Final Report On Design Development of Hi

Final Report on
Design, Development of High Precision Explosive

Slurry Filling System
Project Investigators
Dr. Virendra Kumar Dr. H. Muthurajan
Scientist ‗F‘ Associate Professor
Joint Director National Centre for NanoScience
Armament Research & Development and NanoTechnology,
Establishment Mumbai – 400 098
Pune – 411 021
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Abstract
Microelectric Detonators (MED) is the new and emerging field in the miniaturize
electro explosive devices. MEDs are used in field with extremely sensitive primary explosive
material for initiating secondary explosives. To use MEDs in field we have to put slurry of
primary or secondary explosive materials on the surface of MED for making physical contact
between primary explosive and MED. MED can be initiated by imparting sufficient electrical
energy to produce plasma on the surface of MED and it in turn initiates the high sensitive
primary explosive pasted on its surface. In view of this we have designed and developed
three axis stage including X,Y and Z axis control with dispensing control mechanism.
Mechanical parts with linear actuator, lead screw and linear guide has been designed by us
and fabricated for X, Y and Z axis stages. All mechanical parts are integrated to make
standalone semi-automatic dispensing system. For dispenser design we have modified a
manually operated bottle top dispenser such that its dispensing action can be automatically
controlled from PC.
For controlling mechanical movement of dispenser, stepper motors with linear
actuator having different holding torque, weight and current has been used for X, Y and Z
axis. We have fabricated slurry filling system having three stepper motors for controlling X
axis, Y axis, and Z axis (piston bottle top dispenser) movement respectively.We have also
designed 2 Amp stepper motor driver having option to select half and full step pulse sequence
to be applied for stepper motor.The driver can precisely drive the stepper motor with the
minimum resolution of 3 µm. The driver has been tested with stepper motor with linear guide
assembly for every axis separately. Whole assembly is integrated with embedded system to
automatically control its operation through PC. The embedded software is designed and
tested with the slurry filing system.
This report also contains detailed SOP on preparation of various Nano explosive inkusing
different techniques such as Supercritical fluid precipitation processes, Gas anti – solvent
(GAS) Method, Rapid Expansion of Supercritical Solution into Aqueous Solution (RESS–
AS) Method, Crystallization Method, Sonocrystallization Method, Cooling crystallization
Method, Nozzle assisted Solvent/nonsolvent Method, Prefilming twin-fluid nozzle assisted
solvent/nonsolvent Method, Spray drying Methods, Ultrasonic Spray Method, Spray freeze-
drying Method , Spray freezing into liquid (SFL) Method, Electrospray crystallization
Method, Sol-gel processing, Template technique, Rigid template, Wet chemical-assisted soft
template, Physical vapor deposition (PVD) and Inkjet printing. Hence this document can be
used for design & development of production grade automated explosive slurry filing system
in large scale.
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Table of Contents
Chapter 1................................................................................................................................................. 6
SYNTHESIS METHODS FOR SLURRY OF HIGH ENERGETIC NANOMATERIALS ......................................... 6
Introduction ............................................................................................................................................ 6
1.1 Supercritical fluid precipitation processes ........................................................................................ 7
1.1.1 Gas anti – solvent (GAS) Method ............................................................................................... 7
1.1.2 Rapid Expansion of Supercritical Solution into Aqueous Solution (RESS–AS) Method.............. 9
.............................................................................................................................................................. 14
1.2 Crystallization Method .................................................................................................................... 15
1.2.1 Sonocrystallization Method ..................................................................................................... 15
.......................................................................................................................................................... 19
1.2.2 Cooling crystallization Method ................................................................................................ 20
1.3 Nozzle assisted Solvent/nonsolvent Method ................................................................................. 23
1.3.1 Prefilming twin-fluid nozzle assisted solvent/nonsolvent Method ......................................... 27
1.4 Spray drying Methods ..................................................................................................................... 30
1.4.1 Ultrasonic Spray Method ......................................................................................................... 30
1.4.2 Spray freeze-drying Method .................................................................................................... 32
1.4.3 Spray freezing into liquid (SFL) Method ................................................................................... 34
1.4.4 Electrospray crystallization Method ........................................................................................ 35
1.5 Sol-gel processing ........................................................................................................................... 35
1.6 Template technique ........................................................................................................................ 37
1.6.1 Rigid template .......................................................................................................................... 37
1.6.2. Wet chemical-assisted soft template ..................................................................................... 39
1.7 Physical vapor deposition (PVD) ..................................................................................................... 41
1.8 Inkjet printing .................................................................................................................................. 42
Chapter 2............................................................................................................................................... 45
VARIOUS METHODS FOR EXPLOSIVE SLURRY SYNTHESIS ..................................................................... 45
Introduction .......................................................................................................................................... 45
2.1. 1, 1-Diamino-2, 2-dinitroethylene (FOX-7) .................................................................................... 47
2.1.1 Method 1.................................................................................................................................. 47
2.1.2 Method 2.................................................................................................................................. 47
2.1.3 Method 3.................................................................................................................................. 48
2.1.4 Solubility of FOX-7 .................................................................................................................... 49
2.1.5 Spectral Studies:....................................................................................................................... 50
2.1.6 Thermal and sensitivity studies ............................................................................................... 50
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2.1.7 Application ............................................................................................................................... 50
2.2 Ammonium salt of dinitramidic acid (ADN) .................................................................................... 51
2.1.1 Methods of Preparation of Dinitramide .................................................................................. 51
Method 1: ......................................................................................................................................... 51
Method 2: ......................................................................................................................................... 52
Method 3: ......................................................................................................................................... 52
Method 4: ......................................................................................................................................... 53
Method 5........................................................................................................................................... 53
2.3 2, 4, 6-triamino-1, 3, 5-trinitrobenzene (TATB) .............................................................................. 54
2.3.1 Synthesis and Manufacturing: ................................................................................................. 55
a) Gerenal Scheme: ....................................................................................................................... 55
b. Preparation of Nano TATB: ....................................................................................................... 56
2.4 Bis-(5-nitro-2H-tetrazolato-N2)tetraammine cobalt(III) perchlorate (BNCP) ................................. 58
2.4.1 Method 1.................................................................................................................................. 59
2.4.2 Method 2.................................................................................................................................. 61
a) Preparation of 5-Aminotetrazole mono hydrate (AT) ............................................................. 61
b) Preparation of Sodium 5-nitrotetrazole dihydrate ................................................................... 61
c) Preparation of Carbonato tetra amine cobalt(III) Nitrate (CTCN) .......................................... 62
d) Preparation of BNCP ................................................................................................................. 62
2.5 Infra-Red (IR) Spectroscopy : .......................................................................................................... 64
2.6 Pentaerythritol tetranitrate (PETN) ................................................................................................ 65
2.6.1 Method 1: ................................................................................................................................ 65
2.6.2 Method 2: ................................................................................................................................ 66
Chapter 3............................................................................................................................................... 71
DESIGN OF SLURRY FILING SYSTEM ...................................................................................................... 71
INTRODUCTION ..................................................................................................................................... 71
3.1 Mechanical Part design ................................................................................................................... 74
3.1.1 Rail Block and Rail guide .......................................................................................................... 74
3.1.2 Lead Screw ............................................................................................................................... 75
3.1.2 Sample Mounting Plate ............................................................................................................ 75
3.1.3 Bottle top Dispenser ................................................................................................................ 76
3.1.4 Supporting Assembly ............................................................................................................... 77
3.1.5 X, Y and Z axis ........................................................................................................................... 78
3.2 Electronics Hardware design for Dispenser .................................................................................... 81
3.2.1 Stepper motor ...................................................................................................................... 81
3.2.2 Stepper Motor Driving Setup ............................................................................................... 83
3.2.3 Controller and Embedded program ..................................................................................... 84
2.2.4 Embedded program source code ......................................................................................... 85
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3.2.5 Stepper Motor Driver ........................................................................................................... 92
3.2.6 Design and Schematic .......................................................................................................... 93
3.3 Testing and Results ......................................................................................................................... 97
References .......................................................................................................................................... 102
Engineering Drawings of Dispenser Developed under this project .................................................... 108
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Chapter 1: SYNTHESIS METHODS FOR SLURRY OF HIGH ENERGETIC
NANOMATERIALS
Introduction
Energetic materials (explosives and propellants) are used extensively for both civilian and
military applications. Some major considerations for successful weaponization of energetic
materials include performance (e.g. energy density, rate of energy release), long term storage
stability, and sensitivity to unwanted initiation. Nanosized explosives and energetic materials
are attractive to engineer nanosized holes and trenches and for cleaning pinholes and clogged
ducts for fluid transport, and may find applications as propellants. In addition, explosive
nanoparticles can be used as validation standards to challenge the detection limits of modern
instruments built for trace explosive detection. Numerous challenges exist in physical
chemistry that requires careful studies aimed at understanding the physical properties of
nanosized explosives and energetic materials.
It is well known that size, structure and shape have significant influence on properties of
inorganic/organic materials, such as optics, electrics, optoelectronics, gas-sensor, and
magnetic properties. Similarly, micro/nano-energetic materials with distinct structures and
extremely small feature sizes also exhibit structure- and size-dependent properties, including
thermal decomposition, sensitivity and operational performance. Therefore, the controllable
preparation of micro/nanoenergetic materials with different morphologies and sizes is of
great importance for achieving desirable properties. However, it is more difficult for the
synthesis of micro/nano-energetic materials than that of inorganic nanostructures because
most of energetic compounds feature van der Waals or other weak intermolecular interactions
among molecules, and they are dangerous explosives. Up to now, relatively few facile and
simple approaches have been developed to construct the micro/nanoparticles of energetic
materials. Usually, explosives must be powerful when destroyed, but be sufficiently stable
not explode easily when handled. The unintended explosion of energetic materials can be
prevented by reducing their sensitivity. One of the ways to lower the sensitivity towards
sudden shock is to control the crystal morphology so as to be close to spherical.
Crystallization processes offer the ability to produce crystals within the specifications of
acceptable crystal size, crystal shape and narrow crystal size distribution. These can be
optimized by selecting the right operating conditions of the crystallization process. The
various types of synthesis method have been described below.
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1.1 Supercritical fluid precipitation processes
Supercritical fluids have been used as solvents for a wide variety of applications in the field
of organic and inorganic materials [1-3]. On the basis of above fluids, various supercritical
fluid-based precipitation methods have been developed and have attracted extraordinary
attention due to unique micronization processes compared with conventional crystallization
techniques, such as milling, crushing, spray drying, and crystallization from liquid solution
[4,5]. The supersaturation and nucleation rates, and the size and morphology of
micro/nanoparticles can be easily controlled by varying the process parameters. To date, the
supercritical fluid processes, mainly including gas anti-solvent (GAS) and rapid expansion
supercritical solutions (RESS) process [6], have been used for explosives.
1.1.1 Gas anti – solvent (GAS) Method

Energetic materials at the nanoscale, especially monomolecular nanoexplosives, have
attracted much attention due to their expected excellent performance, including higher energy
release, deflagration rates, detonation velocity, lower activation energy, ignition temperature,
critical temperature of thermal explosion, and mechanical sensitivity [7–12]. Although many
methods have been developed to fabricate nanoexplosives, most of them are difficult.
Employing the reprecipitation method, Zhang et al. fabricated reticular HMX (octahydro-1, 3,
5, 7-tetranitro-1, 3, 5, 7-tetrazocine) nanoparticles with a diameter of about 50 nm and
concluded that the impact sensitivity of the nano-HMX was lower than that of the
micrometer-sized counterpart [13]. In addition, a nano-TATB (triaminotrinitrobenzene)
explosive was prepared using a similar method—that is, solvent anti-solvent recrystallization
in which sulfuric acid acted as the solvent and water was the anti-solvent [14]. Transmission
electron microscopy (TEM) and atomic force microscopy (AFM) analyses confirmed that the
particle size in the prepared samples was smaller than 60 nm. Though the experiments above
were successful in terms of fabricated nanoexplosives, the yield and repeatability were not as
certain as the direct methods. To further improve the recrystallization method, Huang et al.
prepared a nano-HNS (hexanitrostilbene) explosive via prefilming twin-fluid nozzle-assisted
precipitation, wherein nanocrystalline HNS was recrystallized from ultrapure water with two
different surfactants (sodium carboxymethyl cellulose and white dextrin) to modify the
particle surface [15, 16]. As a result, a nanoexplosive with a particle size between 50 and
600nm was created. The nano-HNS was high yield, except for a portion at the submicrometer
scale, because the surfactants surrounding the recrystallized particles retarded their
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overgrowth. Yang et al. used liquid nitrogen as the anti-solvent to fabricate NTO (5-Nitro-
2,4-dihydro-3H-1,2,4-triazole-3-one) nanoparticles with an elongated shape and diameters of
70–90 nm, and the differential scanning calorimetry (DSC) traces showed a 16°C shift in
advance compared to its micrometer form [17].
In the past decade, a promising method to fabricate nanostructure explosives using
supercritical fluid (SCF) technology has been developed rapidly [18–20]. Essentially, this
method is also a recrystallization process and is commonly subdivided into two specific
processes: rapid expansion of supercritical solutions (RESS) and the gas anti-solvent (GAS)
process. The SCF is used as a solvent to dissolve explosives in RESS, whereas it acts as the
anti-solvent to extract the solvent dissolving explosives in the GAS process. Unfortunately, in
the RESS process, the considerably low solubility of most explosives in SCF presents a
challenging problem, even when some cosolvents are added. For example, Stepanov [21]
used both acetone (2 mol %) and acetonitrile (4mol %) as cosolventsto dissolve a few
nitramines into SCF-CO2, by which 100 nm HNIW particles were recrystallized. In the GAS
process, the mass of recrystallized particles can be obtained easily because their solvent is
extracted. In Teipel‘s reports, superfine explosive particles with sizes of about 2–3 µm were
separated via the GAS process by dissolving RDX, HMX, and HNS into acetone,
cyclohexane, and dimethyl formamide (DMF), respectively [22]. It is very difficult to
fabricate explosive particles at the nanoscale due to the longer extraction time during the
GAS process [23–25]. Nevertheless, in comparison to the low yield from the RESS process,
the GAS process may be better and provide a greater possibility to prepare nanometer
explosives by improving the method itself.
Huang et al. [26] has given a combinative sequence based on the GAS method for fabricating
nanoexplosive in which a gel network was employed to limit the overgrowth of the
recrystallized particles. The aerogel matrix can be removed by acid etching and the
nanoexplosive particles are separated.
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Figure1. Schematic diagram for the preparation sequence with three processing
steps of sol-gel, supercritical extraction, and acid etching
Nano Energetic Materials prepared by GAS Method
Energetic Material Particle size Characterization Ref.

HMX 0.1-875 µm FESEM, FTIR, particle size 16
analysis
HMX 4-14 µm SEM, FTIR 17
RDX 2.6-17.7 µm SEM, FTIR, DSC, Particle 26
size analyzer
Structure of HMX Structure of RDX

1.1.2 Rapid Expansion of Supercritical Solution into Aqueous Solution
(RESS–AS) Method
Energetic materials are commonly used either as the main ingredient or an additive in
explosive and propellant formulations. An attractive energetic material provides a high
9
amount of energy release while being relatively insensitive to accidental initiation. However,
there is usually a delicate balance between the two as energetic materials that release more
energy or perform better are often more sensitive to initiation. Because of this, a way to
reduce the sensitivity and increase the performance of an energetic material would be
attractive. One way to achieve these goals is by controlling the size distribution and
morphology of energetic materials. It has been shown for RDX (cyclo-1, 3, 5-trimethylene- 2,
4, 6-trinitramine) and other crystalline monomolecular energetic materials that as the average
particle size is decreased, sensitivity to impact decreases [27, 28]. It was proposed that this
decrease in impact sensitivity comes from a reduction of imperfections or dislocations in a
crystal, which can avalanche when under impact and/or shock. Also, particles with a
spherical shape have been shown to be less sensitive to initiation [29, 30]. Furthermore, near-
spherical particles are more ideal for processing applications in comparison to needle-like
particles [31].
In order to create a high-density and defect-free solid propellant/explosive, the particle size,
morphology, and size distribution must all be controlled. Producing energetic oxidizer
particles on the nanoscale could also be advantageous for performance reasons. If nano-sized
oxidizers were intimately mixed with nano-sized metallic fuels, the diffusion distance
between fuel and oxidizer could be greatly reduced. Also, nano-sized particles have been
known to have different thermodynamic properties in comparison to larger particles. For
example, by decreasing particle size, the surface area-to-volume ratio of a particle increases,
and the particle melting temperature and heat capacity can decrease [32]. In addition, nano-
sized particles are made up of a large percentage of surface molecules, which can carry extra
energy on their surface. This could raise the energy density and energy release rate of a nano-
sized energetic particle.
Some research has already shown performance differences for nano-sized energetic oxidizers;
for instance, a study by Pivkina et al. [33] has shown that nano-sized RDX and ammonium
nitrate powders pressed into pellets burned significantly faster at elevated pressures than
samples made of micrometer-sized powders. These observed results were believed to be
caused by the enhanced surface area of the nano-sized particles, which allowed for enhanced
heat feedback from hot product gases at elevated pressures.
One method of controlling the size and shape when processing energetic materials is through
supercritical fluid precipitation. Supercritical fluids have unique advantages as solvents: they
experience a large change in density beyond their critical point when pressure or temperature
10
is varied and they have gas-like transport properties. The large change in density of
supercritical fluids allows for a high degree of supersaturation (ratio of instantaneous mole
fraction of solute in solution to the equilibrium mole fraction of solute in solution) if they are
used as a solvent and mechanically expanded through a nozzle. Supercritical fluid
precipitation has been used to produce solid particles of significantly smaller size and
different morphology than in conventional liquid solvent precipitation [34]. Both of these
attractive features are ideal for energetic materials because the size and shape of the particles
strongly affects their sensitivity and possibly their performance. One form of supercritical
fluid precipitation is called the Rapid Expansion of a Supercritical Solution (RESS) process.
The RESS consists of saturating a supercritical fluid with the substrate(s) and then
depressurizing this solution through a heated nozzle into a low pressure chamber in order to
cause an extremely rapid nucleation of the substrate(s) in the form of very small particles or
fibers or films when the jet is directed against a surfaces that are collected from the gaseous
stream. The results of previous studies on RESS process showed that the morphology of the
resulting solid material both depends on the material structure (crystalline or amorphous,
composite or pure etc.) and on the RESS parameters (temperature, pressure drop, distance of
impact of the jet against the surface, dimensions of the atomization vessel, nozzle geometry
etc.).It is should be noticed that the initial investigations consisted of pure substrates
atomization in order to obtain very fine particles (typically of 0.5-20 µm diameter) with
narrow diameter distribution, meanwhile the most recent publications are related to mixture
processing in order to obtain microcapsules or microspheres of an active ingredient inside a
carrier.
The RESS process has been used in many industrial fields such as the polymer and
pharmaceutical industries [35]. Initial applications involving energetic materials and the
RESS process was investigated by Teipel et al. [36], in which they produced the energetic
material trinitrotoluene (TNT). More recently, Stepanov et al. [37] used the RESS process to
produce particles of RDX.
Also Huang et al. has recently reported their work in which, RESS process-produced particles
(approximately 110 - 30 nm in diameter) demonstrated a dramatic reduction in impact
sensitivity when compared with military grade RDX. The thermal properties of the particles
were found to be similar to as-received micrometer- sized RDX particles. For these 110 nm-
sized particles, only a small percentage (ca. 3%) of the particle‘s mass was located at the
surface of the particle and an insignificant amount of thermal property alteration is expected.
While the RESS process has produced fine particles in the submicrometer and micrometer
11
size range, calculations based upon formulas for nucleation and growth by precipitation often
predict particles to be less than 100 nm [38].
It is presumed that the extra growth from the RESS process comes from particle coagulation
in the free jet after the nozzle exit, since the mechanical expansions (from supercritical to
ambient pressures) are often highly under-expanded [39]. The particles also tend to be
aggregated together from van der Waals forces, which makes them undesirable for later
processing. To reduce or eliminate coagulation and subsequent aggregation, slightly altered
version of the RESS process has been used, in which a supercritical solution is expanded into
a stabilizing liquid solution often made of water and a dispersant [40].
The dispersant adsorbs or bonds to the particle surface in the aqueous solution to limit the
growth of the particles after they are precipitated. The adsorbed dispersant also can stabilize
the particles in solution, preventing them from permanently agglomerating. If the dispersant
molecules are of a high molecular weight type (e.g. polymers), they can coat the particles to
prevent other particles from coming close enough to permanently agglomerate through the
physical interference (steric effect). This process of expanding supercritical solutions into
water and dispersing agent solutions is called the Rapid Expansion of a Supercritical Solution
into an Aqueous Solution (RESS-AS). A graphical representation of the RESS-AS process is
shown in Figure 2.
Figure2. Graphical representation of the RESS-AS process
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A supercritical solution is mechanically expanded through a nozzle to cause energetic
solution precipitation at high nucleation rates. The nano-size, nucleated particles are then
protected from agglomeration and growing larger via Ostwald ripening by surface adsorption
of a dispersant (usually a polymer, surfactant, or electrolyte).
It has been adopted by many researchers outside the energetic materials field to produce
submicrometer-sized particles from materials that could not be produced at sizes lower than a
micrometer from the RESS process [41–43]. The process has yet to be used in the energetic
material community and should be useful in making nano-sized monomolecular energetic
particles significantly smaller and better dispersed than those produced by the RESS process.
The RESS-AS process is also useful in that the surfaces of the precipitated particles can be
chemically altered in solution by colloidal processing for desirable effects such as making the
particles more compatible with other propellant/explosive ingredients and changing the
surface reactivity of the particles. These benefits are important, because nano-sized particles
need to be handled in the correct environment to avoid undesirable problems such as
permanent agglomeration, which mitigate the benefits of their small size.
Figure3. RESS-AS process diagram. Solvent and energetic solute form a supercritical
solution in the saturation vessel which is later expanded through a nozzle into an aqueous
solution in the particle expansion vessel. A remotely controlled system was used as a safety
precaution
In an another research the laser light scattering imaging system coupled to a gated ICCD
(intensified CCD) camera was used to capture images of individual particles in the ICCD
frames. A large number of individual frames have been processed to recover the particles size
distribution functions. In this approach each single spot corresponding to a particle was
13
resolved and treated separately. One of the advantages of this particle-by-particle treatment is
that it produces particle size distributions without assumptions on the shape of the
distribution functions in the range of the sizes where the inverse Mie problem has unique
solution (smaller than 106 nm for RDX particles). Another advantage is that in the images
one can differentiate light scattering by the turbulent RESS flow from the scattering by the
particles. The technique provides the number density of the particles and the particle size
distribution in the RESS jet. Such information is important for establishing the mechanism of
the particle formation in the RESS process. The light scattering imaging system was
calibrated using standard latex particles with known diameters as well as Rayleigh scattering
from air to determine the absolute sensitivity. Figure 4 shows the experimental setup used in
this work.
The scattering light intensity distribution functions from RDX particles formed by RESS
were determined in situ at different distances from the expansion nozzle. The series of the
intensity distribution functions were converted to the particle size distribution functions using
the absolute sensitivity obtained in the calibrations based on Rayleigh and Mie theories [44].
Figure4. Experimental setup

Nano Energetic Materials prepared by RESS Method
RDX 110-220 nm FESEM, HPLC, XRD, 25

Melting point analysis
14
Structure of RDX
1.2 Crystallization Method

Crystallization is the formation of solid particles within homogeneous phase. The degree of
supersaturation is increased to sufficient level by various means (evaporation of solvent,
cooling or combination of the two), which results into crystallization. The same mechanism is
responsible for the precipitation of the solutes by the addition of an antisolvent. When the
antisolvent is added to the solution, solubility of the solute decreases and the solution
becomes supersaturated. The degree of the supersaturation depends upon the quantity of the
antisolvent added and its distribution in the bulk of the primary solvent.
1.2.1 Sonocrystallization Method

Sonocrystallization is the use of power ultrasound to control the crystallization process.
Crystallization is a complex process involving multiple interacting processes, the control of
which can be difficult, and this is especially the case for organic compounds. Ultrasound is
used principally to influence the nucleation process, thus giving the engineer or a chemist a
level of process control and product tailoring previously unobtainable. Power ultrasound
creates cavitation in liquid media, each cavitation event consists of first the opening of a
small (a few tens of microns) gas or vapor void followed by its violent collapse. Cavitation
events serve as a means of generating nuclei due to high local supersaturation conditions for
new crystals to form and grow. At high intensities, ultrasound can be used instead of seed
crystals, and/or to start nucleation at a lower degree of bulk supersaturation than would
normally be the case as shown in Figure 5.
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Figure5. Effect of sonication on supersaturation
This reduction of the metastable zone width, shown in the illustration, has many significant
benefits such as control over crystal size and habit (shape and morphology). The effect is
most beneficial with large organic molecules, where normally very high supersaturation
levels may be required for the onset of primary and/or spontaneous nucleation. Chow et al.
[45] has shown that the primary nucleation of ice in sucrose solutions can be achieved at
higher nucleation temperatures in the presence of ultrasound. The nucleation temperatures
can be reproduced with a lower standard deviation, and a greater precision than under the
control conditions (without ultrasound).
Advantages of sonocrystallization:
The use of ultrasound provides a non-invasive way of improving crystal properties and
process controllability, chiefly by controlling the size distribution and the habit of the
crystals. The following benefits accrue:
 Improved product and process consistency.
 Improved crystal purity.
 Improved secondary physical properties of the product.
 Shorter crystallization cycle times and less frequent rework.
 Shorter and more reliable downstream processes.
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Additionally, ultrasound can be used to replace seed in gas a nucleate or in difficult-to-
nucleate systems. By varying the power and duration of insonation the crystal size
distribution can be tailored to optimize downstream processing. Figure 5 shows how
ultrasound was used to control the crystal size distribution of dodecanedioic acid [46]. The
solid line shows the base case where no ultrasound was used; the dashed line shows where
ultrasound was used only to nucleate the solution; and the chain linked line shows where
ultrasound was used continuously throughout the crystallization. Insonation to nucleate
shows a marked increase in the mean crystal size, whereas continuous insonation has
dramatically reduced the mean crystal size.
Crystal size, habit and yield are a function of the growth rate and the supersaturation history.
Low supersaturation favors modest rates of nucleation and relatively slow growth at similar
rates over the crystal surfaces, leading to a crystal with a compact habit which flows well
during its dry handling. In the absence of further nucleation, and with controlled maintenance
of the level supersaturation, these crystals will grow to a large size which is easy to process in
downstream operation. At high supersaturation, on the other hand, both nucleation and
growth rates are high, favoring a low mean size and in some cases extreme habits (wide size
distribution and morphological variation). There may also be scope to use ultrasound to
generate bursts of secondary nuclei, and thus manipulate the spread of the size distribution
and the product properties. By controlling the supersaturation level at the point of nucleation
(synonymous with cavitation) and the subsequent growth rate, there is a less tendency to
produce multiple or agglomerated crystals which contain occluded mother liquor [47].This
significantly increases the degree of purification achievable in the crystallization step.
Ultrasound can also be used to deagglomerate.
Improving or debottlenecking downstream processes is one of the major drivers for
employing sonocrystallization. Manipulating the size and habit of the product crystals can be
made to achieve the following benefits:
• More rapid filtration: crystals of a more uniform size and compact habit can be filtered
much more rapidly.
• Similarly, better access to the inter crystal voids greatly improves the speed of washing and
drying, as well as the decontamination level achievable.
• The milling of crystals is a messy process which risks mutual contamination of product and
environment. By sonically tailoring crystal size distribution, the milling step may be
eliminated altogether.
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• Powder filling operations can be made much more reliable and trouble-free because
sonically nucleated crystals usually flow much better (due to rounding of) than those
produced conventionally. The bulk density of the product may also be improved; doubling of
bulk density is possible, which is very essential for explosive materials for use.
Mohan et al. [ultrasonic paper] has prepared CL-20 by Sonocrystallization method. The
experimental setup is shown in figure 6. Sonication bath experiments were performed in a
stainless steel low powered ultrasonic bath, (Dakshin Ltd., India) the internal dimensions of
the bath were: length = 0.15 m, breadth = 0.15 m and height = 0.15 m. The bath has three
transducers located at the bottom, arranged in a triangular fashion. The bath was driven at 20
kHz frequency and it had a power rating of 120 W. The bath was scaled and mapped for its
static and dynamic pressure fields in all the three directions using hydrophone.
Characterization of the sonication bath was made in terms of the pressure intensities at
various locations in the bath. The local pressure intensity was measured using a hydrophone.
The signal from the hydrophone was amplified through a charge amplifier and the signal was
then fed to a FFT (Fast Fourier transform) based spectrum analyzer. The resultant output
directly gives the mean pressure intensity in atmosphere (after using the supplied cavitation
curves) for the corresponding frequencies. Water was taken in the ultrasonic bath as a
cavitating medium and was filled up to a height of 14 cm. The pressure intensities were
measured at different locations. Figure 6 shows a schematic of experimental set up.
Figure6. Experimental setup of pressure intensity measurement by hydrophone with FFT

based spectrum analyzer
The complete experimental set up is shown in Figure 7. The solution (solute + solvent) was
taken in the conical flask. The conical flask was kept in the ultrasonic bath (filled with water).
18
The precipitation was done by adding the antisolvent through the addition column (dumped
or controlled addition). Air condenser was attached to the flask to avoid the evaporation of
the solvents due to ultrasonic irradiation and resultant temperature increase. The temperature
of water was increased by5ºC in 27 min (which is maximum in this system) continuous
sonication. The temperature rise of the solvent and antisolvent (kept in the conical flask) was
insignificant due to the evaporative cooling of the solvent and antisolvent as solvent and
antisolvent get easily vaporized and use its own sensible heat maintaining the temperature
nearly constant. Long air condenser was attached to recover the vapors formed by
condensation. Thus rise in the temperature is not an important factor for this system. The
precipitate was filtered out using vacuum filtration unit at the end of the antisolvent addition
or sonication based on the operating conditions.
Figure7.Experimental set up
Nano Energetic Materials prepared by Sonocrystallization Method

CL-20 5 µm SEM, FTIR, H-NMR, DSC, 1
sensitivity test
CL-20 95 nm DSC, SEM, FTIR, XRD, HPLC 2
CL-20 400-700 nm SEM, FTIR, XRD, DSC 3
RDX 0.1 – 1 µm SEM, TEM, XRD, HPLC 24
Structure of RDX Structure of CL-20
19
1.2.2 Cooling crystallization Method
Cooling crystallization has achieved a great success in the synthesis of energetic materials
with special structures and narrow size distribution [48]. For this technique, the type of co-
solvent, cooling rate and solvent composition are the important process parameters to control
the morphology and size of the crystals. However, it is difficult to reduce the size of the
products when the energetic compounds are used as target sources. Han and coworkers
recently studied the solubility and recrystallization of highly hydrogen-bonded 1, 3, 5-
triamino-2, 4, 6-trinitrobenzene (TATB) in various ionic liquid solvent systems [49]. They
synthesized TATB microparticles grown by the cooling crystallization process in ionic liquid
dimethylsulphoxide (DMSO) co-solvent systems.
It is known that the spherical crystals of energetic materials exhibit improved performance
over non-spherical crystals, such as insensitivity to sudden shock, processability and packing
density [50, 51]. Vijayalakshmi et al. fabricated spherical 3-nitro-1, 2, 4-triazol-5-one (NTO)
particles in NTO: water: N-methyl-2-pyrolidone (NMP) ternary system by using cooling
crystallization technique [63]. By adjusting the process parameters, such as cooling rate,
agitator configuration and speed, a selective particle size distribution ranging from 10 to 200
mm could be achieved. Kim and his coworkers used a similar assembly method to prepare
spherical NTO particles in the co-solvent of water and NMP [52-56].
The spherical particles with average diameter ranging from 30 to 300 mm were acquired in
the ratio of NTO/NMP ranging from 0.2 to 0.6 and in the ratio of water/NMP ranging from
1.0 to 4.8 at the cooling rate of 10 K/min. Besides, Kim‘s group used octahydro-1, 3, 5, 7-
tetranitro-1, 3, 5, 7-tetrazocine (HMX) as seed to direct the zero-dimensional (0D) core-shell
structure growth of HMX/NTO by two-step cooling crystallization [57].
The typical scanning electron microscopy (SEM) images of these energetic composites in
Figure 8 reveal that the surface of the core-shell HMX/NTO structures is compact and
uniform. They pointed out that the agglomeration kinetic for the coating of NTO on HMX
core particles was correlated with the 3rd power of the solution supersaturation and the 2nd
power of the number of the suspended particles.
20
Figure8. (a) Diagram of experimental apparatus and (b)-(g) effect of supersaturation on
coating morphology
Kwang et al. [58] has also used batch crystallization method for the agglomeration of NTO
on the surface of HMX particles in water-NMP solvent. The batch crystallization apparatus
used for the production of effective coatings is described in figure 9. It consists of 250ml-
double jacketed crystallizers, a programmed thermostatic bath, agitator with marine propeller
type stirrer (diameter, 30mm) and separation apparatus with a sieve. Water/ethylene glycol
mixture was used as a thermostatic media, and circulated in the inner double jacketed
crystallizer. The temperature of the thermostatic media was controlled by refrigerator with an
electrical heater and controller with an accuracy of 0.05 K.
21
Figure9.Schematic drawingfor experimental apparatus
The study of Denis et al. [59] introduces the conception of an apparatus to crystallize
continuously nanosized explosive or more generally nanosized organic materials. Figure 10
shows the experimental setup used for the synthesis of nano- RDX. The explosive is
dissolved in a solvent, for example, acetone, in a concentration below the saturation point. In
general, the installation runs with a 1–3 wt.-% RDX/acetone solution. When the ultrasonic
piezo transducer is turned on, it produces an aerosol on the upper liquid surface which is
further transported by an inert gas like nitrogen. This gas has the double task such as to gain a
good output of the installation and to space the droplets in order to limit their coalescence.
The aerosol is transported by the gas flow. It enters an oven which is in different zones
differentially heated. In the case of RDX, a temperature between 90 and 140ºC is applied.
The differentially heating is set to a maximum power at the entry of the oven and reduced
after the first half of the oven length to avoid a possible oven overheating. As the aerosol
enters into the oven, the liquid evaporates, and the explosive crystallizes. The nanoparticles
of RDX flow out of the oven where they continue to be dried. They then enter an electrical
precipitator composed of two electrodes between which a high electrical tension of 8–15 kV
is applied. It charges the particles which then deposit on the two electrodes. Most of the
quantity of the nano-RDX agglomerates on the outer cylindrical cathode. The electrical
precipitator is surrounded by a chamber heated above the condensation temperature of the
solvent to avoid dissolution of the RDX. Then, the gas flow, composed of nitrogen and
22
gaseous acetone, goes through a condenser in order to regain all the acetone in a liquid state.
The mixture nitrogen–acetone may also be re-injected in the first part of the installation.
Figure10. A diagrammatic representation of the crystallization apparatus
Nano Energetic Materials prepared by Cooling Crystallization Method

TATB 10-50 µm FTIR, DCS, TG/DTA, 31
Sensitivity test
NTO 10-200 µm FTIR, H-NMR, SEM, 20
DSC, TG/SDTA, HPLC
NTO 30-300 µm SEM 21
O N
N
Structure of TATB Structure of NTO N
H NO2
1.3 Nozzle assisted Solvent/nonsolvent Method
Since the first use of solvent/nonsolvent method in the preparation of organic nanocrystals by
Nakanishi in 1993 [60], this technology has been extensively adopted in the field of energetic
materials due to its facility and versatility [61]. The method mainly includes a rapid mixing of
concentrated solution of the objective compound in a good solvent with excess of a poor
23
solvent, leading to the nucleation and growth of the molecules to small-sized particles with
desired structures. The significant difference between the solubilities of the target molecules
in the good and poor solvents and the good compatibility of the two solvents are essential.
A series of energetic micro/nanoparticles were successfully fabricated by using this method.
For example, Liu et al. reported that reticular nano-sized HMX was simply constructed at
room temperature [62]. SEM and TEM show that the spherical HMX particles with diameter
of about 50 nm aggregate into reticularly structured conglomerates. Subsequently, Li et al.
prepared HMX microcrystals and studied their microscopic morphologies [63, 64]. Moore
and coworkers also obtained submicron-sized HMX by pouring a solution of HMX in
acetone into a cold nonsolvent with strong stirring [65, 66]. Van der Heijden‘s group and
Arya‘s group prepared hexahydro- 1,3,5-trinitro-1,3,5-triazine (RDX) and 2,20,4,40,6,60-
hexanitrostilbene (HNS) ultrafine particles, respectively.
Nano Energetic Materials prepared by Nozzle assisted Solvent/Nonsolvent Method

SEM, TEM, XRD, DSC,
HMX 50 nm 9
Drop weight impact
FESEM, DSC, Raman
spectroscopy, Neutron
HMX 1-2 µm 10
powder diffraction,
Sensitivity test
TEM, AFM, DSC, XRD,
TATB 27-41 nm 32
TGA, BET
Structure of HMX Structure of TATB
24
The above mentioned method has been used to synthesize the energetic compounds with
desired size and special morphology, but it suffers with an issue of process scale-up.
Therefore, an instrument with high-pressure jet, which can lead to a rapid nucleation in
continuous reaction and crystallization, producing the nanoscale energetic particles with high
yield and mass production, was developed in the past few years. Wang and his coworkers
reported the fabrication of submicron HMX and RDX by spraying a solution of the nitramine
explosive into water at different process parameters [67].
Guangcheng and coworkers [68] has prepared nano-TATB. The preparation instrument
schematic drawing is shown in Figure 12. The solution containing the objective compound
(Figure 11A) is driven by pressured air and atomized by a nozzle to small droplets with high
speed. The droplets collide with an ultrarapid nonsolvent flow (Figure 11B) which is also
driven by pressured air. The violent collision results in rapid crystallization and the particles
formed are very fine.
Figure11. Schematic drawing of preparation instrument: (A) Solution flow, (B) ultrarapid
nonsolvent flow.
In another report Arash and their coworkers [69] has synthesized nano-keto-RDX using this
method. They have used a preparation instrument made of stainless steel for experiment and
25
its schematic drawing shown in Figure 12. A stream of dry air with pressure of 6 bars and
ambient temperature was blown through the pipe (2). Its flow rate was controlled using valve
(1). The test solution (3) containing K-RDX/acetone solution sucked, atomized, and mixed
with air stream. The converging diverging section (5) produced enough suction to mix
appropriate amount of solution with air. Fine control of the flow rate of the solution was
achieved by stop cock (4). A high-speed stream carrying fine sample droplets penetrated the
water in container (8) through nozzle (6). The agitator (7) at 1,000 rpm maintained the
uniformity of the liquid in container (8). It was observed that very fine particles of K-RDX
were produced in this process and they were collected through valve (9). The K-RDX product
was filtered, washed, and dried as nano-K-RDX particles.
Figure12. Schematic drawing of preparation instrument
Nano Energetic Materials prepared by Nozzle assisted Solvent/Nonsolvent Method

Impact sensitivity, Detonation
HMX 925 nm 12
velocity
26
HMX 617 nm SEM, XRD 13
Impact sensitivity, Detonation
RDX 560 nm 12
velocity
RDX 60 nm SEM, TEM, XRD, TGA, DSC 22
NO2
N
H2C CH2
Structure of HMX Structure of RDX
N N
1.3.1 Prefilming twin-fluid nozzle assisted solvent/nonsolvent
O2N Method
CH2 NO2
Bayat and coworkers used a similar method to prepare the submicron particles of HMX and
systemically investigated the influence of the experimental parameters, such as antisolvent
temperature, compressed air flow rate, and nozzle diameter [67], on the size of HMX particle,
while Shokrolahi and coworkers obtained the crystalline nanoparticles of ketoderivative of
RDX (K-6) [70].
Recently, Jing et al. also prepared the high-purity HNS nanocrystals with high specific
surface area and narrow particle size distribution by using a prefilming twin-fluid nozzle
assisted precipitation method. Structure of the prefilming twin-fluid nozzle is illustrated in
Figure 13. The non-solvent is driven along the co-axial annular passage and formed to a thin
swirl liquid film (thickness 10 µm) by the liquid distributor with spiral slots, which is
inclined at an angle (α) relative to the central axis of the nozzle. The outlet diameter of the
coaxial annular passage is 2.5mm. The solvent containing object compound is driven through
the inner stainless pipe (0.7mm i.d.) in order to form a jet stream with high velocity. At the
exit of the nozzle the solvent stream impinges on the thin swirl film and interacts with each
other.
27
Figure13.Prefilming twin-fluid nozzle
The prefilming twin-fluid nozzle is mainly based on both impinging [71, 72] and prefilming
[73, 74] fluid jet effect of the high-pressure jet with high velocity. Impinging fluid jet effect
caused by high-pressure and high-velocity fluid jets can create high turbulence at their point
of impact, and so as to produce a chemical reaction which forms a reaction product under
high super-saturation leading to a rapid nucleation in a continuous reaction and
crystallization, which is followed by the direct production of small controlled particle size
crystals. In this process, each jet has sufficient linear velocity to achieve high intensity micro-
mixing of the solvent and the non-solvent before nucleation. The principle of prefilming fluid
jet effect is that the non-solvent is driven along a surface within the nozzle as a swirling film,
arriving at the nozzle edge, which interacts with the solvent at an angle to generate shear
force on each other. These two high-pressure and high-velocity fluid jets are sheared to
micro-droplets which are accelerated because contacts between two fluid jets are violently
agitated in the small geometry nozzle to complete uniform micromixing prior to the crystal
nucleation and then rapidly precipitate the ultra-fine particles. As we can see in Figure 14, the
solvent containing the objective compound is driven by a metering plunger pump into the
inner pipe of the prefilming twin-fluid nozzle as continuous fluid jet.
28
Figure14. Experimental setup
This fluid jet contacts with the chilled ultra-pure water fluid jet which is also pumped by
another metering plunger pump. Rapid recrystallization occurs in the field of contact between
these two fluid jets on the edge of twin-fluid nozzle and fine particles are formed. Barrier
separation with a barrier width of 50 nm, was used to carry out the separation process and
drying procedure was conducted on the freeze drier.
Nano Energetic Materials prepared by Prefilming twin fluid Nozzle assisted

Solvent/Nonsolvent Method

SEM, BET, HPLC, XRD, DSC,
HNS 90-150 nm 18
TGA/SDTA
HNS 60-500 nm SEM, BET, HPLC, DSC 19
NO2 O2N
Structure of HNS
O2N CH HC O2N
29
NO2 O2N
1.4 Spray drying Methods
During last two decades, many efforts have been given into development of energetic
materials with reduced sensitivity. New energetic compounds with insensitive property which
is come from their molecular structures such as triaminotrinitrobenzene (TATB), 1, 1-
diamino-2, 2-dinitroethene (DADNE), and 7-amino- 4, 6-dinitrobenzofuroxan (ADNBF)
have been synthesized. However, the high production cost and relatively weak performance
of such explosives limit general applications [75, 76]. In parallel, the relationship between the
sensitivity and the physical properties (e.g., crystal size, morphology, purity, and crystal
defects, etc.) of high-energetic materials has been also extensively studied [77-83].
In particular, crystal defects such as internal voids, dislocations, and inclusions are known to
be directly related with the shock sensitivity of the explosives because they act as hot spots,
which are specific regions that readily interact with the surrounding stimuli [84, 85].
Therefore, improving the crystal quality of widely utilized high energetic materials such as
RDX and HMX is an efficient alternative for development of explosives with reduced-
sensitivity [86, 87]. In general, it is known that the shock sensitivity of high-energetic
materials is reduced as crystal size decreases because the critical temperature to ignite an
explosive increases significantly by decreasing the size of hot spots [89, 90].
Grinding and milling are general methods for size reduction of particles. However, those
methods are not recommended for energetic materials due to the possibility of accidental
ignition as well as the difficulty in manufacturing uniform Submicrometer sized particles
[91]. Damage on the crystal surface is another problem of physical grinding [92].
Submicrometer crystals of high energetic materials can be produced by the crystallization
with nozzle-assisted drowning-out [93, 94]. However, filtration of crystal suspension is a
very time-consuming process for submicrometer scaled particles. In addition, droplets
violently atomized generally lead to agglomeration or coalescence. As a consequence, they
induce morphological problems such as obstruction of close packing, poor binder
distribution, and bad crystal roundness. Supercritical fluids also have been applied to obtain
ultrafine high-energetic materials [95-99].
1.4.1 Ultrasonic Spray Method

Spray drying is widely utilized to manufacture submicrometer or nanosized particles, in part
because the apparatus is simple and continuous and can be scaled easily for mass production
[100-102]. Among various atomization techniques, ultrasonic spray is one of the favored
30
methods because of its outstanding energy-efficiency, affordability, and the inherently low
velocity of initial droplets [103]. In recent years, spray drying has been employed for the
particle formation of high-energetic materials. Kim et al. tried to introduce evaporation
crystallization by ultrasonic spray into formation of submicrometer-sized RDX particles
[104] and it was found that acetone is a suitable starting solvent.
Recently, Spitzer et al. also reported that submicrometer-sized RDX crystals can be obtained
by ultrasonic spray from a 1% RDX/acetone solution in a furnace at 90°C [105]. Qiu et al.
reported that RDX-based nanocomposite consists of RDX crystals with size of 0.1-1 μm can
be produced by ultrasonic spray from a RDX (5 wt %) / binder (1 wt %) / acetone solution
[106]. Jun et al has described the function of ultrasonic spray while the synthesis of nano
RDX in their work. Figure 15 represents a schematic experimental setup for evaporation
crystallization of RDX by ultrasonic spray.
Figure15. Schematic diagram of experimental setup for evaporation crystallization with

ultrasonic spray
The main equipment consists of an ultrasonic nebulizer with a 1.7 MHz ultrasonic transducer
for formation of micro droplets from RDX/acetone solution, an electric furnace for
evaporation of acetone, a bag filter for collection of RDX particles, and a water jet aspirator
pump (Jeio Tech, VE-11, Korea) for transportation of acetone vapor and air mixture. A 100 g
of starting solution was added in the ultrasonic nebulizer (a width of 5 cm, a length of 25.2
31
cm, and a height of 10 cm) which is made of polytetrafluoroethylene (PTFE). The height of
solution was maintained at 1 cm. In this setup, the volume generation rate of RDX/acetone
aerosol was found to be about 10 mL/min. The temperature of the solution was maintained at
25°C by circulating cooling water around the container. The electric furnace was equipped
with an 80 cm long quartz tube reactor with an internal diameter of 2.8 cm and an actual
heating length of 50 cm. A water-jet aspirator was served to transport the aerosol by
controlling the pressure in the entire apparatus. The pressure reduction by an aspirator is
dependent on the vapor pressure of water, which are a function of water temperature and the
residual content of acetone.
1.4.2 Spray freeze-drying Method

Spray freeze-drying (SFD) technique, which is considered as one of the advanced ways for
the fabrication of nanoparticles, has been widely used for the synthesis of nanostructures of
biological medicaments and inorganic materials [107-109]. The particles obtained by this
method generally possess the intriguing advantages, such as molecular scale homogeneity
because of flash freezing in the cryogen, and minimal agglomeration because of the
sublimation of the water ice in the low-temperature vacuum drying condition [110, 111].
So far, this system has been used to synthesize the nanostructures of energetic materials. In
the early years, [godfather] reported the fabrication of three dimensional (3D) nano-network
structures of NTO [112]. Since the formed ice limits the aggregation of small particles, the
obtained NTO particles have an elongated shape and the size of the particles is in the range of
70-90 nm. With a similar technique, 1, 1-diamino-2, 2-dinitroethylene (FOX-7) 3D grid
nanostructures with different unit sizes were also prepared by the freeze-drying technique
mentioned above [113].
The preparation process of FOX-7 3D grid nanostructures is shown in Figure 16(a). The
typical SEM images in Figure 16(b), (c) indicate that the resulting FOX-7 3D structures are
constructed from one-dimensional nanostructures. The size and reticular structures of the as-
resulting nano-FOX-7 could be easily controlled by adjusting the concentration of the
aqueous solution of raw materials. The further investigation on a possible formation
mechanism of this structure reveals that a high degree of super cooling under the liquid
nitrogen conditions leads to a high nucleation rate, and the small particles and ice are rapidly
formed due to the rapid heat transfer between the aqueous solution and the cryogen. After the
32
sublimation of ice, the small particles with a relatively high energy start to aggregate by self-
assembly, leading to the formation of 3D grid structures. A scheme of this growth process is
summarized in Figure 16(d). More importantly, this facile synthesis strategy may represent a
general approach for the preparation of nanostructures of other water-solubility energetic
compounds.
Figure16. (a) Flow chart of FOX-7 quasi-three-dimensional grids fabricated via SFD
technique; (b) low magnification; (c) high magnification of SEM images of FOX-7
nanostructures prepared with CFOX-7 ¼ 0.1 g/L; (d) a probable formation process of FOX-7
network structures under the same super cooling rate
Nano Energetic Materials prepared by Spray Freeze Drying Method

CL-20 1 µm SEM, XRD, DSC, BET 4
33
FOX-7 100 nm FE-SEM, TG-DSC, XRD 6
RDX 405 nm SEM, AFM, Raman spectra 23
RDX 1 µm SEM, XRD, DSC, BET 4
NO2
O2NN NNO2 H2N NO2 N
H2C CH2
O2NN of CL-20 NNO2
Structure Structure of FOX-7 Structure of RDX
N N
H2N NO2 O2N CH2 NO2
O1.4.3
2
NN Spray freezing into
NNOliquid
2
(SFL) Method
It is a novel process developed to produce microparticles or nanoparticles. Particles are
formed by atomization of an aqueous feed solution containing the objective compound into a
cryogenic liquid (e.g., liquid nitrogen or liquid carbon dioxide). Another objective is to
develop and demonstrate the use of novel SFL particle engineering technology to minimize
the particle size of explosive crystals and to determine the properties of the fine particles so
obtained. The SFL apparatus made by Guangcheng et al. for the synthesis of nano NTO is
shown in Figure 17. Pressurized air (Figure 17A) at 1.6MPa was cooled and dried. The stirrer
(Figure 17F) was set at 550–600 r/min. The cryogenic liquid cell (Figure 17H) was coated
with heat insulation.
Figure17. Experimental apparatus for the spray freezing into liquid process (A) Pressured air,
(B) NTO solution, (C) atomization nozzle, (D) valve, (E) liquid nitrogen, (F) stirrer, (G)
solution cell, (H) cryogenic liquid cell
34
1.4.4 Electrospray crystallization Method
Electrospray crystallization is one of the effective methods to achieve the nano- and
submicron-sized crystals [114]. With the aid of high potential difference, the electrostatic
forces could overcome the surface tension, and any flow arriving at the tip of the nozzle is
directly emitted as a jet of liquid droplets. As a result, a mist of ultrafine solution droplets is
generated, and the subsequent solvent evaporation leads to the formation of submicron-sized
crystals [115]. For example, Radacsi‘s group developed an electrospray crystallization
method (Figure 18) to prepare the agglomerated RDX hollow spheres with the size of around
4 mm and spherical particles with a size ranging from 200 to 600 nm under the different
potential differences [116]. Reus and his coworkers prepared the encapsulated RDX -
trinitrotoluene (TNT) spherical nanoparticles by using the elecrospray technique, and the
composition of the particles needs further investigation [117].
Figure18. Process scheme of electrospray crystallization
1.5 Sol-gel processing

Sol-gel processing is a feasible way to prepare the inorganic/organic nanocomposites under
mild conditions [118-122]. The stoichiometry and homogeneity of the nanocomposites can be
easily controlled by using this method, and therefore this method could dramatically improve
current state-of-the-art technology. Moreover, the solegel chemistry has the ability to
construct the nanostructured materials with special shapes, such as uniform net-shape
geometric solids, fibers, films, and powders with nanoscale size [123, 124].
Tillotson‘s group used the solegel processing to prepare the composite nano-energetic
materials [125]. In this process, RDX or PETN was first loaded into the pores of the wet
35
monolithic gel and then was kept there upon supercritical solvent extraction drying, which
helps restrain the growth of the explosive particle beyond the nanometer and submicron scale.
Brill and his coworkers prepared various unusual energetic composites, in which CL-20
nanoparticles were uniformly coated with energetic polymer gels using solegel method [126-
128]. Ingale et al. demonstrated that the silica xerogels incorporated with nanocrystalline
PETN or PETN/ TNT were synthesized, in which the content of energetic materials ranges
from 50% to 90% (w/w) [129,130]. Our group used this strategy to prepare laminate-like
structured HMX/ammonium perchlorate (AP)/resorcinol-formaldehyde (RF) aerogel with
uniform pores [131]. Recently, Luo and his coworkers reported the preparation of
AP/RDX/SiO2 nanocomposite energetic materials [132]. They found that the distance
between the SiO2 colloidal particles was enlarged due to the presence of RDX and AP, which
is contributed to the lower crosslinking structure and the bigger pores.
Nano Energetic Materials prepared by Sol-gel Method
CL-20 20-200 nm TEM, AFM, XRD, FTIR, DSC 5
HMX 100 nm FIB-SEM, TEM, XRD, HPLC 14
PETN DSC 29
NO2
N
NNO2 H2C CH2
O NN
2
Structure of CL-20 Structure of HMX
O2NN NNO2 O2N N N NO2
H2C CH2
O2NN NNO2 N
O2N O H2C CH2 O NO2 NO2
C
O2N O H2C CH2 O NO2
Structure of PETN
36
1.6Template technique
The template technique is a straight forward approach to fabricate micro/nanostructures by
inducing the target materials to grow according to the patterns of the templates. This strategy
provides a simple way for the synthesis of micro/nanomaterials with desired shape and size,
and has been widely applied in the construction of different dimensional
micro/nanostructures. The templates adopted in this method can be generally divided into two
sorts: rigid and soft ones.
1.6.1 Rigid template

The rigid template method for the preparation of micro/nanostructures has been developed
independently in various fields of nanotechnology. It has become one of the most common
methods in the fabrication of inorganic, organic and polymeric micro/nanomaterials [133-
138]. Now the commonly used templates include ordered porous membranes [139], silica
[140], nanochannel glass [141], monodisperse colloids [142], and iontrack-etched polymers
[143].
During the past several years, this technique has also been used to prepare the energetic
nanocomposites. Smeug et al. investigated the confinement of energetic molecules inside
carbon nanostructures by molecular structure and total energy calculations [144]. The
calculation results predict that each energetic molecule, including FOX-7, RDX, HMX, 3,6-
di-(hydrazino)-1,2,4,5-tetrazine (DHT), 3,6-diazido-1,2,4,5-tetrazine (DiAT), 3,30-azo-bis(6-
amino-1,2,4,5-tetrazine) (DAAT), and N-oxides of DAAT could be stabilized by 32-53 kcal/
mole if a carbon nanotube (CNT) with appropriate size is selected. Recently, Huand his
coworkers achieved the fabrication of KNO3@CNTs nano-energetic materials by combining
the wet chemical-assistant electrophoretic deposition (EPD) with rigid template method
(Figure 19(a)) [145]. The TEM images of KNO3@CNTs nanocomposites are shown in
Figure 19(b)-(d). It can be seen that the hollow cavities of CNTs are homogeneously filled
with crystalline KNO3 without any impurities attached on the outer surface.
Several host-guest nanocomposites, such as 2,4,6-trinitrophenol (PA)/mesoporous carbon
FDU-15, FOX-7/FDU-15 and CL-20/mesoporous silica SBA-15, were prepared based on
self-assembly of energetic molecules in nanometerscale channels of an ordered mesoporous
material [146-148]. The design and synthesis of these kinds of materials are beneficial to
understand the reaction characteristics of energetic ordered arrays and further fabricate the
micro/nanodevices with high performance and efficiency. Similarly, FOX-7 immobilized in
37
the pores of silica MFI-type zeolite nanocrystals was fabricated by Mintova and his
coworkers [149].
Choosing a porous chromium (III) oxide (Cr2O3) matrix produced by the combustion of
ammonium dichromate as a template, the RDX/Cr2O3 nanocomposites were obtained via a
facile solvent evaporation process by Spitzer and his coworkers [150,151]. The method may
be suitable for the preparation of a wide range of sensitive explosive compositions embedded
in the porous materials.
Figure19. (a) Schematic model of EPD. The Cu thin-film microbridge on the glass substrate
was set as cathode and Pt plate as anode. The distance between the cathode and the anode
was adjusted to be 1 cm. (b)-(d) TEM images of the KNO3@CNTs achieved by wet chemical
method
Nano Energetic Materials prepared by Rigid Template Method
38
XRD, DSC, SEM, H-NMR, Raman
FOX-7 90-100 nm 7
spectra
RDX 27
H2N NO2 NO2

N
H2C CH2
Structure of FOX-7 Structure of RDX N N
H2N NO2 O2N CH2 NO2
1.6.2. Wet chemical-assisted soft template
So-called soft templates can be dissolved in the liquid phase, mainly including surfactant
micelles and copolymers [152-154]. It is well-known that the surfactant micelles and inverse
micelles with different shapes (spherical, rod-like, and so on) are formed in the solutions
when their concentrations reach the critical micelle concentration (CMC) [155]. Thus, these
micelles can then be used as the soft templates for the fabrication of organic and inorganic
micro/nanostructures. It is well-known that TATB is not soluble in the most common
solvents due to significant intra- and inter-molecular hydrogen bonds [156,157], and thus
most of methods commonly used in the synthesis of organic nanomaterials, such as solvent
volatilization, rigid template, and vapor deposition, are not suitable for the fabrication of
TATB nanostructures. In the recent work of [godfather], a ternary microemulsion system of
water/dioctyl sulfosuccinate sodium salt (AOT)/toluene was developed to directly synthesize
one-dimensional (1D) twinned TATB nanobelts [158]. A series of experiments confirm that
the urea as an aminating reagent plays a key role in the formation of highly crystalline
nanobelts with perfect mirror symmetry, because the aminating reaction could be easily
controlled by adjusting the hydrolysis rate of urea. By using this route, besides twinned
nanobelts, various TATB micro/nanostructures, such as particles, leaves, banana leaves, and
wedge-shaped ribbons with different sizes, could be directly prepared by changing the
experimental parameters. Subsequently, we developed a facile surfactant-assisted self-
assembly technique for constructing 3D dendritic 2, 6-diamino-3, 5-dinitropyrazine (ANPZ)
microstructures in nontoxic ethanol solvent using urea as the aminating reagent (Figure 20(a)-
(d)) [159]. With the assistance of surfactant Pluronic P123 block copolymer, the size and
39
morphology of ANPZ micro/nanostructures can be easily tailored by varying the operating
conditions. Moreover, the growth mechanism of ANPZ dendrites was also proposed on the
basis of a detailed time-dependent morphology evolution study, as illustrated in Figure 20(e).
Recently, Mandal and his coworkers synthesized the spherical particles of FOX-7 by using
the concept of a micelle-based nanoreactor [160]. The diameters of these spherical particles
are in the range of nanometer to submicrometer. Significantly, the size and shape of FOX-7
particles can be adjusted by varying the water-surfactant molar ratio in the microemulsion
system.
Figure20. (a)-(c) SEM images of the as-prepared ANPZ sample; (d) TEM images of a single
microrod (e) Schematic illustration of the possible growth process of dendritic ANPZ
microstructures and their building blocks
Nano Energetic Materials prepared by Wet chemical assisted Template Method

FOX-7 10 µm SEM, DSC, H-NMR, FTIR 8
RDX 1.8-27.4 µm SEM, TEM, AFM, DSC, BET 28
TATB 33
40
NO2 NH2
H2N NO2 N O2N NO2
H2C CH2
Structure of FOX-7 Structure
N of RDX
N Structure of TATB
H2N O2N H2N NH2
NO2 CH2 NO2
1.7 Physical vapor deposition (PVD) NO2
PVD is a simple and outstanding method for preparing nanomaterials, and has achieved great
success in the synthesis of inorganic nanostructures and polymeric thin films [161-163]. The
morphology, size, and dispersity of the products are easily controlled by tuning the
experimental conditions, such as saturation level, temperature, and time. Frolov et al.
reported the first synthesis of nano-RDX, nano-HMX, nano-NH4NO3, or their composites by
employing vacuum sublimation and condensation process [21,164-166]. The obtained
energetic particles have an average diameter of about 50 nm. Although this technique has a
low yield, it provides useful information for the design and fabrication of energetic molecule
micro/nanostructures. Zhang synthesized PETN films with desired surface morphology in a
controllable and reproducible way by thermal evaporation on different substrates [167,168].
Recently, 2D one-molecule thick single-crystalline nanosheets of LLM-105 supported on
highly oriented pyrolytic graphites (HOPG) were prepared by vapor self-assembling method
at 220°C and atmospheric pressure (Figure 21) [169]. The nanosheet with rectangular shape
and lateral dimension, which is very sensitive to electricity and force stimuli, provides an
opportunity to write optional patterns and fabricate high-sensitive force sensor.
41
Figure21. (a) Topographical image of a LLM-105 nanosheet in contact mode. (b) High-
magnification current image of LLM-105 nanosheet with size of 20 nm-20 nm under the
conductive AFM mode with load of 0.2 nN, bias of 0.2 V, and scanning rate of 0.5 Hz. (c)
The logo pattern of our institute, ICM, wrote on an explosive nanosheet of LLM-105. (d)
Dynamic force microscope (DFM) topographical of LLM-105 nanosheet on HOPG, the dark
squares in nanosheet in regions of 50 nm-50 nm and 200 nm-200 nm were scanned at bias
value of 5 V with conductive AFM
Nano Energetic Materials prepared by PVD Method
PETN 40-300 nm AFM, PSD 30
O2N O H2C CH2 O NO2

C
1.8 Inkjet printing O2N O H2C CH2 O NO2
It is noteworthy that inkjet printing technique has been recently extended as a low-cost
processing method in the field of energetic materials due to its advantages of excellent
accuracy and surface finishes. For example, this technology was explored as a new way to
directly deposit and pattern energetic materials for trace explosive detection application
[170,171]. Lee reported the inkjet-print RDX crystals, which were dispersed in a cellulose
acetate butyrate (CAB) matrix by direct-phase transformation from organic solvent-based all
liquid inks. They found that a variety of crystal morphologies could be obtained by changing
the ink deposition parameters [172,173]. They also reported that this effective strategy is used
42
to control the droplet coalescence during inkjet printing, and consequently to tailor the
nanoscale morphology of organic composites [174]. They found that the decrease in
coalescence increased the evaporation rate of solvent, the supersaturation of the solutes, and
the nucleation density of the organic crystals. Utilizing this method, the average size of PETN
crystals dispersed in an adhesive binder [poly (vinylacetate) or a chlorinated wax] matrix
from 0.2 to 100 mm was easily tailored (Figure 22). In addition, the inkjet technique was also
used to prepare other energetic samples (HMX, TNT and NH4NO3) with controlled size and
distribution by Hernandez-Rivera and coworkers [175].
Figure22. (a) Surface morphology of a single layer deposition printed under maximum
coalescence-like conditions using a d1,2 of 5 mm; (b) surface morphology of a multilayer
deposition printed under minimum coalescence-like conditions using a d1,2 of 100 mm (c)
and (d) higher magnification images of characteristic morphology in areas labeled ―c‖ and
―d‖, respectively, in (b)
Nano Energetic Materials prepared by Inkjet Method
TNT FTIR 34
CH3
O2N NO2
NO2
43
44
Chapter 2: VARIOUS METHODS FOR EXPLOSIVE SLURRY SYNTHESIS
Introduction
There is no modern defense system or type of weaponry that does not rely on energetic
materials- either in the form of an explosive fill or as a propellant (e.g., from
guns,rifles,missles and rockets). In addition, energetic materials are used in a multitude of
critical defense components ranging from shaped charged, acuatators and delay lines to
detonators.
The quest for novel high energy materials (HEMs) with highest possible performance and
low vulnerability led to the development of advanced insensitive power packed materials
such as triaminotrinitrobenzene (TATB), nitrotriazolone (NTO), dinitrotetraoxa
diazatetracyclo dodecance (TEX) and 2, 6-diamino-3, 5-dinitropyrazine-N-oxide (LLM-105).
Many of these insensitive HEMs are at various stages of pilot plant production in different
countries. Even though these explosives are insensitive towards external stimuli, their
performance is less than benchmark explosive RDX. All over the globe research and
development programs to develop insensitive HEMs with higher performance.
Primary considerations in developing explosives include processability and the ability to
attain insensitive munitions (IM) characteristics. Properties that are advantageous for IM
systems includes high decomposition temperature, low impact and friction sensitivity, no
phase transitions when the substance is subjected to rapid volume expansion or contraction,
no autocatalytic decomposition, spherical crystal morphology, good adhesion of the binder
matrix, no voids brought about by solvent or gas bubbles, high chemical and phase purity.
The potential to develop energetic materials with IM properties is not limited to new
materials [58-60]. The sensitivity of well-established energetic materials can be reduced through
various material improvements and can be related to their chemical as well as physical
characteristics. However, the physical characteristics such as the crystal size, shape,
morphology, purity, internal and external defects and the microstructure of the
intercrystalline voids play vital role in sensitivity of HEMs,processing and performance We
will discuss the different types of precursors and production methods segregated based on the
names of the energetic materials[35].
Explosive Substances
45
Commercial Chemical
Chemical Explosives Products for Non-explosive
Purposes
Primary Secondary
Explosives Explosives Propellant
Military Commercial Gun Rocket

Explosives Explosives Propellant Propellant
Primary Military Commercial Gun Rocket

Explosives Explosives Explosives Propellant Propellant
Lead azide, TNT, RDX, Gelatines, Single- base, Double-base,
Lead styphnate, PETN, Tetryl, ANFO, Double - base, Composite,
Mercury etc Emulsion Triple- base, Liquid fuels
fulminate, slurries,
The HEMs can also be classified by simply their etc
nitration Blackpowder,
method few examples & Oxidizers.
are stated
Tetrazene,
below etc
in the following figure 23 etc etc
Figure23: Classification of explosive composition by nitration reaction
46
2.1. 1, 1-Diamino-2, 2-dinitroethylene (FOX-7)
FOX-7 is emerging as a potential candidate for its use in insensitive high explosive. The
R&D work on FOX-7 is continuously pursued with great interest in many developed
countries where the process has been scaled up to pilot plant level. Many research
publications are appearing in the literature mentioning the potential of FOX-7 for insensitive
applications. However, none of the processes discloses the actual processes parameters for
the synthesis of FOX-7[35].
FOX-7 was first synthesized in 1998 by Latypov et al.[36] (Scheme 1.) since then different
synthetic methods have been developed and FOX-7 is now synthesised in a pilot plant on a
multi-kilogram scale in NEXPLO Bofors, Sweden.
FOg-7 (2, Scheme 2) is prepared by the hydrolysis of 2-(dinitromethylene)-4, 5-

imidazolidinedione (6) with aqueous ammonia. Compound 4 may be prepared by two basic
methods2.
2.1.1 Method 1
The nitration of 2- methylimidazol (5) with mixed acid produces postulated intermediate 2-
dinitromethylene-4, 4-dinitro-5-imidazolidinone, (6) which decomposed at room temperature
to give the compound (4). This method was found to be very important to control the
temperature of the nitration reaction. The product was isolated as a solid in low yield (<15%).
2.1.2 Method 2
47
The reaction of acetamidine hydrochloride (7) with diethyl oxalate (8) provides the mixture
of 2-methoxy-2-methyl-4, 5-imidazolidinedione (9) and 2-methyl-4, 5-imidazolidinedione
(10). This product mixture 9 and 10 or 9 alone are nitrated by mixed acid to from 2-
(dinitromethylene)-4, 5-imidazolidinedione (4).
2.1.3 Method 3
The synthetic route to FOX-7 is based (Scheme 3) upon the nitration of 4, 6-dihydroxy-2-
methylpyrimidine (11) in mixed acid at low temperature. This reaction leads to the
precipitation of 2-dinitromethyleme-5, 5-dinitrodihydropyrimidine-4, 6-dione (12) which is
easily hydrolyzed in water to FOX-7 and dinitromethane. The starting material is prepared
from acetamidine hydrochloride (7) and diethylmalonate (13) in the presence of sodium in
ethanol. However, in contrast to compound 7 it is easily isolated and purified for further
nitration
48
Dinitro methane (DNM) salts, suitable as intermediates and starting material for production
of explosives and propellants. Potassium dinitromethane was first prepared by Villiers[37] in
1884 by reduction of bromodinitromethane, which was obtained4 in low yield. Free
dinitromethane5 unstable pale yellow oil, decomposes readily at ambient temperature.
Dinitromethane salts are obtained from the alkali salts of dinitroethylene by oxidative
nitration of nitroethanol. Dinitromethane is also reported to be prepared by nitration of
halogenated olefins, such as trichloroethylene. Potassium dinitromethane (14) was prepared
[40-41] from chloronitromethane (Scheme 4).
2.1.4 Solubility of FOX-7

FOX-7 is a bright yellow crystalline powder. The product isolated directly from the above
reaction is typically of high purity with a particle size of the order of 5–15 micron and density
of FOX-7 is 1.88 g/cm3 (crystal density). FOX-7 is only slightly soluble in common organic
49
solvents and water but readily dissolves in dipolar aprotic solvents such as dimethyl
sulfoxide, N, N-dimethyl formamide and 1-methyl-2-pyrrolidinone[35].
2.1.5 Spectral Studies:

The purity FOX-7 was found out to be higher than 99.6%. The UV spectrum of FOX-7
indicates the following absorbance: a stronger band at 215.95 nm (for normal carbon–carbon
double bond: 165 nm) for π→π* transition corresponds to ethylene carbon–carbon double
bond (C C). The higher value clearly indicates that the presence of extensive π conjugation in
the molecule and a stronger band at 279 nm for n→π* transition due to the presence of nitro
groups. The IR spectrum of FOX-7 showed the presence of primary amino groups at 3408,
3330, 1636 cm−1 and nitro groups at 1520, 1472 cm−1 in the molecule. 1H NMRspectrum
of the FOX-7 sample showed a single broadened signal of four hydrogen atoms of two amino
groups with the chemical shift δ 8.64 ppm. 13C NMR spectra showed two signals, a signal
of carbon attached with amino group at 128.1 ppm and a signal of carbon attached with nitro
group at 158.3 ppm. The IR spectrum of KFOX-7 reveals stretching vibration frequencies at
3399, 3315 (NH2), 1655 and 1551 cm−1 for carbon–carbon double bond and nitro groups,
respectively.1
2.1.6 Thermal and sensitivity studies

The DSC thermogram of FOX-7 indicates two decomposition steps with peak maxima
(Tmax) at 240.10 ◦C (Δ=−473 J/g) and 279.43 ◦C (Δ=−542 J/g). The spark sensitivity test of
FOX- 7 results indicates no ignition for five consecutive tests, at spark gap energy of 5 J (10
kV, 30 ◦C, 55% RH).1
SEM Images were also taken for the product.1
2.1.7 Application
FOX-7 has interesting properties as a high explosive and has also application in the synthesis
of nitrogen heterocycles. The compound is also special for its good insensitivity on one hand
and high performance on the other hand. Thus, this compound is a potential candidate for of
LOVA (low vulnerability ammunition) 8.
50
Figure 24. (a) Planar structure and (b) layered structure of FOX-7. C, N, O, and H atoms are
indicated in gray, blue, red, and white, respectively. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of the article.)[43]
2.2 Ammonium salt of dinitramidic acid(ADN)

Ammonium salt of dinitramidic acid NH4N (NO2)2 (ADN) has attracted wide interest as a
potentially useful energetic oxidizer for rocket propellants because of its clean and
environment-friendly exhaust products during burning. ADN contains one N―(NO2)2 groups
and its synthesis requires new type of N-nitration. The protonated form of the anion i.e.,
dinitramidic acid 1 is one of the strongest inorganic acids10 and numerous simple and
complex salts have been prepared. The ammonium salt of dinitramidic acid 2 (ADN) is
widely known at present. Dinitramide salts were reported from USA[45] in 1988, while
Russians used these salts in 1971 in various missile programs12. The simplest class of
nitramine is the nitro derivative of ammonia[47,49] i.e., nitramide NH2NO2. It is unstable and
decomposes readily at ambient conditions. The alkyl derivatives of dinitramine (R―N
(NO2)2) have low stability and cleave to form nitronium ion (NO+2) and the anion R―NNO-
2.1.1 Methods of Preparation of Dinitramide

Method 1:
The established method of preparation of alkyl dinitramine 4 practiced earlier[50] is via N-
nitromethylcarbamate followed by nitration with nitronium ion as shown in Scheme 4.
51
Method 2:
The four-step method shown in Scheme 4 was later modified by a one-step synthesis by
nitration of aliphatic isocyanates using stoichiometric quantities of NO2BF4 and HNO3 in
acetonitrile17. The reaction is shown in Scheme 5.
This route differs from Scheme 4, as it involves only one step and requires the use of nitric
acid and high quality NO2BF4.
Method 3:
Dinitramide salts were synthesized by ß-elimination reaction of 1-(N, N-dinitramino)-2-
(trimethylsilyl) ethane 5 catalyzed by CsF [52,53]. The reaction is normally carried out below
0oC. The 1-(N, N-dinitramino)-2-(trimethylsilyl) - ethane was synthesized by a reaction of an
isocyanate with a mixture of HNO3 and NO2BF4 as shown in Scheme 2. The yield of the
desired 2-(trimethylsilylethyl)-N, N-dinitramine precursor was about 25%.
52
In Scheme 6, substitution of CsF by other metal fluoride salts in the ß -elimination reaction
results in other dinitramide salts. Dinitramide salts were also prepared by ion exchange
reaction of cesium dinitramide using AMBERLYST 15 sulphonic acid resin charged with the
appropriate cation, followed by elution with a suitable solvent.
Method 4:
Yet another method of preparing dinitramide salts makes use of nitramide (NH2NO2) as a
starting material and NO2 BF4 as a nitrating agent[53]. The reaction was carried out at 20oC
to form the free acid HN (NO2)2 as shown in Equation 7.
The free acid was then reacted with a corresponding base such as ammonia, hydrazine or
metal hydroxides (MOH), where M is the desired metal cation, to form the desired
dinitramide salt. The product yield was about 60%.
Method 5
The reaction of an ionic nitronium salt such as NO2BF4 or N2O5 with ammonium carbamate 6
yields the intermediate dinitramidic acid[54]. The reaction was carried out in the temperature
range of 30oC to 40oC followed by neutralization either with ammonia, hydrazine, primary
and secondary amine, or salt of the formula AX, where A is mono, di or trivalent metal
cation, to give the corresponding dinitramide salt. The product yield was 15%. The reaction is
shown in Eq. (8)
53
The methods for the synthesis of dinitramidic acid involve dinitration of primary amines that
are made weakly basic by suitable substituents. The nitrating agents used include NO2BF4,
N2O5, NO2HS2O7 or 100% HNO3 in presence of acid catalysts. The product yield varies from
5 to 70 % depending on the nitrating agent and the reactant. Numerous salts of dinitramide
consisting of metal, organic and inorganic derivatives are prepared. Ion exchange is proved to
be an excellent and convenient method for the synthesis of various dinitramide salts. An
account of preparation of these salts by different methods is also given.
2.3 2, 4, 6-triamino-1, 3, 5-trinitrobenzene

NH2 (TATB)
O2N NO2
H2N NH2
Among the various insensitive high explosives, 2, 4, 6-triamino-1, 3, 5-trinitrobenzene,
NO
commonly known as TATB, is an attractive2 insensitive explosive as it satisfies the safety
requirements at high temperatures and its resistance to accidental initiation and explosion. In
addition it easily forms eutectic with other explosives such as 1, 3, 5, 7- tetranitro-1, 3, 5, 7-
tetrazocane (HMX), trinitrotoluene (TNT), and several others.
It was first obtained in 1888 by Jackson and Wing. It is a yellow-brown coloured substance
which decomposes rapidly just below its melting temperature. It has excellent thermal
stability in the range 260-290°C and is known as a heat-resistant explosive. Some of the
properties of TATB are
Table 1: Properties of TATB (1, 3, 5-triarnino-2, 4, 6-trinitrobenzene)
Characteristics Explosive Materials
Colour Yellow-brown crystalline solid
Molecular weight 258.1
Melting temperature/"C 350
Decomposition temperature/"C 350
Thermal ignition temperature/"C 384
54
Crystal density at 20"C/g cm -3 1.93
Energy of formation/kJ kg-' - 425.0
Enthalpy of formation/kJ kg-' - 597.9
The potential of TATB as an insensitive explosive was realized during the 1960s. TATB is
used in modern nuclear warheads in the military, deep oil well explorations in the civilian
community, and as a reagent in the manufacture of liquid crystal displays. It is used
extensively in the USA. In recent years it is the preferred conventional secondary high
explosive in nuclear weapons[55].
Dobratz 22cites Jackson and Wing as the earliest workers to mention TATB in 1888, although
it was left to Flurscheim and Holmes[57] to synthesize pure TATB by ammoniation of
pentanitroaniline. Many processes yield TATB with a small percentage of chlorine but recent
attempts to make chlorine-free TATB have been documented. TATB exhibits both
monoclinic and triclinic crystal structures and is classified as a heat resistant explosive.
2.3.1 Synthesis and Manufacturing:

a) Gerenal Scheme:
The current industrial method is to nitrate 1, 3, 5- trichlorobenzene to give 2, 4, 6-trichloro-

1, 3, 5-trinitrobenzene. Nitration is carried out at 423K using a mixture of nitric and sulfuric
acids. It is reacted with ammonia in a toluene medium to yield the product[58].
55
b. Preparation of Nano TATB:
TATB was added into concentrated sulfuric acid at room temperature. After complete
dissolution, the solution was filtered to remove insoluble impurities. The filtrate and some
ultrapure water were added into the instrument. Through rapid crystallization, a yellow
suspension containing nano- TATB colloid particles was obtained, filtered and washed to
remove residuary acid until the PH value of the eluate reached 6 – 7. The pasty substance was
collected and freeze-dried. A green-yellow nano-TATB product was obtained.
TATB has a simple ring structure with long C–C bonds and short C-N bonds with six
fractured hydrogen bonds. Agrawal [14] states that there is strong evidence of inter-and
intramolecular hydrogen bonds. These strong hydrogen bonds induce a strong dipole-dipole
van der Waals–Keesom force and affect properties such as boiling and melting points, which
are evident in TATB.
X-ray diffraction studies have indicated two molecules per unit cell and extensive O–N and
N–H hydrogen bonding, and a layered structure. This gives rise to polarity and dispersion
56
forces, and affects salvation and physical properties. TATB is a planar molecule with a
triclinic centro symmetric lattice. Based on the structures shown in Figure 27, Huang et al.
[53] evaluated the vibrational frequencies, and the assignments are shown in Table 1. Except
for the weak bands, all other bands have been verified in the experimental spectrum.
Figure25:XRD diagram of nano-TATB (a) and micron TATB (b).Reproduced from Ref. [26].
A more detailed assignment of vibrational frequencies has been carried out by Liu et al. [61].
The simulated infrared spectra agree well with the experimental data shown in Figure 25.
Figure 26:Experimental IR Spectrum of TATB. Reproduced from Ref. 24
Table 2: Summary of assignment of vibrational modes, cm-1.

57
Symmetrical N–H stretching 3220.9
Unsymmetrical N–H stretching 3322.5
Unsymmetrical N–O stretching 1571.3
Symmetrical N–O stretching 1235.6
C–N stretching [amino group] 1613.1; 779.56
C–N stretching [nitro group] 1321.5
Skeletal stretching [ring] 1448.4; 1181.2; 1031.4
Weak bands 932.54; 539.32; 741.48
The Differential Scanning Calorimetry (DSC) thermogram [62]in Fig. 26 shows that TATB
exothermic decomposing temperature lies between 360 and 390 ◦C indicating its excellent
thermal stability and heat resistance
Figure 27: DSC Profile of TATB. Reproduced from Ref. [28].
2.4 Bis-(5-nitro-2H-tetrazolato-N2)tetraammine cobalt(III)

perchlorate (BNCP)
58
The conventional primary explosives such as lead azide, despite being excellent detonating
agents, suffer from serious drawbacks of hydrolytic instability, high sensitivity towards
mechanical stimuli and incompatibility with metals as well as metal alloys commonly used as
structure materials in initiating devices. Efforts are in progress in Research and Development
laboratories all over the globe to develop lead-free safe primary explosives based on
energetic coordination compounds [66-71]. One of the major advantages of energetic co-
ordination compounds is the presence of near stoichiometric fuel/oxidizer content. A few
studies undertaken on relationship between co-ordinate compound structures and explosive
properties have brought in focus nitrate/perchlorate complexes of transition metal ions with
nitro/ amino tetrazoles and triazoles as energetic ligands [72-74].
High energy inorganic co-ordination compound; pentaammine (5-cyno-2H-tetrazolato-N)
cobalt (III) perchlorate (CP) has been reported as a detonant for specific applications [43, 44].
However, it is no longer manufactured, as one of its starting materials; cyanogen falls under
the restricted list of Environmental Protection Agency.Tetraamminecis-bis-(5-nitro-2H-
tetrazolato-N2) cobalt(III) perchlorate (BNCP) is another interesting compound reported by
various researchers [45–49], as a promising lead-free primary explosive for semi-conducting
bridge applications. The research programme on BNCP is being actively pursued by Sandia
National Laboratories, USA and it is under development at Pacific Scientific-Energetic
Materials Co., USA.
Bis-(5-nitro-2H-tetrazolato-N2)tetraammine cobalt(III) perchlorate (BNCP) is a deflagration-
to-detonation (DDT) explosive structurally similar to CP, a 5-cyanotetrazolatocobalt complex
used in national defense applications since 1979. BNCP is a more powerful explosive and
undergoes DDT more rapidly than CP. The synthesis of its two precursors as well as the
preparation of BNCP will be described[75].
2.4.1 Method 1
The sodium salt of nitrotetrazole[73], carbonatotetraammine cobalt (III) nitrate (CTCN)[74]
and bis-(5- nitro-2H-tetrazolato-N2)tetraammine cobalt(III) perchlorate (BNCP) were
synthesized (Scheme 11 ) on the lines of the reported methodology[78-80]. The new
precursors viz., carbonato tetraammine nickel (III) nitrate (CTNN), carbonato triammine
copper(II) nitrate (CTCuN), carbonato triammine zinc(II) nitrate (CTZnN) and metal (Ni, Cu
and Zn) analogues of BNCP viz., bis-(5-nitro-2H-tetrazolato- N2)tetraammine nickel(III)
perchlorate (BNNP), mono- (5-nitro-H-tetrazolato-N)triammine copper(II) perchlorate
59
(MNCuP) and mono-(5-nitro-H-tetrazolato-N)triammine zinc(II) perchlorate (MNZnP) were
synthesized on the similar lines (Scheme 11)[78-80].
60
.
2.4.2 Method 2
The synthesis of BNCP consist of four steps as follows
a) Preparation of 5-Aminotetrazole mono hydrate (AT)
5-Aminotetrazole mono hydrate is prepared by treating dicyanamide with sodium azide in

acidic medium at 650C. The chemical reaction involved in this reaction is represented in step
A of BNCP synthesis. 5-Aninotetrazole mono hydrate is abbreviated as AT for our
convenience.
Step I:
b) Preparation of Sodium 5-nitrotetrazole dihydrate
5-Nitrotetrazole is the most energetic of the tetrazoles[81,88]. The diazotization of 5-

aminotetrazole mono hydrate (AT) in presence of excess sodium nitrite and Copper sulphate
gives the complex cupric salt intermediate Cu(NT)2.HNT.4H2O, which was then converted
to the sodium salt NaNT.2H2O using reported methods [49,50,51].
61
Step II
c) Preparation of Carbonato tetra amine cobalt(III) Nitrate (CTCN)
The synthesis of CTCN was accomplished by method as reported by schlessinger G.

procedure[86].
Step III
Co (NO3) + 3NH3 (aq) + (NH4)2Co3 + ½ H2O2
[Co (NH3)4CO3] NO3 + NH4NO3 + H2O
CTCN
d) Preparation of BNCP
The preparation of BNCP was accomplished by conventional co-ordination chemistry

methods as shown in the following sequence
Step IV (a)
CTCN + HClO4 H2O [Co (NH3)4.2H2O] ClO4 + CO2 + HNO3
Step IV(b)
62
Steps I, II and III are well known and are described in a variety of literature sources. In step
IV (a), ATCP was prepared essentially by acidifying CTCN with aqueous perchloric acid
(3%) and a solution of sodium 5-nitrotetrazole dihydrate was added drop by drop into the
aqueous complex (ATCP) over 40 minutes. During addition, the mixture temperature was
strictly controlled in between 800C to 900C using water bath. When the addition is completed,
then the reaction mixture was digested with vigorous stirring for 3 hours at 800C. Slow
cooling of the reaction mixture to the room temperature (about 250C) will provide the
precipitated product. This can be achieved by keeping the reaction mixture for overnight
digestion. The precipitated product thus obtained, was filtered through watman filter paper
No. 54, under slow suction.
Figure 28. Block diagram of various stages involved in BNCP synthesis
Method 1 Method 2 Method 3 Method 4

Cyanamide, Aminoguanidine Cyanamide Dicyanamide
Hydrozoic acid Nitrate Hydrazine Sodium azide
HN
2
C NH
N N
N
5-aminotetrazole
NO2
N
N N - Tetraamminecarbanato
HClO4 5-nitrotetrazole
N cobalt(III)nitrate
(CTCN)
NO2
N Cl O 4
N N
N NH
3 N NO2
+
H3N Co N
BNCP
H3N N
N
NH3
63
2.5 Infra-Red (IR) Spectroscopy :
The IR spectrum of prepared compound shows a strong band near 3476, 1846 and 840 cm-1,
which may confirm to be (NH3) and (NH3) groups. There are two strong frequencies at
1564 and 1326 cm-1, which may be assigned to asymmetric and symmetric vibrations of
(NO2) group, while other two strong bands at 1440 and 1230 cm-1may be assigned to
tetrazole ring vibrations. The other vibrational frequencies at 2162 (s,b), 1070 (s,b), 962 (b)
and 628 (s) may therefore be assigned to  (CN) and bending vibration of perchlorate (ClO-
4), ClO4, vs(ClO4) and  d(ClO4) respectively[85].
Table 2. Spectral Characterization (IR) of BNCP Table 3. Spectral characterization (IR)
of BNCP after 1600C
Frequencies
Frequencies Assignments
(cm-1)
Assignments (cm-1)
3450 (bs)  (NH3)
3476 (bs)  (NH3)
2162 (b)  (CN)
2166 (b)  (CN)
1870 (b)  (NH3)
1866 (s,b)  (NH3)
1564 (s,sharp) asym(NO2 group)
1564 (s,sharp) asym(NO2 group)
1440 (s, sharp) tetrazole ring
1440 (s, sharp) tetrazole ring
1326 (s, sharp) sym (NO2 group)
1326 (s, sharp) sym (NO2 group)
1230 (s) tetrazole ring 1230 (s) tetrazole ring
1088 (s,b) d(ClO-4)
1070 (s,b) d(ClO-4)
962 (b) s(ClO-4)
840 (s)  (NH3)
630 (s) d (ClO-4)
840 (s)  (NH3)
630 (s) d (ClO-4)
O
O O
O + O Cl
N
O
N
H H
N NN H O +O
N N
H H N
+
N Co N
H N
N
H H
N N
H Figure
H 30: Ball & Stick model
H H
of BNCP molecule (micro
64
architect of BNCP molecule)
developed using the software
RasMol version 2.5
Figure 29. IR Spectrum of BNCP
2.6 Pentaerythritol tetranitrate (PETN)
O2N O H2C CH2 O NO2

C
O2N O H2C O NO2which exhibits considerable
CH2explosive
Pentaerythritol tetranitrate (PETN) is a powerful
brisance on detonation (VOD ∼ 8310 m/s at d = 1.77 g/cm3). It is the most stable and least
reactive of the common nitrate ester explosives. The relatively high sensitivity of PETN to
friction and impact means that it is usually desensitized with phlegmatizers like wax and the
product is used in detonation cord, boosters and as a base charge in detonators.
Pentaerythritol tetranitrate can be mixed with synthetic polymers to form plastic bonded
explosives (PBXs) like detasheet and Semtex-1A. A cast mixture of PETN and TNT in equal
proportions is known as pentolite and has seen wide use as a military explosive and in booster
charges. The physical, chemical and explosive properties of PETN commend its use as a high
explosive.
2.6.1 Method 1:
Pentaerythritol tetranitrate (PETN) is a powerful high explosive with importance for both
commercial and military applications. It is therefore unsurprising that work has been focused
Synthetic routes to polyols and derivatives on the synthesis of nitrate ester analogues of
pentaerythritol.
65
Pentaerythritol trinitrate(1) is a key starting material for the synthesis of many of these
analogues. Pentaerythritol trinitrate has been synthesized via the controlled nitration of
pentaerythritol with mixed acid. The yields for this nitration average 48% after the removal
of PETN.54 Pentaerythritol trinitrate is also obtained from the nitration of pentaerythritol
mono-acetate ester followed by selective hydrolysis of the acetate group.Marans and co-
workers55 used pentaerythritol trinitrate to synthesize a number of aryl and alkyl esters,
including the formate, propionate, oxalate, succinate, benzoate, 3, 5-dinitrobenzoate, and
ortho-, meta-, and paranitrobenzoate esters. The paranitrobenzoate ester has also been
prepared from the nitration of pentaerythritol monobenzoate with mixed acid[90]
Hiskey and co-workers[91] prepared a series of O-nitro amino nitrates by reacting the parent
aminoalcohols with absolute nitric acid followed by precipitation of the salt with an organic
solvent. Two of these compounds, show similar thermal stability to PETN but are less
sensitive to impact. Such compounds show a useful solubility in water and have potential for
use as sensitizers in explosive slurries.
2.6.2 Method 2:
PETN is prepared by nitrating pentaerythritol. Pentaerythritol is made by mixing
formaldehyde with calcium hydroxide in an aqueous solution held at 65-70oC. Nitration of
pentaerythritol can be achieved by adding it to concentrated nitric acid at 25-30oC to form
PETN. The crude PETN is removed by filtration, washed with water, neutralized with sodium
carbonate solution and recrystallized from acetone. This manufacturing process for PETN
results in 95% yield with negligible by-products. The process is summarized in Reaction.
66
67
Table 3. : Synthesis methods and precursors for various Explosives
Explosive Precursor / Remarks Ref
Synthesis Method to obtain Nano EM
Remark
DNPP 3-carboxy-6-nitropyrazol[4,3-c]pyrazole was 3-carboxy-6- 70% yield 95
treated with 98% HNO3 at 45 8C to give nitropyrazol[4,
DNPP 3-c]pyrazole
LLM-119 It was synthesized by amination of DNPP DNPP Lower yield 96 a
using hydroxylamine-O-sulfonic acid in
aqueous base
LLM-119 It was synthesized by amination of DNPP DNPP Better yield as 96b
using O-(mesitylenesulfonyl) hydroxylamine compared to
previous method
FOX-7 or Its synthesis involved the nitration of 2- 2-methyl-4- It is an insoluble 97
DADE methyl-4-nitroimidazole with conc. H2SO4 nitroimidazole yellow solid
and HNO3 to give a mixture of parabanicacid
and 2 (dinitromethylene) 4,5-
imidazolidinedione. The product was treated
with ammonium hydroxide at pH 8–9 to yield
FOX-7 as
LLM-105 Reacting commercially available 2, 6- 2,6- 98
dichloropyrazine, with NaOCH3 to yield 2- dichloropyrazi
methoxy-6-chloropyrazine.This compound ne + NaOCH3
was nitrated with mixed acid at 70oC, then
treated with NH4OH in CH3CN at 60oC to
yield 2, 6-diaminopyrazine.Oxidation of
ANPZ with a mixture of
trifluoroacetic acid and 30% H2O2 yielded
LLM-105
ANPyO Nitration with mixed acid at 60–65oC of 2, 6- 2,6- Density= 99

diaminopyridine to yield2,6-diamino-3,5- diaminopyridin 1.878 g/ml &
dinitropyridine,followed by oxidation with a e + nitrating mp>340oC
mixture of acetic acid and 30% H2O2. mixture.
68
TNPyOx It was synthesized by 100
the acid catalyzed cyclization of potassium
acid-2,2-
dinitroethanol.
LAX-112 It was synthesized by the treatment of 3,6- 3,6-bis(3,5- 102
bis(3,5-dimethylpyrazolyl) 1,2,4,5-tetrazine dimethylpyraz
with ammonia at 90oC in a pressure vessel to olyl) 1,2,4,5-
yield 3,6-diamino-1,2,4,5-tetrazine,followed tetrazine +
by oxidation with OXONE in water or glacial ammonia
acetic acid and 84%
H2O2
DAF It was synthesized by the condensation of Hydroxyl 103
hydroxylamine with a variety of reagents amine +
including dithiooxamidea, cyanogenb, glyoxalc dithiooxamide/
, and glyoximed to yield diaminoglyoxime cyanogen/glyo
followed by xal/glyoxime
cyclization to DAF by treatment with aqueous
base at 180oC in a pressure vessel
BPAF It is synthesized 3,4-bis(picrylamino) 3,4- 86% yield 104
furazan by reacting dichloroglyoxime with bis(picrylamin
aniline, followed by heating the o)
dianilinoglyoxime with NaOH ethylene furazan +
glycol to yield the dianilinofurazan. Nitration dichloroglyoxi
with conc. HNO3 (at 25oC) yielded me + aniline
BPAF in
DABF 3,4- Enhanced 14% 103
bis(hydroxyimi overall yield
nomethyl)furo
xan +
hydroxylamine
DNFX It was synthesized by the nitration of Nitrating It is stable -15 to 104
glyoxime followed by cyclization of mixture + -20 oC
the resulting dinitroglyoxime with N2O4. glyoxime
69
TNCB By the oxidative nitration of 1,3- Nitrating Mp=165oC) 105
dinitrocyclobutane with AgNO3 and NaNO2. mixture+ 1,3- Density= 1.83
dinitrocyclobut g/ml.
ane +
AgNO3+NaNO
2
3-Methyl 4- condensation of acetaldehyde with ethyl-2,2- 106

nitro- dinitroacetate and NaN3
1,2,3-triazole
ANTZ By oxidation of the methyl group (of the 3-Methyl 4- Mp=290 oC 106
above compound) with KMnO4 to the 4- nitro-
carboxy-derivative, followed by conversion of 1,2,3-triazole
the acid to an amino group using classical
methods.
TNGU It was synthesized using trans-1,2,3- 1,2,3,- 110
tris(nitramino)cyclopropane by the nitration tris(acetamido)
of 1,2,3,-tris(acetamido) cyclopropane with cyclopropane
Ac2O/HNO3 or TFAA/HNO3, followed by
ammonolysis of the amide groups, and
subsequent acidification of the tris–
ammonium salt
N5+AsF6- It was synthesized by the condensation of N2F+AsF6- Stable at R.T. 107
+ - o
N2F AsF6 with HN3 at -78 C in anhydrous can be stored for
HF. week at -78oC
ADN It is synthesized by nitration of ammonium Ammonium 108a
nitrourethane with N2O5 in CH2Cl2 to yield nitrourethane
the non-isolated dinitrourethane followed by
treated with ammonia.
ADN It can also be synthesized by nitration of Sulfonamide 108b
sulfonamide derivatives followed by derivatives
treatment with metal hydroxides and ion-
exchange
BDNA Its synthesis involved the condensation of tris tris 109
70
(hydroxymethyl) nitromethane with tert- (hydroxymethy
butylamine and formaldehyde to yield 3-tert- l)
butyl-5-hydroxymethyl5-nitrotetrahydro-1,3- nitromethane+
oxazine.This was treated with aq.HCl to yield tert-butylamine
2-tert-buty laminomethyl-2-nitro- +
1,3propanediol hydrochloride which was formaldehyde
cyclized under Mitsunobo conditions to 1-
tert-butyl-3-hydroxymethyl3-nitroazetidine
hydrochloride. This was treated with NaOH
and oxidatively nitrated to yield 1-tert-butyl-
3,3dinitroazetidine
TNAZ The nitrolysis of BDNA with NH4NO3 and BDNA 57% overall 109
Ac2O yield
K-6 It was synthesized by reacting urea, Urea 21-57% yield 112
formaldehyde and tert-butyl amine to yield +formaldehyde
the product 5-tert-butyl-2-oxo- +tert-butyl
1,3,5hexahydrotriazine to this further amine
nitrolysis of the tert-butyl group and further
nitration gave K-6
Chapter 3: DESIGN OF SLURRY FILING SYSTEM
INTRODUCTION
Dispensing slurry of explosive materials dot by dot (with repeatability and
reproducibility) on to the Micro electric detonator is tedious and complex process. For
production point of view it is necessary to have a precise and automatic high explosive slurry
71
filing system. Many industries in the market has designed slurry filing systems but that are
very costly, some of them are Douglas Instruments, Fisnar, DL Technology, BanSeokGroup,
Y&D Technology, Nordson EFD, Musashi and most of them uses bulky compressor module
for operating the dispenser syringe. So effort has been taken to minimize the cost of dispenser
without losing its precision, accuracy and repeatability. Dispensers are used in many areas
like Chemical industry, pharmaceutical industry, electronics fabrication industry, Automobile
industry etc.
Most important task carried out here is to dispense a specific volume of liquid form
dispenser syringe on to the miniature detonator as a target sample. As this technique is often
employed up to several times per hour, the dispenser used to perform such a task should be
user friendly. There are many manual dispensing apparatus available in market like Pipet,
Peristaltic pump, Bottle top Dispenser, etc. Dispensers are widely used in assembly line
production of electronic circuit boards with computer controlled method for placing surface
mount adhesive at high speed. Here computer controlled dispenser is designed with X, Y and
Z axis control.
The dispenser is having three mechanical axes driven by single phase DC stepper
motors. Different stepper motors are used with suitable torque, current rating and step angle
for all the three axes. Motors are selected by calculating the approximate weight to be carried
out by the particular axis. The stepper motor selected are having 1.8º of step angle and the
mechanical movement can be achieved with the full step angle is 6.25 µm as per specified in
datasheet. By using micro stepping sequence we can achieve desired resolution for
mechanical movement of stage. Manualbottle top dispenser is modified in such a way that it
can be used todispense slurry of energetic materialas per mechanical movement of Z axis
linear actuator. In Z axis assembly a bottle top dispenser is fitted vertically so that it must
align properly to the starting position of stage and should cover whole area of mounting plate.
Its vertical movement can be calibrated in terms of slurry to be dispensed on sample area and
calibration data has been saved into PC software. PC software will have effective GUI to
remotely control the action to be taken by dispenser mechanical parts. Samples are mounted
on the X axis stage mounting plate having 100 holes of 2.5mm diameter and 6mm depth.
The problem statement was to design a dispenser for filling slurry of explosive
materials on to the MED sample precisely and automatically. Micro Electric Detonator based
on Semiconductor Bridge technology is designed and developed by scientist from
Armaments Research and Development Establishment (ARDE). Extensive testing of MED
has been carried out by ARDE to validate reliability, safety, functional time, energy for
72
initiation, etc. It is scientifically observed by ARDE that MED chip has successfully passed
all tests. Hence dispenser is designed specifically to automate the primary explosive filling
task for enabling bulk production of MED. The system can also be used for any dispensing
applications.
Table 4: Specifications of MED developed by ARDE
Specifications of MED Mk-1 Micro Electric Detonator
Size: Diameter 2.5mm, Height
6.5mm
Shape: Cylindrical
DC- AFC 1000mA for 10mS
DC- NFC 500mA for 5 Minutes
AC-AFC 100 µF, 5.0V
AC-NFC 100 µF, 3.0V
Resistance 4Ω
Functional delay <10µS
73
3.1 Mechanical Part design
Mechanical module for dispenser has been designed in Catia software. The fabrication
and integration of all spare part of dispenser has been done in the lab. The mechanical parts
of dispenser mainly consist of linear rail and rail guide and that are integrated with linear
actuator stepper motor with a supporting plate. Lead screw integrated with stepper motor
converts rotational movement in the linear and consequently moves the sample mounting
plate forward and reverse.
3.1.1 Rail Block and Rail guide

For providing support to the sample mounting plate we have used rail block and guide
assembly. The main function of this assembly is to make the smooth movement of the sample
mounting plate along with stepper motor screw. The schematic drawing of the rail block is
shown in figure 31 and consequent drawing for rail is shown in figure 32. The rail block used
here is a flange type rail block which enables the flexibility to insert nut either from top or
bottom side of block to fit it on rail.
Figure 31. Rail block designed for each axis
74
Figure 32. Rail for each axis
3.1.2 Lead Screw

Stepper motor integrated with lead screw named as stepper motor linear actuator is
used for converting rotational movement of stepper motor into linear movement to carry the
load linearly in forward and reverse direction. The linear movement precision of the axis
depends on the mechanical properties of lead screw like pitch, diameter, friction coefficient
etc.
3.1.2 Sample Mounting Plate

The MED samples is having the Height 6.5mm and diameter 2.5mm, to fit the MED
samples on to sample mounting palate we designed the plate having 100 holes having
diameter of 2.6mm and depth of 5 mm. The sample holder plate can holds the MED sample
while doing the explosive material filling process. The figure 33 shows the drawing of
Sample mounting plate designed and manufactured using aluminum material.
75
Figure 33. Sample mounting plate (MED holders)
3.1.3 Bottle top Dispenser

We have taken a bottle top dispenser from Borosil having maximum dispensing
capacity of 2.5ml. The dispenser comes with the 100 ml bottle reservoir for chemical
dispensing. The figure 34 shows the design of bottle top dispenser.
76
Figure 34: Bottle top dispenser
3.1.4 Supporting Assembly

The supporting assembly is used to hold the X, Y, Z axis assembly along with motors.
The supporting assembly is fabricated from a MS material so that it should be rigid and heavy
to firmly support the assembly. The supporting assembly is designed so that it provides the
flexibility to move the dispenser up and down by using a knob provided at the back side of Z
axis support plate. In addition dispenser tip can be manually adjusted using this knob. Figure
35 shows the drawing of dispenser supporting assembly.
77
Figure 35. Base plate supporting assembly for x,y,z axis
3.1.5 X, Y and Z axis

Stepper motor linear actuator is used to make an assembly for X, Y and Z axis. The
lead screw with nut is used to convertrotational motion into linear motion. One end of
Stepper motor is mounted on the base plate and another end is connected to vertical plate
with lead screw bearings as shown in figure 36. In addition, assembly is having rail and rail
block for providing slider support for sample mounting plate along with lead screw. The
same assembly has been used for all three axes. Fully assembled slurry filing system is shown
in figure 37.
78
Figure 36. Assembly for individual X, Y and Z axis
79
Figure 37. CAD design of fully assembled slurry filing system
80
3.2 Electronics Hardware design for Dispenser
Slurry filing system is having three axis stage with stepper motors to drive the
individual axis in forward and reverse directionwith fine control for angle of movement and
in turn linear movement of each axis. The fine control of movement for individual axis is
achieved by incorporating ever cooled stepper motors in each axis. The stepper motor is
having standard full step angle of rotation and that is 1.8°. Stepper motor with linear actuator
is calibrated for angular to linear displacement and as per manufactures specification stepper
motor will convert 1.8° full step angular movement into 6.25µm linear movement. Hence
stepper motor used here for linear movement of X, Y and Z can have minimum resolution of
6.25µm for full step excitation sequence to stepper motor. Linearactuation resolution of the
axis can be varied with the help of micro stepping sequence used as excitation means for
stepper motor. The stepper motor with linear actuator used for X, Y and Z axis are having
different current rating and torque.
3.2.1 Stepper motor
Stepper motor is the electromechanical part that converts electrical energy into
mechanical energy by means of electromagnetic action. The most crucial part of stepper
motor is having stator and rotor. Stepper motor works on the input electrical pulses and that
converts electrical pulse into discrete mechanical movements. The rotating part of stepper
motor that is shaft or spindle rotates in discrete step progressively when proper command of
input pulses are applied to it. The applied input pulses have some relationship with
functioning of stepper motor. The sequence of applied electrical pulses to stepper motor is
directly related to the direction of rotation of shaft or spindle. The speed of rotation of stepper
motor is directly related to the frequency of applied pulses and the length of rotation is
directly related to the number of input pulses. Figure 38 shows the internal schematic view of
bipolar stepper motor. The wires provided in bipolar stepper motor are green, black, red and
81
blue for applying excitation electrical pulse sequence for the desired speed and direction of
motion.
Figure 38. Stepper motor schematic
Stepper motors with linear actuator are used in the design of slurry filing system. The
stepper motors used for X, Y, Z axis are NEMA 17 BH42SH38, BH42SH47,BH42SH60
respectively. The technical specifications for each of the stepper motor used in the design of
slurry filing system are listed below.
Table 5: NEMA 17 BH42SH38 for X axis

Sr. No Parameter Value Unit
1 Rated Voltage 2.85 V
2 Current / Phase 1.68 A
3 Resistance / Phase 1.70 ±10%
4 Inductance / Phase 1.80 ±20% mH
5 Holding Torque 0.36 Nm
6 Rotor Inertia 54 G-CM 2
7 Weight 0.38 K G.
8 No of Lead 4 N°
9 Linear Step size - 6.25 micron per full step
Table 6: NEMA 17 BH42SH47 for Y axis

82
3 Resistance / Phase 1.7 ±10%
4 Inductance / Phase 2.5 ±20% mH
7 Weight 0.475 K G.
8 No of Lead 4 N°
Table 7: NEMA 17 BH42SH60 for Z axis

3 Resistance / Phase 12 ±10%
4 Inductance / Phase 18 ±20% mH
7 Weight 0.590 K G.
8 No of Lead 4 N°
3.2.2 Stepper Motor Driving Setup
To drive the stepper motor as per our step size requirement we require the electronic
hardware setup as shown in figure 39. The controller part in this figure is used to send
customized pulse sequence to stepper motor as per user‘s requirement of achieving stepper
motor step resolution. In addition, it also sends commands to driver for controlling stepper
motor direction and speed. The program inside the controller runs indefinitely as far as
controlling is supplied with power supply. The all controlling task of the controller depends
on the logic of the program downloaded inside the controller. The stepper motor driver is the
most important part and it is unavoidable part of stepper motor controlling setup. The main
purpose of the driver here is to provide voltage and current levels as per the stepper motor
requirement, it is a type of amplifier which receives low voltage pulses from controller and
83
supplies high voltage high current pulses for driving the stepper motor. The stepper motor is
the electromechanical module used to move the load.
Figure39. Stepper motor driving module
3.2.3 Controller and Embedded program
For controlling the X,Y and Z axis movement of dispenser we have used a
PIC16F877A microcontroller from Microchip. The controller is having sufficient
Input/Output ports for connecting stepper motor driver pins. The controller is having 8KB
program memory to store dispenser movement logic to fill explosive slurry material on 100
quantities of MED samples fitted on to the mounting plate (sample holder) of dispenser.
Embedded program flowchart is designed to precisely control the stepper motor
movement to automatically dispense explosive material on to the sample. The flowchart for
the slurry filling system is shown in figure 40.
84
Start
Read
Command
from PC
No
IF Command
is start
Yes
Move Z Move X Move Y

Stop
Axis Axis Axis
Repeat 9 times
for 100
samples
Fig. 40. Flowchart for dispenser program
Z axis movement of dispenser controls the amount of explosive material to be
dispensed on the sample. The amount of liquid to be dispensed with the vertical movement of
Z axis also depends on the viscosity of explosive material. The program will start from one
the sample at one corner of plate and consequently move and completes 100 sample filling
task. The program firstly makes the vertical movement of Z axis to dispense the liquid, then x
and y axis moves to take samples one by one under the syringe mounted on z axis. In this
way all 100 samples will be filled with primary explosive materials in one shot.
2.2.4 Embedded program source code
The program for PIC16F877A is written in embedded C language to enable the
automation in dispensing action for slurry filing system. Program is written in MPLAB IDE
85
and compiled into hex file using XC8 compiler, the source code for the program is listed
below.
/*
* File: newmainWD.c
* Author: lenovo
*
* Created on September 28, 2015, 10:08 AM
*/
#include <stdio.h>
#include <stdlib.h>
/*
*
*/
#include"newfileWD.h"
#include"string.h"
void RS232();
void motorxr();
void motorxf();
void motoryr();
void motoryf();
void motorzr();
void motorzf();
void CMDclr();
int NOPul();
void motor();
void start_fill();
char CMD[5],ok;
unsigned int
i=0,j=0,l=0,Pvalue=0,Decx=0,Decy=0,Decz=0,Linex=0,Liney=0,count=0,mx=0,my=0;
int k=0,Dec=0,r=0,m=0,n=0,p=0,tr=0;
int fr=0;
char axisxf[5]="MXF>",axisxr[5]="MXR>", axisyf[5]="MYF>",axisyr[5]="MYR>",
axiszf[5]="MZF>",
axiszr[5]="MZR>",line[5]="LIN>",stop[5]="ART>", start[5]="STR>",
starta[5]="STA>",home[5]="HME>";
void main(){
ADCON1=0x07;
TRISA0=0;
TRISA1=1;
TRISA2=0;
TRISA3=1;
TRISD=0x00;
TRISB=0x00;
PORTB=0x00;
RS232();
86
while(1){
if(RCIF){
CMD[i]=RCREG;
TXREG=CMD[i];
while(!TRMT);
i++;
}
if(i>3&&CMD[3]!='>')i=0;// make command count zero when it is exceding command

resistor length
if(!strcmp(CMD,axisxf)){
Decx=NOPul();i=0;r=0;Dec=0;
CMDclr();
}
if(!strcmp(CMD,axisyf)){
Decy=NOPul();i=0;r=0;Dec=0;
CMDclr();
}
if(!strcmp(CMD,axiszf)){
Decz=NOPul();i=0;r=0;Dec=0;
CMDclr();
}
if(!strcmp(CMD,axisxr)){
Decx=NOPul();i=0;r=1;Dec=0;
CMDclr();
}
if(!strcmp(CMD,axisyr)){
Decy=NOPul();i=0;r=1;Dec=0;
CMDclr();
}
if(!strcmp(CMD,axiszr)){
Decz=NOPul();i=0;r=1;Dec=0;
CMDclr();
}
if(!strcmp(CMD,line)){//enter line length to be drawn
Linex=NOPul();i=0;r=1;Dec=0;
Liney=NOPul();i=0;r=1;Dec=0;
CMDclr();
}
if(!strcmp(CMD,start)){// Start the drawing line and dispenser movement as per command
value
motor();fr=0;
//PORTA=0x00;
PORTB=0x00;
PORTD=0x00;i=0;Decx=0;Decy=0;Decz=0;Dec=0;
for(j=0;j<Linex;j++){
if(mx>28800)break;
motorxf();
PORTAbits.RA0=0;PORTAbits.RA2=1;
if(j%5==0){if(PORTAbits.RA1==1)motorzf();
87
else{
while(PORTAbits.RA3==1)motorzr();
}
}
}
for(j=0;j<Liney;j++){
if(my>25600)break;
motoryf();
if(j%5==0){if(PORTAbits.RA1==1)motorzf();
else{
}
}
}
Linex=0;Liney=0;
PORTDbits.RD2=1; // ENA(0 make drier output enable and logic 1 make output
disable
disable
PORTBbits.RB2=1; // ENA(0 make drier output enable and logic 1 make output
disable
CMDclr();
}
if(!strcmp(CMD,starta)){
for(j=0;j<120;j++){// Z axis Movement
PORTD=0xF0;
motorzf();
PORTD=0X00;
disable
}
//TON();while(!tr);tr=0;
j=0;while(j<40){j++;i=0;while(i<4000)i++;}
//for(j=0;j<40;j++)for(int i=0;i<4000;i++);
start_fill();
//motor();
CMDclr();
PORTA=0x00;
PORTB=0x00;
}
if(!strcmp(CMD,home)){
while(mx!=0)motorxr();
while(my!=0)motoryr();
CMDclr();
}
if(!strcmp(CMD,stop)){
88
PORTA=0x00;
CMDclr();
PORTB=0x00;
}
PORTDbits.RD2=1; // ENA(0 make drier output enable and logic 1 make output disable
PORTBbits.RB2=1; // ENA(0 make drier output enable and logic 1 make output disable
}
}
void CMDclr(){
for(k=0;k<=3;k++){
CMD[k]=0;i=0;
}
}
void motorxf(){mx=mx+1;
PORTDbits.RD4=1; // DIR(1 make clockwise rotation of motor and logic 0 make
anticlockwise rotation
PORTDbits.RD3=1; // PUL
p=0;while(p<30){p++;}
p=0;while(p<30){p++;}
}
void motorxr(){mx=mx-1;
p=0;while(p<30){p++;}
p=0;while(p<30){p++;}
}
void motoryf(){my=my+1;
p=0;while(p<30){p++;}
p=0;while(p<30){p++;}
}
void motoryr(){my=my-1;
p=0;while(p<25){p++;}
p=0;while(p<25){p++;}
89
}
void motorzf(){
PORTBbits.RB1=1; // DIR(1 make clockwise rotation of motor and logic 0 make
PORTBbits.RB0=1; // PUL
p=0;while(p<30){p++;}
p=0;while(p<30){p++;}
}
void motorzr(){
PORTBbits.RB1=0; // DIR(1 make clockwise rotation of motor and logic 0 make
p=0;while(p<25){p++;}
p=0;while(p<25){p++;}
}
void RS232(){
TX9=0; // 8 bit transmission
TXEN=1;// Transmit enable
SYNC=0; //Asynchronus mode
TXSTA=0x60;
SPEN=1;
RX9=0; // 8 bit reception
CREN=1; // Enable serial receive
RCSTA=0x90;
SPBRG=12;
}
int NOPul(){
for(j=0;j<=4;j++){ // Enter 4 Digit and 'H' as termination indicator
while(!RCIF);
Pvalue=RCREG;
TXREG=Pvalue;
switch(Pvalue){
case 0x30:Dec=10*Dec+0;break;
default: Decx=10*Decx+0;
}
}
return(Dec);
90
}
void motor(){
for(j=0;j<Decx;j++){//28800
if(r==1)motorxr(); // DIR(1 make clockwise rotation of motor and logic 0 make
else motorxf(); // DIR(1 make clockwise rotation of motor and logic 0 make anticlockwise
rotation
disable
disable
disable
if(mx>28800)break;
}
for(j=0;j<Decy;j++){//25600
if(r==1)motoryr(); // DIR(1 make clockwise rotation of motor and logic 0 make
else motoryf(); // DIR(1 make clockwise rotation of motor and logic 0 make anticlockwise
rotation
disable
disable
disable
if(mx>25600)break;
}
for(j=0;j<Decz;j++){
if(r==1)motorzr(); // DIR(1 make clockwise rotation of motor and logic 0 make anticlockwise
rotation
else motorzf(); // DIR(1 make clockwise rotation of motor and logic 0 make anticlockwise
rotation
disable
disable
disable
}
}
void start_fill(){int K;
K=0;while(K<=9){K++;
m=0;while(m<=8){m++;
// X axis Movement
if(fr==0x0000){j=0;while(j<=3200){j++;motorxf();}}
else if(fr==0xFFFF){j=0;while(j<=3200){j++;motorxr();}}
disable
91
disable
disable
j=0;while(j<=60000){j++;}
// Z axis Movement
if(PORTAbits.RA1==0){PORTAbits.RA0=1;PORTAbits.RA2=0;
}
j=0;while(j<=100){j++;motorzf();}
disable
disable
disable
j=0;while(j<=40){j++;i=0;while(i<=4000){i++;}}
}
// Y axis Movement
if(K<=9){
j=0;while(j<=2800){j++;motoryf();}
disable
disable
disable
}
// Z axis Movement
j=0;while(j<=100){j++;motorzf();}
disable
disable
disable
j=0;while(j<=40){j++;i=0;while(i<=4000){i++;}}
fr=~fr;
}
while(j<=25200){j++;motoryr();}
//while(j<=28800){j++;motorxr();}
}
3.2.5 Stepper Motor Driver
Driver is the crucial part for providing sufficient driving current for achieving the
movement of stepper motor in the automation system. Driver is composed of high current
92
circuitry that provides the sufficient current for converting electrical pulse into mechanical
movement. Stepper motor driver is designed to achieve customized step sequence to be
applied for fine movement control of stepper motor. The stepper motor driver designed here
can provide two step sequences for stepper motor movement and that are full step sequence
and half step sequence. The full step sequence provided by stepper motor driver will give the
resolution of 1.8° for angular motion and linear actuator with lead screw will convert angular
movement into 6.25µm of linear movement. Half step sequence will divide the step size of
stepper motor movement by the factor of 2 and giving the fine resolution for the movement of
stepper motor. To achieve more fine resolution of stepper motor movement Microstepping
electrical pulse sequence can be used as per application requirement. Here we have designed
a stepper motor driver that provides half and full step sequence for achieving linear
movement of stage for 6.25µm and 3.125µm respectively. The maximum load current rating
for driver designed and tested is 2 Amps and stepper motor used in the design of slurry filing
system and having current rating of less than 2 Amp hence driver deigned is efficient and
reliable to drive the stepper motor. The driver has been evaluated for its electrical and
functional characteristics. The driver has external control interfacing connector to connect a
PLC or microcontroller to control the action of stepper motor. The stepper motor rotation in
clockwise and anticlockwise direction can be controlled by applying the specific logic control
signal from microcontroller.
3.2.6 Design and Schematic
The stepper motor driver is designed using an H bridge driver IC L298 and a stepper
motor controller IC L297 compatible with L298. The L298 is an integrated monolithic circuit
in a 15-lead Multiwatt and PowerSO20 packages. It is a dual full bridge high current and high
voltage driver IC designed to accept TTL logic level and control the functioning of relay,
solenoids, DC and Stepping motor. L298 is operated with DC voltage in the range of 3 volt to
93
46 volt and it can drive the load having current consumption demand of maximum up to 2
Ampere. The schematic shown in figure 41 is the driver used for operating stepper motor for
full step and half step sequence. The stepper motor driver is designed and tested in lab for its
performance with stepper motor. With the help of driver shown in schematic 2 stepper motor
can bedriven in to two modes that are full stepping mode and half stepping mode in turn
giving the linear movement resolution of 6.25µm and 3.125µm respectively.
Figure 41: 2 Ampere stepper motor driver
Driver specifications:
1. Input supply power :< 46 volt
2. Maximum output current: 2 Ampere.
3. Operating temperature: -25 to 130 °C
4. Logic control voltage: 5 Volt
94
3.2.7 Micro-stepping Driver
The driver IC L298 used in previous design has more number of disadvantages like
requires more external component and produces more heat if used for long time to
compensate these shortcomings of L298 we have designed the Microstepping driver module
using DRV8825 IC. It comes in SMD package and requires few external components. In
addition it has more number of on chip functions.
DRV8825 is the bipolar stepper motor driver IC with on chip micro stepping indexer
of full, ½, ¼, 1/8, 1/16, 1/32 step options. DRV8825 has two phase output for connecting to
bipolar stepper motor, the maximum current that can be supplied per phase to stepper motor
inductive load is 2.5 A. Supply voltage range to be connected driver IC to drive stepper motor
is 8.2-45 volt and IC can be configured in multiple decay current mode.
DRV8825
STEP
Stepper Motor
+ +M -
DIR Driver
Controller
2.5A/phase -
Decay Mode
Step Size
nFAULT
1/32 µsteps
Figure 1: Stepper Motor driver controller
Design Requirements:
Sr. No Parameter Reference symbol Example Value
1 Supply voltage VM 24 V
2 Motor winding resistance RL 1.7 Ω
95
3 Motor Winding Inductance L 1.8 mH
4 Motor Full Step Angle θstep 1.80/step
5 Target Microstepping Level nm 8µsteps per step
6 Target Motor Speed v 120 rpm
7 Target Full-Scale Current Ifs 1.25A
Detailed design procedure:
To start with the design of stepper motor driver module requires the desired motor
speed and micro stepping level. If the specific application requires constant speed then a
square wave of constant frequency Fstep must be applied to STEP pin of DRV8825.
For a desired motor speed (v), microstepping level (nm), and motor full speed angle (θstep),
µ𝑠𝑡𝑒𝑝𝑠 360° 𝑟𝑜𝑡𝑎𝑡𝑖𝑜𝑛𝑠

𝑛𝑚 × 𝑟𝑜𝑡𝑎𝑡𝑖𝑜𝑛 × 𝑣
𝑠𝑡𝑒𝑝 𝑚𝑖𝑛𝑢𝑡𝑒
𝐹𝑠𝑡𝑒𝑝 µ𝑠𝑡𝑒𝑝𝑠 𝑠𝑒𝑐𝑜𝑛𝑑 = 𝑠𝑒𝑐𝑜𝑛𝑑𝑠 °
60 × 1.8
𝑚𝑖𝑛𝑢𝑡𝑒 𝑠𝑡𝑒𝑝
µ𝑠𝑡𝑒𝑝𝑠 360° 𝑟𝑜𝑡𝑎𝑡𝑖𝑜𝑛𝑠

8 × 𝑟𝑜𝑡𝑎𝑡𝑖𝑜𝑛 × 120
𝑠𝑡𝑒𝑝 𝑚𝑖𝑛𝑢𝑡𝑒
𝐹𝑠𝑡𝑒 𝑝 µ𝑠𝑡𝑒𝑝𝑠 𝑠𝑒𝑐𝑜𝑛𝑑 = 𝑠𝑒𝑐𝑜𝑛𝑑𝑠 °
60 × 1.8
𝑚𝑖𝑛𝑢𝑡𝑒 𝑠𝑡𝑒𝑝
Fstep=11.52 KHz (Fstep maximum can be set is 250 KHz)

Movement of rotation for linear actuator with Fstep of 11.52 kHz is 0.78125 µm. stepper
motor provides more resolution when we go for higher microstepping. Highest resolution that
can be possible with DRV8825 and stepper motor BH42SH38-1684LA is around 195 nm.
θstep can be found in the datasheet of particular stepper motor, in this case stepper motor
model number BH42SH38-1684LA designed by Bholanath Pvt. Ltd is having 1.8° of step
angle.For the DRV8825, the microstepping level is set by the MODE pins and can be any of
the settings in Table 1.Higher microstepping will mean a smoother motor motion and less
audible noise, but will increase switching losses and require a higher Fstep to achieve the same
motor speed.
Table 1: Microstepping index selection logic
96
Sr. no MODE2 MODE1 MODE0 STEP MODE
1 0 0 0 Full step (2-phase excitation) with 71% current
2 0 0 1 1/2 step (1-2 phase excitation)
3 0 1 0 1/4 step (W1-2 phase excitation)
4 0 1 1 8 microsteps/step
Current regulation:
In a stepper motor, the set full-scale current (IFS) is the maximum current driven through
either winding. This quantity mainly depends on the xVREF analog voltage and the sense
resistor value (Rsense). During stepping, IFS defines the current chopping threshold (ITRIP) for
the maximum current step.
𝑥𝑉𝑅𝐸𝐹(𝑉)
𝐼𝐹𝑆 (𝐴) =
𝐴𝑣 × 𝑅𝑠𝑒𝑛𝑠𝑒 (𝛺)
𝑥𝑉𝑅𝐸𝐹(𝑉)
𝐼𝐹𝑆 (𝐴) =
5 × 𝑅𝑠𝑒𝑛𝑠𝑒 (𝛺)
To set targeted IFS=1.25A with Rsense=0.2 Ω, xVREF should be 1.25 V.
Decay Mode:
The DRV8825 supports three different decay modes: slow decay, fast decay, and mixed
decay. The current through the motor windings is regulated using a fixed-frequency PWM
scheme. This means that after any drive phase, when a motor winding current has hit the
current chopping threshold (ITRIP), the DRV8825 will place the winding in one of the three
decay modes until the PWM cycle has expired. Afterward, a new drive phase starts. The
blanking time, tBLANK, defines the minimum drive time for the current chopping. ITRIP is
ignored during tBLANK, so the winding current may overshoot the trip level.
3.3 Testing and Results

Dispenser designed for dispensing slurry of material on the surface of MED has been
designed with three axis control using stepper motor linear actuator. Extensive testing of
97
stepper motor has been carried out for its movement for half step sequence and full step
sequence. The angular to linear movement of stepper motor specified in datasheet is 6.25µm
and 3.125µm for full and half step sequence respectively. The same has been verified using
Mitutoys Dial gauge in the dispenser system. The mounting plate of the dispenser has 100
holes to put MED samples in each hole so that dispenser will automatically move the
mounting plate sequentially to accurately dispense slurry of explosive material on each
sample. In one stroke 100 samples can be pasted with explosive material approximately.
Time taken by dispenser to carry out the task of putting explosive slurry on to MED sample
in approximately less than 10 Minutes. The embedded software has been designed in
MPLAB IDE to carry out automatic task of explosive filling on to the MED samples.
Controller module is tested with embedded program for its performance and accuracy.
The movement of all there axis X, Y and Z is measured by applying different no of
pulses from controller to driver. Pulses applied to rotate the stepper motor in discrete steps
precisely convert the rotational motion into linear motion and that is measured using micro
dial gauge meter from Mitutoyo brand. Linear displacement of each axis is measured using
micrometer dial gauge instrument. Reading for different number of pulses is recorded to test
the reputability of linear movement of each axis. The table 2 shown below is having linear
movement of each axis recorded using micrometer dial gauge instrument.
Table 8: Measurement of linear movement for stage
Sr. Initial Final No. of Displacement(µm) Displacement

Position(µm) Position(µm) pulses for single
no
pulse(µm)
1 224 258 10 34 3.4
2 258 351 20 93 4.65
3 351 433 30 82 2.733
4 433 575 40 142 3.55
5 575 729 50 154 3.08
6 729 913 60 184 3.06
7 913 1145 70 232 3.314
8 1145 1374 80 229 2.8625
9 1671 1969 90 298 3.11
10 1969 2280 100 311 3.11
98
Sr. Initial Final No. of Displacement(µm) Displacement
Position(µm) Position(µm) pulses for single
no
pulse(µm)
11 2280 3236 300 956 3.186
12 3236 4798 500 1562 3.124
13 4798 7011 700 2213 3.1614
14 7011 10122 1000 3111 3.11
15 10122 13990 1300 3868 2.97
16 13990 18686 1500 4696 3.13
Linear displacement for stage is practically measured for different number of pulses and same
has be tabulated in table 2. The measurement is taken to practically calculate the linear
displacement of half stepping sequence for stepper motor. As per specification data sheet
from stepper motor manufacturer linear displacement that can be achieved using stepper
motor is 3.125µm. The practical results revels that linear displacement for stepper motor is
around 3µm with less than ±5% accuracy.
99
Fig 42 –Micrometer dial gauge meter reading for the data provided in table 8
100
Specifications:
General:
1. Full stroke dispensing capacity: 2.5ml
2. Reservoir capacity: 100ml
3. Dispensing resolution: 10µl
4. X,Y,Z axis stage precision: 3.125 µm
5. X,Y,Z stage accuracy: <±5%
6. Manual and PC control interfaces
Electrical:
1. Motor Type: Step Motor
2. Microstepping: full and half
3. Advances per step: 6.25µm and 3.125µm
4. Operating voltage: 24 Volt DC @2 A
101
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Engineering Drawings of Dispenser Developed under this project
108
FIGURE 1: DISPENSER SUPPORTING ASSEMBLY
FIGURE 2: RAIL BLOCK
FIGURE 3: BEARING
FIGURE 4: LINKING PLATE
FIGURE 5: RAIL
FIGURE 6: LEAD SCREW NUT
FIGURE 7: BEARING HOLDER
FIGURE 8: SAMPLE
PLATE
FIGURE 9: MOTOR BRACKET
FIGURE 10: ALENKEY SCREW
FIGURE 11: BASE PLATE (Z)
FIGURE 12: BASE PLATE (X)
FIGURE 12: BASE PLATE(Y)
FIGURE 13: BOTTLE TOP DISPENSER
FIGURE 14: X,Y,Z AXIS ASSEMBLY
FIGURE 15: SLURRY FILING SYSTEM

Final Report On Design Development of Hi

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Final Report on

Design, Development of High Precision Explosive

1.1.1 Gas anti – solvent (GAS) Method

Nano Energetic Materials prepared by GAS Method

Energetic Material Particle size Characterization Ref.

Structure of HMX Structure of RDX

Figure2. Graphical representation of the RESS-AS process

Figure4. Experimental setup

RDX 110-220 nm FESEM, HPLC, XRD, 25

1.2 Crystallization Method

1.2.1 Sonocrystallization Method

Figure6. Experimental setup of pressure intensity measurement by hydrophone with FFT

Nano Energetic Materials prepared by Sonocrystallization Method

Structure of RDX Structure of CL-20

Figure10. A diagrammatic representation of the crystallization apparatus

Nano Energetic Materials prepared by Cooling Crystallization Method

Energetic Material Particle size Characterization Ref.

Nano Energetic Materials prepared by Nozzle assisted Solvent/Nonsolvent Method

Structure of HMX Structure of TATB

Figure12. Schematic drawing of preparation instrument

Nano Energetic Materials prepared by Nozzle assisted Solvent/Nonsolvent Method

Energetic Material Particle size Characterization Ref.

Nano Energetic Materials prepared by Prefilming twin fluid Nozzle assisted

Energetic Material Particle size Characterization Ref.

1.4.1 Ultrasonic Spray Method

Figure15. Schematic diagram of experimental setup for evaporation crystallization with

1.4.2 Spray freeze-drying Method

Nano Energetic Materials prepared by Spray Freeze Drying Method

Energetic Material Particle size Characterization Ref.

Figure18. Process scheme of electrospray crystallization

1.5 Sol-gel processing

CL-20 20-200 nm TEM, AFM, XRD, FTIR, DSC 5

HMX 100 nm FIB-SEM, TEM, XRD, HPLC 14

1.6.1 Rigid template

Nano Energetic Materials prepared by Rigid Template Method

H2N NO2 NO2

Nano Energetic Materials prepared by Wet chemical assisted Template Method

PETN 40-300 nm AFM, PSD 30

O2N O H2C CH2 O NO2

Military Commercial Gun Rocket

Primary Military Commercial Gun Rocket

Figure23: Classification of explosive composition by nitration reaction

FOg-7 (2, Scheme 2) is prepared by the hydrolysis of 2-(dinitromethylene)-4, 5-

2.1.4 Solubility of FOX-7

2.1.5 Spectral Studies:

2.1.6 Thermal and sensitivity studies

2.2 Ammonium salt of dinitramidic acid(ADN)

2.1.1 Methods of Preparation of Dinitramide

2.3 2, 4, 6-triamino-1, 3, 5-trinitrobenzene

2.3.1 Synthesis and Manufacturing:

The current industrial method is to nitrate 1, 3, 5- trichlorobenzene to give 2, 4, 6-trichloro-

Figure 26:Experimental IR Spectrum of TATB. Reproduced from Ref. 24

Table 2: Summary of assignment of vibrational modes, cm-1.

Figure 27: DSC Profile of TATB. Reproduced from Ref. [28].

2.4 Bis-(5-nitro-2H-tetrazolato-N2)tetraammine cobalt(III)

5-Aminotetrazole mono hydrate is prepared by treating dicyanamide with sodium azide in

b) Preparation of Sodium 5-nitrotetrazole dihydrate

5-Nitrotetrazole is the most energetic of the tetrazoles[81,88]. The diazotization of 5-

c) Preparation of Carbonato tetra amine cobalt(III) Nitrate (CTCN)

The synthesis of CTCN was accomplished by method as reported by schlessinger G.

The preparation of BNCP was accomplished by conventional co-ordination chemistry

Figure 28. Block diagram of various stages involved in BNCP synthesis

Method 1 Method 2 Method 3 Method 4