polymers

Article
Comparative Study on Thermal Response Mechanism of Two
Binders during Slow Cook-Off
Xinzhou Wu 1 , Jun Li 2 , Hui Ren 1, * and Qingjie Jiao 1

1 State Key Laboratory of Explosion of Science and Technology, Beijing Institute of Technology,
Beijing 100081, China
2 Science and Technology on Aerospace Chemical Power Laboratory, China Aerospace Science and Technology
Corporation, Xiangyang 441003, China
* Correspondence: [email protected]

Abstract: The HTPE (hydroxyl-terminated polyether) propellant had a lower ignition temperature
(150 ◦ C vs. 240 ◦ C) than the HTPB (hydroxy-terminated polybutadiene) propellant in the slow
cook-off test. The reactions of the two propellants were combustion and explosion, respectively. A
series of experiments including the changes of colors and the intensity of infrared characteristic peaks
were designed to characterize the differences in the thermal response mechanisms of the HTPB and
HTPE binder systems. As a solid phase filler to accidental ignition, the weight loss and microscopic
morphology of AP (30~230 ◦ C) were observed by TG and SEM. The defects of the propellant caused
by the cook-off were quantitatively analyzed by the box counting method. Above 120 ◦ C, the HTPE
propellant began to melt and disperse in the holes, filling the cracks, which generated during the
decomposition of AP at a low temperature. Melting products were called the “high-temperature
self-repair body”. A series of analyses proved that the different thermal responses of the two binders
were the main cause of the slow cook-off results, which were likewise verified in the propellant
mechanical properties and gel fraction test. From the microscopic point of view, the mechanism of
HTPE’s slow cook-off performance superior to HTPB was revealed in this article.
Citation: Wu, X.; Li, J.; Ren, H.; Jiao,
Q. Comparative Study on Thermal Keywords: HTPB; HTPE; slow cook-off; mechanical properties; microstructure
Response Mechanism of Two Binders
during Slow Cook-Off. Polymers 2022,
14, 3699. https://doi.org/10.3390/
polym14173699 1. Introduction
Academic Editor: Abdel-Hamid Solid propellant, the fuel of a solid engine, is playing an increasingly important role
I. Mourad in solid propulsion technology and modern aerospace technology because of its simple
Received: 30 July 2022
structure, convenient storage, short launch preparation time and strong mobility. In
Accepted: 20 August 2022
the international community, the chemical names of binders commonly represent solid
Published: 5 September 2022
propellants. Binder is mainly used to uniformly mix oxidants, plasticizers, curing agents
and so on, so that the slurry of propellant can obtain certain rheological properties [1].
Publisher’s Note: MDPI stays neutral
With the developments of high energy and low vulnerability of propellants, the binder has
with regard to jurisdictional claims in
become an important factor in safety regulation.
published maps and institutional affil-
Hydroxy-terminated polybutadiene (HTPB) is a liquid prepolymer [2], and due to its
iations.
excellent physical properties, such as low viscosity, low glass transition temperature [3],
high mechanical and thermal stability, lifting the load of solid propellant, etc. [4], it is
widely used as a binder to make solid propellants have a stable burning rate and low-
Copyright: © 2022 by the authors.
pressure exponent. HTPB bonds aluminum powder and ammonium perchlorate (AP)
Licensee MDPI, Basel, Switzerland. solid powder [5,6], under the action of isocyanate (TDI), propellant crosslinking, curing
This article is an open access article and forming a certain geometric shape and mechanical strength [7,8]. Compared with
distributed under the terms and the carboxyl-terminated polybutadiene (CTPB) binder, HTPB shows better extensibility
conditions of the Creative Commons at a low temperature, and exhibits better thermodynamic and anti-aging properties [9].
Attribution (CC BY) license (https:// HTPB does not contain any energetic groups; it has no contribution to improving the
creativecommons.org/licenses/by/ energy output and combustion rate of the solid propellant. So, the research of HTPB
4.0/). focuses on how to enhance energy with modifications. Under the condition of keeping the

Polymers 2022, 14, 3699. https://doi.org/10.3390/polym14173699 https://www.mdpi.com/journal/polymers

Polymers 2022, 14, 3699 2 of 17

mechanical properties of HTPB, experts try to introduce various high-energy groups into the
polymer backbone, hoping to further improve the overall energy of the propellant [10–15].
Toward the functionalization goal, the preparation of a hydroxyl-terminated polystyrene-b-
polybutadiene-b-polystyrene triblock copolymer (SBS) with high cis-1, 4 content via a novel
nickel catalyst was reported. A hydroxyl group was successfully introduced at the end of
the triblock copolymer (HO–SBS–OH) by FT-IR, 1 H-NMR and 13 C NMR methods [16].
As of recently, with the requirement of low vulnerability of the propellant, missile
weapons should withstand six examinations, i.e., a fast cook-off test, slow cook-off test, gap
test, bullet impact test, fragment impact test and jet test according to the U.S. MIL-STD-
2105D and NATO STANAG 4439 [17]. The HTPB propellant failed to pass the slow cook-off
test and exploded, which was the most rigorous low vulnerability test. Compared with
the HTPB propellant, the HTPE (hydroxyl-terminated polyether) propellant composed of
hydroxyl-terminated polyether only combusted in the slow cook-off test, and the response
degree declined. Someone believed that the HTPE binder introduced a block structure in the
molecular chain, which generated low molecular oligomers during thermal decomposition,
and then delayed the formation of combustible molecules, thus reducing the response
characteristics of propellants to the slow cook-off test [18,19]. HTPE has a tendency to
replace HTPB in solid propellants so as to pass slow cook-off experiments.
Up to now, the mechanism of HTPB and HTPE binders in a slow cook-off test lacked
the analysis detailed. Most analyses focused on these factors such as charge size [20,21],
and concluded that AP is the main factor during the slow cook-off of HTPB and HTPE
propellants [22,23]. However, little research studies the durability and degradation of poly-
meric materials during the slow cook-off process, especially the changes in the mechanical
properties [24,25] and decomposition path [26] of binders. It is an interesting topic to study
the change pattern of a small number of polymeric materials in a propellant slow cook-off,
and to study the effect of the decomposition of polymeric materials on the overall slow
cook-off result from a microscopic perspective. In this article, HTPB and HTPE propellants
used in propellant charge were compared with a small slow cook-off test instrument. Ignit-
ing temperatures of the two solid propellants, the decomposing mechanism of HTPB and
HTPE and the interaction reactions between a binder and AP (Ammonium perchlorate)
were analyzed. From the micro-view, differences between the two binders during the slow
cook-off response to thermal stimulation were investigated in order to explain how the
HTPE propellant could improve the safety compared with the HTPB propellant.

2. Materials and Methods

2.1. Materials and Instruments
The HTPB binder(III) was purchased from the Liming Chemica Research Institute of
Chemical Industry(Luoyang, China). The HTPE binder was purchased from the Science and
Technology on Aerospace Chemical Power Laboratory(Xiangyang, China). TDI (Industrial
grade) was purchased from the School of Chemistry and Chemical Engineering Inner
Mongolia University(Hohhot, China). Aluminum powder (FLQT1 grade) was purchased
from Angang industrial micro aluminum powder Co., Ltd. (Anshan, China). AP(III) was
purchased from Dalian north potassium chlorate Co., Ltd. (Dalian, China). The molecular
formulas of the two binders and curing agents are shown in Figure 1.
A scanning electron microscope (SEM), JSM-6360LV, Voltage 15 kV, working distance
12 mm, vacuum 1.0 × 10−5 Pa was obtained from Japan Co., Ltd. (Tokyo, Japan). An
optical microscope, MEF4M, was obtained from Germany Leica Microsystems Ltd. (Wetzlar,
Germany). A Fourier transform infrared spectrometer (FTIR), Model 5700, was obtained
from the American Thermal Electron Corporation(Waltham, MA, USA). A cupping machine,
INSTRON4202, was obtained from the American Instron Corporation (Boston, MA, USA).
A small cook-off test instrument, HTSSC I-002, was made by the Science and Technology in
Aerospace Chemical Power Laboratory (Xiangyang, China). The mass of the test sample
is 1~1000 g, the temperature control accuracy is ±1 ◦ C and the experimental temperature
 machine, INSTRON4202, was obtained from the American Instron Corporation (Boston,
MA, USA). A small cook-off test instrument, HTSSC І-002, was made by the Science and
Technology in Aerospace Chemical Power Laboratory (Xiangyang, China). The mass of
Polymers 2022, 14, 3699 3 of 17
the test sample is 1~1000 g, the temperature control accuracy is ±1 °C and the experimental
temperature range is 20~350 °C. A thermogravimetric differential scanning calorimeter
(TG-DSC), SDTQ600, was obtained from American TA Instruments (New Castle, DE,
range is 20~350 ◦ C. A thermogravimetric differential scanning calorimeter (TG-DSC),
USA).
SDTQ600, was obtained from American TA Instruments (New Castle, DE, USA).

Figure 1. Structural formulae of HTPB, HTPE and TDI.

Figure 1. Structural formulae of HTPB, HTPE and TDI.
2.2. Methods
2.2. Methods
Samples preparation: the HTPB binder and TDI curing agent were mixed evenly in a
Samples
beaker according preparation:
to the curing the HTPB
parameterbinder and[27],
of 1.0 TDIpoured
curing into
agent were mixed
a special mold,evenly
defoamedin a
beaker
under aaccording
vacuum,to the curing
cured parameter
at a constant of 1.0 [27],of
temperature poured◦
50 C into a special
for 168 h andmold, defoamed
demolded after
under
curingatovacuum,
make the cured
shape atrequired
a constant fortemperature
the experiment. of 50Adjusting
°C for 168theh and demolded
curing parameter after
to
curing
1.3, theto makebinder
HTPE the shape
film required
was prepared for thebyexperiment. Adjusting the curing parameter to
the same process.
1.3, the HTPE binder
Propellant film wassamples
preparation: prepared by the
were same process.
prepared by using a vertical kneader, and the
binderPropellant preparation:
and oxidizer were mixed samples were prepared
in a certain order andby using
ratio a vertical
(HTPB kneader,
propellant and the
formulation
ratio: HTPB binder/AP/Al/auxiliary = 10/70/18/2, HTPE propellant
binder and oxidizer were mixed in a certain order and ratio (HTPB propellant formulation formulation ratio:
HTPE HTPBbinder/AP/Al/auxiliary = 20/72/5/3) at a mixing ◦
ratio: binder/AP/Al/auxiliary = 10/70/18/2, HTPEtemperature of 50~55 C. These
propellant formulation ratio:
samples
HTPE were mixed for 120 min
binder/AP/Al/auxiliary = and cast under
20/72/5/3) at a amixing
vacuum, where the casting
temperature of 50~55 temperature
°C. These
was 50~55 ◦ C. Then, they were cured at a constant temperature of 50 ◦ C for 168 h.
samples were mixed for 120 min and cast under a vacuum, where the casting temperature
Slow cook-off
was 50~55 °C. Then,test:theythewereresponse
cured at characteristics of the HTPB
a constant temperature ofand HTPE
50 °C scaled-down
for 168 h.
solidSlow
engines with a specimen size of φ100 mm × 200 mm were
cook-off test: the response characteristics of the HTPB and HTPE scaled-downstudied. The thickness
of the shell and end cover was 3 mm, the material was 45# steel
solid engines with a specimen size of Ф100 mm × 200 mm were studied. The thickness and the heating rate was
of
3.30 ◦ C/h. Meanwhile, the HTPB and HTPE propellants were tested at a heating rate of
the shell and end cover was 3 mm, the material was 45# steel and the heating rate was 3.30
3.30 ◦ C/h
°C/h. in a small
Meanwhile, thecook-off
HTPB and test apparatus. The microstructure
HTPE propellants were testedofatpropellants at different
a heating rate of 3.30
temperatures
°C/h in a smallduring
cook-off thetest
cook-off process
apparatus. Thewas analyzed by aofscanning
microstructure electron
propellants microscope.
at different tem-
Material tensile test: the propellant samples were processed
peratures during the cook-off process was analyzed by a scanning electron microscope. into standard dumbbell-
shaped dimensions
Material tensileandtest:analyzed for modulus,
the propellant samples maximum elongation
were processed intoand maximum
standard tensile
dumbbell-
shaped dimensions and analyzed for modulus, maximum elongation and maximum tem-
strength at different slow cook-off temperatures. Considering the different ignition ten-
peratures
sile strengthof different
at differentsolid propellants
slow cook-off[28], the HTPB propellant
temperatures. Considering was tested
the 220 ◦ C
belowignition
different
and the HTPEof propellant ◦
temperatures differentwas tested
solid below 140
propellants [28],C.the
TheHTPB
samples were taken
propellant wasout and cooled
tested below
to room temperature, and tensile tests were carried out at
220 °C and the HTPE propellant was tested below 140 °C. The samples were taken a speed of 100 mm/min. In out
the
mechanical test, three groups of tests were completed and the
and cooled to room temperature, and tensile tests were carried out at a speed of 100group with larger deviation
was removed.
mm/min. In the mechanical test, three groups of tests were completed and the group with
Gel percentage test: the solid propellant was processed into 10 mm × 10 mm × 1 mm
larger deviation was removed.
thin sheets, and about 3 g samples were weighed and placed in a flask at the grinding
Gel percentage test: the solid propellant was processed into 10 mm × 10 mm × 1 mm
mouth. Then, 100 mL trichloromethane solution was added and the sample was soaked
thin sheets, and about 3 g samples were weighed and placed in a flask at the grinding
for about 12 h. The sample and extract were transferred to a Soxhlet extractor, and 100 mL
mouth. Then, 100 mL trichloromethane solution was added and the sample was soaked
trichloromethane solution was added into a single-mouth flask, and heated in a water
for about 12 h. The sample and extract were transferred to a Soxhlet extractor, and 100 mL
bath at 80 ◦ C for 6 h. The extracted samples were transferred to a surface dish, placed in a
trichloromethane solution was added into a single-mouth flask, and heated in a water
fume hood to remove a large amount of solvent and then transferred to a vacuum oven to
bath at 80 °C◦for 6 h. The extracted samples were transferred to a surface dish, placed in a
maintain 40 C for drying under vacuum. After drying for 1 h, the sample was taken out
and placed in the dryer to cool to room temperature before weighing. The operation was
repeated until the weight of the specimens remained the same.
Infrared spectrum test: a Fourier transform infrared spectrometer was used to scan
20 times in the air atmosphere for spectral accumulation. The scanning range was from
4000 to 400 cm−1 with a resolution of 4 cm−1 ; the heating range was from 20 to 320 ◦ C with
 fume hood to remove a large amount of solvent and then transferred to a vacuum oven to
maintain 40 °C for drying under vacuum. After drying for 1 h, the sample was taken out
and placed in the dryer to cool to room temperature before weighing. The operation was
repeated until the weight of the specimens remained the same.
Infrared spectrum test: a Fourier transform infrared spectrometer was used to scan
Polymers 2022, 14, 3699 20 times in the air atmosphere for spectral accumulation. The scanning range was from 4 of 17
4000 to 400 cm with a resolution of 4 cm ; the heating range was from 20 to 320 °C with
−1 −1

a heating rate of 2 °C/min. The functional groups of HTPB and HTPE propellants were
tested at room
a heating of 2 ◦ C/min.and
rate temperature Theslow cook-off
functional progress,
groups respectively,
of HTPB and HTPE andpropellants
the changes in
were
these
testedfunctional groups’ contents
at room temperature with temperature
and slow cook-off progress,were analyzed.
respectively, and the changes in
theseThermogravimetric
functional groups’analysiscontentstest:
with2~5 mg samples
temperature were
were experimented on under the
analyzed.
air atmosphere and different
Thermogravimetric heating
analysis test: rate.
2~5 mgThesamples
experimental accuracy wasonabout
were experimented under0.1 μg,
the air
and the experimental
atmosphere and different temperature rangeThe
heating rate. was from room accuracy
experimental temperaturewas to 500 0.1
about °C µg,
withanda
heating rate of 0.1 temperature
the experimental °C/min to 50 range
°C/min. was from room temperature to 500 ◦ C with a heating
rate of 0.1 ◦ C/min to 50 ◦ C/min.
2.3. Slow Cook-Off Test on a Scaled-Down Solid Engine
2.3. Slow Cook-Off Test on a Scaled-Down Solid Engine
Figure 2a,b show the physical and schematic diagrams, respectively. Temperature
sensors Figure
were2a,b
placed show the physical
to record and schematic
the temperature fielddiagrams, respectively.change
and the temperature Temperature
of the
solid propellant. They were placed on the outer surface and center of the Φ 100 of
sensors were placed to record the temperature field and the temperature change mm the× solid
200
propellant.
mm They solid
scaled-down were engine.
placed onTothe outer surface
improve and center
experimental Φ 100
of thethe
efficiency, HTPB × 200 mm
mmpropellant
scaled-down
was heated to 70 solid
°C atengine. To improve
a heating efficiencyexperimental
of 1.0 °C/minefficiency,
firstly andthe HTPB
then heatedpropellant was
at a heating
heated to 70 ◦ CToat afurther
heating efficiency ◦
of 1.0 C/min firstlythe
and thenreduced-ratio
heated at a heating
rate of 3.30 °C/h. shorten the experimental period, HTPE
◦ C/h. To further shorten the experimental period, the HTPE reduced-ratio solid
solid
rate of 3.30
engine was heated to 100 °C at a rate of 2.0 °C/min firstly and then at 3.30 °C/h during the
engine was heated ◦ ◦ ◦
slow cook-off test. to 100 C at a rate of 2.0 C/min firstly and then at 3.30 C/h during the
slow cook-off test.

Figure 2. (a) The scaled-down solid engine slow cook-off device diagram and (b) schematic diagram.
Figure 2. (a) The scaled-down solid engine slow cook-off device diagram and (b) schematic dia-
gram. It can be seen from Figure 3a that the temperature field of the reduced-ratio solid
engine was very uniform in the slow heating process of 3.30 ◦ C/h. By linear fitting, the
It can
heating beof
rate seen
the from
HTPBFigure 3a that solid
scaled-down the temperature
engine was 3.31 field◦of theand
C/h, reduced-ratio solid
that of the HTPE
engine was very uniform in the slow heating process of 3.30
scaled-down solid engine was 3.29 ◦ C/h. The heating rates all met the experimental °C/h. By linear fitting, the
heating rate of(<0.5
requirement the HTPB
◦ C/h).scaled-down solid engine of
The internal temperature wasthe3.31
HTPB °C/h, and that ofsolid
scaled-down the HTPE
engine
scaled-down solid engine was 3.29 °C/h. The heating
◦ rates all
increased sharply at 55 h and responded at 244 C. The temperature of the HTPE scaled met the experimental re-
quirement (<0.5 °C/h). The internal temperature of the HTPB scaled-down
solid engine increased sharply at 13 h, and the ignition temperature was determined to solid engine
increased
be 150 ◦ Csharply at 55 hFigure
by tangency. and responded
3b shows at the244 °C.results
field The temperature
of the HTPB ofscaled-down
the HTPE scaled solid
solid engine increased sharply at 13 h, and the ignition temperature
engine after the end of response. The shell barrel section was torn and fully expanded was determined to be
150 °C by
along thetangency. Figure and
axial direction, 3b shows
the endthecap
field
wasresults of the
broken fromHTPB scaled-down
the threads. There solid
wasen-no
gine after charge
residual the endatofthe response.
site, andThethe shell
shell barrel
showed section
signs was torn and
of ablation. fullywere
There expanded along
no explosive
the axialon
craters direction, and the
the ground. Twoend of cap
the was
witnessbroken from
plates themore
had threads.
thanThere was no dent,
one obvious residual
but
charge at the site, and the shell showed signs of ablation. There
none of them were perforated and the remaining two plates had no obvious dents were no explosive craters
and
on the ground.Collectively,
perforations. Two of the the witness plates
response hadofmore
level than one
the HTPB obviousindent,
propellant but none
the slow of
cook-off
them weredetermined
test was perforatedas andan the remaining
explosion. two3c
Figure plates
shows hadthenofield
obvious
resultsdents
afterand
the perfora-
response
tions.
of theCollectively,
HTPE scaled-downthe responsesolidlevel of the
engine, HTPB
which propellant
shows that the in shell
the slow cook-off
barrel test was
was intact, one
side of the end cover was intact and the other side was torn in half. There was no residual
charge at the scene, and the shell had traces of ablation. There were no craters on the
ground and no dents and perforations in the four witness plates. The experimental results
were judged to be combustion.
 determined as an explosion. Figure 3c shows the field results after the respons
HTPE scaled-down solid engine, which shows that the shell barrel was intact, one
the end cover was intact and the other side was torn in half. There was no residua
at the scene, and the shell had traces of ablation. There were no craters on the grou
no dents and perforations in the four witness plates. The experimental results were
Polymers 2022, 14, 3699 5 of 17
to be combustion.

Figure 3. (a) The scaled-down solid engine slow cook-off test curve, (b) the wreckage of HTPB
Figure 3. (a) The scaled-down solid engine slow cook-off test curve, (b) the wreckage of HT
propellant, and (c)pellant,
the wreckage
and (c)of HTPE
the propellant.
wreckage of HTPE propellant.

The experiments with the φ100 mm × 200 mm reduced-ratio engine show that the
The experiments with the Ф100 mm × 200 mm reduced-ratio engine show
ignition temperature of the HTPB propellant was about 244 ◦ C and the response grade was
ignition temperature of the HTPB propellant was about 244 ◦°C and the respons
an explosion. The ignition temperature of the HTPE propellant was about 150 C, and the
was an explosion. The ignition temperature of the HTPE propellant was about 150
response level was lower than HTPB, which was combustion only.
the response level was lower than HTPB, which was combustion only.
3. Results and Discussion
3. Results and Discussion
The fuel in solid engines generally consists of Al, AP and binder systems, and the igni-
tion temperature of aThe slowfuel in solid
cook-off engines 100
is between generally
and 300consists
◦ C. Theofoxidation
Al, AP and binder systems,
temperature
of Al is above 600ignition
◦ temperature
C [29,30], which is of a slow
much cook-off
higher is between
than the ignition100 and 300 °C.
temperature of aThe oxidation t
solid
engine in a slowature
cook-offof Al is above
test, indicating600 °Cthat[29,30], which
Al powder is much
mainly actshigher thanconductor
as a heat the ignition
in temper
a solid engine and has little influence on slow cook-off temperature. Therefore, the main acts as
a solid engine in a slow cook-off test, indicating that Al powder mainly
factors affectingconductor
the ignition in aofsolid engine
the solid and has little
propellant wereinfluence on slow
studied about APcook-off temperature
and binder
fore,
components, respectively. the main factors affecting the ignition of the solid propellant were studied ab
and binder components, respectively.
3.1. Response Behavior of AP during Slow Heating
The content3.1.
of APResponse
in solidBehavior of AP during
engine charge Slow Heating
is the highest and more than 70% in some solid
propellants [31]. Other Thestudies
contenthave of APshown thatengine
in solid the thermal
chargedecomposition
is the highest and mechanism
more than 70% i
of AP is mainly solid
concentrated
propellantsin two[31].stages:
Other the low-temperature
studies have shown that stagethe thermal◦ C)
(250–350 and
decomposition
the high-temperature ◦
nism ofstage AP is(>350
mainlyC). The main mechanisms
concentrated in two stages:are thethe electron transfer
low-temperature stage (250–
mechanism [32,33] andand the the proton transferstage
high-temperature mechanism
(>350 °C).[34,35].
The main In the study of the
mechanisms aremain
the electron
factors of solid mechanism
engine ignition, [32,33]the andlow-temperature
the proton transfer decomposition
mechanism stage of In
[34,35]. APthewas
study of th
mainly concerned. factors of solid engine ignition, the low-temperature decomposition stage of A
The TG-DSC curves
mainly and reaction activation energy of AP were analyzed. The DSC
concerned.
curve showed an endothermic
The TG-DSC peakcurves
and two andexothermic peaks, among
reaction activation which,
energy the endother-
of AP were analyzed. T
mic peak was 243.2 ◦ C,showed
and thisan temperature range wasandthetwo
crystal transitionpeaks,
peak (rhombic
curve endothermic peak exothermic among which, th
crystal to cubic crystal) of AP. The DSC curve showed that the ignition
thermic peak was 243.2 °C, and this temperature range was the crystal temperature of AP transitio
was 294.6 ◦ C. Kinetic parameters of AP were calculated by the Ozawa
(rhombic crystal to cubic crystal) of AP. The DSC curve showed that the method and theignition t
Kissinger method: they were 117.8 kJ/mol and 106.1 kJ/mol, respectively.
ature of AP was 294.6 °C. Kinetic parameters of AP were calculated by the Ozawa
According andto the thecharacteristics
Kissinger method: of thethey
slowwerecook-off
117.8test,
kJ/molthisand
paper
106.1 focused
kJ/mol,onrespectively.
the
decomposition characteristics of AP at 30~250 ◦ C. The weight loss rate of AP at different
temperatures is shown in Figure 4. AP began to produce trace weight loss at 150 ◦ C. With
the increase in temperature, the weight loss rate increased gradually. When the temperature
was higher than 200 ◦ C, the weight loss rate increased rapidly. When the temperature
reached 230 ◦ C, the weight loss rate reached 31.5%.
 Accordingtotothe
According thecharacteristics
characteristicsofofthe
theslow
slowcook-off
cook-offtest,
test,this
thispaper
paperfocused
focusedon onthe
the
decomposition characteristics of AP at 30~250 °C. The weight loss rate of AP
decomposition characteristics of AP at 30~250 °C. The weight loss rate of AP at different at different
temperaturesisisshown
temperatures shownininFigure
Figure4.4.AP
APbegan
begantotoproduce
producetrace
traceweight
weightloss
lossatat150
150°C.°C.With
With
theincrease
the increaseinintemperature,
temperature,thetheweight
weightloss
lossrate
rateincreased
increasedgradually.
gradually.When
Whenthe thetempera-
tempera-
Polymers 2022, 14, 3699 ture was higher than 200 °C, the weight loss rate increased rapidly. When the
ture was higher than 200 °C, the weight loss rate increased rapidly. When the temperature temperature
6 of 17
reached 230 °C, the weight loss rate reached
reached 230 °C, the weight loss rate reached 31.5%. 31.5%.

Figure
Figure4.4.
Figure The mass-loss
Themass-loss
4.The rate
rateofof
mass-lossrate AP
ofAP with
APwith temperature.
withtemperature.
temperature.

The morphologies
morphologiesofof
Themorphologies
The AP
ofAPAPatat
ataaalow
low temperature
lowtemperature
temperaturewere were studied
werestudied with
studiedwith SEM.
withSEM. The
SEM.The experi-
Theexperi-
experi-
mental
mental results
results are
are shown
shown in
in Figure
Figure 5. The
The surface
surface of
of AP
AP was
was smooth
smooth below
below 100
100 ◦ C. When
°C. When
mental results are shown in Figure 5. The surface of AP was smooth below 100 °C. When
the temperature continued to rise to 190 ◦ C, no visible defects and holes appeared on the
the temperature continued to rise to 190 °C, no visible defects and holes
the temperature continued to rise to 190 °C, no visible defects and holes appeared on the appeared on the
surface. When the temperature continued to increase to 200 ◦ C, some tiny holes appeared
surface.When
surface. Whenthethetemperature
temperaturecontinued
continuedtotoincrease
increasetoto200
200°C,
°C,some
sometiny
tinyholes
holesappeared
appeared
on the surface. Finally, ◦ C, obviously.
on the surface. Finally, when reaching 230 °C, holes and defects
on the surface. Finally, when reaching 230 °C, holes and defects appeared obviously.appeared obviously.

Figure 5. AP surface conditions at different temperatures.

Figure5.5.AP
Figure APsurface
surfaceconditions
conditionsatatdifferent
differenttemperatures.
temperatures.
AP is the main gas-producing substance in the solid propellant, and its reaction affects
the response grade of a solid propellant in a slow cook-off test directly. Through exploring
the decomposition temperature of AP, it was found that AP will decompose violently
only when it is above 200 ◦ C, which is higher than the response temperature of the HTPE
propellant and close to that of the HTPB propellant. It is speculated that AP is the main
ignition factor of HTPB propellant.
 AP is the main gas-producing substance in the solid propellant, and its reaction af-
fects the response grade of a solid propellant in a slow cook-off test directly. Through
exploring the decomposition temperature of AP, it was found that AP will decompose
violently only when it is above 200 °C, which is higher than the response temperature of
Polymers 2022, 14, 3699 the HTPE propellant and close to that of the HTPB propellant. It is speculated that AP7isof 17
the main ignition factor of HTPB propellant.

3.2.3.2.
Thermal
ThermalResponse of HTPB
Response of HTPB Film Filmat Different
at DifferentTemperatures
Temperatures
In In
order to study the ignition characteristics
order to study the ignition characteristics of the
of the HTPB
HTPB film cured
film curedby by
TDI in the
TDI in the
slow cook-off condition, DSC was used to study the ignition temperature
slow cook-off condition, DSC was used to study the ignition temperature of the HTPB film. of the HTPB
film.
The TheDSCDSC curve
curve of the
of the HTPB HTPB filmfilm
beganbegan to climb
to climb at about
at about 320.5 320.5 °C, followed
◦ C, followed by aby a
strong
strong exothermic peak at 367.7
◦ °C. The TG curve shows that the
exothermic peak at 367.7 C. The TG curve shows that the HTPB film began to lose weight HTPB film began to lose
weight
at 282at◦ 282
C and°Cthe
andweight
the weight loss ratelossreached
rate reached
34% at34%430 at
◦ C.430
The°C. The Ozawa
Ozawa methodmethod and
and Kissinger
Kissinger
methodmethodwere usedwereto used
calculate to calculate
the kinetic theparameters
kinetic parameters
of the HTPB of the HTPB
film’s film’s exo-
exothermic peak
thermic
as 161.3peak as 161.3
kJ/mol andkJ/mol and 159.7
159.7 kJ/mol, kJ/mol, respectively.
respectively.
TheThesurface of the
surface HTPB
of the HTPB film was
film wasobserved
observed at different
at differenttemperatures
temperatures in the process
in the process
of the slow cook-off. The experimental results are shown
of the slow cook-off. The experimental results are shown in Figure 6. The HTPB in Figure 6. The HTPB film at at
film
room temperature (20 °C) ◦ was light yellow translucent. With the
room temperature (20 C) was light yellow translucent. With the temperature increasing, temperature increasing,
thethecolor of of
color thethe
HTPB
HTPB film filmgradually
gradually deepened,
deepened, andand after 150150
after °C,◦ C,
thetheraterate
of of
thethe
color
color
deepening
deepening waswasobvious.
obvious. When When it reached
it reached 190190 ◦
°C, the whole
C, the wholefilm hadhad
film become
become brown,
brown,andand
all all
of it
ofbecame
it became dark brown
dark brown at 200
at 200 °C.◦ C.
TheThereason
reasonforfor
thethedeepening
deepening of the color
of the may
color maybe be
that thethe
that colored groups
colored groups were were produced
produced by by
thethe
decomposition
decomposition of the HTPB
of the HTPB film, andand
film, theythey
increased with the rising temperature.
increased with the rising temperature.

Figure
Figure 6. The
6. The morphology
morphology of HTPB
of HTPB filmfilm at different
at different temperatures.
temperatures.

TheThe total
total reflection
reflection infraredtest
infrared testresults
resultsofofthe
theHTPB
HTPB film
film at
at different
different temperatures
temperaturesare
shown in Figure 7. The stretching vibration peak of C–O was at 1076 cm −1 , the vibration
are shown in Figure 7. The stretching vibration peak of C–O was at 1076 cm , the vibration
Polymers 2022, 14, x FOR PEER REVIEW −1 8 of 18
peak
peak of C=C
of C=C on benzene
on the the benzene
ring ring was
was at at 1533
1533 cm−the
cm−1 and
1 and the N–H vibration peak was at
N–H vibration peak was at 1537
cm1537
−1. cm−1 .

Figure 7.
Figure The infrared
7. The infrared spectrum
spectrum of
of HTPB
HTPB film
film at
at room
room temperature.
temperature.

The changes of various groups in the HTPB film during the slow cook-off were ana-
lyzed, especially the changes in the N–H bond and C–O bond. The change of the N–H
bond with temperature is shown in Figure 8a. From room temperature to 200 °C, the N–
Polymers 2022, 14, 3699 8 of 17
Figure 7. The infrared spectrum of HTPB film at room temperature.

The changes of various groups in the HTPB film during the slow cook-off were ana-
lyzed,The changesthe
especially of changes
various in
groups
the N–Hin the
bondHTPB
and film
C–Oduring the change
bond. The slow cook-off were
of the N–H
bond with temperature is shown in Figure 8a. From room temperature to 200◦ °C, theN–H
analyzed, especially the changes in the N–H bond and C–O bond. The change of the N–
Hbond
bond with
wastemperature
divided into is two
shown in Figure
stages. 8a. From
The first stage room temperature
was between roomtotemperature
200 C, the N–H
and
bond was divided into two stages. The first stage was between room temperature and
120 °C, and the peak strength of N–H was maintained. When the temperature was higher
120 ◦ C, and the peak strength of N–H was maintained. When the temperature was higher
than 120 °C, the strength of the N–H bond decreased gradually, and when the temperature
than 120 ◦ C, the strength of the N–H bond decreased gradually, and when the temperature
was higher than 170◦°C, the strength of the N–H bond decreased significantly. It is be-
was higher than 170 C, the strength of the N–H bond decreased significantly. It is believed
lieved that the breakdown of the urethane bond in the HTPB film during the slow cook-
that the breakdown of the urethane bond in the HTPB film during the slow cook-off process
off process resulted in the decrease in the peak strength of the N–H bond. The breaking
resulted in the decrease in the peak strength of the N–H bond. The breaking of the N–H
of the N–H bond resulted in the formation of amino or alkyl radicals and the release of
bond resulted in the formation of amino or alkyl radicals and the release of CO . After the
CO2. After the breaking of the N–H bond, it may rearrange and form an aniline2structure.
breaking of the N–H bond, it may rearrange and form an aniline structure. The reaction
The reaction process is shown in Figure 8b.
process is shown in Figure 8b.

Figure8.
Figure (a)Variation
8.(a) Variation trend
trend of
of N–H
N–H relative
relative absorbance
absorbance and
and (b)
(b) decomposition
decomposition reaction
reaction process.
process.

The variation of the C–O bond at different temperatures in the process of the slow
The variation of the C–O bond at different temperatures in the process of the slow
cook-off is shown in Figure 9a. The C–O bond was also divided into two stages. The first
cook-off is shown in Figure 9a. The C–O bond was also divided into two stages. The first
stage is that the peak strength of C–O was maintained between room temperature and
stage◦ is that the peak strength of C–O was maintained between room temperature and 170
170 C. In the second stage, when the temperature was higher than 190 ◦ C, the strength
Polymers 2022, 14, x FOR PEER REVIEW 9 of
of
18
°C. In the second stage, when the temperature was higher than 190 °C, the strength of the
the C–O bond gradually weakened, and when the temperature was higher than 190 ◦ C,
C–O bond gradually weakened, and when the temperature was higher than 190 °C, the
the strength of the C–O bond decreased significantly. It is believed that the breakage of
strength of the C–O bond decreased significantly. It is believed that the breakage of the
the carbamate bond resulted in the decrease in the peak strength of the C–O bond during
carbamate
slowslow bondprocess
cook-off resulted
ofinthe
theHTPB
decrease
film.in the peak
The strength
breakage of C–O
of the the C–O bond
bond led during
to the
the cook-off process of the HTPB film. The breakage of the C–O bond ledthe
to for-
the
mation of carbamoyl or alkoxy radicals, and the decomposition of carbamoyl radicals
formation of carbamoyl or alkoxy radicals, and the decomposition of carbamoyl radicals into
ammonia
into ammonia radicals and and
radicals CO2.CO The possible reaction process is shown in Figure 9b.
2 . The possible reaction process is shown in Figure 9b.

Figure
Figure 9. (a) Variation
9. (a) Variation trend
trend of
of C–O
C–O relative
relative absorbance
absorbance and
and (b)
(b) decomposition
decompositionreaction
reactionprocess.
process.

A
A comparative
comparative analysis
analysis of
of the
the variation
variation of the N–H
of the N–H bond and C–O
bond and C–O bond
bond atat different
different
temperatures
temperatures shows that the peak strength of the N–H bond decreased faster than that
shows that the peak strength of the N–H bond decreased faster than that of
of
the C–O bond, and it is believed that the breakage of the N–H bond was earlier than that
of the C–O bond. The aniline structure or carbamoyl group formed by the decomposition
of HTPB films was the colored group, which was the direct cause of the deepening color
in HTPB film’s slow cook-off process.
 Figure 9. (a) Variation trend of C–O relative absorbance and (b) decomposition reaction process.
Polymers 2022, 14, 3699 9 of 17
A comparative analysis of the variation of the N–H bond and C–O bond at different
temperatures shows that the peak strength of the N–H bond decreased faster than that of
the C–O bond, and it is believed that the breakage of the N–H bond was earlier than that
the C–O bond, and it is believed that the breakage of the N–H bond was earlier than that of
of the C–O bond. The aniline structure or carbamoyl group formed by the decomposition
the C–O bond. The aniline structure or carbamoyl group formed by the decomposition of
of HTPB films was the colored group, which was the direct cause of the deepening color
HTPB films was the colored group, which was the direct cause of the deepening color in
in HTPB
HTPB film’s
film’s slow
slow cook-off
cook-off process.
process.
3.3.3.3.
Thermal
ThermalResponse
Responseof HTPE
of HTPE Film at Different
Film Temperatures
at Different Temperatures
TheThe ignition temperature of the HTPE
ignition temperature of the HTPE film film was wasstudied
studiedby by
DSC.
DSC.TheTheDSC DSCcurvecurve
showed a wide exothermic peak at 212.9 °C. ◦ The Ozawa method
showed a wide exothermic peak at 212.9 C. The Ozawa method and Kissinger method and Kissinger method
were
were used
used to to
calculate
calculatethe
thekinetic
kineticparameters
parameters of of the HTPE
HTPE film;
film;they
theywere
were139.1
139.1 kJ/moland
kJ/mol
and138.2
138.2kJ/mol,
kJ/mol,respectively.
respectively.
TheThe surface
surfaceof of
the
theHTPE
HTPEfilm filmatat different temperaturesininthe
different temperatures theprocess
process ofof
thethe
slowslowcook-
cook-off
off was was observed.
observed. The
The experimental
experimental results
results areare shown
shown in in Figure
Figure 10.10. The
The HTPE
HTPE film
film was
waslight
light yellow
yellow andand translucent
translucent at room
at room temperature
temperature (20 ◦(20
C).°C).
WithWith the temperature
the temperature in-
increasing,
creasing,
the HTPE the film
HTPE filmgradually
color color gradually
deepened. deepened.
When the When the temperature
temperature 140 ◦ C, 140
reachedreached the °C,
HTPE
thefilm
HTPE film became
became soft andsoft andand
sticky, sticky, andsubstances
liquid liquid substances
appeared appeared
in some in someWhen
areas. areas.the
When the temperature
temperature 160 ◦ C, 160
reachedreached °C, thefilm
the HTPE HTPEhadfilmbeenhad been completely
completely degraded degraded
to a brown to agel.
In the
brown process
gel. In the of the slow
process cook-off,
of the the HTPE
slow cook-off, thefilm’s
HTPE binder
film’snetwork degraded
binder network and broke
degraded
andthe chain
broke thethrough a color change
chain through a color analysis.
change analysis.

Figure
Figure TheThe
10. 10. morphology
morphology of HTPE
of HTPE filmfilm at different
at different temperatures.
temperatures.

A total reflection infrared test was carried out on the HTPE film at different tem-
peratures during the slow cook-off process (because it is liquid at 160 ◦ C, no infrared
experimental analysis was conducted on it). Infrared experimental results at room temper-
ature are shown in Figure 11. Among them, the C–O–C stretching vibration peak was at
1276 cm−1 , and the N–H bending vibration peak was at 1537 cm−1 .
The change of the N–H bond with temperature is shown in Figure 12. From room tem-
perature to 140 ◦ C, the peak strength of the N–H bond increased firstly and then decreased
gradually. When the temperature was less than 100 ◦ C and in the slow cook-off process, the
weak post-curing phenomenon of the carbamate bond happened. When the temperature
was between 100 ◦ C and 120 ◦ C, the N–H bond was stable. When the temperature exceeded
130 ◦ C, the N–H bond began to weaken, indicating the start of breakage.
The change rule of the C–O–C bond was studied at different temperatures in the
process of the slow cook-off. The experimental results are shown in Figure 13. From room
temperature to 140 ◦ C, the C–O–C bond decreased with the increase in temperature, and
this process began to weaken at 100 ◦ C, and accelerated after 120 ◦ C. The ether bond
breakage of the HTPE film occurred after 120 ◦ C during the slow cook-off process. The slow
cook-off process of the HTPE film was a comprehensive breaking process of the carbamate
bond and ether bond. The breakage of the ether bond was earlier than the carbamate bond.
 A total reflection infrared test was carried out on the HTPE film at different temper-
atures during the slow cook-off process (because it is liquid at 160 °C, no infrared experi-
mental analysis was conducted on it). Infrared experimental results at room temperature
Polymers 2022, 14, 3699 are shown in Figure 11. Among them, the C–O–C stretching vibration peak was at101276 of 17
cm−1, and the N–H bending vibration peak was at 1537 cm−1.

Figure 11. The infrared spectrum of HTPE film at room temperature.

The change of the N–H bond with temperature is shown in Figure 12. From room
temperature to 140 °C, the peak strength of the N–H bond increased firstly and then de-
creased gradually. When the temperature was less than 100 °C and in the slow cook-off
process, the weak post-curing phenomenon of the carbamate bond happened. When the
temperature was between 100 °C and 120 °C, the N–H bond was stable. When the tem-
perature exceeded 130 °C, the N–H bond began to weaken, indicating the start of break-
age.
Figure
Figure11.
11.The
Theinfrared
infraredspectrum
spectrumof
ofHTPE
HTPEfilm
filmat
atroom
room temperature.
temperature.

The change of the N–H bond with temperature is shown in Figure 12. From room
temperature to 140 °C, the peak strength of the N–H bond increased firstly and then de-
creased gradually. When the temperature was less than 100 °C and in the slow cook-off
process, the weak post-curing phenomenon of the carbamate bond happened. When the
temperature was between 100 °C and 120 °C, the N–H bond was stable. When the tem-
perature exceeded 130 °C, the N–H bond began to weaken, indicating the start of break-
age.

Polymers 2022, 14, x FOR PEER REVIEW 11 of 18

Figure 12. (a)

(a) Change trend of N–H relative absorbance and (b) decomposition reaction process.
process.

The change rule of the C–O–C bond was studied at different temperatures in the pro-
cess of the slow cook-off. The experimental results are shown in Figure 13. From room
temperature to 140 °C, the C–O–C bond decreased with the increase in temperature, and
this process began to weaken at 100 °C, and accelerated after 120 °C. The ether bond break-
age of the HTPE film occurred after 120 °C during the slow cook-off process. The slow
cook-off process of the HTPE film was a comprehensive breaking process of the carbamate
bond and
Figure ether
12. (a) bond.
Change Theofbreakage
trend of the
N–H relative ether bond
absorbance andwas
(b) earlier than thereaction
decomposition carbamate bond.
process.

The change rule of the C–O–C bond was studied at different temperatures in the pro-
cess of the slow cook-off. The experimental results are shown in Figure 13. From room
temperature to 140 °C, the C–O–C bond decreased with the increase in temperature, and
this process began to weaken at 100 °C, and accelerated after 120 °C. The ether bond break-
age of the HTPE film occurred after 120 °C during the slow cook-off process. The slow
cook-off (a) Change
Figure 13.process trend
of the of C–O–C
HTPE film wasrelative
relative absorbance
absorbance and
a comprehensive and (b)
(b) decomposition
process ofreaction
decomposition
breaking reaction process.
process.
the carbamate
bond and ether bond.
3.4. Microstructure andThe breakage
Defect of the
Statistics ether bond
of Propellant was earlier
during the Slowthan the carbamate
Cook-Off Process bond.
3.4. Microstructure and Defect Statistics of Propellant during the Slow Cook-Off Process
In the process of the slow cook-off, the damage of the HTPB and HTPE propellants was
In the process of the slow cook-off, the damage of the HTPB and HTPE propellants
visually displayed by scanning electron microscopy (SEM), and the defects of propellants
was visually displayed by scanning electron microscopy (SEM), and the defects of propel-
were further quantitatively analyzed by the fractal dimension method [36,37]. These
lants were further quantitatively analyzed by the fractal dimension method [36,37]. These
collected SEM images were binarized to obtain new matrix data. By using the statistical
collected SEM images were binarized to obtain new matrix data. By using the statistical
method of box-counting dimension, r squares were divided, and the number of non-empty
method of box-counting dimension, r squares were divided, and the number of non-
squares N were counted. After taking the logarithms, using the correlation between
empty squares N were counted. After taking the logarithms, using the correlation between
logarithms, the slope was taken to obtain the box dimension, and the corresponding sta-
tistical defects were obtained by counting the box dimension values at different stages.
The results in Figure 14 show that both the HTPB propellant binder matrix and solid
filler will change with the increasing temperature. At 70 °C, the matrix structure of the
Polymers 2022, 14, 3699 11 of 17

logarithms, the slope was taken to obtain the box dimension, and the corresponding
statistical defects were obtained by counting the box dimension values at different stages.
The results in Figure 14 show that both the HTPB propellant binder matrix and solid
filler will change with the increasing temperature. At 70 ◦ C, the matrix structure of the
HTPB propellant binder was intact, and the surface of AP particles was smooth, without
the obvious interface “separation” phenomenon. At 170 ◦ C, the N–H bond began to break,
and at 190 ◦ C, the C–O bond began to break. The main cause of increasing cracks was
the breakage of carbamate bond. After 200 ◦ C, some micro-cracks appeared in the HTPB
propellant matrix. On the surface of AP particles, micro-defects appeared gradually with a
large number of holes. The AP particles can be found to escape from the binder system
during the slow cook-off process. Combined with the decomposition mechanism of AP
mentioned above, it is considered that the defects or cracks in the HTPB propellant during
Polymers 2022, 14, x FOR PEER REVIEW
the slow cook-off process were caused by three reasons. They are cracks in the12binderof 18

matrix, holes in the oxidizer and “separation” at the interface.

Figure14.
Figure Defectfigure
14.Defect figureofofHTPB
HTPBpropellant
propellantatatdifferent
differenttemperatures
temperaturesduring
duringslow
slowcook-off.
cook-off.

Comparedwith
Compared withthe
the HTPB
HTPB propellant,
propellant, thethe
HTPEHTPE propellant
propellant sample
sample was was
heatedheated
to 140to
140 ◦ C, and a total of 6 nodes between 70 ◦ C and 140 ◦ C were selected. The surface defects
°C, and a total of 6 nodes between 70 °C and 140 °C were selected. The surface defects of
of structural damage and box-counting dimension statistics indicated by SEM are shown in
structural damage and box-counting dimension statistics indicated by SEM are shown in
Figure 15.
Figure 15.
Figure 15 shows that when the temperature was below 70 ◦ C, the binder matrix
Figure 15 shows that when the temperature was below 70 °C, the binder matrix struc-
structure of the HTPE propellant was complete and the surface of AP particles was smooth.
ture of the HTPE propellant was complete and the surface of AP particles was smooth.
There was no obvious interface “separation” phenomenon between the matrix and solid
There was no obvious interface “separation” phenomenon between the matrix and solid
filler particles. With the temperature increasing, the most obvious cracks appeared at
filler particles. With the temperature increasing, the most obvious cracks appeared at the
the interface between the binder matrix and AP particles. At 120 ◦ C, the breakage of the
interface between the binder matrix and AP particles. At◦ 120 °C, the breakage of the C–
C–O–C bond occurred, and the N–H bond broke at 130 C. As a result, the HTPE binder
O–C bond occurred, and the N–H bond broke at 130 °C. As a result, the HTPE binder
system broke and degraded. The melt composed of the HTPE binder system’s products
system broke and degraded. The melt composed of the HTPE binder system’s products
gradually covered the micropores of AP, and filled the defects between the AP and binder
gradually covered the micropores of AP, and filled the defects between the AP and binder
interface. When the temperature reached 140 ◦ C, there were no obvious holes and defects
interface.
(in FigureWhen the temperature
15), and a complete and reached
dense140 °C, there
structure were
was no obvious
formed again. holes and defects
The results of the
(in Figure 15), and a complete and dense structure was formed again.
box-counting dimension show that the defects increased firstly and decreased at 120 The results of the
◦ C,
box-counting dimension show that the defects increased firstly and
and the maximum defect was 7.8%. When the temperature reached 140 C, the defect decreased◦ at 120 °C,
and the maximum
reduced defect
to only 4.2%, was 7.8%.
which When consistent
is basically the temperature
with thereached
surface140defect
°C, the
of defect re-
the HTPE
duced to only 4.2%, which
propellant at room temperature. is basically consistent with the surface defect of the HTPE pro-
pellant at room temperature.
Polymers 2022, 14, x FOR PEER REVIEW 13 of 18
Polymers2022,
Polymers 14,x3699
2022,14, FOR PEER REVIEW 1312ofof18
17

Figure 15. Defect figure of HTPE propellant at different temperatures during slow cook-off.
Figure
Figure15.
15.Defect
Defectfigure
figureof
ofHTPE
HTPEpropellant
propellant at
at different
different temperatures
temperatures during
during slow
slow cook-off.
cook-off.
3.5. Mechanical Properties of Propellant during the Slow Cook-Off Test
3.5.Mechanical
3.5. MechanicalProperties
PropertiesofofPropellant
Propellant during
during the
the Slow
Slow Cook-Off
Cook-Off Test
The mechanical properties of two propellants at differentTest temperatures are shown in
FiguresThe16–18.
The mechanical
mechanical properties
It can properties
be seen from oftwo
of two propellants
propellants
Figure 16a thatat at
the different
different
maximum temperatures
temperatures areshown
are
tensile strength shown
of the in
in
Figures 16–18.
Figurespropellant
HTPB It
16–18. It can can be seen
be seen
increased from
fromthen
firstly, Figure
Figure 16a that
16a thatand
decreased the maximum
theincreased
maximumattensiletensile strength
190 °C.strength
Below 150 of
of °C,the
the
HTPB propellant increased firstly, thendecreased
decreased andincreased
increased at190
190 ◦ C. Below 150 ◦ C,
HTPB
the σmpropellant
increased increased
due to thefirstly, then
post-curing of the HTPBand propellants.at The°C. Below 150 °C,
post-curing in-
the
the σ
σ m increased
increased due
due totothe
thepost-curing
post-curing of the
of HTPB
the HTPBpropellants. The
propellants.
creased the σm of the HTPB propellants but at a relatively slow rate. Between 150 °C and
m
post-curing
The increased
post-curing in-
the σ of the HTPB propellants but at a relatively slow rate. Between 150 ◦ C and 190 ◦ C,
creased
190 m
°C, the σm of the HTPB
themaximum tensilepropellants
strength began but at
toadecline,
relatively slow rate.
indicating Between
that 150 °C and
the post-curing of
theHTPB
190
the maximum
°C, tensile was
thepropellant
maximum strength
tensile beganCombined
strength
complete. tobegan
decline,
to indicating
decline,
with that experimental
the post-curing
the indicating
FTIR of the it
that the post-curing
results, HTPB
can of
propellant
the
be HTPB
seen that was
C–Ocomplete.
propellant andwas
N–H Combined
complete. with
bonds ofCombined
the the with
FTIRthe
polyurethane experimental
FTIR
in HTPBresults,
the experimental
propellantit can
results, beit seen
began canto
that
be
break C–O
seenat thatand
this C–ON–H andbonds
temperature N–H of the polyurethane
bonds
segment. of
Thethebreakage in
polyurethane the in
resulted HTPB
the propellant
in a HTPB
rapid began
propellant
decline tomaxi-
began
in the break to
at this temperature
break tensile
at this strength
temperaturesegment. The
segment. breakage resulted
The breakage in
resulted a rapid decline
in a rapid was in
decline the maximum
in the maxi-
mum of the HTPB propellant. When the temperature higher than
◦ C,190
tensiletensile
mum strength of the of
strength HTPB propellant.
thestrength
HTPB When When
propellant. the temperature was higher
the temperature than 190
wasagain.
higher than the
190
°C, the maximum tensile of the HTPB propellant increased Oxidative
maximum
°C, the maximum tensile strength
tensile of the
strength HTPB propellant
of the 16b.
HTPB increased
propellant again. Oxidative
increased crosslinking
crosslinking occurred as shown in Figure The vinyl in HTPB was again.
oxidized Oxidative
by AP,
occurred as shown in Figure 16b. The vinyl in HTPB was oxidized by AP, and the double
crosslinking
and the double occurred
bond was as shown
openedin to Figure 16b. Thebonds,
form peroxide vinyl indicating
in HTPB was thatoxidized
oxidativeby AP,
cross-
bond was opened to form peroxide bonds, indicating that oxidative crosslinking is stronger
and the is
linking double
strongerbond waschain-broken
than opened to form peroxide bonds,
degradation. In the indicating that oxidative
whole temperature range,cross-
the
than chain-broken degradation. In the whole temperature range, the mechanical properties
linking is stronger
mechanical propertiesthanofchain-broken degradation.
the HTPB propellant are theIn the whole
result temperature
of the interactionrange,
between the
of the HTPB propellant are the result of the interaction between oxidation crosslinking and
mechanical
oxidation properties and
crosslinking of the HTPB propellant
chain-breaking are the result of the interaction between
degradation.
chain-breaking degradation.
oxidation crosslinking and chain-breaking degradation.

Figure16.
Figure (a)The
16. (a) Therelationship
relationshipbetween
betweenmaximum
maximumtensile
tensilestrength
strengthand
andtemperature
temperaturein
inHTPB
HTPBand
and
HTPE
HTPE propellant
propellant (b)
(b) oxidation
oxidation of
of C=C
C=C in
in HTPB.
HTPB.
Figure 16. (a) The relationship between maximum tensile strength and temperature in HTPB and
HTPE propellant (b) oxidation of C=C in HTPB.
Polymers2022,
Polymers 2022,14,
14,xxFOR
FORPEER
PEERREVIEW
REVIEW 14 of
14 of 18
18
Polymers 2022, 14, 3699 13 of 17

Figure17.
Figure
Figure 17. Therelationship
17.The
The relationshipbetween
relationship betweenmodulus
between modulusand
modulus andtemperature
and temperaturein
temperature inHTPB
in HTPBand
HTPB andHTPE
and HTPEpropellant.
HTPE propellant.
propellant.

Figure18.
Figure
Figure TheThe
18.The
18. relationship
relationship
relationship between
between
between maximum
maximum
maximum elongation
elongation
elongation and temperature
and temperature
and temperature in and
in HTPB
in HTPB HTPB
and and
HTPE
HTPE
HTPE propellant.
propellant.
propellant.

Themodulus
The
The modulusand
modulus andmaximum
and maximumelongation
maximum elongationof
elongation ofthe
of theHTPB
the HTPBpropellant
HTPB propellantat
propellant atdifferent
at differenttemper-
different tempera-
temper-
tures are
atures are shown
are shown
shown in in Figures
in Figures 17
Figures 17 and
17 and 18.
and 18. The
18. Themaximum
The maximum elongation
maximum elongation decreased
elongation decreased gradually.
decreased gradually. When
gradually.
atures ◦ C, the
the temperature
When the the temperaturewas
temperature was below 150
was below
below 150 maximum
150 °C,
°C, the elongation
the maximum
maximum elongation decreased slowly.
elongation decreased Combined
decreased slowly.
slowly.
When
with the analysis
Combined with thetheofanalysis
maximum
analysis tensile strength,
of maximum
maximum tensileitstrength,
is mainlyitcaused
strength, is mainly
mainly by post-curing.
caused byby post-The
post-
Combined with of tensile it is caused
post-curing
curing. The increased
The post-curing the crosslinking
post-curing increased
increased the and decreased
the crosslinking
crosslinking and the maximum
and decreased
decreased the elongation
the maximum of the
maximum elonga- HTPB
elonga-
curing.
film. Between 150 ◦ C and 190 ◦ C, the maximum elongation decreased rapidly, and oxida-
tion of the HTPB film. Between 150 °C and 190 °C, the maximum
tion of the HTPB film. Between 150 °C and 190 °C, the maximum elongation decreased elongation decreased
tive crosslinking played a major role. When the temperature was higher than 190 ◦ C, the
rapidly,and
rapidly, andoxidative
oxidativecrosslinking
crosslinkingplayedplayedaamajormajorrole.
role.When
Whenthe thetemperature
temperaturewas washigher
higher
maximum elongation was stable. It indicates that the HTPB propellant had broken-chain
than 190
than 190 °C,
°C, the
the maximum
maximum elongation
elongation was was stable.
stable. ItIt indicates
indicates thatthat the
the HTPB
HTPB propellant
propellant
degradation and resulted in a flat maximum elongation. The modulus was the result of the
had broken-chain
had broken-chain degradation
degradation and and resulted
resulted in in aa flat
flat maximum
maximum elongation.
elongation. The The modulus
modulus
combined effect of tensile strength and elongation, which further indicates that the HTPB
was the result of the combined effect of tensile strength and
was the result of the combined effect of tensile strength and elongation, which further elongation, which further
propellant is a combined process of oxidation crosslinking and degradation chain-breaking
indicates that the HTPB propellant is a combined process of
indicates that the HTPB propellant is a combined process of oxidation crosslinking and oxidation crosslinking and
during slow cook-off.
degradation chain-breaking
degradation chain-breaking during during slowslow cook-off.
Based on the above analysis, it cancook-off.
be seen that in the slow cook-off process of the
Based on
Based on the
the above
above analysis,
analysis, itit can
can bebe seen
seen that
that in
in the
the slow
slow cook-off
cook-off process of of the
the
HTPB propellant, the change in the bond network structure is influencedprocessby two factors:
HTPB propellant,
HTPB propellant, the the change
change in in the
the bond
bond network
network structure
structure is is influenced
influenced by by two
two factors:
factors:
oxidative crosslinking and chain-breaking degradation. When oxidative crosslinking plays
oxidative crosslinking
oxidative crosslinking and and chain-breaking
chain-breaking degradation.
degradation. When When oxidative
oxidative crosslinking
crosslinking
a leading role, the modulus and maximum tensile strength of the HTPB propellant increase,
plays
whileaathe
plays leading
leading
maximum role, the
role, the modulusdecreases.
modulus
elongation and maximum
and maximum When tensile
tensile strength
chainstrength
degradation ofof the
the HTPB
HTPB
plays propellant
propellant
a leading role,
Polymers 2022, 14, x FOR PEER REVIEW 15 of 18

Polymers 2022, 14, 3699 14 of 17

increase, while the maximum elongation decreases. When chain degradation plays a lead-
ing role, the modulus and maximum tensile strength decrease. In different temperature
the modulus
segments, the and maximum
result tensilebystrength
is determined decrease.
a combination of In
twodifferent
factors.temperature segments,
the result is determined by a combination of two factors.
Compared to the experimental results of the HTPB propellant, the mechanical prop-
erties Compared
of the HTPE to propellant
the experimental
can be results
seen inof the HTPB
Figures propellant,
16–18. the mechanical
Under different proper-
temperatures,
ties of the HTPE propellant can be seen in Figures 16–18. Under different
the maximum tensile strength and maximum elongation of the HTPE propellant de- temperatures,
the maximum
creased tensile
gradually. strengthwith
Compared and the
maximum elongation HTPE
HTPB propellant, of the HTPE propellant
propellant decreased
also had a post-
gradually. Compared with the HTPB propellant, HTPE propellant also had a post-curing
curing phenomenon, but the post-curing phenomenon was very weak. Combined with
phenomenon, but the post-curing phenomenon was very weak. Combined with those FTIR
those FTIR experimental results, it can be seen that the C–O–C ether bond of the HTPE
experimental results, it can be seen that the C–O–C ether bond of the HTPE propellant was
propellant was broken and then melts were formed. The breakage of bonds and melts
broken and then melts were formed. The breakage of bonds and melts formed by products
formed by products result in a significant decrease in the maximum tensile strength and
result in a significant decrease in the maximum tensile strength and maximum elongation.
maximum elongation. However, the modulus of the HTPE propellant increases firstly and
However, the modulus of the HTPE propellant increases firstly and then decreases. It is the
then decreases. It is the result of the interaction of the C–O–C ether bond and N–H bond.
result of the interaction of the C–O–C ether bond and N–H bond.
3.6.
3.6.Change
ChangeofofPropellant
PropellantGel
GelFraction
Fraction
The gel fraction of a solid propellantrefers
The gel fraction of a solid propellant referstotothe
themass
massratio
ratio between
between thethe
gelgel gener-
generated
ated after solidification of the binder system and the total binder system in the
after solidification of the binder system and the total binder system in the solid propellant. solid pro-
pellant. This parameter is related to the properties of the propellant
This parameter is related to the properties of the propellant elastomer network underelastomer network
under
certaincertain conditions,
conditions, so theso the measurement
measurement of thisof this parameter
parameter has practical
has practical significance
significance for the
for the of
study study of the mechanical
the mechanical properties
properties and storage
and storage aging properties
aging properties of a propellant
of a propellant [38–40].
[38–40]. The changes
The changes in gel fraction
in gel fraction of theand
of the HTPB HTPB
HTPE andpropellants
HTPE propellants during
during the slowthe slow
cook-off
cook-off are compared
are compared in Figure 19. in Figure 19.

80 HTPB
HTPE

70

60
Gel/%

50

40

30
60 80 100 120 140 160 180 200 220
T/℃
Figure
Figure19.
19.The
Therelationship
relationshipbetween
betweengel
gelfraction
fractionand
andtemperature
temperatureof
ofHTPB
HTPBand
andHTPE
HTPEpropellant.
propellant.

ItItcan
canbebeseen
seenthat
thatthe
thegel
gelfraction
fractionofofthe
theHTPB
HTPBpropellant
propellantincreased
increasedfirstly,
firstly,and
andde-de-
creased at
creased at 190 ◦°C.
C. When
Whenthe thetemperature
temperature gotgot
to 200 ◦ C, the number of gel fractions increased
to 200 °C, the number of gel fractions in-
around around
creased 80%. The main
80%. factors
The mainaffecting the change
factors affecting of change
the propellant gel fractiongel
of propellant arefraction
post-curing,
are
oxidative crosslinking
post-curing, oxidative and chain-breaking
crosslinking degradation ofdegradation
and chain-breaking the binder network. Post-curing
of the binder net-
and oxidative
work. Post-curingcrosslinking will increase
and oxidative the gelwill
crosslinking percentage,
increase while
the gelthe degradation
percentage, of chain
while the
degradation of chain breaking will decrease the gel percentage. In the slow cook-offpropel-
breaking will decrease the gel percentage. In the slow cook-off process of the HTPE pro-
lant,ofthe
cess gelHTPE
the fraction decreased
propellant, thewith
gel the increasing
fraction temperature
decreased with thedue to the breakage
increasing of the
temperature
ether
due to bond.
the breakage of the ether bond.
3.7. Change Analysis of Propellant Slow Cook-Off Process
3.7. Change Analysis of Propellant Slow Cook-Off Process
During the slow cook-off test, the cracks in the binder matrix, the holes in the oxidizer
During the slow cook-off test, the cracks in the binder matrix, the holes in the oxidizer
and the “separation” of the interface are the three reasons for defects or cracks in the HTPB
and the “separation” of the interface are the three reasons for defects or cracks in the HTPB
propellant. In the heating process, increasing defects made the burning surface of the
HTPB propellant increase sharply. Figure 20 shows the schematic diagram of defect and
 resulting in an explosion of the HTPB propellant.
After the HTPE propellant was heated to 120 °C, the products generated by the break-
age of the carbamate bond and ether bond formed a “high temperature self-repair body”.
The “high temperature self-repair body” covers the surface of AP and will repair the de-
Polymers 2022, 14, 3699
fects and holes of AP and interface. The holes and cracks of the HTPE propellant can15also
of 17
be filled by these melts. The burning surface of the HTPE propellant will not increase
greatly. The “high temperature self-repair body” covering on AP reduces the sensitivity
of AP to pressure, so that the burning rate and burning surface of the HTPE propellant
crack formation. The breakage of the HTPB binder occurred at 170~190 ◦ C. When the
will not increase sharply at a high temperature. The internal pressure of the solid engine
temperature rose to about 200 ◦ C, AP holes appeared, and small white spots can be seen on
will not rise sharply because of the “high temperature self-repair body”. Thus, the re-
gray balls in the diagram. When the temperature rose further to 230 ◦ C, further breakage
sponse intensity of the HTPE solid engine in the slow cook-off test was reduced and its
of the HTPB binder occurred, and AP separated from the fractured crosslinked network,
low vulnerability was improved.
resulting in an explosion of the HTPB propellant.

Figure 20. The evolution of propellant defects and repair.

Figure 20. The evolution of propellant defects and repair.
After the HTPE propellant was heated to 120 ◦ C, the products generated by the
4.breakage
Conclusionsof the carbamate bond and ether bond formed a “high temperature self-repair
(1) The
body”. The ignition of the HTPBself-repair
“high temperature propellant in thecovers
body” process theofsurface
the slowof cook-off is mainly
AP and will repair
caused by the
the defects andhole of AP
holes at 200
of AP and°Cinterface.
and the separation
The holes of andAPcracks
from ofthethe
binder
HTPE system. The
propellant
ignition
can alsotemperature
be filled by of the melts.
these HTPE propellant
The burning is mainly
surface affected by thepropellant
of the HTPE HTPE binder. In
will not
the slow cook-off
increase greatly. process,
The “high thetemperature
carbon–carbon double bond
self-repair body” oncovering
the HTPBonpolymer chainthe
AP reduces is
opened andofoxidized
sensitivity crosslinking
AP to pressure, occurs.
so that With therate
the burning occurrence
and burning of post-curing, theHTPE
surface of the C–O
bond and N–H
propellant willbond have a tendency
not increase sharply at of aincreasing firstly andThe
high temperature. theninternal
decreasing and break-
pressure of the
solid
ing at engine
170~190will°C,not rise separates
which sharply because
the solid of the “high originally
particles temperature self-repair
attached body”.
to the Thus,
crosslink-
thenetwork.
ing response Theintensity of the HTPE
post-curing solid engine
phenomenon of thein HTPE
the slow cook-off is
propellant test was reduced
weak, and the de-and
its low vulnerability
composition was improved.
of the C–O–C ether bond and N–H bond happens during the slow cook-off.
These products will melt after 140 °C, and coat and fill between solid particles.
4. Conclusions
(2) The mechanical properties of the solid propellant change with the slow cook-off
(1) The ignition
temperature: under the of combined
the HTPB effect
propellant in the process
of oxidative of theand
crosslinking slow cook-off is mainly
degradation chain-
caused bythe themodulus
hole of AP at 200 ◦ C propellant
and the separation
breaking, of the HTPB increasesofgradually;
AP from the the binder
maximum system. The
elonga-
ignition
tion temperature
decreases of the
gradually HTPE
with the propellant
increasing istemperature;
mainly affected andby thethemaximum
HTPE binder.
tensile In
the slowincreases
strength cook-off process, the carbon–carbon
firstly, decreases secondly and double
thenbond on theThe
increases. HTPB polymer
HTPE chain
propellant
is opened
mainly and oxidized
undergoes crosslinking
bond breakage and occurs. With thewhich
decomposition, occurrence
makesofthepost-curing,
modulus and the
C–O bond and N–H bond have a tendency of increasing firstly and then decreasing and
breaking at 170~190 ◦ C, which separates the solid particles originally attached to the
crosslinking network. The post-curing phenomenon of the HTPE propellant is weak, and
the decomposition of the C–O–C ether bond and N–H bond happens during the slow
cook-off. These products will melt after 140 ◦ C, and coat and fill between solid particles.
(2) The mechanical properties of the solid propellant change with the slow cook-off
temperature: under the combined effect of oxidative crosslinking and degradation chain-
breaking, the modulus of the HTPB propellant increases gradually; the maximum elonga-
tion decreases gradually with the increasing temperature; and the maximum tensile strength
increases firstly, decreases secondly and then increases. The HTPE propellant mainly under-
goes bond breakage and decomposition, which makes the modulus and maximum tensile
strength decrease gradually, and the maximum elongation increase continuously.
(3) In the slow cook-off process, the gel fraction of the HTPB propellant increases due
to post-curing and oxidative crosslinking and decreases due to chain breakage. Compared
Polymers 2022, 14, 3699 16 of 17

with the HTPB propellant, the gel fraction of the HTPE propellant decreases continuously
due to the breakage of the ether bond. In the microscopic analysis, the gap and crack of
the HTPB propellant always increase, while the HTPE propellant shows the effect of melt
filling and decreases at the end. The analysis concludes that the breakage of urethane
and ether bonds of the HTPE binder system occurs after 120 ◦ C, which is the root cause
of the difference in thermal response of the two propellants. The HTPE propellant will
then generate a “high temperature self-repair body”; the molten products cover the defects
and holes of the AP and interface. Because of that, the degree of response of the HTPE
propellant will be reduced, and the low vulnerability of the HTPE propellant is improved.

Author Contributions: Conceptualization, X.W. and H.R.; methodology, X.W. and J.L.; validation, X.W.
and J.L.; investigation, J.L. and Q.J.; resources, J.L. and H.R.; data curation, X.W.; writing—original
draft preparation, X.W.; writing—review and editing, X.W. and H.R.; supervision, Q.J.; project admin-
istration, H.R. and J.L.; funding acquisition, H.R. and J.L. All authors have read and agreed to the
published version of the manuscript.
Funding: This research was funded by the National Natural Science Foundation of China, grant
number 21975024.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Acknowledgments: Thanks to the Science and Technology on Aerospace Chemical Power Laboratory
for experimental assistance.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or
in the decision to publish the results.

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