Defence Technology 15 (2019) 615e620

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Defence Technology
journal homepage: www.elsevier.com/locate/dt

Surface modification of ammonium nitrate by coating with surfactant

materials to reduce hygroscopicity
Baha I. Elzaki a, b, *, Yue Jun Zhang a
a
School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, Jiangsu, China
b
Department of Chemical Engineering, College of Engineering, Karary University, Omdurman, 12304, Sudan

a r t i c l e i n f o a b s t r a c t

Article history: Ammonium nitrate (AN) is promising oxidizer in green propellants. In this work, the physical coating
Received 27 October 2018 method was improved to modify the surface of ammonium nitrate particles with different surfactant
Received in revised form materials to reduce hygroscopicity. Cetylalcohol, stearic acid, stearyl alcohol, palmic acid, lauric acid,
10 December 2018
stearsmide, tetradecylamine, dodecylamine, and tetradecanol were used as coating surfactant agents.
Accepted 22 January 2019
Available online 31 January 2019
The hygroscopicity was tested for ammonium nitrate with and without coating. Fourier transform
infrared (FTIR) and scanning electron microscopy (SEM) were used to characterize the surface of coated
and uncoated ammonium nitrate. The mass ratio of coating layer and decline of absorption rate of
Keywords:
Ammonium nitrate (AN)
ammonium nitrate coated by cetylalcohol were 1.00%, and 28.40%, respectively. The results indicate that
Coating coating with cetylalcohol surfactant have advantages over the other surfactants in term of low mass ratio
Hygroscopicity of coating layer, and high decline of moisture absorption rate. Thus, cetylalcohol would be a promising
Modification surface coating surfactant material for ammonium nitrate. The idea and approach presented in this study have
Surfactant potential to made hydrophobic layer on the surface of particles to reduce hygroscopicity of AN, and also
help the researcher to improving anti-hygroscopicity of ammonium salts.
© 2019 Production and hosting by Elsevier B.V. on behalf of China Ordnance Society. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
Ammonium nitrate (AN) is produced by the reaction of anhy-
drous ammonia gas (NH3), and aqueous nitric acid (HNO3) [1e3].
AN is present as a major component in the most industrial explo-
sive, such as amatol, AN fuel oil (ANFO), and it is also used in fer-
tilizers [4e8]. AN has a considerable interest in potential eco-friend
oxidizing agent in solid propellants [9,10]. The risk of commonly
used oxidizer ammonium perchlorate (AP) in solid propellants was
realized with the hydrogen chloride (HCL) with water form hy-
drochloric acid, which produces obvious signal easily traced and
highly toxic smoke leading to significant damage in the environ-
ment, therefore AN will become possible replacement after treat-
ment its drawback such as hygroscopicity, phase transitions, and
low performance [11e15]. However, its use of large rocket motors
and as solid propellant is restricted due to the hygroscopicity
[16,17], because of the molecules polarity of AN, it can easily absorb
* Corresponding author. School of Chemical Engineering, Nanjing University of
Science and Technology, Nanjing, 210094, Jiangsu, China.
E-mail address: bahaelzaki@njust.edu.cn (B.I. Elzaki).
Peer review under responsibility of China Ordnance Society
moisture from the surrounding. There are different kinds of coating
methods such as physical, chemical, and encapsulation coating
methods, which are belonged to one of the main ways to reduce the
hygroscopicity of AN particles [18]. The surfactant materials has
been used to reduce the hygroscopicity of AN in the different study
such as mineral jelly, calcium stearate, kaoline, octadecane amine,
resin wax and silane coupling agent KH792 [19e21]. Although the
study of anti-hygroscopic of AN using different coating agent and
coating method, obtained under certain conditions of moisture
absorption rate, a large decline-coated sample have been reported
in the previous literatures. However, many challenges are still
remaining. For instance, the index evaluation of AN hygroscopic
effect did not precisely mention the mass ratio of the coating layer.
Moreover, the hygroscopicity test conditions of AN coated remain
unclear. As example, the time of moisture absorption is quite short,
while both the particles size of AN and the size of weighting bottle
are unknown, as well as the process of surface modification of AN
have not been thoroughly mentioned, particularly the coating time
and temperature [22e24]. In this paper, the physical coating
method with the ten different surfactant materials directed at
reducing hygroscopicity was used in the surface modification of AN.
Moreover, the phenomenon of water droplets on surface of AN

https://doi.org/10.1016/j.dt.2019.01.004
2214-9147/© 2019 Production and hosting by Elsevier B.V. on behalf of China Ordnance Society. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
616 B.I. Elzaki, Y.J. Zhang / Defence Technology 15 (2019) 615e620
particles were explained. The surface morphologies of AN particles
were monitored by electronic scanning microscope, and the surface
of coated AN particles are assayed by FTIR spectra. Furthermore,
this paper presents the effect of surfactant amount on the moisture
absorption rate and mass ratio coating layer.
2. Experimental procedures
2.1. Materials
Ammonium nitrate supplied by Kecheng fine chemical CO. Ltd
(
99.0% Shanghai, China), chloroform (
99.0%, Shanghai Ling Feng
Chemical Reagent Co. LTD, China) and cyclohexane (
99.5% In-
dustrial development zone, Chengdu, China). Surfactant materials
used cetylalcohol, stearic acid, octadecylamine, stearyl alcohol,
palmic acid, lauric acid, stearsmide, tetradecylamine, dodecyl-
amine, and tetradecanol (
99.0% Chengdu Kelong Chemical Re-
agent, China).
2.2. Procedure of coating processing
Physical coating method was improved to modify the surface of
AN particles [17,23]. 6g of AN coated by 2 g of surfactant materials
in the mixture of solvents consist of 15 ml chloroform and 15 ml
cyclohexane. Choosing the solvents for coating has been based on
the solubility of surfactant materials, and AN insoluble in solvents.
The reaction was started with stirring at constant temperature
60  C. After 2 h the heating was stopped, and then the temperature
was gradually decreased within 8 he30  C, at this stage the water of
bath heating was changed, and when the temperature reached to
25  C. AN coated was filtered by vacuum filter, and dried at a certain
temperature with considering the melting and boiling point of each
surfactant materials. Finally, the hygroscopicity test was carried out
under conditions 5 g AN 60  30 mm weighing bottle at tempera-
ture of 35  C, humidity (67.5%), and time of absorption rate tested
24 h.
2.3. Evaluation and characterization of results
Ammonium nitrate samples coated with surfactant materials
and the anti-hygroscopicity performance of coating will be
assessed by evaluated and characterized the results. The evaluation
indexes are mainly increasing the decline of the moisture absorp-
tion and the mass ratio of coating layer, and the main character-
ization methods are scanning electron microscopy observation, and
infrared characterization.
2.3.1. Measurement of moisture absorption rate
The moisture absorption rate of ammonium nitrate is the rate of
changing on the moisture absorption rate of samples before and
after test the hygroscopicity of coating ammonium nitrate [21].
According to GJB770B-2005 “hygroscopicity dryer balance method”
[22], in this study, 5 g of AN sample will put in 60  30 mm
weighing bottle without a cap will be placed into a desiccator
containing saturated solution of strontium chloride (relative hu-
midity 67.5%) the temperature at 35  C for 24 h. The sample will be
scaled up from 5 g to 20 g AN and the test conditions will be used to
measure the moisture absorption rate: the relative humidity is 92%
by using the saturated solution of potassium nitrate in the bottom
glass desiccator inside oven constant temperature at 35  C, the
amount of modified AN is 20 g put inside the 60  30 mm weighing
bottle without cover and time of absorption rate tested 24 h. The
following equation will be calculated the moisture absorption rate
(HR):
M  M0
HR ¼  100% (1)
M0
Where: HR-moisture absorption rate, %
M0- The weight of sample before absorbed moisture, g
M- The weight of the sample after absorbed moisture, g
Meanwhile, according to the above methods, the ammonium
nitrate samples will be measured moisture absorption rate and
uncoated blank sample, the decline of the moisture absorption rate
calculated by the following equation:
HR1  HR
A¼  100% (2)
HR1
Where: A-decline of hygroscopicity, %
HR1-absorption rate of blank AN sample, %
HR-absorption rate of coated AN sample, %
2.3.2. Determination method of the mass ratio of coating layer
The determination method of the mass ratio of the coating layer
will be improved to achieve more accuracy than previous literature
[21] as following steps:
Firstly: a filter paper of 18 cm diameter was wetted with
deionized water.
Secondly: the filter paper placed into an oven for 1 h at the
temperature 100  C, then the filter paper was weighed (WB).
Thirdly: the sample of the coated AN after absorption humidity
was dissolved in deionized water, and filtered through a tapered
funnel, and the filter paper was washed several times with deion-
ized water, and placed in an oven at 100  C for 1 h.
Finally, the filter paper was weighed again (WA).
The mass ratio of the coating layer was calculated by the
following equation:
M1
W¼  100 (3)
M0
Where: W- mass ratio of coating layer to AN particles, %, M0- Blank
AN particles, g, M1- The weight of coating layer (WA- WB), g.
2.3.3. Fourier transform infrared (FTIR) characterization
The surface of modified AN with cetylalcohol, stearic acid,
stearyl alcohol, and AN without coating samples were character-
ized by Fourier transform infrared spectroscopy (FTIR). IR spectra
will be recorded in the range 400-4500 cm1 on FTIR spectropho-
tometry (Thermo Scientific Nicolet, I S10, Thermo Fisher USA) using
KBr pellets.
2.3.4. Scanning electron microscopy (SEM) observation
The surface of coated AN samples were observed with scanning
electron microscopy (JEOL JSM 6380LV, Japan), based on the SEM
pictures of AN/cetylalcohol, AN/stearic acid, AN/Stearyl alcohol and
AN without coated were observed the surfaces morphology to
examine the particles in details.
3. Results and discussion
3.1. Performance of coated AN, and hygroscopicity test
Table 1 showed the moisture absorption rate, mass ratio of
 B.I. Elzaki, Y.J. Zhang / Defence Technology 15 (2019) 615e620 617

Table 1
The performance of anti-hygroscopicity of AN/surfactants.

No Surfactants Moisture Absorption Rate (HR)/% Mass Ratio of coating layer/% Decline/%

1 Cetylalcohol 8.27 1.00 28.40

2 Stearic acid 8.57 1.20 25.80
3 Octadecylamine 9.03 1.14 21.82
4 Stearyl alcohol 9.16 0.57 20.69
5 Palmitic acid 10.46 1.14 9.44
6 Lauric acid 10.46 1.09 9.44
7 Tetradecanol 10.50 1.7 9.09
8 Tetradecylamine 10.62 3.21 8.05
9 Dodecylamine 10.72 3.02 7.19
10 Stearamide 11.11 2.14 3.81

Fig. 1. The effect of amount of surfactants materials in the decline of moisture absorption rate and mass ratio of coating layer, (a) Cetylalcohol; (b) Stearic acid.

coating layer and decline of AN coated with ten different kinds of
surfactant materials. The data from hygroscopicity test clearly
indicate that cetylalcohol was best one of surfactant materials used
as coating of AN with decreased of moisture absorption rate from
11.55% (AN control) to 8.27% with lower mass ratio of coating layer
of 1.00%, and high decline of absorption rate of 28.40%. Stearic acid
and octadecylamine were found to be the second and third superior
results, respectively, while stearyl alcohol, palmitic acid, lauric acid,
tetradecanol, tetradecylamine, dodecylamine, and stearamide fol-
lowed the order in sequence. Moreover, increasing the mass ratio of
coating layer may greatly reduce the performance. This result
clearly indicates that, the decline of moisture absorption rate of AN
coated by cetylalcohol and mass ratio of coating layer were quite
significant compared to those reported in Previous studies [19,25].
These results fit to be a basis for surface modification of ammonium
nitrate particles to improvement the anti-hygroscopicity.
3.2. Effect amount of surfactant materials
Effect amount of surfactant materials: The influence of the
amount of surfactant materials on the decline of moisture ab-
sorption rate and mass ratio of coating layer were studied using
different amounts of cetylalcohol and stearic acid (0.5, 1.0 1.5, 2.0.
and 2.5 g) to coat AN particles. The regression of decline of moisture
absorption rate was increased to high value at 2.0 g, and then
decreased at 2.5 g. This phenomenon is because the polar head of
surfactant not absorb in the surface of AN particles, but stuck with
other polar head together and cause hydrophilic surface leads to
increased hygroscopicity. Thus, the decline of absorption rate was
decreased, and the mass ratio of coating layer directly proportional
with the amount of surfactant materials as obviously shown in
Fig. 1(a and b).
3.3. The phenomenon of water droplets on surface of AN particles
Table 2 shows the moisture absorption rate, mass ratio of
coating layer and decline of ammonium nitrate coated with cetyl-
alcohol and stearic acid using different amount of surfactant and
strong hygroscopicity test conditions. The results showed that the
cetylalcohol significantly outperforms stearic acid with higher
decline and lower mass ratio coating layer and also no water
droplet on surface as depicted in Fig. 2. Nevertheless, after absorbed
water droplets the stearic acid was the best. There are two reasons
to form water droplets on surface of AN after coated by surfactant.
The first one is because the cracked of coating layer due to the hard
filtration process. The second one is that the evaporation solvent
was agglomerated two particles together during drying process as
shown in Table 3, and Fig. 3. These results provide clear understand
of coating AN by surfactant materials, and the particles did not
deliquesce compared with literature [26].

Table 2
The performance of anti-hygroscopicity of AN/Cetylalcohol and Stearic acid.

No Surfactants Surfactant amount/ Hygroscopicity before absorb water (HR)/ Mass ratio of coating layer/% Decline before absorb water/ Decline after absorb water/
g % % %

1 Cetylalcohol 8 8.38 1.30 16.78 e

2 Stearic acid 8 7.83 1.32 22.24 70.80
3 Cetylalcohol 6 7.44 0.37 26.12 e
4 Stearic acid 6 7.54 0.47 25.12 91.46
618 B.I. Elzaki, Y.J. Zhang / Defence Technology 15 (2019) 615e620

Fig. 2. The phenomenon of water droplets on surface after hygroscopicity test sample Fig. 4. FTIR spectra of the AN/cetylalcohol (a), AN/stearyl alcohol (b), uncoated AN (c),
No.(4) in Table 2. AN/stearic acid (d).

3.4. FTIR spectra characterization
Surface modified of AN particle with cetylalcohol, stearic acid
and stearyl alcohol were monitored by using FTIR measurement as
depicted in Fig. 4. It is observed that upon the surface modification
of AN and surfactant materials, two peaks appear in the region
3000-2800 cm1, which are attributed to CH3 stretching vibrations
(a, b, c). Whereas, these peaks were not observed in the FTIR
recorded for blank AN. It was important to note that a medium
intense peak is observed at 1703 cm1 for modified AN particles by
stearic acid. This peak originated mainly due to carbonyl group C ¼
O stretching of the stearic acid (d). FTIR spectrum results showed
that cetylalcohol and stearic acid existed on the surface of AN
particles.
3.5. SEM observations
To observe the surface morphology of coating ammonium ni-
trate particles. Different scale bar of 100 mm, 50 mm, and 10 mm
Electron micrographs are demonstrated in Fig. 5. These figures
present the surface morphology of AN/cetylalcohol (a) which
showed a clear difference in the shape particles and the surface
smooth as compared to AN/stearic acid (b), which have fractured on
surface of particles, and stearyl alcohol (c), which have cracked, and
it can be seen this hollow clear on the surface, and also appear on
the particles surface of AN without coating (d), and also show the
clear difference between the coated AN and AN without coating. In
contrast in the AN coated with cetylalcohol no hollow particles
were found. In addition, adhesion between particles cannot be seen
in all samples this explains no caking and agglomeration happened
after coating AN particles.
4. Conclusions
In this study physical coating method was improved to modify
surface of AN particles with ten different kinds of surfactant ma-
terials. Our conclusions are listed below:
(i) The cetylalcohol has been found to be the best surfactant
materials for coating AN among all tested materials with
significant mass ratio of coating layer 1.0% and decline of
moisture absorption 28.40%.
(ii) Strong hygroscopicity test conditions were used in this work
as relative humidity 92%, time of hygroscopicity test 24 h.

Table 3
The performance of anti-hygroscopicity of AN particles coated by 1.5 g Stearic acid.

No. Hygroscopicity before absorb water Hygroscopicity after absorb water Mass Ratio of coating Decline before absorb water Decline after absorb water
droplets/% droplets/% layer/% droplets/% droplets/%

1 9.46 8.84 0.82 19.15 23.60

2 9.82 5.59 1.30 15.13 51.69
3 9.25 3.91 0.84 18.57 65.67

Fig. 3. The phenomenon of water droplets on surface after hygroscopicity test samples in Table 3.
 B.I. Elzaki, Y.J. Zhang / Defence Technology 15 (2019) 615e620
Fig. 5. Scanning electron microscope of surface modification of AN coated by cetylalcohol (a), stearic acid (b), stearyl alcohol(c), and uncoated AN (d), the scale bar represents 10, 50
and 100 mm. Electron micrographs.
(iii) In the AN/stearic acid, AN/stearyl alcohol and AN without
coating samples were hollow and crack. In contrast the AN/
cetylalcohol particles were solid and smooth surface.
(iv) AN/stearic acid after hygroscopicity test observed water
droplets on surface. In contrast, no water droplets on the
surface of AN/cetylalcohol.
(v) The cetylalcohol showed a promising coating surfactant
material for ammonium nitrate, and it should be subjected
for further investigations as anti-hygroscopicity.
Conflicts of interest
The authors declare that there is no conflict of interests
regarding the publication of this paper.
References
[1] Nagayama S, Katoh K, Higashi E, Nakano K, Kumagae K, Habu H, et al. Dif-
ferential scanning calorimetry analysis of crystal structure transformation in
spray-dried particles consisting of ammonium nitrate, potassium nitrate, and
a polymer. J Therm Anal Calorim 2014;118(2):1215e9.
[2] Zygmunt B, Buczkowski D. Influence of ammonium nitrate prills' properties
on detonation velocity of anfo. Propellants, Explos Pyrotech 2007;32(5):
411e4.
[3] Rolf F-M. Production of ammonium nitrate. 1972. Patent 3,690,820.
[4] Kajiyama K, Izato Y-i, Miyake A170. Thermal characteristics of ammonium
619
nitrate, carbon, and copper (ii) oxide mixtures. J Therm Anal Calorim
2013;113(3):1475e80.
[5] Lewis WK, Harruff BA, Gord JR, Rosenberger AT, Sexton TM, Guliants EA, et al.
Chemical dynamics of aluminum nanoparticles in ammonium nitrate and
ammonium perchlorate matrices: enhanced reactivity of organically capped
aluminum. J Phys Chem C 2010;115(1):70e7.
[6] Liu L, Li F, Tan L, Ming L, Yi Y. Effects of nanometer ni, cu, al and nicu powders
on the thermal decomposition of ammonium perchlorate. Propellants, Explos
Pyrotech 2004;29(1):34e8.
[7] Kohga M, Handa S. Preparation of combined ammonium perchlorate/ammo-
nium nitrate samples by freeze drying. J Energetic Mater 2017;35(3):276e91.
[8] Tan L, Liu D, Xu S, Wu Q, Xia L. Effect of mixing methods on the thermal
stability and detonation characteristics of ammonium nitrate and sodium
chloride mixtures. Propellants, Explos Pyrotech 2017;47:1e11.
[9] Chaturvedi S, Dave PN. Review on thermal decomposition of ammonium ni-
trate. J Energetic Mater 2013;31(1):1e26.
[10] Kwok QS, Kruus P, JONES DE. Wettability of ammonium nitrate prills.
J Energetic Mater 2004;22(3):127e50.
[11] Videla AR, Polanco C, Escalona N. Phenomenological model of the effect of
organic polymer addition on the control of ammonium nitrate caking. Powder
Technol 2017;315:114e25.
[12] Gezerman AO, C_ orbacioglu BD. Effects of calcium lignosulfonate and silicic
acid on ammonium nitrate degradation. J Chem 2014:6e12.
[13] Nagayama S, Katoh K, Higashi E, Hayashi M, Kumagae K, Habu H, et al.
Moisture proofing of spray dried particles comprising ammonium nitrate/
potassium nitrate/polymer. Propellants, Explos Pyrotech 2015;40(4):544e50.
[14] Lafci A, Guruz K, Yucel H. Investigation of factors affecting caking tendency of
calcium ammonium nitrate fertilizer and coating experiments. Nutrient Cycl
Agroecosyst 1988;18(1):63e70.
[15] Wei Y, Cai BH. Study on surface modification of ammonium nitrate. In:
Advanced materials research, vol.399. Trans Tech Publ; 2012. p. 1989e93.
[16] Jos J, Mathew S. Ammonium nitrate as an eco-friendly oxidizer for composite
solid propellants: promises and challenges. Crit Rev Solid State Mater Sci
620 B.I. Elzaki, Y.J. Zhang / Defence Technology 15 (2019) 615e620
2017;42(6):470e98.
[17] Damse R. Waterproofing materials for ammonium nitrate. Def Sci J
2004;54(4):483.
[18] Malash G, Hashem H. Improving the properties of ammonium nitrate fertilizer
using additives. Alexandria. Eng. J. 2005;44(4):685e93.
[19] Zhang X-d, Li J-m, Yang R-j, Zhao X-q. Surface modification of phase stabilized
ammonium nitrate and its application in solid composite propellants. Chin J
Explos Propellants 2009;1:002.
[20] Zhang J, Yang R-j. Study on surface properties of coated ammonium nitrate.
Energetic Mater Chengdu 2004;12(1):1e5.
[21] Yu Zhicheng Y. Coating and modification of ammonium nitrate particles.
China: Master Dissertation Nanjing University of Science & Technology; 2013.
[22] Elzaki BI, Zhang YJ. Coating methods for surface modification of ammonium
nitrate: a mini-review. Materials 2016;9(7):502.
[23] Hu K, Luo N, Huang W, Ma X, Xu X. Test and study on the modification of
ammonium nitrate by coating its surface. Explos Mater 2006;35:14e7.
[24] Hou Ying Y. Study on the hygroscopicity of several surfactant coating mate-
rials. In: Proceedings of the national symposium on green manufacturing and
applied technology for fine chemicals; 2016.
[25] Hou Ying Y. Preliminary study on the anti- hygroscopicity of materials for
coating ammonium nitrate particles. master dissertation Nanjing University of
Science & Technology; 2017.
[26] A. W. Adamson, A. P. Gast, et al, Physical chemistry of surfaces.