MISSILE TECHNOLOGY CONTROL REGIME (MTCR): THE

C O N F I D E N T I A L STATE 104822


PARIS FOR EST: HELEN SMITH
LONDON FOR CHRIS PALMER
CANBERRA FOR CAROL HANLON

E.O. 12958: DECL: 10/01/2033
TAGS: MTCRE ETTC KSCA MNUC PARM TSPA FR UK AS

SUBJECT: MISSILE TECHNOLOGY CONTROL REGIME (MTCR): THE
PERCHLORATE FAMILY OF CHEMICALS

Classified By: ISN/MTR Director Pam Durham.
Reasons: 1.4 (B),(D),(H).


1. (U) This is an action request. Please see paragraph 2.


2. (C) ACTION REQUEST: Department requests Embassy Paris
provide the interagency cleared paper "The Perchlorate Family
of Chemicals" in paragraph 3 below to the French Missile
Technology Control Regime (MTCR) Point of Contact (POC) for
distribution to all Partners. Department also requests
Embassy London provide paper to the MTCR Information Exchange
(IE) Co-Chair (John Andrews),and Embassy Canberra provide
paper to the Australian MTCR Plenary Chair for 2008/2009
and/or appropriate staff. Info addressees also may provide
to host government officials as appropriate. In delivering
paper, posts should indicate that the U.S. is sharing this
paper as part of our preparation for the Information Exchange
that will be held in conjunction with the MTCR Plenary in
Canberra (November 3-7). NOTE: Additional IE papers will be
provided via septels. END NOTE.


3. (C) BEGIN TEXT OF PAPER:

(CONFIDENTIAL REL MTCR)


The Perchlorate Family of Chemicals

Perchlorate is the chemical name used for the salts of
perchloric acid. All perchlorates are strong oxidizing
agents, and as such, they have found application in energetic
formulations to include propellants, explosives, and
pyrotechnics. Numerous perchlorate salts exist. However,
this paper will only deal with ammonium perchlorate (NH4ClO4,
AP),potassium perchlorate (KClO4, KP, or PP) and sodium
perchlorate (NaClO4, NaP, or SP) because of either their
energetic properties or their potential use in creating more
energetic perchlorates. AP is the most important perchlorate
in terms of solid propellants for ballistic missiles and is
controlled specifically by the Missile Technology Control
Regime (MTCR). Neither KP nor NaP is controlled specifically
by the MTCR. KP has limited value in solid propellants for
ballistic missiles, although it may be used in a mixture for
igniters. There is no known use of NaP directly in solid
propellants for ballistic missiles. However, both NaP and KP
can be converted to
AP.

This paper will discuss the preparation of perchlorates, the
use of perchlorates in energetic formulations with emphasis
on solid propellants for ballistic missiles, and the current
MTCR controls on perchlorates.

Preparation of Perchlorates

Almost all commercial perchlorate preparation-including that
of AP and KP-involves the oxidation of sodium chloride to
sodium perchlorate. Sodium perchlorate is most often
converted to the other more widely used perchlorate salts
including AP and KP, but can also be used itself in some
applications.

Complete preparation of perchlorates can be costly in terms
of resource consumption and technical expertise. Both
processes, oxidation to sodium perchlorate and conversion of
sodium perchlorate to other perchlorate salts, require some
degree of technical know-how and equipment. The oxidation
process is a larger technical challenge and requires more
specialized equipment. On the other hand, conversion of
sodium perchlorate to AP or KP is much simpler, and the
purchase of sodium perchlorate may be more attractive to
programs of concern since it avoids the expense and
difficulties of the sodium perchlorate oxidation process.
Therefore, the lack of MTCR control on sodium perchlorate
allows for the potential for a country/entity to make AP with
less investment in equipment, facilities, and process
engineering.


Oxidization of Sodium Chlorate and Sodium Perchlorate

The oxidation of sodium chloride to sodium perchlorate is
conducted in two stages. Sodium chloride (NaCl) is first
oxidized to sodium chlorate (NaClO3) and then to sodium
perchlorate (NaClO4). Both oxidation stages are electrolytic
(electrochemical) processes conducted in aqueous solution.
Water is the source of oxygen incorporated into the chloride
to make the chlorate and perchlorate species. Sodium
chloride is the best starting material for the synthesis of
chlorates and perchlorates by this process because all of the
sodium salts (chloride, chlorate, and perchlorate) are
readily soluble in water.

The oxidation of sodium chloride to sodium chlorate and
sodium perchlorate normally requires two steps and requires
specialized equipment (electrolytic cells and anodes) and
substantial technical knowledge to engineer the process and
to make and maintain the equipment. The oxidation steps also
require significant electrical power input, and the cost of
the electrical power must be reasonably inexpensive to make
low-cost perchlorate. The second stage of the oxidation
process requires substantially more electric power because it
becomes more difficult to add the fourth oxygen atom to the
molecule in the conversion of chlorate to perchlorate.

At the completion of the second oxidation stage, sodium
perchlorate, typically in the form of its monohydrate (NaClO4
with one H2O) can be obtained from the aqueous solution by
concentration, precipitation, and filtration. However, since
sodium perchlorate has only limited uses, the aqueous
solution of sodium perchlorate is more often used in the
preparation of other perchlorates such as AP and KP.

Conversion of Sodium Perchlorate to AP and KP

Both AP and KP are less water soluble than NaP. Therefore,
they can readily be precipitated from an aqueous solution of
NaP by addition of the appropriate ammonium or potassium
salt. For example, to make AP, ammonium chloride can be
added to precipitate AP and leave the very soluble sodium
chloride in solution. Conversely, to make KP, potassium
chloride is added to precipitate KP and leave sodium chloride
in solution. Both AP and KP can be isolated in good yield by
concentration, precipitation, and filtration. The isolated
perchlorate (either AP or KP) is typically recrystallized
from water to obtain the desired purity and particle size
before further use.

The process equipment used to convert sodium perchlorate to
AP or KP is not specialized and involves relatively low
technology. It is an ordinary assemblage of steel, tanks,
pumps, heat exchanger, and piping.


Other Conversion Processes for KP to AP

Processes to convert KP to AP have been reported in the
chemical literature and several patents exist. These
processes will not be discussed in detail, however, as they
generally involve non-aqueous solvents and/or ion exchange
resins. The use of these types of organic materials with
perchlorates poses increased safety risks (fire and
explosion) compared to the aqueous process used in the
conversion of NaP to AP. Furthermore, we are not aware of
the large-scale, commercial demonstration of any of the
processes for converting KP to AP. However, the existence of
these potential processes for conversion of KP to AP must be
acknowledged. These processes could be used by a
country/entity that needs AP, but lacks the ability to
make/obtain NaP and has access to KP.

Uses of AP, KP, and NaP

AP is the most widely used oxidizer in solid propellant
formulations. AP can also be used in explosive and
pyrotechnic formulations. Typical composite propellants
contain 60 to 70% AP. Solid rocket motors used in the
various stages of ballistic missiles are loaded with
thousands of kilograms of propellant. Therefore, large
quantities of low-cost, high-quality AP are required to make
a substantial number of ballistic missiles of any type.

KP can be used as an oxidizer in solid propellant
formulations, but it is inferior to AP in terms of
performance. The theoretical specific impulse values of
KP-based formulations are approximately 15% lower than
corresponding AP-based formulations. The low performance
compared to AP is the principle reason KP is not widely used
in ballistic missiles. However, in the past KP has been used
in some solid rocket motors for ballistic missiles and
battlefield rockets.

KP cannot be used as a direct substitute for AP, and any
substitution would require a complete redesign of the solid
propellant rocket motor. In addition to lower specific
impulse performance, formulations containing KP have higher
density values (KP is denser than AP),different burning
characteristics (burning rate, pressure exponent, temperature
sensitivity),and signature (KCl is a combustion species)
than formulations containing AP, all of which are key factors
for solid rocket motor design. This replacement of oxidizers
would most likely require significant design changes and a
motor requalification effort.

KP is widely used as the oxidizer in explosive and
pyrotechnic formulations. The Merck Index lists other uses
for KP in photography, analytical chemistry, and in at least
some medical treatments. Most of the explosive formulations
with KP are used for commercial purposes since military
explosives typically contain high energy explosives such as
PETN, HMX, and RDX. Furthermore, the use of KP and other
perchlorates in commercial explosives has diminished recently
due to environmental concerns over groundwater contamination
by perchlorates. The pyrotechnic formulations with KP
include automotive airbag inflation units, fireworks, flares,
and initiation/ignition materials.

Sodium perchlorate has only limited uses, and is used
primarily as a precursor to the other perchlorate
salts-especially AP and KP. The use of sodium perchlorate in
energetic formulations is hampered significantly by its
tendency to pick up moisture. The fact that its most stable
crystalline form is a monohydrate also makes it less
attractive in energetic formations. Like KP, sodium
perchlorate has been used in explosive and pyrotechnic
formulations and to treat hyperthyroidism, although such uses
do not appear to be widespread.

Current MTCR Control of Perchlorates

The MTCR Technical Annex contains several items dealing with
perchlorates in general as well as specific perchlorates.

MTCR Technical Annex item 4.C.3 controls any perchlorate when
it is mixed with powdered metals or other high energy fuel
components. Binary mixtures of a perchlorate with a powdered
metal or a high energy fuel component would be expected to be
extremely dangerous to handle. Therefore, this section of
the MTCR Technical Annex deals with complete formulations or
sub-mixes where sufficient other ingredients are present to
make the combination safe to handle. Complete formulations
are often shipped in ignition devices or some other smaller
component of a ballistic missile.

Specific perchlorates are mentioned in MTCR items 4.C.2.b.16
(hydrazinium perchlorate),4.C.2.b.17 (hydrazinium
diperchlorate),and 4.C.4.b.1 (ammonium perchlorate). Of
these specifically controlled perchlorates, AP is the most
important to solid propellant formulations for ballistic
missiles.

Sodium perchlorate and potassium perchlorate are not
specifically controlled by the MTCR. Individually, neither
sodium perchlorate nor potassium perchlorate can be directly
used in the manufacture of solid propellant formulations used
in ballistic missiles. However, both sodium perchlorate and
potassium perchlorate are of concern -- SP to a greater
degree -- and both can be used as precursors for AP
production. Therefore, a country/entity that desires AP for
use in ballistic missiles but lacks the ability to oxidize
chlorides to perchlorates could obtain sodium perchlorate or
potassium perchlorate and convert it to AP.

END TEXT OF PAPER.


4. (U) Please slug any reporting on this or other MTCR
issues for ISN/MTR. A word version of this document will be
posted at www.state.sgov.gov/demarche.
RICE


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