizer [20–23]. To understand the compati-
small scale, shaped charge attack test method. The estab- bility of polyNIMMO binder with different plasticizers
lished approach has shown that the rubbery nature of the (Scheme 1), thermal, rheological, and computational studies
polyNIMMO binder desensitizes the main energetic filler, at the molecular level may be of useful to get a better in-
HMX and the content of binder is kept to a minimum as it sight for the selection of a suitable plasticizer [24–26].
is energetic itself [14]. The compatibility of filler
2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane
(CL-20) with polyNIMMO has been examined [15]. However,
no study has been performed for the compatibility of poly-
NIMMO with plasticizers, which is crucial while processing.
The solid loading, which contributes to the rheological
properties and therefore affects the processability and me-
chanical properties of the propellants, is largely determined
by the polymeric binder used. Furthermore, the reduction
of viscosity of polyNIMMO facilitates high solid loading in
both fuel and oxidizer of the propellant. The knowledge of
the compatibility is vital for the design and preparation of
propellants and high explosives possessing desirable me-
chanical, rheological and ballistic properties suitable for
specific purposes [16]. The polymer consisting of nitrate
ester linkage ( ONO2) side chain imparts energy to the
polymer, but is also a likely source of chemical degradation
[9]. PolyNIMMO has a glass transition temperature (Tg) at
Scheme 1. Molecular structures of energetic binder polyNIMMO
approximately 33 8C. The glass transition temperature of (dimeric form) and all energetic plasticizers.
good binder must be lower than the service temperature,
(usually 40 8C to 55 8C depending on the application),
especially when the propellant is case-bonded, to avoid
Methodology
failure of the motor during firing.
The energetic binder polyNIMMO was synthesized and
characterized as reported in the literature [8, 10–12]. Ener-
getic plasticizers viz. bis(2,2-dinitro propyl) acetal (BDNPA)
[27, 28], dinitro-diaza-alkanes (DNDA-57) [29], 1,2,4-butane-
triol trinitrate (BTTN) [30], N-N-butyl-N’(2-nitroxy-ethyl) nitr-
amine (BuNENA) [31] and diethylene-glycol dinitrate
(DEGDN) [30] were also synthesized and characterized in
lab by reported methods. Other chemicals and reagents
used in this study were purchased and used as such. All
To obtain a high specific impulse, it is always recom- the energetic plasticizers (20 % w/w) were hand mixed with
mended to plasticize with optimum energetic plasticizers, polyNIMMO (80 % w/w) and kept at room temperature.
which have a low glass transition temperature, low viscosi- After 24 h, these blends were observed for any phase sepa-
ty, low ability to migrate, high oxygen balance, and which ration and then used for further studies, as mentioned in
should also be thermally stable [17]. A plasticizer has usual- the Results and Discussion section. DSC samples (weights
ly changed the properties by reducing stiffness and permit- between 5 to 10 mg) were sealed in an aluminum pan.
ting easier processing of a given polymer/plasticizer system Thermal decomposition and glass transition temperatures
[18]. Plasticizer has been used in different fields for differ- of all polymer blends were determined in the temperature

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Compatibility of the Energetic Binder PolyNIMMO with Energetic Plasticizers

range of 60 8C to 400 8C, with a constant heating rate of

10 K min 1 in a nitrogen atmosphere, using Perkin-Elmer
DSC (DSC-7) and TA instrument DSC Q20 respectively. Tg
was determined as the intersection of the low temperature
side of the baseline with the tangent through the inflection
associated with the rising heat capacity. A stress control
Rheometer (Model-Stress Tech, Rheologica Instruments AB,
Sweden) was used to measure the shear rate sweep tests.
The instrument was equipped with a 20 mm diameter par-
allel plate (20 ETC) at gap of 0.5 mm. The steady shear data
were collected from shear rate sweep from 1 to 100 s 1. All
experiments were carried out at a constant temperature of
30 8C. A pre-shear period, 30 s, was used to standardize the
handling of samples before measurement.
For the computational studies, all geometries were fully
optimized by employing popular Becke three-parameter ex-
change functional and the nonlocal correlation functional Figure 1. DSC curves (Heat flow endo up vs. temperature) of pure
of the Lee, Yang, and Parr (B3LYP) method [32, 33] in con- polyNIMMO (PLN) and polyNIMMO mixed with different plasticiz-
junction with a 6-311(d,p) basis set. Such types of method ers.
have already been employed in other works where inter-
molecular interactions play a role [34–36]. Harmonic fre-
quency calculations at the same level of theory were used main decomposition process in the temperature range of
to characterize the stationary points as minima and to pro- 195–225 8C with only one exothermic peak temperature at
vide thermal and zero point corrections. Full geometry op- 216.5 8C. It has been observed that the decomposition tem-
timization calculations were also performed at the M052X/ perature (Tmax) i.e. 216.5 8C, is not effectively distorted by
6-311G(d.p) level to describe noncovalent interactions the addition of 20 % of energetic plasticizer in all the cases.
better than density functional, which are currently in Resultant temperatures of decomposition remained unaf-
common use. All quantum chemical calculations were per- fected when the plasticizer was added. Therefore, all the
formed using a Gaussian 09, Revision C.01 program [37]. plasticizers could be considered as compatible with poly-
The interaction energy (DEi°) model is a powerful tool to NIMMO, as per the safety norms. The decomposition
explain the reactivity in bimolecular reactions [38,39]. By energy of polyNIMMO decreases with the addition of plasti-
definition, the interaction energy is EInter = EBlend (EBinder + cizers due to the polar interactions between the carbon
EPlasticizer). and the nitrate ester group as it depends on the strength
of the interaction between binder and plasticizer [43]. Ac-
cording to evaluated standards [44, 45] of compatibility for
Results and Discussion explosive and it’s contact materials, the decomposition of
polyNIMMO by the addition of plasticizers is minimal with
Thermal Studies
exothermic peak expanse from 214 8C to 217 8C. This
Thermal analysis was performed to observe any alteration means; that all the binary systems, viz. polyNIMMO/BDNPA,
in the decomposition pattern of the binder entity in the polyNIMMO/BuNENA, polyNIMMO/BTTN, polyNIMMO/
presence and absence of plasticizer. To understand the DEGDN, and polyNIMMO/DNDA-57 have a deviation of
plasticizing effect of given plasticizers on polyNIMMO  2 8C (falls in “A” rating) from Tmax, which is acceptable as
binder, thermal decomposition temperature (Tmax) [1] and far as compatibility is concerned. Therefore, the results,
glass transition temperature (Tg) were determined with dif- such as lack of variation in the peak format, absence of
ferential scanning calorimeter (DSC). For this purpose, all new peaks, and the similar decomposition peak pattern
the plasticizers under consideration were mixed with the with and without plasticizer, point towards the compatibili-
binder thoroughly at a ratio of 80 : 20 (binder:plasticizer) as ty of polyNIMMO with the studied energetic plasticizers
suggested in the literature [40–42]. After thorough mixing (Table 1).
of various energetic plasticizers (20 %) to the polyNIMMO The glass transition temperature (Tg) of some mixtures of
binder (80 %) individually, no phase separation or any other polymer and plasticizer for the effect of monomer mixture
sign of heterogeneity was observed at room temperature, on the Tg’s of copolymers systems have been studied in the
even after 24 h or more, signifying the physical compatibili- literature [12, 46–51]. Since, the molecular flexibility of the
ty of the studied energetic plasticizers with polyNIMMO plasticizer is an important mechanism for altering the brit-
binder. The decomposition peak profiles of DSC analysis are tleness of polymers via plasticization, the implication of this
shown in Figure 1, along with the corresponding peak tem- observation can be obtained from the deviations of Tg. In
peratures (Tmax). The DSC curve of polyNIMMO shows the the presented study, the effect of adding plasticizer was

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Table 1. Evaluated standards of compatibility for explosives and contacted materials.

SNO Deviation from Tmax [8C] Rating Description
1 2 A Safe for use in any explosive formulation
2 3–5 B Safe for testing purposes in a short period of time
3 6–15 C Not recommended for use with explosive items
4 > 15 D Hazardous. Should not be used under any condition

observed in terms of Tg of polyNIMMO, which again indi- thermodynamic compatibility of energetic binder with en-
cates the compatibility of plasticizers with polyNIMMO. ergetic plasticizers [41, 49, 50].
Maximum lowering of Tg ( 52 8C) was observed in the
cases of BuNENA and DEGDN, where as BDNPA has shown
Rheological Studies
minimum lowering of Tg at 38.85 8C (Figure 2). BTTN and
DNDA-57 have shown moderate lowering of Tg at A binder/plasticizer system is said to be compatible if it
46.41 8C and 43.12 8C, respectively, All these polyNIM- forms a homogeneous mixture for a long time. The maxi-
MO/plasticizer blends give single and reduced glass transi- mum amount of a plasticizer retained by a binder system,
tion temperatures, which confirms the compatibility of pol- without oozing out during storage when amalgamated
yNIMMO binder with the plasticizers. The reduction in co- into a polymeric binder, is defined as the limit of compati-
hesive forces of attraction between polymer chains increas- bility of that plasticizer [51]. Rheological study of the com-
es chain mobility leading to lowering of Tg when plasticiz- patibility of energetic binder polyNIMMO with all the five
ers are incorporated in to the polymer. Thus, it is the plasticizers was performed using the same samples as the
plasticizer’s function to reduce the forces between the above thermal studies. A shear rate sweep from 1 to
macromolecules and thereby increase chain mobility, 100 S 1 was conducted at a constant temperature of 30 8C
reduce viscosity, which, in turn, leads to a “softening” or to study the flow behavior of polyNIMMO and polyNIMMO/
“plasticization” of the polymeric material [12, 47, 48]. The plasticizer blends (Figure 3). Newtonian behavior was ob-
single Tg value for all combinations has further confirms the served for pure polyNIMMO with a constant viscosity of
presence of a single phase homogeneous system and the 15460 cPs at 30 8C, at a varying shear rate. Such a higher

Figure 2. Low temperature DSC curves of pure polyNIMMO and polyNIMMO mixed with different plasticizers.

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Compatibility of the Energetic Binder PolyNIMMO with Energetic Plasticizers

ried out. As in the experimental study, all five energetic

plasticizers viz. DNDA-57, BuNENA, DEGDN, BTTN, and
BDNPA were considered. To emulate the polyNIMMO poly-
mer, its corresponding dimeric unit was used for comput-
ing interaction energies with plasticizers as mentioned ear-
lier. Since, DNDA-57 plasticizer is a mixture of three homo-
log compounds viz. DNDA-5, DNDA-6, and DNDA-7
(Scheme 2), DNDA-6 was considered to study the compati-

Figure 3. Shear rate sweep test of pure polyNIMMO and polyNIM-

MO mixed with different plasticizers.

viscosity of virgin polyNIMMO may not be appropriate for

solid loadings of more than 50 % (w/w). The viscosity of
binder/plasticizer blend was reduced drastically, along with
an increase in flow behavior after the addition of 20 % (w/
w) energetic plasticizers. The blends showed different vis- Scheme 2. Chemical structures of components of DNDA-57 plasti-
cosity although the quantities of the plasticizer added to cizer.
the binder remained same. The addition of DEGDN and
BuNENA imparts close and maximum effect in reducing the
viscosity upto 1720 cPs and 1808 cPs, respectively, bility of DNDA-57 with polyNIMMO, as it contains both
(Figure 3). A similar effect is also observed with other plasti- methyl and ethyl groups at its terminal positions. The
cizers, but not to the same extent. The plasticizers BDNPA stable forms of binder and plasticizers obtained through
and DNDA-57 lowered the viscosity of the polymer poly- optimization were considered for the examination of their
NIMMO to 7169 cPs and 3476 cPs, respectively, whereas, mutual compatibility via intermolecular interaction studies.
BTTN lowered the viscosity of polyNIMMO to 4897 cPs from At this point, the interactions of plasticizer with two seg-
15460 cPs. The observed decrease in viscosity and increase ments of polyNIMMO-2 were explored, taking into account
in flow behavior is attributed to the improved plasticizing several different geometries of interaction. The optimized
effect on the polymer. The compatibility of the binary sys- structures of adducts between two polyNIMMO-2 segments
tems of polyNIMMO/plasticizer increase in the order: and plasticizer as the models of binder/plasticizer system
BDNPA < DNDA-57 < BTTN < BuNENA  DEGDN. are presented in Figure 4, along with the resultant inter
The plasticizer properties, ability of lowering the Tg of molecular interactions indicated with dotted lines. Two di-
the binder, having Tmax values within the standards of com- meric segments of polyNIMMO and individual plasticizer
patibility and considerably lowering the viscosity, makes all were brought together manually in a Gaussian visualizing
five plasticizers, DEGDN, BuNENA, BDNPA, BTTN, and tool and allowed them to optimize towards possible
DNDA-57, suitable as potential candidates for energetic modes of interactions. The relative reactivity of the five
binder polyNIMMO. Moreover, the BuNENA/polyNIMMO plasticizers with polyNIMMO-2 was examined by computing
and DEGDN/polyNIMMO blends show a maximum lowering interaction energies for the purpose of evaluating their re-
of glass transition temperature and viscosity. These desira- spective compatibility properties towards polyNIMMO. In
ble characteristic properties of BuNENA and DEGDN make all cases, the optimization of the various starting geome-
them the most suitable plasticizers for polyNIMMO for ach- tries converged to different interaction modes, in which the
ieving maximum solid loading and better processing. plasticizer molecule was oriented by the C H groups or by
the NO2 group in between two binder fragments. The com-
puted intermolecular distances and free energies reveal
DFT Studies
that the molecular C H groups play the main role in the in-
To predict the factors responsible for the resultant flow be- teraction of plasticizer, which is oriented mainly by the C H
havior of binder/plasticizer mixtures and the physical com- groups towards two segments of polyNIMMO-2. The two
patibility of polymeric networks of binder with the energet- fragments of polyNIMMO-2 form a complex with BDNPA
ic plasticizer molecules, it is crucial to understand the inter- through six C H···O type interactions, (2.287 , 2.291 ,
molecular interactions between binder and plasticizer. 2.346 , 2.519 , 2.512  and 2.535 ) and two O H···O
Therefore, quantum chemical calculations employing the type hydrogen bonding interactions at a distances of
DFT method at M052X/6-311G(d,p) level of theory were car- 2.128  and 2.139 . A complex of two molecules of poly-

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computed interaction energy results, in terms of electronic

and Gibbs free energies, suggest that BDNPA prefers to in-
teract more strongly with polyNIMMO-2, whereas DEGDN
and BuNENA have the same or less affinity to interact
(Table 2). The computed interaction energy trend of ad-
ducts of polyNIMMO2-plasticizer-polyNIMMO2 was found
to be well matched with the experimental viscosity trend.
Therefore, the interaction ability of plasticizers predicted
using two segments of polyNIMMO-2 may be of more utili-
ty in mimicking the plasticizer introduction between the
polymeric segments of the binder.
The introduction of plasticizer in between the polymeric
layers of binder causes weakening the intermolecular inter-
actions of polymer segments. Consequently, binder/plasti-
cizer mix held loosely as compared to the pure binder.
Herein, the binding energies of intermolecular interactions
of polymer segments in presence of plasticizer are report-
ed. More negative value of such binding energy indicates
the tightly holding of polymer chains suggesting relatively
higher viscosity of resultant binder/plasticizer mix. Similarly,
lower negative value of binding energy indicates the loose-
ly holding of polymer chains suggesting relatively lower
viscosity of resultant binder/plasticizer mix. Based on this
Figure 4. Optimized geometries of adducts of two segments of
criterion and the binding energies listed in Table 2, the an-
polyNIMMO dimer and energetic plasticizer at M052X/6-311G(d,p)
level. (grey: carbon; dark grey: oxygen; black: nitrogen; white: hy- ticipated relative trend of resultant viscosity of binder/plas-
drogen). ticizer blend exactly matches with the viscosity trend ob-
tained from experimental rheological study.

NIMMO-2 with BTTN involves four C H···O type interac-

tions (2.385 , 2.408 , 2.563 , and 2.456 ), and two O
Conclusions
H···O (2.345  and 2.077 ) type hydrogen bonding interac-
tions. A complex of polyNIMMO-2 and BuNENA consists of To understand the compatibility of binder/plasticizer, the
two hydrogen bonds (2.107  and 2.000 ), and two weak effects of the addition of five different energetic plasticiz-
C H···O type interactions, (2.534 , 2.604 , and 2.580 ). ers, viz. BDNPA, DNDA-57, BuNENA, BTTN, and DEGDN, in
Similarly, the distances 2.354 , 2.298 , and 2.540  corre- the energetic binder polyNIMMO were studied in detail,
spond to C H···O type interactions, whereas 2.025  and employing thermal, rheological, and computational tech-
2.008  correspond to O H···O interactions of hydrogen niques. The experimental studies revealed that all five plas-
bonding in the case of DNDA-57. DEGDN shows two C ticizers are compatible with the energetic binder polyNIM-
H···O interactions, (2.521  and 2.522 ), and two O MO. Negligible deviation from decomposition temperature
H···O type interactions, (2.089  and 2.107 ), as observed and lowering of glass transition temperature (Tg) were seen
in the case of BDNPA. The electronic interaction energies for binder when plasticizers were added. Among all five
(kJ mol 1) for the formation of the complex of polyNIMMO- plasticizers, BuNENA and DEGDN lower Tg to a maximum
2 with different plasticizers, viz. BDNPA, DNDA-57, BTTN, extent (about 52.0 8C), whereas BTTN lowers to minimum
BuNENA, and DEGDN, were found to be 170.7, 133.5, extent ( 38.9 8C). Similarly, a maximum increase in flow be-
111.7, 108.4, and 106.7, respectively (Table 2). The havior (lowering of viscosity) was observed by the addition

Table 2. Electronic and Gibbs free energies [kJ mol 1] computed at two different levels of theories for the interaction between plasticizers
and binder (polyNIMMO-2).
SNO Plasticizer B3LYP/6-311G(d,p) M052X/6-311G(d,p)
Electronic energy Free energy Electronic energy Free energy
1 BDNPA 72.0 45.6 170.7 1.3
2 DNDA-57 89.1 28.5 133.5 3.8
3 BTTN 53.1 63.2 111.7 41.8
4 BuNENA 63.2 42.3 108.4 45.6
5 DEGDN 58.2 57.3 106.7 46.4

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Compatibility of the Energetic Binder PolyNIMMO with Energetic Plasticizers

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&8& www.pep.wiley-vch.de  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/prep.201600058
ÝÝ These are not the final page numbers!
Compatibility of the Energetic Binder PolyNIMMO with Energetic Plasticizers

FULL PAPERS
S. K. Shee,* P. N. Shah, J. Athar, A. Dey,
R. R. Soman, A. K. Sikder, S. Pawar,
S. Banerjee*
&& – &&
Understanding the Compatibility of
the Energetic Binder PolyNIMMO
with Energetic Plasticizers:
Experimental and DFT Studies

DOI: 10.1002/prep.201600058 www.pep.wiley-vch.de  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim &9&
These are not the final page numbers! ÞÞ