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Properties of Hydroxyl‐Terminal Polybutadiene (HTPB) and Its Use as a Liner

and Binder for Composite Propellants: A Review of Recent Advances

Article  in  Propellants Explosives Pyrotechnics · April 2022

DOI: 10.1002/prep.202100283

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doi.org/10.1002/prep.202100283 pep.wiley-vch.de

Properties of Hydroxyl-Terminal Polybutadiene (HTPB) and

Its Use as a Liner and Binder for Composite Propellants:
A Review of Recent Advances
Javier Carlos Quagliano Amado,*[a] Pablo Germán Ross,[a] Lidia Mattos Silva Murakami,[b] and
Jorge Carlos Narciso Dutra[b]

Abstract: This paper reviews hydroxyl-terminal poly- vant to its role in liners and propellants. We have also re-
butadiene (HTPB) used as liner and binder for composite viewed analytical techniques such as Fourier Transform
propellants, applied in rocket motors studied throughout Infrared Spectroscopy (FTIR) as a characterization technique
the last decades, emphasizing the recent advances. The for HTPB and HTPB-based polyurethanes. Reflection and
contribution aims to show the importance of HTPB in the transfectants FTIR may be a future trend in studies about
propellant composition and on the liner coating of the polymeric matrices for liners and propellants, and in the
rocket motor, which is in contact with the propellant grain. area of propellant formulations that use energetic binders,
This paper also shows that many researchers have thor- graphene and nanomaterials.
oughly studied several properties of HTPB, which are rele-
Keywords: binder · composite propellant · Hydroxyl-Terminal Polybutadiene (HTPB) · liner

1 Introduction cific role as binder in composite propellants [19–22], as a

liner [23–25], and as thermal insulation [26–28].
Hydroxyl-terminated polybutadiene (HTPB) is a telechelic Different types of HTPB are all characterized by low
polymer with more than two terminal hydroxyl groups ac- glass transition temperatures, excellent hydrophobicities,
cording to its functionality mainly used for manufacturing high levels of reactive functionalities, and low volatile con-
adhesives and coatings from one side and as a binder for tents. Despite its primary use in composite propellants, the
composite rocket propellant on the other side. It is a trans- facile reaction of HTPB polyols with curing agents such as di
lucent liquid with a characteristic odor and almost zero tox- and polyisocyanates provides an attractive route to the
icity, which has a viscosity similar to that of corn syrup. preparation of general-purpose polyurethane (PU) elas-
HTPB was introduced in the 1960s in the United States [1– tomers. These are used as castable elastomers, caulks, adhe-
3] after being developed by researcher Karl Klager, who is sives, sealants, waterproof membranes, foams, adhesives,
credited with the development of HTPB in the United potting and encapsulation compounds, and other rubber
States. He was an Austrian-born chemist who moved to the fabricated materials [29].
United States in 1950 [4]. Even though the development of HTPB comes from radical or anionic polymerization of
HTPB began in 1961, NASA did not launch it until the end 1,3-butadiene. The usual reaction to obtain HTPB is the free
of the1960's due to the popularity of polybutadiene acryl- radical polymerization that occurs at temperatures between
onitrile (PBAN) and carboxyl-terminated polybutadiene 100 and 150 °C in the presence of hydrogen peroxide, in a
(CTPB) formulations. HTPB did not see actual use in a rocket common solvent such as isopropanol, acetone, or meth-
motor until 1968 when Aerojet used it in a motor grain for- anol. On the other side, living anionic polymerization uses
mulation for the Astrobee D, a NASA-sponsored meteoro-
logical sounding rocket [5]. Other reports state that the
HTPB binder was first tested in a rocket motor in 1972 [6]. [a] J. C. Quagliano Amado, P. G. Ross
Many foundational research has been published about Applied Chemistry Department, Institute for Scientific and Techni-
HTPB shortly after its introduction [7–9]. However, very few cal Research for the Defense (CITEDEF), Ave. JB de La Salle 4397
reviews were specifically devoted to HTPB general features B1603ALO, Buenos Aires, Argentina
during that time [10–12]. Since then, still only a minor num- *e-mail: [email protected]
[email protected]
ber of reports were published giving a general overview of [b] L. Mattos Silva Murakami, J. C. Narciso Dutra
HTPB properties [13–16] as far as our investigation has InstitutoTecnológico de Aeronáutica (ITA), Praça Marechal Eduardo
found. Other publications concentrated in particular aspects Gomes, 50, Vila das Acácias, CEP 12228-900, São José dos Campos,
such as chemical modifications of HTPB [17, 18] and its spe- SP, Brazil

Propellants Explos. Pyrotech. 2022, e202100283 (1 of 19) © 2022 Wiley-VCH GmbH

Review J. C. Quagliano Amado, P. G. Ross, L. Mattos Silva Murakami, J. C. Narciso Dutra

anionic initiators such as lithium or lithium compounds [12]. ple, for propellants used in ballistic missiles, the range of
Several HTPB grades obtained by radical polymerization re- temperatures of use goes from 18 to 43 °C, while in air-to-
action using hydrogen peroxide as an initiator under semi- air uses, this stability interval should be even greater [41].
batch or continuous reaction are currently available on the These highlight the vital role of HTPB in composite propel-
market, such as R-45HTLO, R-45M, and R-20LM [30]. HTPB lant quality and stability, as we will describe hereon.
possessing high content of 1,4-units was synthesized by Figure 1 shows a scheme of HTPB-based Propellants,
anionic polymerization of butadiene, using alkyl-lithium from a formulation in the laboratory or pilot plant to cast-
containing silicon-protected hydroxyl group as initiator and ing in SRM, which are then ready for launching.
cyclohexane as solvent. This resulted in an increased elon- Its main properties are excellent hydrolytic stability,
gation at break compared to free radical polymerized HTPB good adhesion to different substrates, compatibility with
[31]. Zhu and colleagues [32] compared three different pol- plasticizers (spreadability), stability at low temperatures
ymerization methods for HTPB (radical, anionic, and ring- (down to 70 °C) and high capacity to absorb mineral fill-
opening metathesis). Although the main structures of ers. In addition, we found microstructure, functionality, vis-
HTPBs synthesized via the three polymerization methods cosity, and molecular mass among the most relevant HTPB
are similar, some molecular structure parameters are differ- properties influencing composite propellants’ character-
ent and could have a significant impact on the application istics. We will describe in this review each of these proper-
of HTPB. These changes decide on their possible uses. ties.
The only producer of military-grade HTPB in the US is
the Cray Valley company, belonging to the French company
Total. Another manufacturer is Evonik in Germany, however, 1.1 HTPB Microstructure
aimed at civil applications. Evonik makes an R-45HT product
that is not missile grade (as the R-45 M). This is an im- The microstructure of HTPB consists of three significant
portant point concerning availability for rocketry applica- configurations: cis, trans, and vinyl. Binder microstructure
tions. For example, US law prohibits the use of imported plays an essential role in the processability and mechanical
HTPB in certain weapon systems. HTPB manufacturer coun- properties of the propellant. The contents of these config-
tries are also found in Asia as India at the Vikram Sarabhai urations in the backbone of the polymer chain determine
Space Center (VSSC), China at Zibo Qilu Chemicals, Lanzhou the properties of end products.
Petrochemical and Idemitsu Kosan from Japan, although An ideal HTPB should have a trans: cis: vinyl ratio of
this list is not complete. 55 : 25 : 20. As a rule of thumb, increasing the trans content
On the other hand, in South America, the Brazilian com- enhances the tensile strength of the cured polymer, while
pany Petroflex (merger of a conglomerate of rubber compa- increasing the cis content usually enhances the elongation.
nies) produced HTPB until recent years and it is right now Furthermore, an increased vinyl content leads to enhance-
resuming production. Studies compared Petroflex HTPB ment in viscosity of uncured polymer matrix because the
with established HTPB R-45 M and R-45HT showing that is a presence of pendant vinyl group acts as an anchor and pre-
comparable product in terms of its rocketry uses [33]. Since vents the molecular slippage i. e., flow is restricted [42].
2019, the defense company Avibras acquired the technol- The properties of HTPB vary considerably depending on
ogy to produce HTPB in Brazil. At Lorena plant, located in the supplier. The most commonly obtained microstructure
São Paulo, an estimated production of 2,200 tons per year has a ratio of trans: cis: vinyl domains of 60 : 20 : 20. This
is foreseen by 2022–2023 [34, 35]. Currently, Avibras is the composition depends on the type of chemical synthesis
only HTPB manufacturing company in the Southern Hemi- used [43].
sphere. Argentina tried to produce HTPB in the province of Nuclear magnetic resonance (NMR) identified primary
Córdoba, but production was limited to laboratory scale and secondary hydroxyls in different HTPB microstructures
[36]. HTPB is a speciality product with an estimated cost of [44]. Also, the microstructure was determined by Fourier-
$55 per kilogram [37]. The world market was estimated at transform infrared spectroscopy (FT-IR) using Attenuated To-
120 million dollars in 2016, with an increasing trend [38, 49]. tal Reflectance (ATR) assembly was utilized for studying fac-
Its use as a composite propellant binder for solid rocket tors that affect it. Although the variation of initiator quan-
motor (SRM) is the most ubiquitous and relevant role tity and polymerization time severely affected OH value,
among its many uses. The ideal binder maximizes the pro- molar mass (Mn) and viscosity, microstructure changes were
pellant performance as it generates a high fuel value and relatively insignificant [45].
exhibits specific mechanical properties after curing for pro- Substituents affect the structure, although not the mi-
longed periods [40]. In this sense, HTPB must meet some crostructure of trans: vinyl: cis domains (Figure 2). For ex-
basic requirements. For example, the propellant must have ample, the presence of ferrocene in the HTPB has a strong
a limited viscosity to be processed without difficulties. effect on the structure, producing segregation of the soft
Moreover, this condition extrapolates to the HTPB binder. and hard segments in the PU obtained [46].
On the other hand, the propellant must not lose its proper- As said, microstructure influences mechanical proper-
ties in a wide range of temperatures to be valid. For exam- ties. Increasing trans content and decreasing vinyl content

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Properties of Hydroxyl-Terminal Polybutadiene (HTPB)…

Figure 1. HTPB-based Propellants: Formulation and Casting in SRM ready for launching.

Figure 2. Microstructure of hydroxyl-terminated polybutadiene.

significantly improved the mechanical properties such as 1.2 Functionality and Hydroxyl Groups
tensile strength and percentage elongation of the corre-
sponding PUs [47]. Functionality is defined as the average number of reactive
groups per molecule and thus becomes the most important
property of the prepolymer. In particular, for HTPB, the
functionality is the number of hydroxyl groups per polymer
chain. It is an important parameter because it determines

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Review J. C. Quagliano Amado, P. G. Ross, L. Mattos Silva Murakami, J. C. Narciso Dutra

the type of polymeric network formed. Functionality has viscosity data of the HTPB-TDI system showed a linear rela-
been thoroughly studied since early studies about HTPB tionship with temperature, with a change in slope at 45 °C
[8, 48]. The functionality calculation is usually made dividing [60]. Additives also affect viscosity. The addition of a nano-
the molecular weight by the equivalent weight. Several clay to HTPB decreases the end of mix viscosity of propel-
methods have been utilized to estimate functionality, such lants [61]. The type of catalyst influenced the extent of vis-
as gel elution method [49, 50]. Modern methods include cosity build-up in different HTPB-isocyanate systems,
13 C-NMR spectral data for determining functionality dis- measured by differential scanning calorimetry (DSC) [62].
tribution [51]. The functionality type distribution (FTD) of Sekkar et al. [63] studied the effect of dibutyl tin laurate cat-
HTPB can be also found by 1H-NMR techniques [52, 53]. alyst (DBTDL) concentration on the viscosity of HTPB cura-
Functionality can vary depending on the analytical tive systems. They observed that, based on viscosity data,
method utilized, such as gel point, dynamic mechanical, the cure reaction between TDI or isophorone diisocyanate
thermal analysis (DMTA), and tensile tests [54]. The higher (IPDI) with HTPB polymer occurred in two stages because of
the HTPB functionality, the stiffer the HTPB-PU network and the difference in reactivity between the isocyanate groups
the lesser the cure time [45]. present in IPDI and TDI.
The number of OH groups is determinant for HTPB- Overall, these findings show that viscosity studies are
based PU properties. For example, the triol/diol ratio of 2 : 1 worth to be continued to make propellant compositions
is suitable for resin with OH values in the range of 40–50, more process friendly, considering the technical difficulties
but, in the case of lower OH value resins, other combina- involved in mixing during propellant manufacturing. Also, it
tions, like triol/diol ratios of 3 : 1 at R = 0.8 and a ratio of 1 : 3 is an easily measurable parameter to monitor curing and
at R = 0.9 (R is the ratio of NCO to OH groups), are found to chemorheological properties of liners and propellants.
give optimum combinations of tensile strength and elonga-
tion. In higher OH value resins, the influence of the triol/
diol ratio is less significant [55]. Functionality is one of the 1.4 Thermal Stability of HTPB Binders
most critical factors that determine binder network struc-
ture. Different HTPB grades are available in the market to The study of thermal stability is justified because the ther-
such an end. mal degradation of HTPB binder is one of the most critical
factors that control the combustion rate of composite pro-
pellants within a specific range of operating pressures.
1.3 HTPB and HTPB-Based PU Viscosities Decomposition of HTPB-based binder under a dynamic
heating program is indicated by two significant stages of
The viscosity of HTPB usable in propellants is generally be- weight loss of different natures and indistinct separation.
tween 5000 and 15000 centipoises (cP). However, as the vis- The first stage is primarily depolymerization, cyclization,
cosity depends directly on the molar mass, the adequate and crosslinking of material not undergoing depolymeriza-
HTPB for SRM propellant manufacture does not have a mo- tion. The second stage is a decomposition of a residue
lecular mass greater than 2500-3000 Daltons. The propel- yielded in the first stage [64, 65]. In PUs based on HTPB, the
lant-grade HTPB R-45HTLO has a viscosity of 8000 cP at cured HTPB polymer’s thermal decomposition process was
23 °C [7]. The HTPB obtained by free radical polymerization predominantly characterized by HTPB (R-45 M resin), con-
generally has a bimodal distribution, with a fraction with a firming that the urethane bond cleavage is the first step in
lower molecular mass and a higher molecular mass [36]. the decomposition. After the urethane bonds are cleaved,
The synthesis method determines its microstructure and and the diisocyanate volatilizes (above approximately
molecular weight distribution [32]. Therefore, batch-to- 430 °C), HTPB behaves as though it had never been cross-
batch variation in HTPB prepolymer in terms of molecular linked [66]. Other authors showed that the thermal degra-
weight and molecular weight distribution may be the root dation of HTPB-based propellant binder occurred in three
cause for the variation or uncertainty in the cured mechan- main stages: the first one due to plasticizer di-octyl adipate
ical properties of the propellant. Further, the authors con- (DOA) decomposition, and the second and third related to
cluded that the viscosity of the HTPB prepolymer, if de- the partial HTPB/IPDI binder and total ammonium perchlo-
termined accurately, is indicative of changes in the rate (AP) thermal decomposition [67].
molecular mass [56]. Regarding this, as mentioned, the vis- Adding the curing agent to the polybutadiene resin in-
cosity of the HTPB increases with an increase in vinyl con- fluenced the energetics rather than the kinetics of HTPB R-
tent [38]. 45 M thermal decomposition [63]. However, Kumar and co-
Numerous studies on the viscosity of HTPB cured with workers [68] in a detailed kinetic and thermodynamic study
isocyanates have been carried out [57–59]. Viscosity was indicated significant variation in the activation energy for
measured to monitor the reaction of HTPB with toluene dii- decomposition with varying isocyanate curative groups in
socyanate (TDI). The increase in apparent viscosity was the HTPB-based PU energetic matrices.
found tooccur of two stages, with the rate constant of the HTPB is generally stable up to temperatures of around
first stage being greater than that of the second [31]. The 300 °C. The thermal stability of PUs obtainable with differ-

Propellants Explos. Pyrotech. 2022, e202100283 (4 of 19) © 2022 Wiley-VCH GmbH

Properties of Hydroxyl-Terminal Polybutadiene (HTPB)…

ent isocyanates hexamethylene diisocyanate (HMDI), IPDI samples of similar hydroxyl value and molecular weight.
and 4,4’-diisocyanate dicyclohexylmethane (H12MDI) based Gumstock properties depended more on the hydroxyl con-
on HTPB polyol is as follows: HMDI-HTPB, IPDI-HTPB, and tent [77]. Fillers influence mechanical properties. These
H12MDI-HTPB in the range 300-420 °C [69]. Increasing the were evaluated for HTPB/TDI, MDI, HMDI, and IPDI with
amount of crosslinking causes less of the sample to decom- three different fillers (carbon black, kaolin and antimony tri-
pose in the first step. oxide) were evaluated, with better values for the HMDI sys-
In rocket motor environments, since HTPB is exposed to tem [78]. The general trend is that when the PU network is
extreme temperatures (above 2000 K), high pressures more crosslinked, the tensile strength is higher, con-
(2.027–10.13 GPa), and heating rates (as high as 106 K/s), sequently with a reduced elongation.
there is very little time for exothermic cross-linking and cyc- Nowadays, polyols are replaced with small diol com-
lization to take place. Therefore, depolymerization becomes pounds in PUs structure to improve their mechanical and
the dominant process [70]. However, despite propellant thermal properties [73]. Manjari and coworkers [55] studied
combustion being faster, the reaction kinetics and mecha- the influence of increasing hydroxyl content from trimeth-
nisms derived from the slow heating rate experiments can ylolpropane (TMP) at the expense of hydroxyl content from
still be used to predict decompositions under combustion butanediol. HTPB resins with high molecular weight, low
condition [71]. functionality, and low hydroxyl value require higher levels
of trifunctional curing agent and higher R values to obtain
outstanding mechanical properties, especially elastic prop-
1.5 Mechanical Properties of HTPB Liners for Composite erties, compared to low molecular weight, high function-
Propellants ality resins.
Although thoroughly studied, research in the mechan-
Mechanical properties of HTPB-based liners mainly depend ical properties of liners for composite propellants is con-
on the curing agent, NCO/OH ratio, chain extender nature, tinuously ongoing, as liner compositions are being devel-
microstructure [72], and crosslinkers [21] (Table 1). oped. Kitinirunkul and coworkers [73] studied the effect of
Table 1 summarizes reports related to mechanical prop- antimony dioxide and Carbon Black on the mechanical
erties of HTPB-based PUs used as liners for composite pro- properties of HTPB/liners, finding an increased elongation
pellants and does not pretend to compile the significant compared to a reference sample. In another study, for-
amount of work done in this particular area. As shown in mulations with HTPB/IPDI liners used two types of carbon
Table 1, for four samples of HTPB with varying hydroxyl black. The tensile strength and the elongation at break val-
content and molecular weights the gumstock properties ues of the standard PU liner were 1.3 MPa and 270 %, re-
(mechanical properties and sol content) cannot be related spectively. After adding 10 % carbon black to the PU liner,
to functionality distribution as would have been possible in the values increased to 1.77 MPa and 370 % [74]. With re-

Table 1. Mechanical properties of HTPB based liners for composite propellants.

HTPB type Curing Filler or Crosslinker Tensile Elongation Reference

Agent strength (%)
(MPa)
HTPB (Zibo Qilong Chem., China) and high 1,4- MDI 1,4-BDO 0.77 to 65 to 650 [72]
cis HTPB 4.57
R45-M IPDI Carbon Black 0.81 to 220 to 860 [73]
1.48
HTPB (Zibo Qilong Chem., China) IPDI Triol (TMP)/Diol (HT) = 1 1.55 100 [74]
HTPB Mw = 3420 Da, Hydroxyl number: 0.64 IPDI Triol (TMP)/Diol (HT) = 0.5 1.5 90 [75]
and functionality = 2.2; from Zibo Elim.
HTPB (ISPO TDI TMP and TEA 0.78 800 [76]
Polymer) Mw 2800 Da plus
Four grades, different OH (21.1 to 40 mg KOH/ TDI – 0.55 to 200 to 600 [77]
g); Mw from 10440 to 19700 0.71
HTPB (Nocil, India) Mw = 2600, Hydroxyl val- MDI, TDI, DOA plus sequential addition of Carbon TDI: 1.5 123 [78]
ue = 37 HMDI, IPDI Black, Sb203, kaolin, and wood resin MDI: 1.6 100.5
as fillers HMDI: 74.3
1.42
HMDI: 153
1.43
TMP: trimethylolpropane; TEA: triethylamine; HT: 1,2,6 hexanetriol; MDI: 4,4’-Diphenylmethane isocyanate (MDI); Mw: molar mass; ISPO:
ISRO-Polyol (derived from castor oil).

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Review J. C. Quagliano Amado, P. G. Ross, L. Mattos Silva Murakami, J. C. Narciso Dutra

spect to the relation between functionality and mechanical measured according to ASTM or other accepted standards,
properties, HTPB with the lowest effective functionality re- as reported [75]. Overall, having mechanical properties of
sulted in the elastomer with the lowest cross-linking density propellants within specifications is fundamental to manu-
and stress at break [32]. facture reliable SRM, able to withstand stress during harsh
The binder impacts the propellant‘s mechanical and transportation and/or storage conditions and of course ex-
chemical properties as well as processing and aging. HTPB treme accelerations during SRM launch.
is preferred to other binders (such as CTPB, PBAN, GAP, or
NC) as it allows high solid loadings [69]. When HTPB acts as
a binder for composite propellants, mechanical properties 1.6 Adhesion of HTPB Liner to Insulator and Propellant
differ from polymer acting as a liner. Table 2 summarizes re-
ports related to mechanical properties of HTPB-based PUs In SRM manufacture, applying a thin layer of HTPB-based
used as a binder for composite propellants. liner ensures a good bond between the insulator and the
As seen in Manjari et al. [55] study, variations in OH propellant. The insulator is bonded to the motor case, and
number lead to broad dispersion in tensile strength and the liner acts as elastomeric heat-shielding materials. Liner
elongation values of composite propellants. HTPB resins compositions should preferably be based on the same
with high molecular weight, low functionality, and low hy- binder system used in the propellant formulations. The in-
droxyl value require higher levels of trifunctional curing terface properties are fundamental to avoid debonding. De-
agent and higher NCO/OH ratios to obtain outstanding me- bonding along the propellant/liner interface is one of the
chanical properties, especially elastic properties, compared primary ways rocket motor structural integrity can fail. Fig-
to low molecular weight, high functionality resins. In anoth- ure 3 shows different components in a cross-section of an
er study, five different HTPB prepolymers with similar OH SRM case, from mixing components to final assembly.
numbers gave propellant mechanical properties in a few in- When storing composite solid propellants for long peri-
stances, contrary to the predicted values even though the ods, specific components such as burning rate catalysts,
NCO/OH ratio (R ratio) was within 0.7–0.9. This highlights plasticizers, and other low molecular weight molecules mi-
the attribution of the molar mass and the variation of the grate into the liner and thermal insulation layers. It in-
molar mass distribution as the root causes for the variation/ variably results in poor mechanical and ballistic properties
uncertainty in the cured mechanical properties of the pro- of the propellants. Consequently, adhesion is impaired. The
pellant [77]. In every case, mechanical properties should be

Table 2. Effect of different HTPB binders on the mechanical properties of composite propellants.

HTPB Propellant composition Tensile strength Elongation Reference

(MPa) (%)
Four grades, different OH (20 to 43 mg KOH/g); 67 % AP, 18 % Al, 10 % HTPB/TDI 1.29 to 1.08 20 to 111 [55]
Mw from 2600 to 4500
OH number 44.7 mg KOH/g; Mw 2586 70 % AP, 17 % Al, 11.74 % HTPB/TDI 3 74 [81]
OH value 41.7 to 42.3 mg KOH/g 67.6 % AP, 18 % Al, 10.78 % HTPB + TDI 0.48 to 0.76 42.56 to 53.4 [56]

Figure 3. Different components in a cross-section of a SRM.

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Properties of Hydroxyl-Terminal Polybutadiene (HTPB)…

typical fracture mode of the interface is the cohesive failure of additives and tailoring NCO/OH ratio, this problem still
within the adhesive. persists, that is why continued research in this area is of ut-
Dilsiz and Ünver [76] have shown that enhancing the most importance.
crosslink densities of liner via a trifunctional aziridine cross-
linking agent inhibited migration. Gercel et al. [77] found
that by using the butylene-imine trimesoylaziridine (BITA) 1.7 Curing Kinetics of HTPB with Isocyanates and
binding promoter in optimized amounts of 1.0 and 1.5 wt % “PotLife”
by weight in the elastomer compositions, it is possible to
optimize the adhesive and bonding properties. They com- During the curing process, chemo-rheology characteristics
pared BITA with tris[1-2-methylaziridinyl] phosphine oxide are in operation, determining HTPB-based PU processability.
(MAPO). They found that bond promoter BITA gives better As the cure proceeds, the molecular size increases, and so
bonding performance between the composite-metal sys- does the cross-linking density, which decreases the mobility
tem and better mechanical properties when compared with of the molecules [14]. The most important events during
the elastomers with the bond promoter MAPO. the curing of thermoplastic polyurethanes (TPUs) are the
For an HTPB binder cured with IPDI isocyanate and a bi- development of viscosity and the reaching of gel point.
functional aziridine (MAPO) as a bond promoter, the max- Consequently, chemorheological analysis is a suitable meth-
imum T-peel values found were for the NCO/OH ratio of od for evaluating TPU curing kinetics [51].
1.15 and the triol/diol ratio of 0.054. These highlight bond- Isocyanates are used for curing HTPB. One of the re-
ing agents’ importance [73, 78]. Kakade and coworkers [79] quirements is that the system has a long cure time (“pot
found that interface properties highly depend upon the life”) to perform motor case lining before crosslinking and
particle size of ammonium perchlorate (AP) and the coarse- liner solidification occurs. The pot-life of a binder system is
fine ratio of AP in the propellant formulation. They stated usually defined as the time interval that the viscosity in-
that as the percentage of fine AP increases, the peel value creases to a specific value, for example, 20,000 mPa.s [86].
decreases. However, it is more frequently found that the Highly-filled composite based on IPDI showed the highest
propellant‘s resistance to peeling increases as fine AP in- crosslinking density (CLD) and modulus in comparison to
creases [47, 80]. other curing agents (HDI, TDI), retaining tensile strength
Increasing the thickness of HTPB-based liner with nitrile and adequate elongation [87]. For long cure, aliphatic iso-
rubber (NBR) and ethylene propylene diene monomer cyanates are used, with less reactivity than aromatic ones.
(EPDM) heat-resistant based insulators improved the adhe- Figure 4 shows the PU liner formed by reaction between a
sion strength of the insulator and propellant.These materi- polyol and TDI (above) and IPDI.
als act as thermal protection for rocket motor cases. Liner Concerning HTPB functionality, as this increases the
cure time considerably affects adhesion strength. The lack stiffer the network is, while the cure time will be shorter. On
of plasticizer in the liner applied by a spray lining machine the other hand, the lower the functionality, the higher the
resulted in excellent adhesion strength, as it required a molecular mass, and the more elastic network is obtained
minimum viscosity for application [80]. For the thickness of for a given number of functional groups. Network structure
the heat-insulation layer, it was stated that as this increases, can be regulated through the isocyanate/hydroxyl ratio
the weakening of the interfacial bonding property becames [88]. Temperature-humidity conditions are fundamental in
more significant [81]. These authors reported that water in attaining the proper cure [89]. The curing ratio NCO/OH is
the insulator consumes the curing agent near the liner/pro- an important parameter that has an intense impact on me-
pellant interface, decreasing the interfacial bonding prop- chanical characteristics of propellant but slightly impacts
erty. Using cyclodextrin as an inhibitor agent in the PU ballistics. DSC was used to measure curing of HTPB and
binder could prevent themigration of plasticizers to the IPDI, following second-order kinetics [90]. It was shown that
EPDM thermal protection [82]. Plasticizers are added to pro- that the order of increased intensities of the tan δ curves
pellants to improve their mechanical properties, impart with four isocyanates reacted with HTPB follow the order
lower viscosity for mixing and augment pot life and adhe- HDI > IPDI > H12MDI > Desmodur E305™. As tan δ repre-
sion. A plasticizer agent like DOA is frequently used to im- sents the ratio of the viscous to elastic response of a viscoe-
prove the casting properties [67]. Plasticizers for solid pro- lastic material (the energy dissipation potential) this trend is
pellants have been modified with high-energy chemical correlated to the decrease in elastic response. This trend
groups, as well as HTPB was modified [83, 84]. Migration of could be also determined by DSC measuring of heat of re-
the volatile low molecular weight plasticizer to (and from) action, as a metrics of cure kinetics [91, 99].
the surface of the formulation is a significant obstacle to us- Related to the effect of different additives on the cure of
ing energetic binders in solid propellant formulations [85]. HTPB and isocyanates, curing of HTPB/IPDI/DOA binder in
The loss of adhesion between the propellant and in- the presence of nano aluminum was studied, showing that,
sulatorisone of the most critical problems in solid propel- for the test conditions, a size reduction of metal particles
lant motors mainly due to the migration of plasticizers to slowed down the increment of the rate of curing, measured
the interface of propellant and insulators. Although the use by viscosity [92, 100]. The curing process of metallo-modi-

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Review J. C. Quagliano Amado, P. G. Ross, L. Mattos Silva Murakami, J. C. Narciso Dutra

Figure 4. PU liner structure formed by reaction between a polyol and TDI (above) and IPDI (below).

fied HTPB (Butacene) and IPDI presents two chemo- faces must withstand extreme accelerations during SRM
rheological stages due to the NCO groups. The same was launch, stressing the importance of attaining an efficient
studied with HMDI. The 80 °C assay reveals a gelation time curing. The majority of the contributions agree in that ali-
of 36 minutes, with a maximum rate at 80 minutes of the pathic isocyanates have a slower rate of cure than the ar-
reaction, and PU formation can be considered complete omatic ones, while retaining tensile strength and elonga-
when close to 6 h. In contrast, the system cured at 50 °C tion within specifications. Bi-curative systems is a promising
only accomplished gelation [51]. It was found that the pot area to study, as permit the regulation of pot life.
life of the system depends on the catalyst mass fraction in
the binder system composedof HTPB and a trimer of
hexamethylene-1,6-diisocyanate (HDI-trimer) with 1,4- 1.8 Binder Network Structure: Effect of Chain Extenders
diazabicyclo[2.2.2]octane (DABCO) as a catalyst. When the and Crosslinkers
mass fraction of DABCO was 0.216 wt%, the pot life of the
HTPB/HDI-trimer binder system reached 4 h. It should be Polymeric binders hold together solid fuel and oxidant par-
noticed that other catalysts such as triphenyl bismuth (TPB), ticles that constitute composite propellants, forming a solid
dibutyl tindilaurate (T-12) and 3,5-dinitro salicylic acid elastic mass that can withstand thermal and mechanical
(DNSA) are preferred instead of DABCO when it comes to stresses. The polymeric binders used most frequently are
composite propellant formulation. Size of catalyst may be polyurethanes or polybutadienes, also used as fuel [98].
considered for DNSA, which is a solid at room temperature Binder formed by HTPB and diisocyanates is constituted by
[93, 94]. soft and hard segments, respectively. The soft segments
An experimental study to determine the dependence of contain macrodiol chains, and the hard segments are
the viscosity and shear stress of HTPB and dimeryl diisocya- formed by diisocyanate and a chain extender diol. The first
nate (DDI) liner on curing time indicated that the liner vis- block provides plasticity to the material, while the second
cosity and shear-stress dependency on time matched to provides rigidity and elasticity through physical crosslinking
pseudoplastic fluid model. For low shear rates, the viscosity due to hydrogen bonds between the urethane groups and
build-up was highest. However, when the shear rates in- hard segments [99]. Figure 5 depicts the binder network
creased, the viscosity build-up slowed down considerably structure, showing the soft and hard segments:
with time, increasing only by one order of magnitude [95]. During curing with isocyanates, eventually, a post gel
A bi-curative system based on TDI and IPDI proved effi- structure of the binder network is achieved, which depends
cient for extending pot life. In general, pot life experienced on several factors, such as the molecular structure of the
with TDI is about 4–5 h, and for IPDI, the same could be network, the number of side chains, and the chain length
around 12–16 h. However, the use of IPDI as a curative is distributions, among others, as thoroughly studied by Sek-
associated with specific adverse issues, as bad adhesion to kar and Kumar [19]. Furthermore, the balance between the
insulator [96]. Numerical models were presented for pre- hard and soft segments dramatically affects the physical
dicting the curing kinetics of HTPB with isocyanates [97] properties of segmented polyurethanes [100]. Therefore,
showing that this is an area of continuous refined research. regulating the hard and soft segment ratio is a tool for tai-
To sum up, curing kinetics determination is fundamental loring properties of TPU formed by HTPB and diisocyanate.
to attain a proper cure and adhesion of liner-propellant and Hydrogen bonding between the rigid segments, as re-
liner-case interfaces. It should be pointed out that inter- vealed in IR-spectroscopy, promotes the segregation of the

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Properties of Hydroxyl-Terminal Polybutadiene (HTPB)…

bonded sites that modify PU properties by changing mor-

phology from linear to the network structure [75]. Various
papers have stressed that increasing crosslinker content im-
proves mechanical properties [21, 75, 108]. Figure 6 shows a
schematic of a branching component, a difunctional chain
extender and a difunctional curative.
The addition of crosslinking mixtures based on trimeth-
ylolpropane (TMP) as crosslinker and 1,3-butanediol (BD) as
chain extender lead to a remarkable enhancement in the
propellant mechanical properties. Samples containing TMP:
BD (2 : 1) provide the highest strength, while samples con-
taining TMP:BD (1 : 2) show the highest strain over all the
NCO/OH ratios [21].
Generally, branching in crosslinker increases the cross-
link density, improving mechanical properties. This con-
clusion was reached and reported by our group [28]. In ad-
dition, different crosslinking mixtures significantly affect the
mechanical properties of HTPB-based composite propel-
Figure 5. Simplified scheme of binder network structure for solid lants, giving multiple possibilities for new formulations.
propellant [Circles represent hard segments (isocyanates plus chain
extenders) and ondulating lines represent soft segments (HTPB
chains)].
1.9 Aging and Antioxidants

The aging of solid propellants refers to the deterioration of

nanosized hard segment domains in the bulk of soft seg- their physical properties with time. It is due to the cumu-
ment in the chain-extended PU elastomer. The phase segre- lative damage done to the grain (such as by thermal cycling
gation imparts exceptional mechanical properties to the and load applications) during storage, handling, or trans-
polymer [74]. According to the crosslinking density, one of port. It can also be due to chemical changes with time, such
the main factors that influence the properties of the propel- as the gradual depletion (by migration or evaporation) of
lant is the type of elastomeric network formed with the certain liquid plasticizers or moisture absorption.
binder. The higher the crosslinking density, the better the Among propellants components, the binder is one of
mechanical properties [101]. particular sensitivity to aging. The binders were shown to
Chain extension agents (extenders) reduce the branch- be highly susceptible to oxidation due to considerable un-
ing of the chains, creating a looser, less rigid polyurethane saturation in the polymer structure and easy access of at-
network. A chain extender has two functional groups div- mospheric oxygen, as in the case of an open core config-
ided by a spacer, which may regulate the hardness of the uration of rocket motors [67]. The reaction of double bonds
material. Crosslinkers link multiple molecules together, such with atmospheric oxygen forms peroxides and epoxides
as telechelic HTPB. Crosslinkers (polyols, amines) have func- [103]. Under such conditions, it is quite possible for the pro-
tionalities of three or more, by which they can react with pellant to age, causing cracks in the combustion surface
more than two monomers or prepolymers, thus forming a and changing the original configuration. This drawback was
crosslink. If the components to be linked are polymers, solved in one contribution by adding 6 % hydroxyl-carbox-
there is no visible difference between curing and cross- yl-terminated polybutadiene (HCTPB) and ferric ions. It fa-
linking [102]. Chain extenders and crosslinkers are two the cilited ionic bonds (COO Fe3 +) formation, proposed as a
most important categories of additives with two or more

Figure 6. Scheme of a branching component, a difunctional chain extender, and a difunctional curative.

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Review J. C. Quagliano Amado, P. G. Ross, L. Mattos Silva Murakami, J. C. Narciso Dutra

strategy to alleviate the inherent self-healing problem for aging limit is usually determined by full-scale motor firings
HTPB elastomer [104, 105]. at various periods after manufacture, say 2 or 3 years [112].
To avoid or at least retard degradation, antioxidants are However, on the other side, it was considered as short a
normally added. The antioxidant most used is 2,6-di-terbu- lifetime of 7.5 years at 20 °C, predicted for composite pro-
tyl hydroxytoluene (BHT). Several studies have evaluated pellants based on HTPB [63]. A shelf life of around 10 years
the effect of antioxidants on HTPB. For example, an increase was reported [113]. A composite propellant formulation
of HTPB reactivity was determined against IPDI when the with an initial elongation of 63.24 % was conditioned at
BHT concentration was reduced during the aging [106]. The 60 °C for a prolonged period, and the time for the elonga-
use of antioxidant 2,2’-methylene-bis (4-methyl-6-tert-butyl- tion to be reduced to 50 % is calculated to be 1.2 years
phenol) (AO2246) increased the oxidation initiation temper- [114]. The final properties of the propellant grain as a func-
ature by 6 °C to HTPB alone [107]. A comparative assess- tion of the time interval between the batch preparation and
ment among AO2246, 2,6-di-tert-butyl-4-methylphenol the day of rocket motor casting were studied in detail for
(BHT),p-phenylenediamine (p-PDA) and triphenylphosphine the Brazilian Aerospace Program. Over the storage time,
(TPP) regarding stabilization of HTPB binder under accel- there was a decrease in elongation, an increase in hardness,
erated ageing (six months at 65 °C) was carried out. AO2246 and a reduction in tensile strength, in accordance to what
yielded the best performance. Meanwhile, BHT was much expected from the specific reports above referred. This de-
less protective. TPP acted as a pro-oxidant, causing severe terioration of mechanical properties is due to the simulta-
degradation of the binder, and p-PDA was not manageable neous occurrence of physical and chemical changes in the
to be assessed due to the lower curing degree of the result- cured propellant.
ing polyurethane [108]. Temperatures around 60 °C accel- One report states that the propellant tends to become
erate aging [109]. softer with increased resting time and hardness reduction
Table 3 summarizes most utilized antioxidants in com- [115]. However, this finding is for the aging of uncured pro-
posite propellants: pellant. HTPB tends to be harder with time when the pro-
In general, deterioration of propellant properties and pellant is fully cured [120].
loss of mass is associated with plasticizer exudation to the Chemical and physical processes associated with the ag-
surface [110]. The aging-related decline plays a vital role in ing of the HTPB binder were studied by Celina and co-
the safe-life estimation of the solid propellant-based rocket workers using thermogravimetric analysis (TGA) [123]. They
motor. Typically, any SRM minimum service life requirement concluded that crosslinking is the dominant process at
is 10 years after casting the propellant and/or after assem- higher temperatures and that the degradation involves only
bly of the rocket motor [111]. With small rocket motors, the limited hardening in the bulk of the material.

Table 3. Most common antioxidants for composite propellants.

Acronym Chemical name Structural formula Reference

AO2246 2,2'-methylene-bis(4-methyl-6-tert-butylphenol [114], [115]

BHT 2,6-di(tert-butyl) hydroxytoluene [113], [115]

pPDA p-phenylenediamine [115]

TPP Triphenyl phophine [115]

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Properties of Hydroxyl-Terminal Polybutadiene (HTPB)…

1.10 Analytical Methods for HTPB Table 5. Requirements for the main analytical parameters for
HTPB, according to the MIL H 85497-81 Type I standard.
A review was published on methods for characterization
Physico-chemical parameter Range values, according to
and determination of polymers used in aerospace, includ- MIL-H 85497-81 type I [Ref. 113]
ing those based on infrared spectroscopy [124]. Table 4
summarizes the main parameters that characterize the dif- Hydroxyl number (mmol/g) 0.75 a 0.85
ferent HTPBs, that determine their performance in a com- Humidity (%) 0.10 maximum
Acid number (mg KOH/g) Not specified
pound propellant.
Viscosity (cP, 25 °C) 4000 a 8000
For comparison, a commercial HTPB from Chinese Zibo Density Not specified
Qilong Chemicals has a molecular mass between 2300 and
3500 Daltons, as can be seen on the company information
website.
To define a particular HTPB application, the main pa- 1.10.2 Hydroxyl Number
rameters that determine the use as a binder or liner for a
composite propellant should be within the ranges estab- Hydroxyl number determines the potential number of
lished by the standards. Table 5 indicates the parameters chemical bonds that HTPB could establish. For hydroxyl
that the HTPB must meet according to the MIL standard number determination, acetylation using acetic anhydride
(from the United States): for OH number determination is considered to be accurate,
For this reason, only R-45 M HTPB resin is almost the reliable, and reproducible when conducted under stand-
only one that could comply with these requirements and is ardized conditions. However, it is labor-intensive and time-
also known as military-grade HTPB. consuming. About its influence on binder properties, we
have already summarized in Table 2 the effect of HTPB OH
number on mechanical properties of composite propellants.
1.10.1 Infrared Spectroscopy (FT-IR) Manjari et al. [55] concluded that HTPB prepolymer with hy-
droxyl number between 40–50 mg KOH/g is favorable for
FT-IR spectroscopy is an essential analytical tool in modern the production of large-scale propellants grains as this elim-
laboratories. Pedreira et al. [124] cites the development of inates batch-to-batch fluctuation in mechanical properties.
an FT-IR methodology, which uses another band, free from FT-IR methodologies for OH number determination were
hydrogen bonds, around 3610 cm 1, observed in solution, developed by our group in medium infrared (MIR) and
with good precision. FT-IR was used to evaluate the hydrox- near-infrared (NIR) for polyesters (OH number range 37–
yl content of HTPB [125], measuring the absorption band at 310 mg KOH/g), without derivatization [28]. Hydroxyl num-
3450 cm 1. At the same time, the formation of epoxides by ber measurement is mandatory for determining the binder
oxidation can be estimated by determining the FT-IR ab- network structure to be formed by HTPB and isocyanates.
sorption of the peak at 3450 cm 1 and its overtone [116].
FT-IR spectroscopy was utilized to quantify the extent of
HTPB reaction with IPDI to polyurethane [117, 118]. The rel- 1.11 Modifications of HTPB: Incorporation of Functional
ative ratio of absorbance of the FT-IR bands at 1710 cm 1 Groups in the HTPB Chain
( C=O stretching of urethane) with that of the peak at
966 cm 1[ C=C-(trans) vibration of HTPB], i. e., A1710/A966 was Numerous papers have been reported on the incorporation
compared, and the extent of urethane content was calcu- of energetic functional groups such as nitro [81] and others
lated [119, 130]. FT-IR was used in combination with NMR [17, 18, 22] having a positive effect on the combustion rate,
[131]. although not on the mechanical properties, which are gen-

Table 4. Main analytical parameters of different HTPBs.

OH number (mg OH equivalent Viscosity (cP), Molecular trans/vinil/cis Functionality Ref.

KOH/g) (meq/g) 30 °C Mass ratio
HTPB R45-HTLO 47.1 0.7–0.85 8000 Mn 2800 60/20/20 2.5 [127]
HPTB from HEMRL, Pune, 42.27 n.a. 5370 Mn 6845 n.a. n.a. [128]
India
HTPB* n.a. 0.78 mmol/g n.a. Mn 2800 n.a. n.a. [129]
HTPB** n.a. 0.65–0.8 mmol/g 2500-5500 2300–3500 25/60/15 n.a.
Polyvest HT (Evonik) 44-51 n.a. 4000-5500 Mn 2900 Mw 57/22/21 2.3-2.7 [126]
6300
HEMRL: High Energy Materials Research Laboratory. n.d.: not determined. n.a.: non available. *: Liming * Limming Institute of Chemical
Technology of China. **: Data from Zibo Qilong Chemical Co., China.

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Review J. C. Quagliano Amado, P. G. Ross, L. Mattos Silva Murakami, J. C. Narciso Dutra

erally outside the specifications [81]. Several polymers were composite propellants: HTPB plus polypropylene glycol
made by chemically modifying HTPB using different meth- (PPG), polysulfide (PS), polyester polyol (PO), and
ods [22, 132–137]. For example, a [4-(dimeth- azidomethylmethyloxetane (AMMO) it was seen that PS
ylsilyl)butyl]alkyl ferrocene grafted HTPB derivative was ap- binder the highest burning rate within the propellants test-
propriate to be used as burning rate accelerator catalyst in ed in this study. Like PS binder, AMMO binder or HTPB
the preparation of a composite gas generator [138]. Though binder increases the burning rate as pressure increases
a great deal of work is carried out to chemically modify [140]. The main problem that arises is the migration of com-
HTPB, functionalization at the terminal carbon is not yet ponents between insulation, liner and propellant [141]. This
fully exploited [139]. This is an area of continuous research, issue has already been addressed in this review and ex-
although not incorporated yet to standard practices in SRM cellent reports and books have been written in this respect
manufacturing. In the coming years, research work in the [4, 96, 119, 139].
area is expected to be carried out.

1.13 Possibilities for Improving Liner and Composite

1.12 Role of HTPB in Composite Propellants Propellant Properties in Relation to the Role of HTPB

The role of HTPB in composite solid propellants is mainly Due to the mismatch of different kinds of material bonded
two-fold: (1) to serve as a binder material to physically ac- together, micro-voids, micro-cracks and, other defects are
commodate different propellant ingredients (such as oxi- unavoidably introduced in the rocket manufacturing proc-
dizer, metal particles, and burn-rate modifiers) in its matrix, ess. The interfaces turn out to be the weakest part of the
and (2) to serve as a fuel constituent to release fuel-rich whole structure [22, 23, 80, 86, 117, 139]. Several strategies
gaseous products when decomposed and pyrolyzed [63]. were developed to preserve the integrity of each layer and
As mentioned above in this review, the liner is first applied the interfaces.
to the insulation bonded to the motor case. Then, the liner The self-healing capability of the HTPB-based liner was
is used as the adhesive to bond the propellant to the in- enhanced by introducing 4,4-dihydroxy diphenyl di-
sulation. A typical liner system reported was a combination thioether into the thermosetting polyurethane chain. The
of R-45M type HTPB with a diisocyanate curing agent and a polyurethane material is applied to the metal surface coat-
carbon filler for strength. With an excess diisocyanate to R- ing, which has a remarkable self-healing function to the
45M, this formulation was designed to act as an adhesive scratches on the metal surface [142]. Hydroxyl-carboxyl-ter-
for insulation and propellant [26]. minated polybutadiene (HCTPB) and Fe3 + were selected to
Several factors influence the obtention of an efficient facilitate the formation of ionic bonds ( COO Fe3 +). It was
liner for composite propellant. HTPB functionality dis- proposed to alleviate the inherent self-healing problem for
tribution is a more critical factor in determining liner life HTPB elastomers. Incorporated HCTPB at a 6 % (w/w) and
than chemical kinetics [37]. To maximize compatibility be- Fe3 + ions into the HTPB elastomer elevated the tensile
tween liner and propellant is desirable to have the same strength from 1.83 to 5.2 MPa [111]. Self-healing of furan
polymer in the liner and binder for composite propellant. modified HTPB PUs has reinforced mechanical strength
Understanding HTPB’s role as a binder for composite pro- [143]. By introducing aromatic disulfides, self-healing was
pellants must first remind the components of solid propel- also imparted, rendering a self-healing polyurethane adhe-
lant. A solid-propellant consists of several chemical in- sive. The adhesive can self-heal at a safe temperature close
gredients: oxidizer, fuel, binder, plasticizer,curing agent, to 80 °C, with an elongation at break above 700 %, a self-
stabilizer, and across-linking agent. The oxidizer is the main healing efficiency of up to 97 %, and excellent thermal sta-
component in mass percent. Binders provide a structural bility. The interface self-healing experiment showed that
matrix in which solid granular ingredients are held together the adhesive could recover the debonding damage at the
by a composite propellant. Therefore, the polymeric binder interface [144].
must be capable of accomodating a large amount of solid Copolymerization of HTPB is another strategy for im-
ingredients, mainly the oxidizer. HTPB fully complies with proving propellant properties but focused on other aspects.
this requirement [14]. HTPB copolymerized withε-caprolactone enhanced propel-
As a liner in a motor case, HTPB-based PUs formulated lant density impulse. Density was increased by 4.4-5 % and
with appropriate modifiers or fillers forms an in-situ pro- calorimetric values by 12–15 % compared to HTPB/DOA-
tective layer at elevated temperatures for withstanding very based compositions [145]. Also, HTPB was blended with gly-
high temperatures. The improved erosion-resistant proper- cidyl azide polymer (GAP), with a positive effect on the flu-
ties eliminate the need for supplemental case insulation idity and leveling of composite propellants. GAP has drawn
that contributes to additional costs and inert weight to the tremendous attention due to its high formation enthalpy,
motor [137]. high density, and low sensitivity [146]. However, HTPB and
When comparing five types of polymeric binders to ex- GAP are incompatible in the long term.The azide group in
amine the role of the binders for the burning rate of AP the GAP is susceptible to a Schiff base rearrangement that

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Properties of Hydroxyl-Terminal Polybutadiene (HTPB)…

eliminated N2 gas.This off gassing can cause cracking as N2 and transfectants (transfectants for liquids and reflectance
is poorly soluble in cured HTPB.Mixtures of HTPB and GAP for solids), to obtain accurate and fast results without re-
have been shown to lead to poor and even hazardous long- quiring sample preparations and specific sample holders
term aging [147]. HTPB and Polyvinyl Chloride (PVC) plasti- that are used in a conventional NIR transmission mode. The
sol blends were studied. Thermogravimetric analysis (TGA) NIR spectrum is composed of many non-fundamental
shows that 100 % mass loss in AP-HTPB based propellants bands, such as overtones (multiples of MIR fundamental
decomposes at 420.3 °C, whereas in the case of AP-PVC bands) and combination bands (sum or difference of MIR
80 % mass loss occurs at 397.6 °C [148]. Backburning of pro- fundamental bands), making it challenging to interpret the
pellants with HTPB was improved with the addition of poly- spectra. Then, spectrum processing as well statistical techni-
ethylene glycol (PEG) polymer [149]. ques are applied in parallel to complement a better spec-
Although not related directly to HTPB, ferrocene and trum analysis. Recent studies of our group in polymers by
ferrocene derivatives increase the burning rate as combus- NIRA analysis without chemometrics application have been
tion catalyzers [150]. Moreover, it is known that ferrocene successfully performed because there was no band overlap
can be grafted on HTPB for this purpose and also to reduce [162]. Therefore, it can be used for the analysis of other pol-
migration [46]. The catalytic effect of different nano addi- ymers of interest in defense, such as HTPB resins [131, 163].
tives was also reported as burn rate enhancers. For exam- We envision renewed interest in studies for determining
ple, nanosized MnO2 addition produced a 23 % enhance- HTPB and PU by FT-IR and NIRA. In particular, reflection and
ment in burning rate [151]. CuO nanocatalyst addition on transflectance in the near-infrared region analysis (NIRA) of
the high-temperature decomposition products of AP re- epoxides in HTPB is currently on study as character-
sulted in the formation of reactive intermediates and a sub- izationtechnique by our group.
sequentsynergistic effect,which led to the complete py-
rolysis of the binder [152]. Nano-Al, nano metals, and nano-
oxides effect on HTPB-based composite propellants were al- 3 Conclusions
ready thoroughly reviewed [153, 154]. Graphene [155] and
graphene oxide (GO) are novel additives for improving the One of the most critical ingredients in the formulation of a
mechanical properties of composite propellants. Mod- composite propellant is the binder, of which HTPB has been
ifications of GO were also utilized with HTPB [156]. Our historically preferred. Binder must comply with a series of
group has particularly studied graphene’s positive effect on parameters specified by quality standards to be used to
liner and insulator properties for composite propellants manufacture propellants.
[157]. If during the operation of an SRM there is a sudden in-
A comparison between ammonium perchlorate/HTPB crease in pressure due to a propellant defect, the integrity
composite propellants having an inert binder and the new of the fuel is compromised, and catastrophic failures may
propellants with active binders shows that the combustion arise. Many SRM incidents occur because of interface fail-
processes of the new propellants differ significantly from ures due to migration or incompatibility between materials.
those of the classical composite propellants. New propel- This is why it is important that the polymer in the liner and
lants have additives such as various energetic oxidizers (oc- binder being the same. As shown in this review, the mor-
togen, ammonium dinitramide, and hexanitro-hexaaza-iso- phology and properties of HTPB containing polyurethane
wurtzitane) [158]. In this sense, many HTPB-based elastomers used in composite propellants have been the
propellant formulations were thoroughly reviewed [159] to- subject of a large number of publications, which are con-
gether with energetic polymers and binders [160], although tinuously increasing. As a result, much effort has been
not the specific matter of this review, and for this reason made to improve the burning rate of compositions while
we will not expand on this. optimizing payload and rocket structural integrity, almost
always in compositions based on HTPB as binder.
Despite the multiple propellant compositions reported
2 Trends and those yet to emerge given the ongoing advances in
many fields (such as novel energetic polymers and nano-
Regarding the characterization of these HTPB-based materi- materials) HTPB is sure to remain the workhorse as a poly-
als, non-conventional FT-IR spectroscopy techniques can be mer for SRM applications for years to come.
of great value, as we have previously reported [161]. More- The future may show a need for modified HTPB with
over, the fact that there are few studies in the near-infrared performance not yet attainable, such as formulations with
(NIR) region, or even the absence of researches with specific improved thermal and mechanical aging properties, and ex-
accessories such as reflectance, NIRA generates great inter- panded capability under extreme temperature operation
est for further research in the resin characterization field. conditions, both high and low.
NIRA accessory involves direct analysis, without the need Concerning future research, we expect that novel pro-
for prior sample preparation. It is considered a non-destruc- pellant formulations based on modified HTPB and blends
tive technique. NIRA analysis uses two modes, reflection will be the leading path for solid rocket performance stud-

Propellants Explos. Pyrotech. 2022, e202100283 (13 of 19) © 2022 Wiley-VCH GmbH
Review J. C. Quagliano Amado, P. G. Ross, L. Mattos Silva Murakami, J. C. Narciso Dutra

ies. In the characterization area, as mentioned above, we

envision new studies in determining HTPB and PU by FT-IR, TPP Triphenylphosphine
as reflection and reflectance by NIRA for epoxides in HTPB. TPUs Thermoplastic polyurethanes
This area is essential because of its capabilities for testing
the aging of propellants and consequently its influence on
SRM expiration date. Finally, in the process area, studies of
ablative and adhesive compositions of HTPB with novel ad-
ditives, such as different nanomaterials -and particularly
graphene oxide- emerge as novel and evolutionary SRM al- References
ternative research path.
[1] A. Defusco, Beginnings of HTPB in the Department of Defense
(DoD). Defense System Information Analysis Center (DSIAC),
Department of Defense, U.S.A., Vol. 3, Number 4, 2016.
4 List of Abbreviations [2] K. Klager, Polyurethanes, the most versatile binder for solid
composite propellants, 20th Joint Propulsion Conference,
AMMO Azidomethylmethyloxetane American Institute of Aeronautics and Astronautics. 1984, Cin-
AP Ammonium perchlorate cinnati, OH, U.S.A. doi: 10.2514/6.1984-1239.
ATR Attenuated total reflection [3] J. Hunley, The history of solid-propellant rocketry – What we
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REVIEW
J. C. Quagliano Amado*, P. G. Ross, L.
Mattos Silva Murakami, J. C. Narci-
so Dutra
1 – 20
Properties of Hydroxyl-Terminal
Polybutadiene (HTPB) and Its Use
as a Liner and Binder for
Composite Propellants: A Review
of Recent Advances

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