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Combustion Study of Poly-Tetrahydrofuran

(PTHF) Based Solid Propellants

Conference Paper · October 2015

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 Combustion Study of Poly-Tetrahydrofuran
(PTHF) Based Solid Propellants
Saugata Mandal, Narendra Yadav and Puran Chandra Joshi
Department of Space Engineering & Rocketry,
Birla Institute of Technology, Mesra, Ranchi–835215, India
Abstract—In the current study an attempt has been
made to formulate solid propellants based on PTHF fuel-
binder and AP oxidizer. The combustion behaviors and
mechanical properties of prepared propellants were analyzed
and compared with conventional HTPB/AP-based composite
solid propellants. The burn rate measurement was
performed in Crawford strand burner. The heat of
combustion was also conducted by Bomb calorimetry.
Thermal degradation and tensile testing were measured with
the help of simultaneous thermal analyzer (STA) and
universal tensile machine (UTM) respectively. Based on the
results, it was found that the burning rate of composite solid
propellant containing PTHF/AP was slightly higher at
elevated pressures. It was also observed that the modulus of
elasticity is higher and is comparable with HTPB/AP-based
solid propellants.
Keywords: Solid Propellants, Combustion Behaviors,
Fuel-binder, Tensile Testing, Burning Rate, Thermal
Degradation
I. INTRODUCTION
Fuel-binder of solid composite propellants (SCP) is
generally a polymer which binds together all the
constituents in the solid-phase [1]. It has usually high
loading capacity upto 80–90% for solid particles. It
influences mechanical properties, propellant processing
complexity, storability and other significant properties.
Many developments have already made and also the
search for new fuel-binder is continued for advances in the
propulsion systems. In this regards, the PTHF is
considered as a promising fuel-binder for the solid
composite propellants [2].
Polytetrahydrofuran (PTHF) is used as an ingredient in
rubber industry and is produced in several grades which
are based on its molecular weights [3]. The product is
commercially available as polymers of low average
molecular weights, between 250–3000 atomic mass unit
(amu). Polymeric PTHF is usually appeared as a white
waxy solid that melts between 20–30°C. the molecular
structure of PTHF is shown in scheme 1.
Fig. 1: Polymerization Reaction of PTHF
It is mass-produced commercially available and
inexpensive compared to hyroxy terminated poly-butadine
(HTPB). It has similar molecular structure as of HTPB
and presence of additional oxygen atom in its molecular
structure leads to better combustion and produces
comparatively less toxic combustion by-products like CO,
CO2 etc. This can results in superior heat of combustion
which are desirable property of solid propellants.
Theoretically its ballistic properties, processing time and
material properties are similar or sometimes superior to
HTPB based propellant [4]. Because of these properties
the PTHF is now being considered as solid propellant fuel-
binder. In such regards, a lot of research is performed
[5,6]. However, the processing condition, mechanical
properties and many more characteristics are remaining
unsolved, till today. In the present work an attempt has
been made to process PTHF/AP-based propellant and
evaluate its combustion and material properties. The
HTPB has also been used in the formulation of solid
propellants, and a comparative study on their molecular
structure, physical properties and combustion performance
with PTHF has been conducted.
II. EXPERIMENTAL
A. Materials
The chemicals used in the current research and their
specifications are enlisted in Table I.
TABLE 1: CHEMICAL USED FOR PROPELLANT PREPARATION
Chemicals Grade Supplier
PTHF Industrial Sigma-Aldrich India Pvt. Ltd.
HTPB R45M-HTPB SDSC, Sriharikota, India
AP Industrial Tamilnadu Chlorate, Madurai, India
IPDI Analytical Chemporium India Pvt. Ltd.
DOA Analytical Fulka Analytical, Germany
Glycerine Laboratory E-Merck India Pvt. Ltd.
B. Preparation of Solid Composite Propellants
Two fuel-binders viz. PTHF and HTPB were used in
current study. Propellant samples with fuel-binders, PTHF
and HTPB were prepared separately by using AP oxidizer
and isophorone diisocyanate (IPDI) as a curing agent. The
dioctyl adipate (DOA) was used as plasticizer which
lowers down the viscosity and hence improve the mixing
capacity of solid propellants. The compositions of other
ingredients were the same for propellants. Bimodal AP
was used for both cases and glycerin was additionally used
as a cross linking agent for PTHF fuel-binder. Detailed
composition of formulation for each propellant sample is
shown in Table II. Two test samples of
PTHF/IPDI/glycerin with AP were prepared initially with
 Combustion Study of Poly-Tetrahydrofuran (PTHF) Based Solid Propellants 205

2 molar ratios i.e., 1.00:2.00:0.33, 1.00:1.50:0.33 and removed from the mould and were stored in a desiccator
AP/fuel-binder ratio as 80:20. The prepared propellant to avoid the absorption of moisture.
samples were found to be brittle. Thus reduction in
AP/fuel-binder composition was considered in subsequent AP was used as oxidizer for both the composition thus it
experimental process. was processed first. It was grinded in a special pulveriser
machine and then using test sieves and sieve-shaker the
The molar ratio of PTHF/ IPDI/ glycerine 1.00:1.50:0.33 required particle size were separated. Two different
with AP/fuel-binder ratio of 70:30 was chosen to prepare particle sizes retained on 100 meshes and 300 meshes
another propellant sample. This sample was effervescent were selected for present study. The coarser to finer
rubbers that there were some bubbles in the rubbery particle size ratio of AP was taken as 3:1 in all the
composition. The bubble contamination in the propellant formulations. The coarser particles sizes were between
influences the burning rate characteristics and, 150–250 microns whereas the finer particles were of
consequently, the reliability of the burning rate. This average size between 53–75 microns.
sample which has some bubbles could not be used as a
propellant. The PTHF/IPDI/glycerin molar ratio was again III. RESULTS AND DISCUSSION
modified to 1.00:2.00:0.33 with AP/fuel-binder ratio of
75:25. This sample where cured for 6 days at 80 C. This A. Burn rate measurements
sample shows good mechanical property and least bubble Burn rate was measured in ambient conditions and
formation was observed on the propellant surfaces. high pressures regions. The burn rate studies at high
TABLE 2: PERCENTAGE D ISTRIBUTION OF PTHF/ AP AND HTPB/ AP- pressures were carried out using Crawford strand burner
BASED SOLID PROPELLANTS
setup. Standard strand burner was used to measure burn
PTHF/AP (Wt %) Ingredients HTPB/AP (Wt %) rate in ambient conditions. For igniting the propellant
--- HTPB 18.92 strands in Crawford bomb electrical heating coil which
16.90 PTHF ---
was inserted at one end of propellant stand was used and
7.60 IPDI 1.46
0.50 DOA 4.60 the time taken to burn the effective length of 50 mm was
56.25 AP (coarse) 56.25 noted. The burn rate was calculated by dividing effective
18.75 AP (fine) 18.75 length of strand to time taken to burn it. Nitrogen gas was
100.00 Total 100.00 used to obtain an inert as well as high pressure atmosphere
The molar ratio of PTHF/IPDI/glycerin used was inside the Crawford bomb. The test strands specification is
1.00:2.00:0.33 with PTHF fuel-binder. The IPDI was used shown in Table III.
as a curing agent and glycerin as a crosslinking agent. The TABLE 3: TEST STRAND SPECIFICATION
following Table II shows the weight (%) of different
Total length 80 m
ingredients used for processing the propellant.
Width 5 mm
The required amounts of AP, PTHF, Glycerin and IPDI Thickness 6 mm
were properly weighed and stored in controlled Effective length 50 mm
conditions. First PTHF may require to be heated to obtain TABLE 4: BURN RATE OF PTHF/AP-BASED SOLID
it in liquid state as its melting point is range of 33-36 C. PROPELLANT AT AMBIENT C ONDITION
Firstly the PTHF and Glycerin were thoroughly mixed for Sl. No. Length (mm) Burn Time (s) Burn Rate (mm/s)
about 20 min, and then IPDI is added and mixed for 1 50 15.58 3.2092
another 25 min, then after AP was added in slots with 2 50 17.29 2.8918
3 50 15.60 3.2051
continuous mixing. Initially coarser AP was mixed
Avg. 50 16.156 3.0946
completely then finer particles are added in slots so that
the finer particles can settle down between the interspatial The PTHF/AP-based solid propellant burn smoothly and
voids formed by coarser particles. flames were bright white and it did not left any residual
The propellant charge was casted in Mild Steel flat plate mass after burning. Table IV presents the burn rate of
mould which were cleaned and properly greased with propellant samples at ambient condition.
Metroark grease and covered by aluminum foil. After TABLE 5: AVG. B URN R ATE OF PTHF/AP-BASED SOLID PROPELLANT AT
casting, the mould was placed on a vibrator for 30 minutes HIGH PRESSURES
to remove air voids which are formed during casting. Pressure Effective Length Avg. Burn Avg. Burn Rate
(psi) (mm) Time (s) (mm/s)
The mould was kept in a hot air oven at 80± 1 °C for a 14.7 50 16.156 3.0946
period of 6 to 7 days, depending upon the composition, to 200 50 8.8933 5.6222
allow the propellant to cure and attain the required 400 50 6.2133 8.0472
mechanical strength. The mould is then taken out of the 600 50 4.984 10.0321
oven and allowed to cool. The propellant samples were 800 50 4.204 11.8934
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206 24 National Conference on IC Engines and Combustion

In high pressures region, the effective length was also In Figure 1 present the variation of burn rate for HTPB/AP
taken as 50 mm. The burning details are presented in and PTHF/AP-based solid propellants. It can be observed
Table V. that the burn rate of HTPB/AP-based propellant
composition has higher in ambient condition. However as
TABLE 6: BURN RATE OF HTPB/AP-BASED SOLID PROPELLANT AT
AMBIENT CONDITION pressure increases, burn rate of PTHF/AP-based propellant
exceeds than HTPB/AP propellant beyond the 150 psi
Sl. No. Length (mm) Burn Time (s) Burn Rate (mm/s) pressure.
1 50 13.32 3.7537
2 50 12.91 3.8729
B. Mechanical Properties
3 50 12.25 4.0816
Avg. 50 12.826 3.8983 Test Method-1 of existing UTM machine has been
The HTPB/AP-based solid propellant burned smoothly adopted for current study, which applicable for
and flames were pale yellow in color and it left some determination of tensile strength, break failure of force
and extension characteristics of test sample at constant
residual mass after the combustion. At ambient condition
rate of displacement. The test specimen is supported by
the burn rate of propellant strands are presented in
clamping a test piece in the stationary jaws so that its
Table VI.
longitudinal axis passes through the centre of the front
TABLE 7: AVG. B URN R ATE OF HTPB/AP-BASED SOLID PROPELLANT AT edge of each jaw. The model dimensions are shown in
HIGH PRESSURES Table VIII.
Pressure Eff. Length Avg. Burn Avg. Burn Rate
(psi) (mm) Time (s) (mm/s)
The Figure 2 presents the stress v/s strain curve of all test
14.7 50 12.826 3.8983 samples and details of analytical results are tabulated in
200 50 9.2866 5.3841 Table IX. It was observed that the Modulus of elasticity of
400 50 6.6536 7.5147 PTHF/AP-based solid propellant specimen is nearly 6
600 50 5.501 9.0892 times greater than HTPB specimen that means PTHF
800 50 4.2856 11.6669
propellant has better elastic properties than HTPB
At higher pressures the effective length was also taken 50 propellant within their elastic limits.
mm and their burning details are shown in Table VII.
TABLE 8: TECHNICAL SPECIFICATION FOR TEST SAMPLES
Thickness 7 mm or less
Width of narrow section 6 mm
Length of narrow section 57 mm
Width overall min. 19 mm or less (as required)
Length overall 183 mm
Gauge length 50 mm

The comparative burn rates data for PTHF/AP and

HTPB/AP-based propellants at pressures domain are
shown in Table VIII.

Fig. 2: Stress vs. Strain Curve for all Propellant

The Ultimate stress is the stress which material can

Fig. 1: Burn Rate vs. Pressures of Propellants
withstand before it ruptures. The ultimate stress for HTPB
specimen has found to be 1.5 times greater than PTHF
specimen which shows the higher load bearing capacity of
HTPB specimen. In both the specimens, upper yield stress
and stress at maximum load is same which indicate the
upper yield and maximum stress points coincide to each
other. In PTHF specimen the ultimate stress and stress at
maximum load is same which means the points coincides
with each other whereas it is different for HTPB specimen
which means they are different points on stress-strain
curve. Toughness has also been measured in regards to
 Combustion Study of Poly-Tetrahydrofuran (PTHF) Based Solid Propellants 207

ability of a material to absorb energy and plastically
deform without fracturing. From stress v/s strain, it can be
concluded that toughness of PTHF specimen has been
found nearly 1.3 times higher compared to HTPB
specimen. As shown in Table IX, the maximum
elongation for PTHF specimen is nearly 2 times more than
HTPB specimen. In the case of HTPB specimen necking
occurs after maximum stress point but for PTHF specimen
necking does not occur. The strain values of both the
specimens are shown with the function of load, stress and
upper yield points, and these values found to be more at
all specified points for HTPB samples, but overall
elongation rate is less compared to the PTHF samples.
TABLE 9: DATA OF STRESS V/S STRAIN MEASUREMENT
concluded that the heat of combustion of PTHF/AP
propellant is 1.03 times higher than HTPB/AP propellant.
D. Thermal Characterization
The combustion of solid composite propellant is a
complex process. It involves decomposition of AP,
reaction between decomposed products and reaction
between AP reactions products and fuel binder. The
exothermic peaks at different temperature may be due
dominating character of a reaction to the others [7,8].

Property PTHF1 PTHF2 Mean S.D HTPB HTPB Mean S.D

1 2
Ultimate 0.118 0.078 0.098 0.029 0.083 0.221 0.152 0.098
stress
(MPa)
Modulus 48.74 43.24 45.99 0.891 7.626 7.934 7.780 0.218
of
elasticity
(MPa)
Stress at 0.118 0.078 0.098 0.029 0.227 0.817 0.224 0.004
Max. load Fig. 3: TGA Thermograms of Propellant Samples
(MPa)
Figure 3 shows the thermogravimetric analysis (TGA)
Strain at 4.743 5.580 5.162 0.592 7.701 6.817 6.962 0.025
Max. Load curves for both propellant compositions. Details study of
(%) TGA data are summarized as; there is 19%, 21.55% and
Stress at 0.118 0.078 0.098 0.029 0.227 0.817 0.224 0.004 48.73% decrease in mass in temperature ranges 225 C -
upper
yield
280 C, 280 C - 320 C and 320 C - 375 C respectively
(MPa) for PTHF/AP -based solid propellant sample. Whereas,
Strain at 4.743 5.580 5.162 0.592 7.701 6.817 6.962 0.025 mass loss of 10.41%, 15.39% and 45.62% is found in
upper temperature ranges of 225 C -280 C, 280 C-320 C and
yield (%)
Strain at 0.052 0.025 0.039 0.019 0.081 0.089 0.085 0.006
320 C-375 C respectively for HTPB/AP-solid propellant
auto break sample. A comparison between decomposition behaviors
(%) of both the propellants is clearly seen in the above Figure.
Stress at 22.920 20.797 21.858 1.501 11.667 7.853 9.765 2.704 It is also observed that decrease in mass for PTHF/AP
auto break
(MPa)
solid propellant is more than HTPB/AP solid propellant
Toughness 0.021 0.012 0.017 0.006 0.015 0.011 0.013 0.003 upto 360 C. Thus, it concludes that the decomposition
(MPa) and vaporization for PTHF/AP-based solid propellant is
faster than HTPB/AP-based solid propellant.
C. Heat of Combustion
The differential scanning calorimeter (DSC) thermograms
Heat of combustion of both solid composite for PTHF/AP and HTPB/AP-based propellant
propellants was determined by using Bomb Calorimeter. compositions are shown in Figure 4. The curves show an
The tests were conducted at 400 psi N2 gas atmosphere. endothermic peak at 247.3 C and three exothermic peaks
For each propellant sample the raise in temperature in at 267.9 C, 301.1 C and 376.9 C respectively for
equal time interval was noted and the heat of combustion PTHF/AP sample. The DSC curve of HTPB/AP-based
of the propellant samples is calculated by equation 1. solid propellant shows that the decomposition of AP
particle takes place at 245.8 C. The first, second, third
= (1)
and fourth exothermic peak occurs at 352.8 C, 446.3 C,
Where, W is water equivalent of Bomb Calorimeter which 456.0 C and 484.5 C respectively. A comparison
is 2576 cal/ C for the calorimeter used in the present between DSC curves for both types of propellants can also
work. M is mass of the sample, be seen in Figure 4. From the thermograms, it can be
H is calorific value of the sample. Heat of combustion for concluded that that the PTHF/AP decomposition and
propellants was found to 1536 Cal/gm for PTHF/AP and vaporization occurs at relatively at lower temperature than
1481 cal/gm for HTPB/AP composition. It also be HTPB/AP propellant [9]. It concludes that less energy is
 th
208 24 National Conference on IC Engines and Combustion
required to form gaseous fuel-binder with oxidizer vapor
for PTHF/AP solid propellant comparatively.
Fig. 4: DSC Curves of Propellant Samples
IV. CONCLUSION
The suitable molar ratio for PTHF/IPDI/Glycerine
composition as a fuel binder is 1:2:0.33. Any other
composition either has poor mechanical properties or
causes bubble formation due to the effervescence of gas
during the curing process.
PTHF/AP propellant has high value of Young’s Modulus
compared to HTPB/AP propellant in their elastic limits.
HTPB/AP propellant is fractures after the necking but
necking does not appeared in PTHF/AP propellant. From
stress v/s strain, it can be concluded that toughness of
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PTHF specimen has found nearly 1.3 times higher
compared to HTPB specimen.
At ambient condition PTHF/AP propellant has lower burn
rate compared to HTPB/AP propellants but beyond
pressure 150 psi the burn rate of PTHF/AP propellant is
marginally higher than HTPB/AP propellants.
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